CN100494069C - Preparing process of nano zinc oxide - Google Patents
Preparing process of nano zinc oxide Download PDFInfo
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- CN100494069C CN100494069C CNB2006101304777A CN200610130477A CN100494069C CN 100494069 C CN100494069 C CN 100494069C CN B2006101304777 A CNB2006101304777 A CN B2006101304777A CN 200610130477 A CN200610130477 A CN 200610130477A CN 100494069 C CN100494069 C CN 100494069C
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- zinc
- ammonia complex
- complex solution
- hot water
- mother liquor
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Abstract
The process of preparing nanometer zinc oxide with low grade zinc oxide containing material includes the following steps: leaching the material with the mixed solution of ammonium bicarbonate and ammonia, separating to eliminate insoluble impurity, redox to eliminate Fe, Mn, Pb and other metal impurity to obtain zinc-ammonia complex solution; heating the zinc-ammonia complex solution to 90-100 deg.c through continuous mixing with hot circular mother liquid or hot water for fast continuous decomposition of zinc-ammonia complex; controlling the flow rate ratio between the circular mother liquid and the zinc-ammonia complex solution in 2-20, separating the basic zinc carbonate crystal continuously from the decomposed solution; drying and roasting at 400-600 deg.c for 1-4 hr to obtain the nanometer zinc oxide product of homogeneous size 10-50 nm.
Description
Technical field
The invention belongs to the inorganic functional material field.The technology of preparing that relates to inorganic nano material, particularly a kind of nano-ZnO preparation: the continuous preparation technology with the presoma zinc subcarbonate is that the production nano-ZnO preparation is come on the basis.
Background technology
The technology of wet production zinc oxide mainly contains two kinds of pickling process and ammonia companion methods.To have an equipment anticorrosion less demanding because the ammonia companion method is compared with pickling process, and advantages such as recovery ammonia capable of circulation and carbonic acid gas become one of main method of producing zinc oxide.Traditional ammonia companion method technology mainly is made up of operations such as leaching, purification, pyrolysis, ammonia absorption, drying and roastings.Because traditional pyrolysis operations generally is will put into a container through purifying the zinc ammonia complex solution that obtains earlier, then with steam or electrically heated, heat up gradually and finish up to the zinc ammonia complex decomposition, it is long periodical operation process of a resolving time, in this process, the nucleus that begins to generate is grown up gradually, and the product that causes producing mainly is the big and uneven zinc oxide of granularity of crystalline particle.
Among the Chinese patent ZL03131516.X, a kind of improvement technology of producing zinc oxide technology at traditional ammonia companion method is disclosed.It adopts zinc baking sand and ammoniacal liquor and bicarbonate of ammonia reaction, through impurity and purification, obtain zinc ammonia complex solution, thin up zinc ammonia complex solution then, the part zinc ammonia complex is decomposed, finish up to the zinc ammonia complex decomposition with steam heating hydrolysis reaction solution then, obtain the zinc subcarbonate crystallization, and then the calcining obtain nano zine oxide, product cut size reaches 30～100 nanometers.
Theoretical and the reaction kinetics principle according to chemical equilibrium, because the decomposition reaction of zinc ammonia complex is a thermo-negative reaction, reactant has water to exist, so traditional thermal degradation method can obtain the degradation production zinc subcarbonate, and the adding of big water gaging also can make zinc ammonia complex decompose.The chemical equation of decomposition reaction is as follows:
3Zn(NH
3)
4CO
3+3H
2O＝ZnCO
3·2Zn(OH)
2·H
2O↓+2CO
2↑+12NH
3↑
Can promote zinc ammonia complex to decompose though add big water gaging in zinc ammonia complex solution, decomposition reaction will reach balance very soon, then need continuation hydrolyzed solution to be heated up by the method for heating, so that impel decomposition reaction to carry out fully.Owing to added a large amount of water during hydrolysis, next in order to impel decomposition reaction to carry out fully, long process of manipulation require to the hydrolyzed solution heating, and the new zinc subcarbonate that produces of thermal degradation will be in original nucleating surface growth afterwards, the crystal that impels the front hydrolyzing process to produce continues to grow up, cause the inhomogeneous or particle increase of zinc subcarbonate grain size number easily, make the finished product zinc oxide granularity be difficult to control.
Summary of the invention
The inventor is theoretical and crystallography principle according to chemical equilibrium, through test of many times, traditional ammonia companion method is produced zinc oxide technology improve.At first the zinc ammonia complex decomposition technique is improved to a successive processes, by the adjustment of processing condition, can controls the size of degradation production zinc subcarbonate grain size number, and then obtain even-grained nano oxidized zinc product by roasting.Its preparation process is as follows: the zinc ammonia complex solution that the ammonia companion method is obtained, circulating mother liquor or hot water with heat mixes continuously, thereby zinc ammonia complex is decomposed fast continuously, the zinc subcarbonate crystallization that simultaneously decomposition is obtained is separated continuously, and mother liquor is through heating and be used for as circulating mother liquor the decomposition of zinc ammonia complex continuously.Velocity ratio when mixing with zinc ammonia complex solution by the Control Circulation mother liquor reaches the purpose of controlling zinc subcarbonate crystalline particle size, and isolated zinc subcarbonate crystallization obtains the nano oxidized zinc product of even particle size through super-dry, roasting.
The present invention is a kind of nano-ZnO preparation, it is characterized in that comprising following process steps:
(1) adopting secondary zinc oxide or zinc baking sand is that the low levels oxidation zinc of 70-80% is raw material in ZnO content, and with the mixing solutions leaching of bicarbonate of ammonia and ammonia, its ratio is Zn:NH
3: CO
2=1:4-4.5:0.9-1 (mol ratio), stirring at normal temperature reaction 2-3 hour separates and removes insoluble impurities, and redox removes metallic impurity such as de-iron, manganese and lead, obtains zinc ammonia complex solution;
(2) with zinc ammonia complex solution, successively mix continuously with hot water and circulating mother liquor, hot water and circulating mother liquor are 90～100 ℃ through the temperature of continuous heat tracing, preferably 95～100 ℃; And circulation is used for decomposing continuously fast of zinc ammonia complex; Velocity ratio when control hot water and circulating mother liquor mix with zinc ammonia complex solution is 2～20, preferably 5～10;
(3) when decomposing continuously, the zinc subcarbonate crystallization that decomposition is finished in the liquid is separated continuously;
(4) with isolated zinc subcarbonate crystallizing and drying, roasting, at 400-600 ℃ of roasting 1-4 hour, preferably 500-600 ℃ roasting 2-4 hour, obtaining the even particle size median size is the nano oxidized zinc product of 10～50nm.
Concrete technical process of the present invention; Referring to accompanying drawing 1: the nano-ZnO preparation process flow diagram.
Zinc ammonia complex solution is to adopt traditional ammonia companion method technology to make.For example adopting low levels oxidation zinc such as secondary zinc oxide or zinc baking sand is raw material, and the mixing solutions leaching with bicarbonate of ammonia and ammonia separates and removes insoluble impurities, and redox removes metallic impurity such as de-iron, manganese and lead, obtains zinc ammonia complex solution.
Zinc ammonia complex solution carries out circulating mother liquor or mixing continuously of hot water with heat.The reaction that zinc ammonia complex decomposes was fast continuously finished in very short time.The pattern of reactor can be unrestricted, but need be with circulating mother liquor or the hot water quick thorough mixing of zinc ammonia complex solution with heat.
Decomposing the zinc subcarbonate precipitation that obtains needs in time to finish the liquid from decomposition to separate, so that obtain the product of target grain size.Separation method can adopt methods such as centrifugation or filtration.
The velocity ratio of circulating mother liquor and zinc ammonia complex solution is the key that obtains the target product granular size.Along with the increase of the velocity ratio of circulating mother liquor and zinc ammonia complex solution, the zinc subcarbonate crystallization median size that obtains will diminish, and the median size of the zinc oxide that drying and roasting obtain also diminishes corresponding.Controlling this ratio is being 2～20, can obtain the zinc oxide product of median size 10～50 nanometers.When this ratio 2 when following, the circulating mother liquor and the shortage of heat of carrying thereof are so that zinc ammonia complex decomposes finishes; When ratio 20 when above, though also can obtain the tiny zinc subcarbonate crystalline particle of particle, it is littler that the crystalline particle that decomposition reaction obtains is difficult to become, and will increase energy consumption.
Circulating mother liquor is heated and the process that shifts preferably is incubated,, need the heat energy that replenishes thereby reduce so that make the working cycle of mother liquor maintain higher temperature range.
Ammonia and carbonic acid gas that decomposition reaction generates can reclaim with common condensation or absorption process, through adjusting the leaching that can be used for secondary zinc oxide.
By technical scheme of the present invention, can produce the nano oxidized zinc product of even particle size.
Description of drawings
Accompanying drawing 1 is a nano-ZnO preparation process flow diagram of the present invention.
Embodiment
Embodiment 1:
Will be in the secondary zinc oxide of ZnO content 80% and the mixing solutions of ammonia and bicarbonate of ammonia, its ratio is Zn:NH
3: CO
2=1:4:0.9 (mol ratio) stirring at normal temperature reaction 2 hours, removes by filter insoluble impurities, removes metallic impurity such as de-iron, manganese and lead, the zinc ammonia complex solution that is purified through redox.Simultaneously continuously squeeze in tubular reactor with pump the hot water of zinc ammonia complex solution and 98 ℃, the velocity ratio of control hot water and zinc ammonia complex solution is 8, finish from decomposition and to isolate zinc subcarbonate precipitation the liquid continuously, and mother liquor is heated to 98 ℃ is recycled to reactor.With isolated zinc subcarbonate drying and 600 ℃ of roastings 2 hours, obtain the very narrow zinc oxide product of size distribution.Measure through transmission electron microscope and XRD line broadening method method, the zinc oxide median size is 40nm, BET specific surface area 55m
2/ g.
Embodiment 2:
Make zinc ammonia complex solution by embodiment 1 same method.Simultaneously continuously squeeze in tubular reactor with pump the hot water of zinc ammonia complex solution and 90 ℃, the velocity ratio of control hot water and zinc ammonia complex solution is 20, finish from decomposition and to isolate zinc subcarbonate precipitation the liquid continuously, and mother liquor is heated to 90 ℃ is recycled to reactor.With isolated zinc subcarbonate drying and 600 ℃ of roastings 2 hours, obtain the very narrow zinc oxide product of size distribution.Measure through transmission electron microscope and XRD line broadening method method, the zinc oxide median size is 10nm, BET specific surface area 62m
2/ g.
Embodiment 3:
Will be in the zinc baking sand of ZnO content 72% and the mixing solutions of ammonia and bicarbonate of ammonia, its ratio is Zn:NH
3: CO
2=1:4.5:1 (mol ratio) stirring at normal temperature reaction 3 hours, removes by filter insoluble impurities, removes metallic impurity such as ferrimanganic and lead through redox, the zinc ammonia complex solution that is purified.Simultaneously continuously squeeze in tubular reactor with pump the hot water of zinc ammonia complex solution and 95 ℃, the velocity ratio of control hot water and zinc ammonia complex solution is 5, finish from decomposition and to isolate zinc subcarbonate precipitation the liquid continuously, and mother liquor is heated to 95 ℃ is recycled to reactor.With isolated zinc subcarbonate drying and 600 ℃ of roastings 2 hours, obtain the very narrow zinc oxide product of size distribution.Measure through transmission electron microscope and XRD line broadening method method, the zinc oxide median size is 30nm, BET specific surface area 58m
2/ g.
Embodiment 4:
Make zinc ammonia complex solution by embodiment 3 same methods.Simultaneously continuously squeeze in tubular reactor with pump the hot water of zinc ammonia complex solution and 100 ℃, the velocity ratio of control hot water and zinc ammonia complex solution is 2, finish from decomposition and to isolate zinc subcarbonate precipitation the liquid continuously, and mother liquor is heated to 100 ℃ is recycled to reactor.With isolated zinc subcarbonate drying and 500 ℃ of roastings 4 hours, obtain the very narrow zinc oxide product of size distribution.Measure through transmission electron microscope and XRD line broadening method method, the zinc oxide median size is 50nm, BET specific surface area 51m
2/ g.
Claims (2)
1, a kind of nano-ZnO preparation is characterized in that comprising following process steps:
(1) adopting secondary zinc oxide or zinc baking sand is that the low levels oxidation zinc of 70-80% is raw material in ZnO content, and with the mixing solutions leaching of bicarbonate of ammonia and ammonia, its ratio is mol ratio Zn:NH
3: CO
2=1:4-4.5:0.9-1, stirring at normal temperature reaction 2-3 hour separates and removes insoluble impurities, and redox removes metallic impurity such as de-iron, manganese and lead, obtains zinc ammonia complex solution,
(2) with zinc ammonia complex solution, successively mix continuously with hot water and circulating mother liquor, hot water and circulating mother liquor are 90～100 ℃ through the temperature of continuous heat tracing; And circulation is used for decomposing continuously fast of zinc ammonia complex; Velocity ratio when control hot water and circulating mother liquor mix with zinc ammonia complex solution is 2～20;
(3) when decomposing continuously, the zinc subcarbonate crystallization that decomposition is finished in the liquid is separated continuously;
(4) with isolated zinc subcarbonate crystallizing and drying, roasting, at 400-600 ℃ of roasting 1-4 hour, obtaining the even particle size median size was the nano oxidized zinc product of 10～50nm.
2, according to the described preparation method of claim 1, it is characterized in that:
(1) with zinc ammonia complex solution, successively mix continuously with hot water and circulating mother liquor, hot water and circulating mother liquor are 95～100 ℃ through the temperature of continuous heat tracing; And circulation is used for decomposing continuously fast of zinc ammonia complex; Velocity ratio when control hot water and circulating mother liquor mix with zinc ammonia complex solution is 5～10;
(2),, obtain nano oxidized zinc product at 500-600 ℃ of roasting 2-4 hour with isolated zinc subcarbonate crystallizing and drying, roasting.
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| CNB2006101304777A CN100494069C (en) | 2006-12-21 | 2006-12-21 | Preparing process of nano zinc oxide |
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| CNB2006101304777A CN100494069C (en) | 2006-12-21 | 2006-12-21 | Preparing process of nano zinc oxide |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229438B (en) * | 2011-06-01 | 2013-04-24 | 华南师范大学 | Interface preparation method of flaky zinc oxide |
| WO2014047763A1 (en) * | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing high-purity nanometer zinc oxide from steel plant smoke and dust by ammonia process |
| WO2014047760A1 (en) | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing high-purity nanometer zinc oxide from electrolytic zinc acid-leaching residues by ammonia decarburization |
| WO2014047764A1 (en) | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing high-purity nanometer zinc oxide from steel plant smoke and dust by ammonia decarburization |
| WO2014047762A1 (en) | 2012-09-25 | 2014-04-03 | 四川巨宏科技有限公司 | Method for producing high-purity nanometer zinc oxide from low-grade zinc oxide ore by ammonia decarburization |
| CN103910377B (en) * | 2014-02-18 | 2015-12-09 | 韶关凯鸿纳米材料有限公司 | A kind of improvement plant film S type nano zine oxide production technique |
| CN105347386A (en) * | 2015-11-19 | 2016-02-24 | 北京三聚环保新材料股份有限公司 | Preparation method of nano-zinc oxide |
| CN107285371A (en) * | 2017-07-21 | 2017-10-24 | 河北博泰环保科技有限公司 | The method for preparing feed grade zinc oxide using blast furnace dedusting ash and zinc waste residue |
| CN110724831A (en) * | 2019-10-31 | 2020-01-24 | 重庆赛迪热工环保工程技术有限公司 | Carbon circulating system and method for producing zinc oxide by industrially recycling zinc |
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