CN102181886B - Method for producing one-dimensional nanometer flake zinc powder by directly electrolyzing strong alkaline solution - Google Patents

Method for producing one-dimensional nanometer flake zinc powder by directly electrolyzing strong alkaline solution Download PDF

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CN102181886B
CN102181886B CN 201110087806 CN201110087806A CN102181886B CN 102181886 B CN102181886 B CN 102181886B CN 201110087806 CN201110087806 CN 201110087806 CN 201110087806 A CN201110087806 A CN 201110087806A CN 102181886 B CN102181886 B CN 102181886B
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China
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solution
electrolysis
electrodeposit
additive
strong base
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CN 201110087806
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Chinese (zh)
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CN102181886A (en
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赵由才
蒋家超
易天晟
张承龙
牛静
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同济大学
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Abstract

The invention provides a method for producing one-dimensional nanometer flake zinc powder by directly electrolyzing strong alkaline solution, relating to the production technology of flake zinc powder. The method is characterized by firstly preparing zinc-containing strong alkaline solution, wherein the solution contains 1-100g/L of Zn, 10-200g/L of OH<->, 5-70mg/L of additive A and 10-110mg/L of additive B; secondly taking a stainless steel plate as an anode and a magnesium plate as a cathode to electrolyze the solution for 1-180min under the following conditions: the distance between the two plates is 0.5-5cm; the current density is 100-2500A/m2; and the solution temperature is 10-100 DEG C, then stopping electrolysis, rapidly taking out the electrodeposit and washing the electrodeposit with water until the pH value of the water is lower than 8; and finally, rapidly vacuum-drying the washed electrodeposit, thus obtaining the one-dimensional nanometer flake zinc powder, wherein the electrolysis waste liquor is returned to be used for preparing the zinc-containing strong alkaline solution. The method has the following advantages and effects: the produced zinc powder has high activity, is flaky and is 10-100nm thick; the method is low in production cost and energy consumption, is simple to operate and is convenient for mass production; and the defects of high cost, high energy consumption, low capacity, difficulty in controlling quality and the like in the traditional production methods are thoroughly overcome.

Description

A kind of method that Direct Electrolysis is produced the 1-dimention nano zinc flake from strong base solution
Technical field
The present invention relates to a kind of method that Direct Electrolysis is produced the 1-dimention nano zinc flake from strong base solution, belong to superfine powder hi-tech production field, belong to especially the zinc flake production technical field.
Background technology
Zinc is a kind of broad-spectrum metal, and very important effect is arranged aspect steel anti-corrosive especially, and used zinc powder has occurred by the megatrend of granular zinc powder to the zinc flake transfer in the anticorrosion industry in recent years.Zinc flake has ultra-thin ultra-fine characteristics, more can be attached to densely metal base surface than particle zinc powder, thereby obtains more excellent rust resistance and corrosion resistance performance.With the protective system of zinc flake preparation, the zinc slabbing is arranged, and zinc consumption is little, and coating is fine and close, even, attractive in appearance, can process the complex components such as super large, overlength, has replaced to a certain extent tradition plating, hot dip.In addition, zinc flake also is used for the industry production such as rubber item, makeup, special plastics.Therefore, zinc flake is applied to the industries such as automobile, boats and ships, aviation, military affairs, traffic, metallurgy, chemical industry, electric power more and more widely, and added value is high, and the market requirement is large, is the functional novel powder material that exploitation is badly in need of in a kind of country.
At present, China's zinc flake mainly is take zinc ingot metal or zinc powder as raw material, adopts ball milled to make.Because the zinc metal is magnetic, sheetization is very difficult, process but also need to make anti-oxidation surface, so its complete processing more complicated, quality is wayward, and cost is higher.Although occurred the zinc flake production technology of comparative maturity abroad, but owing to secret reason, only there are in the world several large-scale companies to produce, domestic also this technological method on top of not, cause the quality gap of domestic zinc flake and imported product larger, and cause being occupied by external producer in the overwhelming majority of the domestic market aspect the zinc flake high-end applications.
Summary of the invention
The object of the invention is to provide that a kind of quality product is high, the simple zinc flake production method of technological operation, utilizes this kind method can produce active high, 1-dimention nano zinc flake that radius-thickness ratio is large, and production cost is low, energy consumption is little, quality controllable.
In order to achieve the above object, the present invention finds in experiment, when electrolysis contains the zinc basic solution, by controlling electrolytic condition and adding suitable additive, can obtain the 1-dimention nano zinc flake, and whole process is not consume alkali in theory simultaneously.Take ZnO powder be dissolved in strong base solution, electrolysis production 1-dimention nano zinc flake process is as example again:
When ZnO is dissolved in strong base solution, have
From strong base solution, during electrowinning 1-dimention nano zinc flake, have
Be that every dissolving 1mol ZnO need consume 2mol OH -, when zinc is carried in follow-up electrolysis, generate again 2mol OH -So,, whole process does not consume alkali, and the gained waste liquid can return for the preparation of the basic solution that contains zinc after the electrolysis, recycles.
The present invention's processing method that Direct Electrolysis production 1-dimention nano zinc flake adopts from strong base solution is as follows: at first, preparation contains the strong base solution of certain zinc concentration, and this solution contains Zn 1-100g/L, OH -10-200g/L, additive A 5-70mg/L, additive B 10-110mg/L; Then, take stainless steel plate as anode, the magnesium plate is negative electrode, this solution of electrolysis, polar plate spacing 0.5-5cm, current density 100-2500A/m 2, solution temperature 10-100 ℃; Behind the electrolysis 1-180min, stop electrolysis, rapidly electrodeposit is taken out, water cleans to wash water pH value and is lower than 8; At last, fast the electrodeposit after cleaning is carried out vacuum-drying, can obtain the only 1-dimention nano zinc flake of 10-100nm of thickness; Electrolysis waste solution returns the basic solution that contains certain zinc concentration for preparation, recycle;
Described additive A is sodium arseniate, or sodium antimonate, perhaps both mixtures in any proportion;
Described additive B is tween 20, tween-80, perhaps sodium lauryl sulphate.
Described strong base solution is OH -Ionic concn is the NaOH solution of 5-200g/L, or KOH solution, or NaOH and KOH mixing solutions in any proportion.
Described magnesium plate can be pure metal magnesium plate, also can be the mass percentage content>50% magnesium and the alloy sheets of titanium of magnesium.
Described electrodeposit after cleaning is carried out vacuum-drying, should keep the Absolute truth reciprocal of duty cycle during its operation and be lower than 0.02-0.10MPa, drying temperature 70-300 ℃, after drying is finished, cool the temperature to<50 ℃ after, namely obtain the 1-dimention nano zinc flake.
The present invention is take strong base solution as medium, and the disclosed method that Direct Electrolysis is produced the 1-dimention nano zinc flake from strong base solution has the following advantages and effect:
(1) advantages such as the present invention's high current efficiency of utilizing the alkali lye electrodeposition to carry zinc to have, high current density, low bath voltage are produced zinc flake, make the production cost of zinc flake only be the 30-50% of traditional ball milled.
When (2) the present invention preparation contained the zinc strong base solution, the zinc raw material can be the materials such as zinc baking sand, oxidation zinc gray, zinc oxide ore, and traditional ball milled must be take high-purity zinc ingot metal or metal zinc as raw material, so raw materials cost reduces greatly.
(3) technical process of the present invention is simple, the production controllability is strong, be convenient to large-scale industrialization production, and initial cost is low, has avoided the shortcomings such as traditional ball milled operational requirement is high, the quality of production is wayward, production capacity is low, investment is large.
(4) active high, the radius-thickness ratio large (thickness is 10-100nm only) of the 1-dimention nano zinc flake that adopts the present invention to produce, when using for the production of coating or as cleaner, consumption still less, better effects if, so have the larger market requirement.
Embodiment
The present invention is further detailed explanation in conjunction with example, but the invention is not restricted to embodiment.
Embodiment one:
Preparation contains the NaOH solution of Zn, wherein contains Zn 30g/L, OH -110g/L, additive A is sodium arseniate, and its content is 50mg/L, and the content of additive B tween 20 is 60mg/L, and take stainless steel plate as anode, the MAGNESIUM METAL plate is negative electrode, this solution of electrolysis, electrolytic condition are current density 1000A/m 2Polar plate spacing 3cm, 50 ℃ of solution temperatures, stop electrolysis behind the electrolysis 40min, rapidly electrodeposit is taken out and water cleans to wash water pH value and is lower than 8, fast the electrodeposit after the cleaning is carried out vacuum-drying (the Absolute truth reciprocal of duty cycle is lower than 0.05MPa, 170 ℃ of drying temperatures), drying finish and after temperature of charge is down to 50 ℃ blowing, namely obtain the only 1-dimention nano zinc flake of 10-100nm of thickness.Electrolysis waste solution returns the basic solution that contains zinc for preparation, recycles.
Embodiment two:
Preparation contains the NaOH solution of Zn, wherein contains Zn 60g/L, OH -180g/L, additive A sodium antimonate 15mg/L, the content of additive B tween-80 are 40mg/L, take stainless steel plate as anode, the MAGNESIUM METAL plate is negative electrode, this solution of electrolysis, electrolytic condition are current density 2000A/m 2Polar plate spacing 4cm, 25 ℃ of solution temperatures, stop electrolysis behind the electrolysis 60min, rapidly electrodeposit is taken out and water cleans to wash water pH value and is lower than 8, fast the electrodeposit after the cleaning is carried out vacuum-drying (the Absolute truth reciprocal of duty cycle is lower than 0.05MPa, 150 ℃ of drying temperatures), drying finish and after temperature of charge is down to 50 ℃ blowing, namely obtain only 10-100nm 1-dimention nano zinc flake of thickness.Electrolysis waste solution returns the basic solution that contains zinc for preparation, recycles.
Embodiment three:
Preparation contains the KOH solution of Zn, wherein contains Zn 10g/L, OH -70g/L, additive A sodium arseniate and sodium antimonate be in the mixture 5mg/L of half and half ratio, additive B sodium lauryl sulphate 20mg/L, and take stainless steel plate as anode, the MAGNESIUM METAL plate is negative electrode, this solution of electrolysis, electrolytic condition are current density 1000A/m 2Polar plate spacing 2cm, 35 ℃ of solution temperatures, stop electrolysis behind the electrolysis 10min, rapidly electrodeposit is taken out and water cleans to wash water pH value and is lower than 8, fast the electrodeposit after the cleaning is carried out vacuum-drying (the Absolute truth reciprocal of duty cycle is lower than 0.1MPa, 120 ℃ of drying temperatures), drying finish and after temperature of charge is down to 50 ℃ blowing, namely obtain only 10-100nm 1-dimention nano zinc flake of thickness.Electrolysis waste solution returns the basic solution that contains zinc for preparation, recycles.

Claims (4)

1. method that Direct Electrolysis is produced the 1-dimention nano zinc flake from strong base solution, it is characterized in that: at first preparation contains the zinc strong base solution, and this solution contains Zn 1-100g/L, OH -10-200g/L, additive A 5-70mg/L, additive B 10-110mg/L; Then, take stainless steel plate as anode, the magnesium plate is negative electrode, polar plate spacing 0.5-5cm, current density 100-2500A/m 2, solution temperature 10-100 ℃, behind the electrolysis 1-180min, stop electrolysis, rapidly electrodeposit is taken out, water cleans to wash water pH value and is lower than 8; At last, fast the electrodeposit after cleaning is carried out vacuum-drying, namely obtain the only 1-dimention nano zinc flake of 10-100nm of thickness; Electrolysis waste solution returns the basic solution that contains certain zinc concentration for preparation, recycle;
Described additive A is sodium arseniate, or sodium antimonate, perhaps both mixtures in any proportion;
Described additive B is tween 20, tween-80, perhaps sodium lauryl sulphate.
2. described a kind of method that Direct Electrolysis is produced the 1-dimention nano zinc flake from strong base solution according to claim 1, it is characterized in that: described strong base solution is OH -Ionic concn is the NaOH solution of 5-200g/L, or KOH solution, or NaOH and KOH mixing solutions in any proportion.
3. described a kind of method that Direct Electrolysis is produced the 1-dimention nano zinc flake from strong base solution according to claim 1, it is characterized in that: described magnesium negative plate can be pure metal magnesium plate, also can be the magnesium alloy plate of the mass percentage content>50% of magnesium.
4. described a kind of method that Direct Electrolysis is produced the 1-dimention nano zinc flake from strong base solution according to claim 1, it is characterized in that: described electrodeposit after cleaning is carried out vacuum-drying, should keep the Absolute truth reciprocal of duty cycle during its operation and be lower than 0.10MPa, drying temperature 70-300 ℃, after drying is finished, cool the temperature to<50 ℃ after, namely obtain the 1-dimention nano zinc flake.
CN 201110087806 2011-04-08 2011-04-08 Method for producing one-dimensional nanometer flake zinc powder by directly electrolyzing strong alkaline solution CN102181886B (en)

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CN102807248B (en) * 2012-07-13 2014-06-25 安徽师范大学 Method for preparing cuprous sulfide nanoarray
CN103122465B (en) * 2012-10-25 2015-06-17 扬州双盛锌业有限公司 Preparation method of flaky metal powder
CN103938229B (en) * 2014-04-10 2017-01-18 同济大学 Method for preparing ultrafine flake zinc powder by adding antimony compound alkali liquor to electrolyze
CN104959135B (en) * 2015-06-29 2017-12-05 华中师范大学 A kind of nanometer zinc catalyst and based on nanometer zinc catalyst efficient catalytic CO2The method for reducing CO
CN105239104A (en) * 2015-10-14 2016-01-13 中国矿业大学 Method for electrolyzing scaly zinc powder by alkaline process
CN105268963A (en) * 2015-10-14 2016-01-27 中国矿业大学 Method for decreasing granularity of zinc powder produced with alkaline process
CN109609978B (en) * 2019-01-14 2020-06-16 上海第二工业大学 Method for electrodepositing flaky zinc in alkaline medium

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