CN1418972A - Method for preparing nano active zinc oxide from low grade zinc containing material - Google Patents
Method for preparing nano active zinc oxide from low grade zinc containing material Download PDFInfo
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- CN1418972A CN1418972A CN 02127937 CN02127937A CN1418972A CN 1418972 A CN1418972 A CN 1418972A CN 02127937 CN02127937 CN 02127937 CN 02127937 A CN02127937 A CN 02127937A CN 1418972 A CN1418972 A CN 1418972A
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Abstract
The method for preparing nano active zinc oxide by using low-grade zinc-containing material includes the following steps: firstly, acid pickling zinc-containing material, making zinc feed into solution in the form of zinc sulfate, making oxidation to remove iron, manganese and arsenic and making reduction to remove the impurities of cadmium and copper etc., purifying zinc sulfate solution, then adding alkali liquor and dispersing agent to obtain precursor basic zinc carbonate, then washing, drying and roasting so as to obtain the nano active zinc oxide.
Description
One, technical field
The invention belongs to ultra tiny technical field of material, be specifically related to a kind ofly, especially low-gradely contain the method that zinc industry raw ore or industrial waste prepare nanometer active zinc oxide from material containing zinc.
Two, background technology
Nanometer active zinc oxide is a kind of novel high function artificial inorganic materials geared to the 21st century, because its particle diameter is little, specific surface area is big, have at aspects such as magnetic, light, electricity and susceptibility common zinc oxide and general active zinc flower incomparable property, thereby purposes is widely arranged at aspects such as rubber, pottery, daily-use chemical industry, coating, magneticsubstances.At present, the method for preparing nano zine oxide is a lot, mainly contains solid-phase synthesis, induced with laser vapor deposition method, spray pyrolysis, hydrothermal synthesis method, chemical precipitation method etc.These methods all are that the pure zinc salt of employing is a raw material basically, have used expensive additive during preparation, the process means complexity, and production cost is high, is unfavorable for industrialization promotion.Low-grade material containing zinc extensively is present in occurring in nature, in metallurgy and the chemical process since its to contain the zinc grade low, the impurity height, general technology of not smelted zinc adopts, and has caused the waste of resource.The inventor utilizes the no low-grade material containing zinc of zinc hydrometallurgy to be raw material at the deficiency that existing nano zine oxide production technique exists, and adopts the direct depositing technology method of wet method infusion solution to prepare nanometer active zinc oxide.Method is easy, and process stabilizing is reliable, and is with low cost, is easy to industrialization promotion.
Three, innovation and creation content
1, the technical problem that will solve
The object of the present invention is to provide a kind of method easy, process stabilizing is reliable, and production cost is low, the quality product excellence, and what be easy to that industrialization promotion uses prepares the method for nanometer active zinc oxide from low-grade material containing zinc.
2, technical scheme
Design of the present invention is such:
At first material containing zinc is carried out acidleach, make zinc enter solution with the form of zinc sulfate, oxidation removes de-iron, manganese, arsenic, impurity such as cadmium, copper are removed in displacement, solution of zinc sulfate is purified, add alkali lye and dispersion agent then and make the presoma zinc subcarbonate, finally make nanometer active zinc oxide through washing, drying, calcining process again.
The present invention proposes is that the method for feedstock production nanometer active zinc oxide comprises following operation with the material containing zinc:
A, acidleach.Material containing zinc is pulverized, carried out twice acidleach with industrial sulphuric acid, the liquid-solid ratio of one section acidleach is 2.5: 1～5.0: 1, and temperature of reaction is controlled at 40～70 ℃, and terminal point PH is controlled at 4.5～5.4, contains when zinc concentration reaches 40～70g/L to filter, and filtrate is zinc sulfate; Filter residue carries out two-stage acid leaching, and its liquid-solid ratio is 2.0: 1～5.0: 1, and temperature of reaction is controlled at 70～90 ℃, and terminal point PH is controlled at 1.0～2.0.The adjusting slurry that two-stage acid leaching filtrate can be used as before one section acidleach uses.
B, zinc sulfate are purified.Solution of zinc sulfate is heated to 50 ℃, and oxygenant to the solution that adds 1.5～2.5 times of reaction theory calculated amount is blush, stirs 30 minutes, to manganese content filtration feed liquid during less than 1mg/L; Again filtrate is heated to 50 ℃, added the reductive agent of 1.0～3.0 times of reaction theory calculated amount, stirred 30 minutes,, make POV zinc to cadmium, copper content filtration feed liquid during respectively less than 1mg/L.
Described oxygenant is KMnO
4, H
2O
2, KClO
3, any in the chlorinated lime; Described reductive agent is zinc powder, Na
2Any among the S.
C, presoma preparation.The POV zinc solution is heated to 30～70 ℃, and press solution zinc content 0.5～4.0% and add dispersion agent, stir and add solution zinc content 2.2-2.4 alkali lye doubly down as early as possible, terminal point PH control 6.8～7.0, the solution zinc content is removed solution during less than 1g/L, obtain heavy zinc filter cake, i.e. presoma zinc subcarbonate.
Described dispersion agent is trisodium phosphate, potassium pyrophosphate, Sodium hexametaphosphate 99, hexa metaphosphoric acid potassium, any in Sodium dodecylbenzene sulfonate and the sulfonate.
Described alkali lye is any in bicarbonate of ammonia, sodium bicarbonate, the yellow soda ash.
D, after washing, dehydrate and calcining process, make after the cooling nanometer active zinc oxide-.
Described washing is with the washing of normal temperature clear water, to the BaCl of washings adding 1% with presoma zinc subcarbonate (heavy zinc filter cake)
2Till no white precipitate produces; Described dehydrating can be finished in the rotary flash distillation machine, dewater to water ratio less than 3%; Described roasting is in 400～480 times roastings 120～150 minutes.Be cooled to 40～50 ℃ and can carry out finished product packing.
3, beneficial effect
Because the present invention utilizes low-grade material containing zinc to make leaching agent with sulfuric acid, make zinc enter solution with the form of zinc sulfate, by oxidation demanganization, iron, arsenic, reduction removes impurity such as cadmium, copper and purifies, make the presoma zinc subcarbonate then, directly make nanometer active zinc oxide after washing, drying, the roasting.This method is easy, and process stabilizing is reliable, and raw material sources are extensive, and auxiliary agent, additive are cheap, so production cost is low, product economy is profitable.Make full use of low-grade zinc ore crude or industrial waste of containing, turned waste into wealth, improved the comprehensive utilization ratio of resource.
Four, description of drawings
The present invention is further illustrated below in conjunction with embodiment, but never in any form the present invention is limited.
Accompanying drawing is transmission electron microscope (TEM) the photo photostat of the prepared nanometer active zinc oxide of the present invention, and scale length is 50nm on the figure, 100,000 times of magnifications.As seen zincite crystal is spherical, and crystal grain diameter is 1-100nm; Press the median size 30nm that the BETL specific surface area is calculated.
Five, embodiment
The ZnO content of the nanometer active zinc oxide that makes with the inventive method reaches 95.88%, and specific surface area is 40m
2/ g, foreign matter content is less than ppm.Every index all is better than HG/T3572-94 standard and German Bayer AG standard.
Embodiment 1
With the zinc oxide raw ore is raw material, contains Zn 18%, and Pb 41%; Cd 3.4%; Fe 2.3%; As 0.5%; S 2.0%; SiO
29.5%.
5 tons of ore powders are broken to particle diameter 0.1mm, and dilute sulphuric acid (or two-stage acid leaching liquid) is sized mixing, and pumps into 20m
3In the batch extractor, steam heating, pneumatic blending slowly adds industrial sulphuric acid (control liquid-solid ratio 3: 1), and controlled temperature is at 40-50 ℃, and pH value is controlled between the 1.0-1.5, uses the liming neutralization solution between the pH value 4.5-5.0 after 1.5 hours, press filtration.
Above-mentioned filter residue is carried out two-stage acid leaching, at 20m
3Add industrial sulphuric acid in the batch extractor, be warming up to 75 ℃, keep pH value between 1.5-2.0, pneumatic blending press filtration after 2 hours (filter residue contains Pb45%, as carrying leady raw materials), filtrate is returned one section acidleach operation as sizing mixing use.
One section pickling liquor is pumped into 15m
3In the oxidation tank, be warming up to 50 ℃, pneumatic blending, the KMnO that adding reaction theory calculated amount is 2 times
4Remove iron, manganese, arsenic, the control pH value blush restir occurred 20 minutes to 5.2-5.4 to solution, and blush does not take off and gets final product press filtration, and filter residue is discarded.
Solution after the oxide treatment is pumped into 15m
3In the purification pot, be warming up to 50 ℃, pneumatic blending, the furnace zinc powder substitution that adds 2.5 times of reaction theory calculated amount removes Cd, and (filter residue is a Spongy Cadmium, contains Cd60% in press filtration after 30 minutes, as carrying the cadmium raw material), filtrate is POV zinc, its composition is Zn60-68g/L; Cd, Cu, Mn, Fe, As all≤1mg/L.
The POV zinc solution is pumped into 20m
3In the heavy zinc can, press 0.5% of solution zinc content and add the dispersion agent trisodium phosphate, extraordinarily go into agricultural ammonium bicarbonate by 2.4 of solution zinc content again, stir depositing zinc, 70 ℃ of holding temperatures, terminal point PH is controlled at 6.8-7.0, and filter pressing gets presoma zinc subcarbonate filter cake.
Presoma zinc subcarbonate filter cake washed with the normal temperature clear water add 1% BaCl to the washings
2No white precipitate produces, press filtration.Then with being dried to water ratio≤2.5% in the rotary flash distillation machine.In 400-450 ℃ of following roasting 120-150 minute, coming out of the stove made 1045kg nanometer active zinc oxide finished product after being cooled to 40～50 ℃ in stoving oven.
Embodiment 2
Make the POV zinc solution by embodiment 1 described mode, the POV zinc solution is pumped into 20m
3In the heavy zinc can, press 4% of solution zinc content and add sodium hexametaphosphate dispersant, extraordinarily go into agricultural ammonium bicarbonate by 2.4 of solution zinc content again, stir heavy zinc, 30 ℃ of holding temperatures, terminal point PH is controlled at 6.8-7.0, and filter pressing gets presoma zinc subcarbonate filter cake.
Press embodiment 1 described mode with the normal temperature clear water washing of presoma zinc subcarbonate filter cake, press filtration, drying, roasting, the cooling of coming out of the stove promptly makes 1050kg nanometer active zinc oxide finished product.
Embodiment 3
To contain zinc smelting scum silica frost is raw material, contains Zn20.80%, Pb14.50%; Cu9.90%; Fe4.50%; SiO
211.20%.
5 tons of raw material pulverizing to particle diameter 0.1mm, are inserted 20m
3In the batch extractor, add the sulfuric acid of 120g/L, admittedly carry out pneumatic blending under 3: 1 condition of liquid/be, controlled temperature is at 80 ℃, after 2 hours, the terminal point pH value is controlled between the 1.5-2.0, and (filter residue contains Pb 30% in press filtration, can be used as and carry leady raw materials), filtrate component is Zn 55.0%, Cu 21.0%; Fe 2.0%.
Pickling liquor is pumped into 15m
3In the displacement tank, add the zinc powder of 2 times of reaction theory calculated amount, 50 ℃ of holding temperatures stir displacement in 60 minutes and remove Cu, press filtration (filter residue is a copper sponge, contains Cu40%, as carrying the cadmium raw material).
Filtrate behind the copper removal pumps into 15m
3In the oxidation tank, be warming up to 50 ℃, adjust pH value, add the KMnO of 2 times of reaction theory calculated amount to 5.2-5.4
4, pneumatic blending removes iron, manganese, arsenic, blush occurs to solution and continues to stir 15 minutes again, and blush does not take off and gets final product press filtration, and filter residue is discarded.
Solution after the oxide treatment is pumped into 15m
3In the purification pot, 50 ℃ of holding temperatures are adjusted pH value to 5.2-5.4, and the furnace zinc powder substitution that adds 2.5 times of reaction theory calculated amount removes remaining Cu, mechanical stirring press filtration after 30 minutes, and filtrate is POV zinc, its composition is Zn 58g/L; Cu, Mn, Fe, As all≤1mg/L.
The POV zinc solution is pumped into 20m
3In the heavy zinc can, press 1% of solution zinc content and add the dispersion agent Sodium dodecylbenzene sulfonate, extraordinarily go into yellow soda ash by 2.2 of solution zinc content again, 60 ℃ of holding temperatures, terminal point PH is controlled at 6.8-7.0, and filter pressing gets presoma zinc subcarbonate filter cake.
Press embodiment 1 described mode with the normal temperature clear water washing of presoma zinc subcarbonate filter cake, press filtration, drying, roasting, the cooling of coming out of the stove promptly makes 1100kg nanometer active zinc oxide finished product.
Claims (7)
1, a kind ofly prepare the method for nanometer active zinc oxide, it is characterized in that: comprise following operation from low-grade material containing zinc:
A, acidleach will contain the pulverizing of zinc ore crude or industrial waste and carry out twice acidleach with industrial sulphuric acid, and one section acidleach terminal point pH value is controlled at 4.5～5.4, filters when zinc concentration reaches 40～70g/L to containing, and filtrate is zinc sulfate; The terminal point pH value that filter residue carries out two-stage acid leaching is controlled at 1.0～2.0;
B, zinc sulfate purify, and solution of zinc sulfate is heated to 50 ℃, and the control pH value adds oxygenant to solution and is blush to 5.2-5.4, stir 30 minutes, to manganese content filtration feed liquid during less than 1mg/L; Filtrate is heated to 50 ℃, adds reductive agent, stirs 30 minutes, to cadmium, copper content filtration feed liquid during respectively less than 1mg/L, makes POV zinc;
The preparation of C, presoma under the heating condition, adds dispersion agent in the POV zinc solution, stirs to add alkali lye down as early as possible, and terminal point PH control 6.8～7.0, the solution zinc content is removed solution during less than 1g/L, makes the presoma zinc subcarbonate;
D, after washing, dehydrate and calcining process, make nanometer active zinc oxide after the cooling
-
2, the method for claim 1 is characterized in that: the liquid-solid ratio of one section acidleach is 2.5: 1～5.0: 1, and temperature of reaction is controlled at 40～70 ℃, and the liquid-solid ratio of two-stage acid leaching is 2.0: 1～5.0: 1, and temperature of reaction is controlled at 70～90 ℃.
3, the method for claim 1 is characterized in that: the oxygenant that adds 1.5～2.5 times of reaction theory calculated amount when pickling liquor is purified; The reductive agent that adds 1.0～3.0 times of reaction theory calculated amount.
4, the method for claim 1 is characterized in that: when presoma prepares, pickling liquor is heated to 30～70 ℃, and press solution zinc content 0.5～4.0% adding dispersion agent, add solution zinc content 2.2-2.4 alkali lye doubly then.
5, the method for claim 1 is characterized in that: described washing is that heavy zinc filter cake is washed to the BaCl of washings adding 1% with the normal temperature clear water
2Till no white precipitate produces; Described dehydrating can be finished in the rotary flash distillation machine, dewater to water ratio less than 3%; Described roasting is in 400～450 ℃ of following roastings 120～150 minutes.
6, as claim 1 or 3 described methods, it is characterized in that: described oxygenant is KMnO
4, H
2O
2, KClO
3, any in the chlorinated lime; Described reductive agent is zinc powder, Na
2Any among the S.
7, as claim 1 or 4 described methods, it is characterized in that: described dispersion agent is any in trisodium phosphate, potassium pyrophosphate, Sodium hexametaphosphate 99, hexa metaphosphoric acid potassium, Sodium dodecylbenzene sulfonate and the sulfonate; Described alkali lye is any in bicarbonate of ammonia, sodium bicarbonate, the yellow soda ash.
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|---|---|---|---|
| CNB021279373A CN1193106C (en) | 2002-11-28 | 2002-11-28 | Method for preparing nano active zinc oxide from low grade zinc containing material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021279373A CN1193106C (en) | 2002-11-28 | 2002-11-28 | Method for preparing nano active zinc oxide from low grade zinc containing material |
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| Publication Number | Publication Date |
|---|---|
| CN1418972A true CN1418972A (en) | 2003-05-21 |
| CN1193106C CN1193106C (en) | 2005-03-16 |
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| CN101700903A (en) * | 2009-11-09 | 2010-05-05 | 常州市麦登橡塑化工有限公司 | Process for preparing nanometer ZnO |
| WO2010096862A1 (en) * | 2009-02-24 | 2010-09-02 | Auszinc Metals & Alloys | Zinc oxide purification |
| CN101979325A (en) * | 2010-11-11 | 2011-02-23 | 中联资源股份有限公司 | Refining treatment method for crude zinc oxide |
| CN101670288B (en) * | 2009-09-24 | 2011-08-31 | 上海市计量测试技术研究院 | Method for preparing gold nano particle modification zinc oxide |
| CN102703694A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for treating low-grade zinc oxide ores by wet method |
| CN103435094A (en) * | 2013-08-20 | 2013-12-11 | 杭州富阳新兴实业有限公司 | Production method for ferrous zinc sulphate monohydrate |
| CN104099479A (en) * | 2014-07-31 | 2014-10-15 | 邱政 | Process for producing zinc compound by acid and alkali combination method |
| CN104386735A (en) * | 2014-11-03 | 2015-03-04 | 苏州市泽镁新材料科技有限公司 | Preparation method of zinc oxide |
| CN104709937A (en) * | 2015-03-19 | 2015-06-17 | 李昭凌 | Zinc oxide concentrate purifying technology |
| CN106430284A (en) * | 2016-09-13 | 2017-02-22 | 苏州市泽镁新材料科技有限公司 | Preparation method of sulfur-doped zinc oxide nano material |
| 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 |
| CN107337230A (en) * | 2017-09-07 | 2017-11-10 | 济源市鲁泰纳米材料有限公司 | A kind of high-activity nano zinc oxide and preparation method thereof |
| CN108996541A (en) * | 2018-08-08 | 2018-12-14 | 沈海红 | A kind of preparation method of nano zine oxide and nano-zinc oxide composite material and preparation method thereof |
| CN110482592A (en) * | 2019-08-19 | 2019-11-22 | 西北矿冶研究院 | A kind of technique with steel-making cigarette ash preparing nano zinc oxide |
| CN111333101A (en) * | 2020-03-09 | 2020-06-26 | 济源市鲁泰纳米材料有限公司 | Nano zinc oxide, preparation method thereof and desulfurizer |
| CN111387351A (en) * | 2020-03-25 | 2020-07-10 | 济源市鲁泰纳米材料有限公司 | Surface-coated nano zinc oxide powder and preparation method thereof |
| CN112110474A (en) * | 2020-07-24 | 2020-12-22 | 浙江工业大学 | Method for preparing ZnO nano material by using zinc-containing wastewater |
| CN112279294A (en) * | 2020-10-29 | 2021-01-29 | 福建冠鑫新材料有限公司 | Production method of zinc oxide |
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- 2002-11-28 CN CNB021279373A patent/CN1193106C/en not_active Expired - Fee Related
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| WO2010096862A1 (en) * | 2009-02-24 | 2010-09-02 | Auszinc Metals & Alloys | Zinc oxide purification |
| CN101670288B (en) * | 2009-09-24 | 2011-08-31 | 上海市计量测试技术研究院 | Method for preparing gold nano particle modification zinc oxide |
| CN101700903A (en) * | 2009-11-09 | 2010-05-05 | 常州市麦登橡塑化工有限公司 | Process for preparing nanometer ZnO |
| CN101979325A (en) * | 2010-11-11 | 2011-02-23 | 中联资源股份有限公司 | Refining treatment method for crude zinc oxide |
| CN101979325B (en) * | 2010-11-11 | 2012-06-27 | 中联资源股份有限公司 | Refining treatment method for crude zinc oxide |
| CN102703694A (en) * | 2012-06-15 | 2012-10-03 | 广西金山铟锗冶金化工有限公司 | Method for treating low-grade zinc oxide ores by wet method |
| CN103435094B (en) * | 2013-08-20 | 2015-07-29 | 杭州富阳新兴实业有限公司 | Containing the production method of ferrous Zinc Sulphate Monohydrate |
| CN103435094A (en) * | 2013-08-20 | 2013-12-11 | 杭州富阳新兴实业有限公司 | Production method for ferrous zinc sulphate monohydrate |
| CN104099479A (en) * | 2014-07-31 | 2014-10-15 | 邱政 | Process for producing zinc compound by acid and alkali combination method |
| CN104099479B (en) * | 2014-07-31 | 2016-03-02 | 邱政 | A kind of using acid and alkali combination method produces the processing method of zinc compound |
| CN104386735A (en) * | 2014-11-03 | 2015-03-04 | 苏州市泽镁新材料科技有限公司 | Preparation method of zinc oxide |
| CN104709937A (en) * | 2015-03-19 | 2015-06-17 | 李昭凌 | Zinc oxide concentrate purifying technology |
| CN106430284A (en) * | 2016-09-13 | 2017-02-22 | 苏州市泽镁新材料科技有限公司 | Preparation method of sulfur-doped zinc oxide nano material |
| 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 |
| CN107337230A (en) * | 2017-09-07 | 2017-11-10 | 济源市鲁泰纳米材料有限公司 | A kind of high-activity nano zinc oxide and preparation method thereof |
| CN108996541A (en) * | 2018-08-08 | 2018-12-14 | 沈海红 | A kind of preparation method of nano zine oxide and nano-zinc oxide composite material and preparation method thereof |
| CN110482592A (en) * | 2019-08-19 | 2019-11-22 | 西北矿冶研究院 | A kind of technique with steel-making cigarette ash preparing nano zinc oxide |
| CN111333101A (en) * | 2020-03-09 | 2020-06-26 | 济源市鲁泰纳米材料有限公司 | Nano zinc oxide, preparation method thereof and desulfurizer |
| CN111387351A (en) * | 2020-03-25 | 2020-07-10 | 济源市鲁泰纳米材料有限公司 | Surface-coated nano zinc oxide powder and preparation method thereof |
| CN112110474A (en) * | 2020-07-24 | 2020-12-22 | 浙江工业大学 | Method for preparing ZnO nano material by using zinc-containing wastewater |
| CN112279294A (en) * | 2020-10-29 | 2021-01-29 | 福建冠鑫新材料有限公司 | Production method of zinc oxide |
| CN114540638A (en) * | 2022-01-11 | 2022-05-27 | 云南云铜锌业股份有限公司 | Zinc leachate purification method |
| CN114540638B (en) * | 2022-01-11 | 2024-02-27 | 云南云铜锌业股份有限公司 | Zinc leaching solution purifying method |
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