CN1401801A - Preparation of active zinc oxide from zinc dross by ultrasonic-microwave process - Google Patents
Preparation of active zinc oxide from zinc dross by ultrasonic-microwave process Download PDFInfo
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- CN1401801A CN1401801A CN02113604A CN02113604A CN1401801A CN 1401801 A CN1401801 A CN 1401801A CN 02113604 A CN02113604 A CN 02113604A CN 02113604 A CN02113604 A CN 02113604A CN 1401801 A CN1401801 A CN 1401801A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
A process for preparing active zinc oxide from floating Zn slags is characterized by that the ultrasonic cavitation and microwave heating are combined. Its advantages are short period and high product quality.
Description
(1) technical field: chemical metallurgy technical field
(2) technical background
At present, the employed zinc raw material that contains of production technique of preparation superfine active zinc oxide is finished product zinc sulfate, zinc acetate, zinc oxalate, zinc nitrate or zinc ingot metal, handle the superfine active zinc oxide presoma with tensio-active agents such as expensive Sodium hexametaphosphate 99 or Sodium dodecylbenzene sulfonatees, general type of heating is adopted in calcining, heating is outside from raw material, through considerable time could from show and in finish calcination process.So existing superfine active zinc oxide production technique owing to cost of material height, process energy consumption height, causes the superfine active zinc oxide production cost very high, has limited the widespread use of superfine active zinc oxide.
(3) summary of the invention
The objective of the invention is to make full use of ultrasonic cavitation and utilize the superiority of microwave heating to prepare superfine active zinc oxide.Ultrasonic wave can produce cavatition when propagating in liquid, the ultrasonic cavitation interaction energy produces localized hyperthermia's (＞4727 ℃) and high pressure (＞50MPa) extreme specific physical environment, for the formation of nucleus provides required energy, make the formation speed of nucleus can improve several magnitude, the raising that nucleus forms speed reduces the crystalline particle diameter, the high temperature that the ultrasonic cavitation effect produces and also reduce the specific surface free energy of tiny crystal grains greatly at a large amount of micro-bubbles of plane of crystal has suppressed the coalescent of nucleus and has grown up.In addition, shockwave that ultrasonic cavitation produced and small jet have porphyrization, can significantly reduce interionic bonding force, can reduce the generation of agglomeration effectively, and ultrasonic cavitation is than traditional stirring efficiency height, speed is fast, therefore crystal is dispersed in the whole solution with uniform molecule, advantages such as microwave heating has from inside to outside, selectivity heating, homogeneous heating, fast, the easy control automatically of heat-up rate, therefore can shorten calcination time with microwave heating, suppress growing up of crystal grain.One, technical process
Zinc dross leaches processing, solution purification removal of impurities, has just obtained the purified solution of zinc sulfate with dilute sulphuric acid, then solution of zinc sulfate is diluted, slowly add ammonium bicarbonate soln and made presoma, put presoma and under the ultrasonic wave condition, carry out dispersion treatment, obtained the superfine presoma, again after filtration, behind washing and the freeze-day with constant temperature,, make superfine active zinc oxide at last with the microwave heating calcining.Two, processing condition
1. the ratio (solid-to-liquid ratio) of zinc dross and sulphuric acid soln: 1: 4～1: 10;
2. sulphuric acid soln concentration: 1.2～2.0mol/L;
3. zinc dross extraction time: 1～2.5h;
4. leaching churning time: 30～60min;
5. adding ammonium persulphate oxidation demanganization condition is: 80～95 ℃ of temperature, pH value 5.0～5.4, reaction times: 2.5～4h, (add-on of ammonium persulphate calculates theoretical value according to manganiferous amount in the raw material by metallurgy, after amount 20%);
6. add the hydrogen peroxide deironing and the arsenic condition is: 80～90 ℃ of temperature, pH:5.0～5.4, reaction times: 3.5～5h, (add-on of hydrogen peroxide calculates theoretical value according to the amount of iron content in the raw material and arsenic by metallurgy, after amount 20%);
7. the impurity conditions such as zinc powder deleading, cadmium, cobalt that add are: during 70～80 ℃ of temperature, pH:5.2～5.4, reaction times: 1～2.5h, (add-on of zinc powder calculates theoretical value according to the content of impurity such as leaded in the raw material, cadmium, cobalt by metallurgy, after amount 20%);
8. superfine active zinc oxide presoma preparation condition: with the above-mentioned vitriol oil zinc solution dilution that obtains is 0.6～1.2mol/L, the ultrasonic dispersing time: 15～20min, (1.0～1.6mol/L) generate zinc subcarbonate to add ammonium bicarbonate soln, (add-on of bicarbonate of ammonia calculates theoretical value according to the zinc content of solution of zinc sulfate by metallurgy, after amount 20%);
9. digestion time: 30～55min;
10. drying conditions: 100～120 ℃ of temperature, time of drying: 6～8h;
11. microwave heating calcination time: 7～16min;
12. microwave frequency: 2450MHz, 450～650 ℃ of calcining temperatures.The technico-economical comparison that reaches:
1. zinc recovery 87～90%;
2. the epigranular of superfine active zinc oxide, reunite less, active high, pattern is spherical cubic crystal structure, median size is 100nm.
The present invention also is suitable for and directly prepares superfine active zinc oxide from finished product zinc sulfate, zinc acetate, zinc oxalate or zinc nitrate.
The advantage that has compared with prior art:
1. the present invention adopts cheap zinc dross, handles presoma with ultrasonic dispersing, avoids using tensio-active agent; Adopt the microwave heating presoma, only need 7～16min just to finish calcination process, shortened calcination time greatly;
2. use the ultrasonication presoma, can obtain the tiny presoma of granularity, and can overcome the generation of agglomeration;
3. calcine presoma with microwave heating, can shorten calcination time, suppress growing up of crystal grain, because homogeneous heating can overcome the uneven local burn-off phenomenon that produces of heating, thereby make good dispersity, the uniform superfine active zinc oxide of particle diameter.
(4) description of drawings
Fig. 1 is a process flow sheet of the present invention
(5) embodiment
Embodiment one: 1. raw material
Zinc dross is taken from certain zinc factory, the per-cent of its composition and weight: Zn 75～80%, and Fe0.5～0.7%, S 1.2～2.0%, Cd (trace), Pb 0.087%, SiO
20.31%, As0.088%, Sb 0.0023%, and Co 0.0006%, and Mn 0.84%, and CI 0.5～2.0%.2. zinc dross leaches
Leach zinc dross 1000g with dilute sulphuric acid (1.4mol/L), leaching condition is: temperature is a normal temperature, leaches and stirs 50min, leaches 2h, and solid-to-liquid ratio is 1: 6.With this understanding, the leaching yield of zinc is 92.5%.Leach liquor can be removed the SiO in the raw material after filtration
23. solution of zinc sulfate purifies
Purification of Zinc Sulfate Solution is divided into three sections purifications, first section demanganization; Second section deironing and arsenic; Impurity such as the 3rd section deleading, cadmium, cobalt.3.1 demanganization
Directly remove manganese in the solution of zinc sulfate with ammonium persulphate, the optimum process condition of demanganization is: 90 ℃ of temperature, and pH value 5.2, reaction 3.0h, the demanganization rate surpasses 99.86%, and the content of manganese is 0.00019g/L.3.2 deironing and arsenic
The zinc solution of last operation is placed in the water-bath, heat then and stir, add hydrogen peroxide, carry out deironing and arsenic, the optimum process condition of deironing and arsenic is: temperature: 85 ℃, and pH:5.2, reaction 4h filters, and deironing and arsenic rate reach more than 99%.3.3 impurity such as deleading, cadmium, cobalt
The zinc liquid of last operation is sent into displacement pot, heat then and stirs, temperature is 75 ℃, adds zinc powder, reacts 2.0h, displaces impurity such as lead, cadmium, cobalt.4. the preparation of superfine active zinc oxide presoma
The optimum process condition of superfine active zinc oxide presoma preparation is: the above-mentioned solution of zinc sulfate dilution that has purified is 0.8mol/L, the concentration 1.5mol/L of bicarbonate of ammonia, ultrasonic dispersing 16min, ageing 50min then, carry out filtration washing, press filtration is carried out dry 6h in 110 ℃ of loft drier, just obtained the superfine active zinc oxide presoma.5. microwave calcination
Microwave oven (2450MHz) heating and calcining superfine active zinc oxide presoma 10 minutes (450～500 ℃ of temperature) makes superfine active zinc oxide.
Embodiment two: 1. raw material
Zinc dross is taken from certain zinc factory, its composition and weight percent: Zn 74～84%, and Fe0.5～0.68%, S 1.6～2.0%, Cd (trace), Pb 0.08%, SiO
20.30%, As0.078%, Sb 0.004%, and Co 0.0008%, and Mn 0.54%, and CI 0.8～2.2%.2. zinc dross leaches
Leach zinc dross 2000g with dilute sulphuric acid (1.8mol/L), leaching condition is: temperature is a normal temperature, leaches and stirs 60min, leaches 1.8h, and solid-to-liquid ratio is 1: 8.With this understanding, the leaching yield of zinc is 93.0%.Leach liquor can be removed the SiO in the raw material after filtration
23. solution of zinc sulfate purifies 3.1 demanganizations
Directly remove manganese in the solution of zinc sulfate with ammonium persulphate, the optimum process condition of demanganization is: 93 ℃ of temperature, and pH value 5.4, reaction 3.5h, the demanganization rate surpasses 99.90%, and the content of manganese is 0.00014g/L.3.2 deironing and arsenic
The zinc solution of last operation is placed in the water-bath, heat then and stir, add hydrogen peroxide, carry out deironing and arsenic, the optimum process condition of deironing and arsenic is: temperature: 90 ℃, and pH:5.4, reaction 3.5h filters, and deironing and arsenic rate reach more than 99.10%.3.3 impurity such as deleading, cadmium, cobalt
The zinc liquid of last operation is sent in the water-bath, heated then and stir, temperature is 70 ℃, adds zinc powder, and reaction 1.5h displaces impurity such as lead, cadmium, cobalt.4. the preparation of superfine active zinc oxide presoma
The superfine active zinc oxide presoma prepares optimum process condition: the solution of zinc sulfate dilution that above-mentioned purification is good is 0.6mol/L, the concentration 1.2mol/L of bicarbonate of ammonia, ultrasonic dispersing 20min, ageing 40min then, carry out filtration washing, press filtration is carried out dry 8h in 120 ℃ of loft drier, just obtained the superfine active zinc oxide presoma.5. microwave calcination
Microwave oven (2450MHz) heating and calcining superfine active zinc oxide presoma 12 minutes (500～550 ℃ of temperature) makes superfine active zinc oxide.
Claims (1)
1. the ultrasonic-microwave integrated process prepares active zinc flower from zinc dross, it is characterized in that: one, technical process
Zinc dross leaches processing, solution purification removal of impurities, has obtained the purified solution of zinc sulfate with dilute sulphuric acid, the purified solution of zinc sulfate is diluted, slowly add ammonium bicarbonate soln and make presoma, put presoma and under the ultrasonic wave condition, carry out the presoma that dispersion treatment has obtained superfine active zinc oxide, again after filtration, behind washing and the freeze-day with constant temperature, with microwave heating calcining, make superfine active zinc oxide at last, two, processing condition
1, zinc dross with the ratio (solid-to-liquid ratio) of sulphuric acid soln is: 1: 4～1: 10;
2, sulphuric acid soln concentration: 1.2～2.0mol/L
3, zinc dross extraction time: 1～2.5h;
4, leach churning time: 30～60min;
5, ammonium persulphate oxidation demanganization condition is: 80～95 ℃ of temperature, pH value 5.0～5.4, reaction times: 2.5～4h;
6, hydrogen peroxide deironing and arsenic condition are: 80～90 ℃ of temperature, pH value 5.0～5.4, reaction times: 3.5～5h;
7, adding impurity conditions such as zinc powder deleading, cadmium, cobalt is: during 70～80 ℃ of temperature, and pH:5.2～5.4, reaction times: 1～2.5h;
8, superfine active zinc oxide presoma preparation condition: the vitriol oil zinc solution dilution that above-mentioned purification is good is 0.6～1.2mol/L, and the concentration dilution of bicarbonate of ammonia is 1.0～1.6mol/L, the ultrasonic dispersing time: 15～20min;
9, digestion time: 30～55min;
10, drying conditions: 100～120 ℃ of temperature, time: 6～8h;
11, microwave heating calcination time: 7～16min;
12, microwave frequency: 2450MHz, 450～650 ℃ of calcining temperatures.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021136041A CN1164776C (en) | 2002-04-12 | 2002-04-12 | Preparation of active zinc oxide from zinc dross by ultrasonic-microwave process |
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| CNB021136041A CN1164776C (en) | 2002-04-12 | 2002-04-12 | Preparation of active zinc oxide from zinc dross by ultrasonic-microwave process |
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| CN1164776C CN1164776C (en) | 2004-09-01 |
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Cited By (18)
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| CN1305555C (en) * | 2004-05-18 | 2007-03-21 | 浙江大学 | Water-soluble ion liquid synthesizing method |
| CN100336924C (en) * | 2005-06-16 | 2007-09-12 | 昆明理工大学 | Method for preparing primary titanium-rich material from high calcium-magnesium-titanium headings |
| CN101476038A (en) * | 2009-01-23 | 2009-07-08 | 佛山市兴民科技有限公司 | Tubular purification method and tubular purification tank |
| CN101633983B (en) * | 2009-08-17 | 2010-12-01 | 蒙自矿冶有限责任公司 | Method for enhancing recovery rate of zinc fusion casting |
| CN101956079A (en) * | 2010-10-29 | 2011-01-26 | 河池市南方有色冶炼有限责任公司 | Rare and noble metal recycling device |
| CN102345011A (en) * | 2011-10-08 | 2012-02-08 | 昆明理工大学 | Method for producing lead agglomerate by carrying out microwave heating on lead carbonate ore |
| CN102433430A (en) * | 2011-08-09 | 2012-05-02 | 四川省菁英矿业开发有限公司 | Method for producing beta-spodumene concentrates by acting microwaves on raw spodumene ores |
| CN102443708A (en) * | 2011-12-08 | 2012-05-09 | 葫芦岛锌业股份有限公司 | Device and method for extracting zinc powder from zinc casting floating slag |
| CN102560147A (en) * | 2011-12-30 | 2012-07-11 | 株洲冶炼集团股份有限公司 | Method for recovering zinc from indium raffinate and zinc scum |
| CN102828033A (en) * | 2012-09-25 | 2012-12-19 | 四川巨宏科技有限公司 | Method for recycling electrolytic zinc acid leaching slag |
| CN104975180A (en) * | 2015-06-24 | 2015-10-14 | 昆明理工大学 | Method and device for leaching blast furnace gas dust through ultrasonic-microwave and ammonia combination method |
| CN105349777A (en) * | 2015-10-19 | 2016-02-24 | 昆明理工大学 | Method for conducting microwave low temperature activation and ultrasonic coupling coupling leaching on oxygen vulcanization mixed ore |
| 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 |
| CN108002423A (en) * | 2017-12-19 | 2018-05-08 | 云南锡业职业技术学院 | The method that a kind of ultrasonic wave and microwave cooperating prepare nano zine oxide |
| CN110819802A (en) * | 2018-08-08 | 2020-02-21 | 昆明理工大学 | Method for strengthening and purifying zinc sulfate solution by microwave heating of zinc powder |
| CN110819801A (en) * | 2018-08-07 | 2020-02-21 | 昆明理工大学 | Method for purifying zinc sulfate solution by microwave heating of zinc powder |
| CN111705213A (en) * | 2020-07-13 | 2020-09-25 | 昆明冶金高等专科学校 | Method and device for purifying zinc sulfate solution by using ultrasonic waves |
| CN113668015A (en) * | 2021-08-23 | 2021-11-19 | 白银有色集团股份有限公司 | Method for reducing zinc electrodeposition power consumption |
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- 2002-04-12 CN CNB021136041A patent/CN1164776C/en not_active Expired - Fee Related
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| CN1305555C (en) * | 2004-05-18 | 2007-03-21 | 浙江大学 | Water-soluble ion liquid synthesizing method |
| CN100336924C (en) * | 2005-06-16 | 2007-09-12 | 昆明理工大学 | Method for preparing primary titanium-rich material from high calcium-magnesium-titanium headings |
| CN101476038B (en) * | 2009-01-23 | 2013-08-21 | 佛山市兴民科技有限公司 | Tubular purification method and tubular purification tank |
| CN101476038A (en) * | 2009-01-23 | 2009-07-08 | 佛山市兴民科技有限公司 | Tubular purification method and tubular purification tank |
| CN101633983B (en) * | 2009-08-17 | 2010-12-01 | 蒙自矿冶有限责任公司 | Method for enhancing recovery rate of zinc fusion casting |
| CN101956079A (en) * | 2010-10-29 | 2011-01-26 | 河池市南方有色冶炼有限责任公司 | Rare and noble metal recycling device |
| CN101956079B (en) * | 2010-10-29 | 2012-08-08 | 河池市南方有色冶炼有限责任公司 | Rare and noble metal recycling device |
| CN102433430A (en) * | 2011-08-09 | 2012-05-02 | 四川省菁英矿业开发有限公司 | Method for producing beta-spodumene concentrates by acting microwaves on raw spodumene ores |
| CN102345011A (en) * | 2011-10-08 | 2012-02-08 | 昆明理工大学 | Method for producing lead agglomerate by carrying out microwave heating on lead carbonate ore |
| CN102443708A (en) * | 2011-12-08 | 2012-05-09 | 葫芦岛锌业股份有限公司 | Device and method for extracting zinc powder from zinc casting floating slag |
| CN102560147B (en) * | 2011-12-30 | 2014-03-26 | 株洲冶炼集团股份有限公司 | Method for recovering zinc from indium raffinate and zinc scum |
| CN102560147A (en) * | 2011-12-30 | 2012-07-11 | 株洲冶炼集团股份有限公司 | Method for recovering zinc from indium raffinate and zinc scum |
| CN102828033A (en) * | 2012-09-25 | 2012-12-19 | 四川巨宏科技有限公司 | Method for recycling electrolytic zinc acid leaching slag |
| CN104975180A (en) * | 2015-06-24 | 2015-10-14 | 昆明理工大学 | Method and device for leaching blast furnace gas dust through ultrasonic-microwave and ammonia combination method |
| CN104975180B (en) * | 2015-06-24 | 2017-08-25 | 昆明理工大学 | The method and apparatus that a kind of ultrasonic microwave joint ammonia process leaches blast furnace dust |
| CN105349777A (en) * | 2015-10-19 | 2016-02-24 | 昆明理工大学 | Method for conducting microwave low temperature activation and ultrasonic coupling coupling leaching on oxygen vulcanization mixed ore |
| 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 |
| CN108002423A (en) * | 2017-12-19 | 2018-05-08 | 云南锡业职业技术学院 | The method that a kind of ultrasonic wave and microwave cooperating prepare nano zine oxide |
| CN110819801A (en) * | 2018-08-07 | 2020-02-21 | 昆明理工大学 | Method for purifying zinc sulfate solution by microwave heating of zinc powder |
| CN110819801B (en) * | 2018-08-07 | 2021-01-22 | 昆明理工大学 | Method for purifying zinc sulfate solution by microwave heating of zinc powder |
| CN110819802A (en) * | 2018-08-08 | 2020-02-21 | 昆明理工大学 | Method for strengthening and purifying zinc sulfate solution by microwave heating of zinc powder |
| CN110819802B (en) * | 2018-08-08 | 2021-01-22 | 昆明理工大学 | Method for strengthening and purifying zinc sulfate solution by microwave heating of zinc powder |
| CN111705213A (en) * | 2020-07-13 | 2020-09-25 | 昆明冶金高等专科学校 | Method and device for purifying zinc sulfate solution by using ultrasonic waves |
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