CN103482680B - A kind of technique of being produced nano zine oxide by secondary zinc oxide - Google Patents
A kind of technique of being produced nano zine oxide by secondary zinc oxide Download PDFInfo
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- CN103482680B CN103482680B CN201310387427.7A CN201310387427A CN103482680B CN 103482680 B CN103482680 B CN 103482680B CN 201310387427 A CN201310387427 A CN 201310387427A CN 103482680 B CN103482680 B CN 103482680B
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Abstract
A kind of technique of being produced nano zine oxide by secondary zinc oxide of the present invention, comprise and leach operation, cleaning section, precipitation operation, calcination process, described leaching operation take secondary zinc oxide as raw material, with hydrochloric acid reaction, generates rough liquor zinci chloridi; Described cleaning section is, controls suitable pH value by leaching the rough liquor zinci chloridi that obtains of operation, and after adding the removal of impurities of clorox once oxidation, adding the twice replaced removal of impurities of zinc powder, obtains the liquor zinci chloridi refined; Described precipitation operation react with sodium hydroxide solution by the refining liquor zinci chloridi obtained in cleaning section, generation zinc hydroxide slip, this slip more after filtration, wash, drying obtains zinc hydroxide; Zinc hydroxide precipitation operation obtained, through the obtained active zinc flower of calcining, achieves the comprehensive utilization and Sustainable development that realize resource, has good economy, environmental and social benefits.
Description
Technical field
The invention belongs to nonferrous metallurgy chemical engineering industry technical field, be specifically related to a kind of technique of being produced nano zine oxide by secondary zinc oxide.
Background technology
China is nonferrous production state maximum in the world, plumbous zinc output the first in the world.Main production process main is at present pyrometallurgical smelting, the secondary zinc oxide waste residue that meeting output is a large amount of in Lead-Zinc Sintering Process, in waste residue, (main component is ZnO to secondary zinc oxide, grade is 45% ~ 80%) proportion is quite large, containing multiple precious metal, there is very large recovery value.Compared with secondary zinc oxide, nano zine oxide is a kind of polyfunctional new inorganic material, and its granular size is about 1 ~ 100 nanometer.Discovered in recent years it in catalysis, optics, magnetics, mechanics etc., show many odd number solution, make it have important using value in many fields such as pottery, chemical industry, optics, biology, medicine.
Ye Shi chlor-alkali big country of China, has the chlor-alkali plant of One's name is legion.In the process of producing polyvinyl chloride, also a large amount of by-product hydrochloric acids can be produced, due to the impact of national policy and economic situation, zero price sales does not process the hydrochloric acid accumulated yet, the words do not processed will affect the normal production of enterprise, at present a lot of chlor-alkali plant takes the treatment process of hydrochloric acid and carbide slag being reacted landfill afterwards, and not only wastes resource like this, also exerts a certain influence to the soil of surrounding and water quality.
Summary of the invention
The object of the invention is to substitute vitriol lixiviation process secondary zinc oxide waste residue to produce nano zine oxide with hydrochloric acid acidleach, a kind of new secondary zinc oxide synthetical recovery process for cleanly preparing is provided.
For achieving the above object, the technical scheme that the present invention takes is, a kind of technique of being produced nano zine oxide by secondary zinc oxide, concrete steps comprise: leach operation, cleaning section, precipitation operation, calcination process, described leaching operation take secondary zinc oxide as raw material, react with concentrated hydrochloric acid, generate rough liquor zinci chloridi; Described cleaning section is, controls suitable pH value by leaching the rough liquor zinci chloridi that obtains of operation, and after adding the removal of impurities of clorox once oxidation, adding the twice replaced removal of impurities of zinc powder, obtains the liquor zinci chloridi refined; Described precipitation operation react with sodium hydroxide solution by the refining liquor zinci chloridi obtained in cleaning section, generation zinc hydroxide slip, this slip more after filtration, wash, drying obtains zinc hydroxide; Described calcination operation is that the zinc hydroxide that precipitation operation obtains is obtained active zinc flower through calcining.
In above-mentioned leaching operation, the volume ratio V of concentrated hydrochloric acid and water
concentrated hydrochloric acid/ V
waterbe 0.75 ~ 1, the mass concentration of concentrated hydrochloric acid is 30 ~ 40%, liquid-solid ratio is 4.5 ~ 5.5L/kg, and temperature of reaction is 40 ~ 70 DEG C, and the reaction times is 40 ~ 120min.
In described cleaning section, pH value controls at 4.5-5, and temperature of reaction is 40 ~ 80 DEG C.
In described cleaning section, clorox add-on is 0.18 ~ 0.21g/kg secondary zinc oxide, and the add-on of zinc powder is 3.75 ~ 4.35g/kg secondary zinc oxide.
Described precipitation operation is added drop-wise in sodium hydroxide solution by liquor zinci chloridi and reacts, and the temperature of precipitin reaction is 60 DEG C ~ 90 DEG C, and the reaction times is 30min ~ 40min, the ratio 2.1 ~ 2.4 of sodium hydroxide and the amount of substance of zinc chloride.
The calcining temperature of described calcination process is 450 ~ 500 DEG C, and the calcination time is 0.5 ~ 1.5h.
The present invention is main with chlor-alkali plant joint construction or solely built by chlor-alkali plant, and its beneficial effect is: one is the product that the raw material (hydrochloric acid, sodium hydroxide, clorox) used in production nano zine oxide process is chlor-alkali enterprises, and cost is low; Two be produce directly can utilize chlor-alkali enterprises in nano zine oxide process sodium hydroxide and hydrochloric acid stoste as raw material, reduce the concentration process of product, reduce production cost further; Three is fully consume the hydrochloric acid (produce one ton of secondary zinc oxide and about use concentrated hydrochloric acid 2.5 ~ 3 tons) that chlor-alkali enterprises process do not fall, not only cost reduces (hydrochloric acid present cost is zero), more be conducive to further developing of enterprise, also saving the carbide slag consumed for processing hydrochloric acid, avoiding the pollution of environment; Four is be sodium chloride brine producing the by product produced in nano zine oxide process, can be used as the raw material of chlor-alkali plant electrolytic saltwater, again sodium hydroxide and hydrochloric acid is generated after electrochemical machining, continue on for the process that secondary zinc oxide produces nano zine oxide, thus eliminate discharging any waste liquor, avoid environmental pollution.Therefore this technique not only solves the two large problems of existing technique, environmental pollution is avoided while reducing production cost, also processed the hydrochloric acid that chlor-alkali enterprises accumulates, had good economic benefit, environmental benefit and social benefit, also realize comprehensive utilization and the Sustainable development of resource.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
(the volume ratio V of reaction conditions to be liquid-solid ratio be 5.5L/kg, concentrated hydrochloric acid and water is reacted with secondary zinc oxide (main component is ZnO, and grade is 82%) and concentrated hydrochloric acid
concentrated hydrochloric acid/ V
waterbe 0.75, the mass concentration of concentrated hydrochloric acid is 36%, temperature of reaction is 40 DEG C, and the reaction times is 120min).Then gained solution is filtered, NaClO solution (0.18g/kg secondary zinc oxide) is added in filtrate, control ph is 5, temperature of reaction 70 DEG C, reaction 2h, ageing 0.5h, then filter, zinc powder (3.75g/kg secondary zinc oxide) is added in filtrate, controlling reacting liquid temperature is 40 DEG C, and displacement 1h, filters, obtain that zinc ion concentration is 1.538mol/L, Fe and Mn concentration is respectively 0.464mg/L, 0.147mg/L, lead, copper, concentration of cadmium ions are the liquor zinci chloridi of 0.361mg/L, 0.011mg/L, 0.036mg/L.Take sodium hydroxide as precipitation agent, be added drop-wise to by liquor zinci chloridi in sodium hydroxide solution, sodium hydroxide is 2.1:1 with the ratio of the amount of substance of zinc chloride, and temperature of reaction is 90 DEG C, and the reaction times is 40min, filters, dry.Then calcine, calcining temperature is 450 DEG C, and calcination time is 1.5h, obtains nano zine oxide solid.The ZnO particle prepared is hexagonal system ZnO, and pattern is spherical, and average grain size is about 40nm; Particle size distribution is even, favorable dispersity, according to productive rate and the purity of the ZnO product prepared under GB/T19589-2004 standard method analysis optimization experiment condition, measurement result is ZnO productive rate is 96.2%, ZnO massfraction 97.5%, purity reaches 2 series products standards.
The present embodiment products obtained therefrom index and GB GB/T19589-2004 set quota are to such as table 1:
Embodiment 2
React with secondary zinc oxide (main component is ZnO, and grade is 82%) and concentrated hydrochloric acid, the volume ratio V of concentrated hydrochloric acid and water
concentrated hydrochloric acid/ V
waterbe 1, the mass concentration of concentrated hydrochloric acid is 30%, liquid-solid ratio is 4.5L/kg, and temperature of reaction is 55 DEG C, and the reaction times is 40min).Then gained solution is filtered, NaClO solution (0.20g/kg secondary zinc oxide) is added in filtrate, control ph is 4.5, temperature of reaction 40 DEG C, reaction 2h, ageing 0.5h, then filter, zinc powder (4.10g/kg secondary zinc oxide) is added in filtrate, controlling reacting liquid temperature is 40 DEG C, and displacement 1h, filters, obtain that zinc ion concentration is 1.503mol/L, Fe and Mn concentration is respectively 0.407mg/L, 0.138mg/L, lead, copper, concentration of cadmium ions are the liquor zinci chloridi of 0.348mg/L, 0.010mg/L, 0.035mg/L.。Take sodium hydroxide as precipitation agent, be added drop-wise to by liquor zinci chloridi in sodium hydroxide solution, sodium hydroxide is 2.4:1 with the ratio of the amount of substance of zinc chloride, and temperature of reaction is 60 DEG C, and the reaction times is 35min, filters, dry.Then calcine, calcining temperature is 480 DEG C, and calcination time is 1h, obtains nano zine oxide solid.The ZnO particle prepared is hexagonal system ZnO, and pattern is spherical, and average grain size is about 80nm; Particle size distribution is even, favorable dispersity, according to productive rate and the purity of the ZnO product prepared under GB/T19589-2004 standard method analysis optimization experiment condition, measurement result is ZnO productive rate is 94.0%, ZnO massfraction 97.7%, purity reaches 2 series products standards.
The present embodiment products obtained therefrom index and GB GB/T19589-2004 set quota are to such as table 2:
Embodiment 3
React with secondary zinc oxide (main component is ZnO, and grade is 82%) and concentrated hydrochloric acid, the volume ratio V of concentrated hydrochloric acid and water
concentrated hydrochloric acid/ V
waterbe 0.9, the mass concentration of concentrated hydrochloric acid is 40%, liquid-solid ratio is 5L/kg, and temperature of reaction is 70 DEG C, and the reaction times is 80min.Then gained solution is filtered, NaClO solution (0.21g/kg secondary zinc oxide) is added in filtrate, control ph is 4.8, temperature of reaction 80 DEG C, reaction 2h, ageing 0.5h, then filter, zinc powder (4.35g/kg secondary zinc oxide) is added in filtrate, controlling reacting liquid temperature is 40 DEG C, and displacement 1h, filters, obtain that zinc ion concentration is 1.546mol/L, Fe and Mn concentration is respectively 0.397mg/L, 0.131mg/L, lead, copper, concentration of cadmium ions are the liquor zinci chloridi of 0.326mg/L, 0.010mg/L, 0.035mg/L.Take sodium hydroxide as precipitation agent, be added drop-wise to by liquor zinci chloridi in sodium hydroxide solution, sodium hydroxide is 2.2:1 with the ratio of the amount of substance of zinc chloride, and temperature of reaction is 75 DEG C, and the reaction times is 30min, filters, dry.Then calcine, calcining temperature is 500 DEG C, and calcination time is 0.5h, obtains nano zine oxide solid.The ZnO particle prepared is hexagonal system ZnO, and pattern is spherical, and average grain size is about 55nm; Particle size distribution is even, favorable dispersity, according to productive rate and the purity of the ZnO product prepared under GB/T19589-2004 standard method analysis optimization experiment condition, measurement result is ZnO productive rate is 96.7%, ZnO massfraction 98.3%, purity reaches 2 series products standards.
The present embodiment products obtained therefrom index and GB GB/T19589-2004 set quota are to such as table 3:
Claims (1)
1. produced the technique of nano zine oxide by secondary zinc oxide for one kind, it is characterized in that, concrete steps comprise: leach operation, cleaning section, precipitation operation, calcination process, described leaching operation take secondary zinc oxide as raw material, react with concentrated hydrochloric acid, generate rough liquor zinci chloridi; Described cleaning section is, controls suitable pH value by leaching the rough liquor zinci chloridi that obtains of operation, and after adding the removal of impurities of clorox once oxidation, adding the twice replaced removal of impurities of zinc powder, obtains the liquor zinci chloridi refined; Described precipitation operation react with sodium hydroxide solution by the refining liquor zinci chloridi obtained in cleaning section, generation zinc hydroxide slip, this slip more after filtration, wash, drying obtains zinc hydroxide; Described calcination process is that the zinc hydroxide that precipitation operation obtains is obtained active zinc flower through calcining; The volume ratio V of concentrated hydrochloric acid and water
concentrated hydrochloric acid/ V
waterbe 0.9, the mass concentration of concentrated hydrochloric acid is 40%, liquid-solid ratio is 5L/kg, and temperature of reaction is 70 DEG C, and the reaction times is 80min; In described cleaning section, pH value controls 4.8, and temperature of reaction is 80 DEG C, reaction 2h, and ageing 0.5h, then filters; Clorox filtrate add-on in described cleaning section is 0.21g/kg secondary zinc oxide, and the add-on of zinc powder is 4.35g/kg secondary zinc oxide; Described precipitation operation is added drop-wise in sodium hydroxide solution by liquor zinci chloridi and reacts, and the temperature of precipitin reaction is 75 DEG C, and the reaction times is 30min, the ratio 2.2:1 of sodium hydroxide and the amount of substance of zinc chloride; The calcining temperature of described calcination process is 500 DEG C, and calcination time is 0.5h.
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| CN104591259B (en) * | 2015-02-09 | 2017-02-22 | 黄有余 | Engraftment type nano-zinc oxide and production process thereof |
| CN106115765A (en) * | 2016-06-16 | 2016-11-16 | 安徽省含山县锦华氧化锌厂 | A kind of ultra-fine grain Zinc oxide powder production technology |
| CN106219594A (en) * | 2016-08-03 | 2016-12-14 | 王凯 | A kind of preparation method of nano zine oxide |
| CN110510661B (en) * | 2019-09-27 | 2021-09-14 | 王建中 | Environment-friendly preparation process of composite closed-loop grafting type battery-grade zinc chloride |
| CN110980799B (en) * | 2019-12-26 | 2022-05-31 | 江西省愚人纳米科技有限公司 | Preparation method of basic zinc chloride for feed |
| CN114906871B (en) * | 2022-06-08 | 2023-05-26 | 桂林理工大学 | Method for preparing nano zinc oxide by using secondary zinc oxide |
| CN115418495A (en) * | 2022-09-29 | 2022-12-02 | 西安建筑科技大学 | Method for preparing nano ZnO from fly ash of mechanical activation calcification roasting electric arc furnace |
| CN115676779B (en) * | 2022-10-27 | 2024-01-30 | 中盐常州化工股份有限公司 | Sodium hypochlorite stabilizer and preparation method thereof |
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| CN102583503B (en) * | 2011-01-18 | 2013-07-17 | 郴州市金贵银业股份有限公司 | Method for preparing activated zinc oxide by utilizing high-arsenic secondary zinc oxide resource ammonia-ammonium process |
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