CN1858001A - Method for preparing different shape zinc oxide by vacuum limit oxygen method - Google Patents
Method for preparing different shape zinc oxide by vacuum limit oxygen method Download PDFInfo
- Publication number
- CN1858001A CN1858001A CN 200510039156 CN200510039156A CN1858001A CN 1858001 A CN1858001 A CN 1858001A CN 200510039156 CN200510039156 CN 200510039156 CN 200510039156 A CN200510039156 A CN 200510039156A CN 1858001 A CN1858001 A CN 1858001A
- Authority
- CN
- China
- Prior art keywords
- zinc
- zinc oxide
- oxygen
- vacuum
- shape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The vacuum oxygen limiting process of preparing zinc oxide in different shapes includes the following steps: smelting metal zinc or metal zinc containing material in furnace, and evaporating zinc melt in a vacuum evaporating chamber; reacting zinc vapor in certain pressure and introduced oxygen inside an oxidizing reactor at certain vacuum degree; and depositing at heating temperature 430-1200 deg.c, the ratio of zinc vapor pressure and oxygen pressure of 1 to 0.01-30 and oxygen pressure of 5-101325 Pa. The process can obtain amorphous, granular, single needle shaped, four needle shaped, multiple needle shaped, sheet or other shape nanometer or micron level zinc oxide product. The said process has low operation temperature, wide material resource, simple production process, low power consumption, low cost, no environmental pollution and other advantages.
Description
Technical field
The present invention relates to a kind of method of preparing different shape zinc oxide by vacuum limit oxygen method, belong to inorganic materials method field.Especially relate to by the vapor pressure of in vacuum environment, under certain temperature, regulating and control metallic zinc and content and the dividing potential drop that limits oxygen with certain vacuum degree, thereby metallic zinc steam is reacted under different physical and chemical conditions with oxygen, prepare the nanometer of different-shapes such as amorphous, particulate state, single needle shape, four needle-likes, spininess shape, sheet or the method method of micron order zinc oxide product.
Background technology
Zinc oxide is a kind of important inorganic functional material, and is very extensive in industry purposes such as rubber industry, coatings industry, electronics, pottery, voltage dependent resistor, makeup, catalyzer, medicine, food.The pattern of the zinc oxide that different preparation method's methods is produced has nothing in common with each other, and the purpose of its use and scope are also different thereupon.That nano level zinc oxide has is amorphous, particulate state, single needle shape, ribbon etc., and micron-sized zinc oxide then also comprises four needle-likes, single needle shape, spininess shape, ribbon and traditional particulate state, acicular type zinc oxide etc.
Nanoscale science and technology is the not emerge science technology of broken hair exhibition that is born phase late 1980s, is subjected to national governments, scientific and technological circle and the public's attention day by day.Nano material is owing to have surface effects, volume effect, quantum size effect and macro quanta tunnel effect, thereby shows characteristics such as unusual machinery, physics and chemistry.Nano zine oxide is meant the zinc oxide of particle diameter at 1～100nm, and nanosecond science and technology are given many new character of these traditional Chemicals of zinc oxide and function, make its range of application more extensive, and the trend that progressively replaces common zinc oxide is arranged.When its size reaches nanometer scale, show many excellences, special nature, as nontoxic and non-migrating, fluorescence, piezoelectricity, absorption and scatters ultraviolet ability etc., give stronger performance of zinc oxide and more purposes.
Nano zine oxide is a kind of good photocatalyst.After water oxygen zinc is being subjected to photon irradiation greater than the energy gap energy, produce that electronics---the hole is right.The hole has very strong oxidisability, at the OH of zinc oxide surface and water
-Reaction generates the very high OH of oxidisability
Free radical, active OH
Free radical can generate inorganicss such as carbonic acid gas and water with the toxic organic compound reaction of many bio-refractories.Harmful organic substances in the water such as organic muriate, agricultural chemicals, interfacial agent, pigment etc., it is difficult fully removing with present water treatment method, and zinc oxide can make organism decompose as photocatalyst.Studies show that, the speed of response of nano zinc oxide particles is 100～1000 times of common zinc oxide particle, and compares with ordinary particle, and it causes scattering of light hardly, and big specific surface area and wide being with are arranged, therefore be considered to one of photocatalyst that has application prospect.Zinc oxide is one of traditional inorganic antibacterial material, and when contacting with bacterium in unglazed environment, zine ion slowly releases, and can combine with cytolemma and membranin, destroys its structure, enters the enzyme that destroys electron transfer system behind the cell, reaches the antimicrobial purpose.Nano zine oxide especially under uviolizing, can decomposite the electronegative electronics that moves freely voluntarily at sunlight, stays the hole of positively charged simultaneously.This hole can become active oxygen with airborne oxygen, and extremely strong chemically reactive is arranged, can with most of organism generation oxidizing reactions (organism that comprises the bacterium class), thereby most germ and virus are killed.It is strong that nano zine oxide absorbs ultraviolet ability, and ((wavelength 280～320nm) all has shielding effect for wavelength 320～400nm) and ultraviolet B radiation to long wave ultraviolet.At nano zine oxide area load argent, copper nano-particle, can obtain better sterilization effect.Nano zine oxide is nontoxic, tasteless, and is non-stimulated to skin, do not decompose, never degenerates, good stability, and this is as white, can be in addition painted according to different objects, and low price.Nano zine oxide is the externally applied medicine of skin, and skin is had functions such as convergence, anti-inflammatory, wrinkle resistant and protection, and the sun-screening agent that can be used for makeup is to prevent ultraviolet injury.In fiber textile and dress ornament thereof, applying nano zinc oxide has antibiotic, mildew-resistant, the peculiar effect of de-odorised.Can be used for producing deodorization, antibiotic, anti-ultraviolet fiber or zinc oxide timber floor and carpet.Nano zine oxide is because the velocity of diffusion that gas passes through than very fast, is again a kind of fabulous catalyzer therefore.Nano zine oxide is little because of its size, specific surface area is big, surperficial key and granule interior different, the surface atom coordination is not congruent, cause the activity site on surface to increase, formed scraggly atomic steps, strengthened the reaction contact surface, the catalytic activity of nano zine oxide and selectivity are far longer than its traditional catalyst.
Rubber industry is the biggest market of zinc oxide, and consumption accounts for the over half of total amount.Nano zine oxide is the most effective inorganic active agent of rubber industry and vulcanization accelerator.Physics-chem characteristics such as nano zine oxide has that particle is tiny, specific surface area is big, good dispersity, loose porous, good fluidity, therefore, good with the affinity of rubber, easily disperse during melting, sizing material give birth to heat low, pull apart little, the good springiness of distortion, improve shop characteristic and physicals.Be used to make the rubber item of high-speed abrasion-proof, meridian tire of using as aircraft wheel tire, sedan limousine etc., have prevent to wear out, advantages such as friction resistant is caught fire, long service life, smooth finish, physical strength, heatproof and the ageing-resistant performance of rubber item have been increased substantially, wear resisting property particularly, consumption is 30%～50% of traditional common zinc oxide consumption only, has reduced the production cost of enterprise, at strength and extension property, give birth to heat, aspect such as aging then is much better than common zinc oxide.
In ceramic industry, the minimum particle diameter of nano zine oxide, big specific surface area and high chemical property, can significantly reduce the sintering densification temperature of material, save energy, make the more densification of composition structure, the homogenizing of stupalith, improve the performance of stupalith, improved its work reliability.Can (1～100nm) goes up the composition and the structure of control material, helps giving full play to the potential performance of stupalith from the nano material's structure level.In addition, because the granular size of ceramic powder has determined the microtexture and the macro property of stupalith, if the particle packing of powder is even, burning till contraction unanimity and uniform crystal particles grows up, particle is more little so, the defective that produces is more little, and the intensity of prepared material is just corresponding high more, and this special performance that some macrobead materials do not possess just may occur.Zinc oxide also can be used as anti-impact, damping, sound-proof material, reinforced composite, pottery or metal-base composites etc.
Zinc oxide free from foreign meter is pure white, and tinting strength and opacifying power are bigger, is only second to titanium dioxide and lithopone.Opacifying power is half of titanium dioxide and zinc sulphide, and tinting strength is the twice of basic lead white.Zinc oxide is a kind of basic color, with the paint vehicle blending non-discoloring characteristics is arranged, and has good fire-resistant, heat-resisting and weathering resistance, is applicable to exterior paint.The naval vessel navigates by water for a long time, is docked in the ocean environment, adopts nano zine oxide to make the coating of naval vessel special use, not only plays the effect of shielding ultraviolet rays, but also can kill various microorganisms, thereby can improve route speed and prolong the maintenance time limit.Make the especially camouflage paint of sedan limousine special use of automobile with nano zine oxide, be added in the finish paint of flash metal luster, along with the variation of angle, can make coating produce abundant and mysterious " colour effect ", make bodywork surface produce preferably imaging effect, add lustre flash of light.
Material obsorbing radar waves (abbreviation absorbing material) means a class functional materials that can effectively absorb the incident radar wave and make its reflection loss.Utilize the character of plasma resonance frequency displacement, can change particle size with change in particle size, the displacement of control ABSORPTION EDGE, manufacturing has the microwave absorbing nano material of certain frequency range, is used for electromagnetic wave shielding, stealth aircraft etc.The research of absorbing material is significant on national defence, and the development of this " stealth material " and quoting is the effective means that improves weapons system existence and penetration ability.Nanometer powder is a kind of very promising New Type Military radar wave absorbing agent.Metal oxides such as nano zine oxide are because advantage such as light weight, thin thickness, wave-sucking performance be strong, and become one of focus of absorbing material research.T-ZnOw (four acicular type zinc oxide crystal whisker) can absorb the microwave of microwave oven wave bands such as (2.45GHz) as microwave heater, and heating efficiency is very high.Put into microwave oven if will fill with the beaker of T-ZnOw, in more than 10 seconds, can reach red heat.Because T-ZnOw (four acicular type zinc oxide crystal whisker) has good thermotolerance, so this whisker can use repeatedly.At present, obtained in fields such as microwave heating elements to use.In daily life, electromagnetic pollution also is on the rise, and utilizes the absorbing property of zinc oxide, reduces electromagnetic harm.
The research of light-colored conductive material in recent years also is one of focus.Conductive zinc oxide is mainly used in coating, rubber, filamentary material and the pottery as the white pigment that conducts electricity.The electroconductibility of zinc oxide can be given plastics and polymkeric substance with static resistance.
On magneticsubstance, adopt nano zine oxide to make raw material, not only manufacturing process can be simplified, but also the homogeneity and the permeability of product can be improved, reduce product cracked loss in sintering procedure, reduce sintering temperature, quality product is significantly improved.Nano zine oxide crystallite metal soft magnetic material has very excellent performance, high magnetic permeability, low-loss, high saturation and magnetic intensity, switch power supply, transformer, transmitter etc. have been applied to, can realize miniaturization of devices, lightness, high frequencyization and multifunction, development in recent years is very rapid.Zinc oxide film is a kind of inorganic piezoelectric membrane, can make microwave ultrasound transverter as thin as a wafer, and is integrated with semiconductor material.
Along with to the going deep into of nano ZnO research, the method for preparing the nano zine oxide powdered material also continues to bring out.Can be divided into three major types preparation methods such as chemical preparation method, physics preparation method and chemical physics preparation method.But generally speaking all be to develop towards with low cost, less energy-consumption, free of contamination direction.
Each components contents of chemical preparation method can accurately be controlled, and can realize molecule---and the uniform mixing on the atomic level can obtain the nanoparticle material of even particle size distribution, controllable shapes by control of process condition.Chemical preparation method can be divided into chemical precipitation method, chemical reduction method, hydrothermal method, thermal decomposition method, microemulsion method, colloidal sol again---several different methods such as gel method, low-temperature solid phase reaction method.Chemical preparation method is to prepare nano zine oxide at present to adopt maximum class methods.Chemical preparation method has certain advantage aspect the scale production of nanoparticle.But easily sneak into impurity in the product, grain is in easy reunion, and preparation process exists a series of problems such as pollution and waits to solve.
Physical preparation method is meant and adopts light, method for electrically that material is evaporated in vacuum or inert atmosphere, makes atom or molecule form nanoparticle then, or to utilize ball milling, spraying etc. be the main preparation method who obtains nanoparticle with the mechanical process.It comprises using vaporization condensation process, mechanical ball milling method, laser method etc.The product minimum grain size that mechanical ball milling method in the physical preparation method obtains can reach nano level, but the ball milling time is long, the abrading-ball contaminated material; The vacuum-evaporation condensation method mainly also only is used for the production of nano metal powder.The laser that adopts steams the method for coagulating, with the zinc salt is the feedstock production nano zinc oxide particles, it is many that this kind method has the nanoparticle kind that can prepare, the product particle diameter is little, narrow particle size distribution, good dispersity, be difficult for reuniting, the purity advantages of higher, and preparation process is more simple and reliable.But laser steams the industrialization of the method for coagulating also to have problems.The employing metallic zinc is a raw material, and the atmospheric evaporation air oxidation process is produced zinc oxide, and the product of acquisition is the particulate state micron order often, is more difficult to get the nano level product.
The chemical physics preparation method comprises spray method, chemical Vapor deposition process, explosion method, supercritical fluid drying, freeze-drying, microwave irradiation, reactive ball milled etc.In the chemical physics synthesis method, spray method is that solution is atomized by various physical means, changes nanoparticle into through physics, chemistry route again, forms hollow phenomenon when the droplet drying that atomizes, hydrolysis or pyrolysis easily.The industrialization of vapor phase process synthesis of nano ZnO also is a problem demanding prompt solution.
The raw material that technique treats adopted of traditional mode of production zinc oxide can be divided into molten zinc oxidation style, zinc carbonate calcining and decomposing method, zinc hydroxide calcining and decomposing method and non-ferrous metal metallurgy absorption method etc.Industrial production technology is generally divided two kinds of direct method and indirect methods.Direct method is directly to be processed into the processing method of zinc oxide from zinc ore concentrate, the high-quality roasting zinc powder is mixed mutually with pulverized anthracite, add a part of binding agent again and be pressed into agglomerate, being placed on the interior air blast of the reverberatory furnace that is added with one deck anthracite block coal in advance heats, at this moment, zinc oxide in the breeze is promptly by the reduction of carbon or carbon monoxide and emit zinc fume, and zinc fume is formed zinc oxide by oxidations such as airborne oxygen, carbonic acid gas again.Direct method output is big, particle is thick, impure height, also can produce acicular type zinc oxide.Indirect method promptly is not directly to produce the processing method of zinc oxide from zinc ore, but zinc ore is refined into earlier zinc ingot metal, is raw material production zinc oxide with zinc ingot metal then.Zinc ingot metal is through fusion and high temperature evaporation, oxidation and cooling and get.Its master operation is that zinc ingot metal (electrolytic process is produced) evaporates metallic zinc at importing high temperature pincers pot after 600～700 ℃ of fusions under 1200～1300 ℃ of temperature, and the reusable heat air carries out oxidation, generates zinc oxide and promptly gets product through the refrigerated separation capture
In the zinc oxide product of different-shape, four acicular type zinc oxide crystal whisker is the comparatively harsh zinc oxide product of working condition.Four acicular type zinc oxide crystal whisker (Tetrapod-like Zinc oxide whisker, be called for short T-ZnOw) be a kind of three-dimensional four acicular single crystal fibres that grow into, it also is the only whisker of finding at present in the whisker family with regular three-D space structure, this unique texture just because of four acicular type zinc oxide crystal whisker, make it be easy in matrix, realize three-dimensional uniform, performance of composites is isotropy, and this is that general crystal whisker materials is difficult to realize.Except having enhancement, T-ZnOw also has outstanding multi-functional characteristic, as wear-resisting, anti-skidding, the noise reduction of excellence, suction ripple, anti-aging, shock resistance, antistatic, anti-algae, antibiotic etc.,, all has very big application potential therefore no matter as structured material or functional materials.Its price also is ten to 20 times of common zinc oxide product, no matter still all is subjected in actual applications especially paying attention in production in recent years.
The preparation method of T-ZnOw ZnOw mainly divides zinc powder preoxidation and zinc powder direct oxidation method at present.Method one is in advance with the zinc powder surface oxidation in the zinc powder preoxidation, be about to high-purity zinc powder and place deionized water for stirring, ageing, drying, make its surface generate certain thickness oxide film, more this zinc powder is prepared four needle-like whiskers in about 1000 ℃ heating of high temperature gasification in about 1 hour oxidation.Oxide film can suppress melt metal zinc from the very fast loss of granule interior in the heat-processed, also controls the rate of migration of oxygen to zinc granule inside, needed time of bonding crystal growth simultaneously.Method two is that the zinc powder that will have oxide film under the inert gas protection is heated to more than the boiling point; be carrier gas then with the rare gas element; zinc fume is introduced oxygen-containing gas or oxygen-containing gas is blown in the zinc fume, zinc is contacted in gas phase with oxygen, generate zinc oxide four needle-like whiskers.Method three is with zinc powder and NH
4 +, CO
3 2-(or HCO
3 -) and H
2O mixes by a certain percentage, generates ZnCO under prescribed condition
3, be heated to specified temp then, ZnCO
3Then slowly be decomposed to form zinc oxide four needle-like product palpuses.Method four is to use the zinc powder through surface oxidation to mix with white carbon black (or clay), and bubbling air carries out oxidation when being heated to 900～1000 ℃, has prepared T-ZnOw.Method five is to be placed in the electric furnace N by the suitable proportion mixing through surface oxidation zinc powder and activated carbon
2And O
2Feed by a certain percentage in the reaction chamber, temperature is controlled at 1050～1150 ℃, and reaction 5h can make long 20～25mm, the needle-like whisker of the about 0.1mm of diameter.
The T-ZnOw size of preoxidation preparation is big, regularity is better.But to the purity (Zn＞99.99%) and the granularity requirements strictness of zinc powder, the pre-oxidation treatment technology of zinc powder is very numerous and diverse.Preparation during raw material the own part of zinc oxidized, the recovery rate of whisker lower (be about 40% of zinc powder quality, in the time of better 80～86%); Preoxidation also will consume a large amount of additive (account for raw material weight 20～50%), has increased the preparation cost of T-ZnOw.
The zinc powder direct oxidation method is promptly directly produced T-ZnOw with the zinc powder oxidation.Method one is the metal zinc ingot fusion to be sprayed into make zinc powder in the water, is 5: 1 batchings by zinc powder and coke ratio, is heated to 950～1050 ℃ in the container of packing into after the mixing in atmosphere, and insulation 10～20min makes zinc oxide and mostly is four needle-like whiskers.Method two is a reaction tubes of zinc powder being put into an end opening, and 500～850 ℃ of temperature of reaction are incubated 0.5～2h, make the whisker of two kinds of forms.Method three is to utilize the principle of air expanded by heating, and the content of control oxygen under 700～1100 ℃ of temperature, through being incubated 3～12min, with zinc granule or zinc metal sheet oxidation, making zinc oxide and mostly is T-ZnOw.The technology of direct oxidation method and equipment are all simpler, are easy to realize industrialization.But be easy to produce the platelet of diauxic growth between the needles of the T-ZnOw that this method makes, the pattern of whisker is degenerated; Direct oxidation also can produce powder shape zinc oxide, is difficult to separate with whisker, and the whisker degradation, recovery rate descends.There is the incomplete problem of part zinc powder oxidation in direct oxidation method, and productivity is lower.Compare with preoxidation, improved if take appropriate measures, direct oxidation method will be the processing method of up-and-coming realization T-ZnOw industrialization.
Zinc powder preoxidation and zinc powder direct oxidation method are produced T-ZnOw, after requirement maybe must be preheating to certain temperature with process furnace with the rapid intensification of process furnace mostly, zinc powder are put into again, zinc powder is evaporated rapidly, reach certain saturation ratio, could obtain the T-ZnOw product, working condition is had relatively high expectations.
Vacuum method is applied to the history that metallurgical process has decades, and mainly in ferrous metallurgy, extraordinary field of metallurgy, to be applied to inorganic oxide material then less relatively aspect preparing industrial.Under vacuum state, carry out, can correspondingly reduce volatilization temperature, save energy.Same industrial scale, under lower temperature, the energy that is consumed will significantly reduce; Because the pressure of external environment is higher than the pressure of the environment that volatilizees, then gaseous matter can not help environment protection to external leakage; The temperature of entire job process is lower simultaneously, and operating environment is better.Therefore, not only can solve under vacuum state under many normal pressures can not treatable problem, can also regulate and control preparation process effectively, reach control environmental pollution, shortened process, save energy, improve the quality of products, fully utilize, reduce labour intensity, purpose such as reduce cost, increase the benefit.
It is predicted that by 2006, the ratio that China Metal zinc output accounts for global output will rise to 25%.China's zinc resource is abundant, and the present invention will have certain promotion meaning to the production and the application of promotes oxidn zinc product.
Contriver Wu Run, the sea of following what is right, Liu Hongfang, Liu Jing, thank long-living, Wang Aihua, Cai Wei's equality and applied for a kind ofly containing the method for producing the ZnO nano whisker the zinc waste from metallurgy with vapour phase processes, its method is that to contain the zinc waste with metallurgy be raw material, put into the heating of vacuum-evaporation chamber after the enrichment again, when the zinc fume flame sprays, rare gas element with the high speed thread imports reaction chamber with this bluster, carries out the synthetic of nano zine oxide.Its application content is referring to " a kind of ZnO nano crystal whisker material and preparation method thereof ", and publication number is CN1458305, and application number is 02115818.5.Wherein do not address and identical summary of the invention of the present invention and claim.。
Contriver Tang becomes spring, Cheng Chun, Ding Xiaoxia, Qi Shouren etc. to apply for the method for a kind of alloy gas controlled evaporation method synthesizing zinc oxide micron, nanofiber, the brass ingot that this method is utilized copper zinc mixed powder or directly used commercial purity is as reactant, the metallic zinc steam that direct oxidation frit reaction thing discharges under the high temperature in air.Its application content is referring to " synthetic micron of alloy gas controlled evaporation method and nano zine oxide fiber ", and publication number is CN1594098, and application number is 200410013391.7.Wherein do not address and identical summary of the invention of the present invention and claim.
Contriver Yang Dajin, Chen Jiaxi, Xu Yafei, Yan Jiangfeng etc. have applied for a kind of production technique and equipment patent of four acicular type zinc oxide crystal whisker, are raw material with industrial zinc ingot metal, and the zinc fume that volatilizes is by high temperature N
2Bring in the whisker reactor, and send into N outward
2Form zinc oxide with the high temperature oxidation stability gas reaction of air mixed, controls reaction speed makes the zinc oxide crystallization, grows up, and forms four acicular type zinc oxide crystal whisker at last, and ZnOw is by N
2Take out of, cool and isolate four acicular type zinc oxide crystal whisker, separate the N of whisker
2Return or as zinc fume bring gas into or as the gas of bringing into of oxidizing gas, whisker transformation efficiency height is four needle-like oxidisability whiskers more than 95% in the product, the direct yield 80～90% of crystal whisker products simultaneously, zinc recovery＞95%.The application content is referring to " production technique of four acicular type zinc oxide crystal whisker and equipment ", and publication number CN1384056, application number are 02113881.8.Wherein do not address and identical summary of the invention of the present invention and claim.
Summary of the invention
The objective of the invention is: zinc oxide is a kind of inorganic structure and functional materials of excellent performance, and is very extensive in industry purposes such as rubber industry, coatings industry, electronics, pottery, voltage dependent resistor, makeup, catalyzer, medicine, food.For satisfying the requirement of different industries to zinc oxide product, improve the quality and the added value of product, development of new prepares the processing method of nanometer or micron order different shape zinc oxide.Adopt general industrial metallic zinc, zinc alloy, metallurgical residues containing zinc (purifying slag, silver-colored cadmia etc.), contain zinc fume in zinc spent catalyst, the pyrometallurgy of zinc factory zinc rectifying tower etc. and be raw material as hard zinc, zinc hydrometallurgy, do not need to prepare in advance metal zinc, reduce processing temperature, raw material sources are wide, and the technological process of production is short, and operational condition is simple, the production process serialization, energy consumption is lower, and production cost is low, environmentally safe.
Ultimate principle of the present invention is: metallic zinc is a kind of evaporable metal that is easier to, and its fusing point is 419.58 ℃, and boiling point is 906 ℃.The saturated vapor pressure of zinc and the theoretical formula of temperature be shown below (pressure unit is atm):
Illustrate that metallic zinc under lower temperature, just can produce bigger vapour pressure.But when producing metal zinc, normal pressure will reach the rate of volatilization of scale operation down, and volatilization temperature must surpass nearly 200 ℃ of boiling point, promptly volatilize under the temperature more than 1100 ℃, otherwise manufacturer does not just reach desired productivity.
The inventor is according to the present situation and the demand for development of zinc oxide product production method, by the relevant documents and materials of careful investigation, in conjunction with the vacuum metallurgy method, be raw material with the material of containing metal zinc, adopt eco-friendly vacuum-evaporation condensation method in enclosed system, to prepare zinc oxide product.Experimental study zinc fume gaseous oxidation condition to the influence of zinc oxide crystallization shape and the rule of morphology change.Experimental study is the result show, different crystallization shape zinc oxide such as that zinc oxide has is amorphous, particulate state, single needle shape, four needle-likes, spininess shape, sheet.Find through repetition test research back simultaneously, physicochemical environment when the crystallization shape that using vaporization condensation process prepares zinc oxide in the zinc oxide process mainly depends on the zinc fume oxidation, the growth conditions of zinc oxide influences crystalline nucleation and process of growth, finally causes the zinc oxide product of different-shape.The degree of supersaturation of gas phase in the controlling reactor as zinc fume dividing potential drop and oxygen partial pressure, is very crucial.Can regulate and control the crystallization shape of zinc oxide by changing preparation condition.Oxygen partial pressure can be regulated and control by air flow in the reactor, and the zinc fume dividing potential drop is then relevant with the zinc vapor pressure size, and promptly Heating temperature is relevant.Because zinc vapor pressure changes with variation of temperature, therefore the zinc fume dividing potential drop changes to be regulated and control by Heating temperature under vacuum environment.Test-results confirms, according to different needs, controlling the Heating temperature of suitable amount of oxygen and zinc raw material, is 430～1200 ℃ in Heating temperature, and oxygen pressure is the uniform nanometer or the micron order zinc oxide product that can obtain different-shape in the scope of 5～101325Pa respectively.Especially for producing four acicular type zinc oxide crystal whisker T-ZnOw product, saved various pretreatment process, greatly reduced preparation temperature, production process can serialization.
Evaporate these characteristics easily according to the metallic zinc heating, necessary higher zinc fume dividing potential drop during in conjunction with the production four acicular type zinc oxide crystal whisker, than relatively harsher specific requirements such as low oxygen partial pressures, the present invention is by obtaining higher zinc vapor pressure under the lesser temps in vacuum environment, fully react with low oxygen then, the gas phase of control reaction is formed and whisker growth institute must satisfied thermodynamics and kinetics condition, prepares four acicular type zinc oxide crystal whisker.
The object of the present invention is achieved like this: the material of metallic zinc or containing metal zinc is put into process furnace, be heated to and make it fusing more than the material melting temperature, metal after the fusing is under the barometric point effect, begin automatic suction vacuum-evaporation chamber, keep certain melt temperature, in vacuum environment, pure metal zinc is with certain vaporator rate and pressure start vaporizer, zinc fume enters oxidation reaction chamber automatically because certain pressure is arranged, with the indoor oxygen reaction of feeding oxidizing reaction; Be raw material perhaps, feed oxidation reaction chamber with the zinc fume in the pyrometallurgy of zinc factory zinc rectifying tower etc.; Keep enough reaction times and indoor oxygen pressures of oxidizing reaction, regulate pressure ratio and other corresponding condition of melting materials capable temperature, vacuum-evaporation chambers temp, zinc fume and oxygen, can obtain the various zinc oxide products of different-shape.Zinc oxide product constantly deposits and is enriched in the feed bin, to the regular hour, with its discharge, handles accordingly after the cooling, and packing becomes the finished product.In the heating under vacuum vaporization temperature is 430～1200 ℃, and oxygen pressure is uniform nanometer or the micron order zinc oxide product that primary product can obtain different-shapes such as amorphous, particulate state, single needle shape, four needle-likes, spininess shape, sheet respectively in the scope of 5～101325Pa.
Particular content of the present invention is as follows:
1, the material of metallic zinc or containing metal zinc evaporates under vacuum condition, obtain certain zinc vaporator rate and vapour pressure, it is indoor that zinc fume enters the oxidizing reaction that has been evacuated to the certain vacuum degree automatically, the purity oxygen reaction indoor with feeding, regulate and control melting materials capable temperature (420～1100 ℃) as required, vacuum-evaporation chambers temp (430～1200 ℃), the pressure ratio of zinc fume and oxygen (1: 0.01～30), the dividing potential drop (5～101325Pa) of the indoor oxygen of restriction oxidizing reaction, the content of oxygen and zinc vapor pressure in the limited reactions atmosphere, the physical and chemical condition of regulation and control zinc oxidation, primary product can obtain amorphous respectively, particulate state, the single needle shape, four needle-likes, the spininess shape, the uniform nanometer of different-shapes such as sheet or micron order zinc oxide product.Oxygen can replenish by certain speed and add, and also can regularly add by indirect mode.Zinc oxide product constantly forms and is enriched in the feed bin, to the regular hour, with its discharge, handles accordingly after the cooling, and packing becomes the finished product.Production process is serialization production, the indirect type discharging.The corresponding processing condition of the nanometer of preparation different shape or micron zinc oxide are as shown in table 1.
2, with above-mentioned summary of the invention 1 described content and method, can adopt metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste material is raw material, but they contain cadmium, arsenic, antimony, bismuth amount of metal and can not surpass 1% respectively.Can also adopt the zinc fume of drawing in pyrometallurgy of zinc factory from the zinc rectifying tower is raw material.
3, with above-mentioned summary of the invention 1 described content and method, can be at a certain amount of rare gas element of the indoor feeding of oxidizing reaction, CO
2, CO, SO
2Gas is as assist gas, and the total pressure in the control reaction chamber and the dividing potential drop of oxygen form different oxidizing atmosphere, but must guarantee that the indoor total gas pressure of oxidizing reaction less than external atmosphere pressure, can obtain the zinc oxide of different-shape.The assist gas total amount changes very little in reaction process, is before each preparation, after oxidation reaction chamber is evacuated, feeds in disposable mode by certain requirement.And oxygen continuous reaction consumes in reaction process is fallen, and must constantly replenish adding by certain speed, also can regularly add by indirect mode.
4, with above-mentioned summary of the invention 1,2,3 described content and methods, can spray into nano level ZrO with oxygen
2, SiO
2, Al
2O
3, TiO
2, ZnO, ZnS, CaO, ZnCO
3, MgO, CaCO
3, mica, zeolite, glass, gac, clay powders or one dimension fibre be as auxiliary agent, the crystallization nucleus increases the speed of growth, the pattern of controlled oxidation zinc.
The nanometer of table 1 preparation different shape or the processing condition of micron zinc oxide
| Vacuum-evaporation chambers temp ℃ | Reaction chamber oxygen pressure (Pa) | |||
| 5～9000 | 9000～17000 | 17000～23000 | 23000～101325 | |
| 430～650 | Amorphous | Amorphous | Amorphous | Amorphous |
| 650～750 | Particulate state, single needle shape | Particulate state, single needle shape | Particulate state | Particulate state |
| 750～850 | Single needle shape, spininess shape | Four needle-likes | Four needle-likes | Particulate state, single needle shape |
| 850～910 | Spininess shape, four needle-likes | Four needle-likes | Four needle-likes, single needle shape | Single needle shape, sheet |
| 910～980 | Sheet, particulate state | Single needle shape, particulate state, | Particulate state, single needle shape | Sheet, particulate state |
| 980～1200 | Amorphous | Amorphous | Particulate state, amorphous | Amorphous |
5, with above-mentioned summary of the invention 1,2,3,4 described content and methods, the zinc evaporator room can be merged into same preparation room with oxidation reaction chamber.Preparation room is divided into two districts, and preceding is the zinc evaporating area, and the back is the oxidizing reaction negative area.The material of metallic zinc or containing metal zinc can be without fusing in advance, and is interrupted and the successive method adds the zinc evaporating area by the mode of bulk or pulverulent material.When adopting the zinc fume of drawing from the zinc rectifying tower to be raw material in pyrometallurgy of zinc factory, must be divided into two chambers, preceding is zinc rectifying tower zinc evaporator room, and the back is the oxidizing reaction settling pocket.
6, with above-mentioned summary of the invention 1,2,3,4 described content and methods, prepare the zinc oxide of different-shape, can be by light-catalysed method load (intersperse or coat) nanometer metallic silver.Its method is to fill to add a certain amount of Silver Nitrate in the tubular reactor of certain water yield in one, adds prepared zinc oxide product again.Adopting UV-light (optical wavelength is less than 400nm) as light source, is raw material with pure water and Silver Nitrate, the aqueous solution is evacuated to certain vacuum tightness, eliminatings such as oxygen in the water and nitrogen.Zinc oxide is suspended in the aqueous solution with certain speed with magnetic stirring apparatus, behind UV-irradiation 1～300min, nanometer metallic silver corpuscle will constantly be deposited on the surface of zinc oxide, the aqueous solution is separated with zinc oxide, and drying obtains to carry the Ag-ZnO that contains of silver 0.005～2% (weight ratio).
Characteristics of the present invention are:
Adopting the vacuum metallurgy method, is raw material with the material of containing metal zinc, adopts eco-friendly vacuum-evaporation condensation method to prepare zinc oxide product in enclosed system.By regulating pressure ratio, oxygen partial pressure, assist gas total amount and other corresponding physical and chemical condition of melting materials capable temperature, vacuum-evaporation chambers temp, zinc fume and oxygen, the content of restriction oxygen, the oxidizing reaction speed of regulation and control zinc fume, under certain vacuum degree condition, acquire the uniform nanometer or the micron order zinc oxide product of different-shapes such as amorphous, particulate state, single needle shape, four needle-likes, spininess shape, sheet.Preparation method's method of the present invention adopts raw material sources wide, and the technological process of production is short, has reduced processing temperature greatly, and operational condition is simple, the production process serialization, and energy consumption is lower, and production cost is low, and environmentally safe easily is automated intelligent control.
Embodiment
Embodiment 1
The zinc oxide for preparing different-shape with purity oxygen.Take by weighing an industry metallic zinc (containing zinc 99.99%) 3kg, put it in the heat fused stove, when temperature rose to about 420 ℃, metallic zinc began fusing.After metallic zinc melts fully, continue to be heated to 650 ℃ of insulations, the vacuum-evaporation chamber links to each other with the steel pipe of heat fused stove with diameter 40mm, keeps certain height poor.Open vacuum pump, the air that vacuum-evaporation is indoor is taken out, and metallic zinc rises that it is indoor to enter vacuum-evaporation under the barometric point effect when certain vacuum is spent, and turns off vacuum pump, stops to vacuumize.The temperature that vacuum-evaporation is indoor is increased to 900 ℃, and metallic zinc is evaporated under vacuum condition, obtains certain zinc vaporator rate and vapour pressure.Open oxygen valve, aerating oxygen.It is indoor that zinc fume enters the oxidizing reaction that is evacuated to the certain vacuum degree, the purity oxygen reaction indoor with feeding, and zinc oxide constantly generates, and the sedimentation of growing up enters in the feed bin.Accumulated the zinc oxide of some amount to the regular hour, with its discharge, handled accordingly after the cooling, packing becomes the finished product.Regulate and control the pressure ratio (1: 0.01～30) of zinc fume and oxygen as required, the dividing potential drop (5～101325Pa) of the indoor oxygen of restriction oxidizing reaction.Oxygen can replenish by certain speed and add, and also can regularly add by indirect mode.Can obtain the uniform nanometer or the micron order zinc oxide product of different-shapes such as amorphous, particulate state, single needle shape, four needle-likes, spininess shape, sheet respectively.
Adopting other other Industrial Metal zinc ingot metal of level, industrial crude zinc, zinc alloy, zinc-containing metal waste material is raw material, sprays into nano level ZrO with oxygen
2, SiO
2, Al
2O
3, TiO
2, ZnO, ZnS, CaO, ZnCO
3, MgO, CaCO
3, Fe
2O
3, NiO mica, zeolite, glass, gac, clay powders or one dimension fibre be as auxiliary agent, or a certain amount of Duo gas of disposable feeding, CO respectively
2, CO, SO
2Gas is as assist gas, the total pressure in the control reaction chamber and the dividing potential drop of oxygen form different oxidizing atmosphere, guarantee that the indoor total gas pressure of oxidizing reaction is less than external atmosphere pressure, utilize above-mentioned preparation method can obtain the zinc oxide of different-shape, and can accelerate reaction process.
Adopting the zinc fume of drawing in pyrometallurgy of zinc factory from the zinc rectifying tower is raw material, utilizes above-mentioned preparation method can obtain the zinc oxide of different-shape, but must be divided into two chambers, and preceding is zinc rectifying tower zinc evaporator room, and the back is the oxidizing reaction settling pocket.
Embodiment 2
Zinc evaporating area and oxidation reaction zone prepare the zinc oxide of different-shape in same preparation room the time.Take by weighing the non-ferrous metal metallurgy byproduct that contains zinc about 80%---silver-zinc crust 2kg, put it in the process furnace of band vacuum seal.Open vacuum pump, the air that vacuum-evaporation is indoor is taken out, and when certain vacuum is spent, begins the heating that heats up.Along with temperature raises, silver-zinc crust begins fusing, and zinc vapor pressure increases, and the zinc velocity of evaporation is accelerated, and zinc fume is constantly accumulation in preparation room.When temperature rises to about 820 ℃, the beginning aerating oxygen, zinc fume is oxidized, and the continuous sedimentation of zinc oxide enters in the feed bin.Continuous supplemental oxygen to certain reaction after the time, is discharged zinc oxide in feed bin, handle accordingly after the cooling, obtains the acicular type zinc oxide powder.When metallic zinc is evaporated to 96% in the silver-zinc crust in the preparation room, stop heating, take out the cooling back, also can directly discharge postcooling.Add new a collection of silver-zinc crust, repeat said process, suitable adjusting process method parameter can prepare the zinc oxide of different-shape.
If metallic zinc powdery material then can add by the successive mode, also can obtain the zinc oxide of different-shape by above-mentioned preparation method.
Adopting other other Industrial Metal zinc ingot metal of level, industrial crude zinc, zinc alloy, zinc-containing metal waste material is raw material, sprays into nano level ZrO with oxygen
2, SiO
2, Al
2O
3, TiO
2, ZnO, ZnS, CaO, ZnCO
3, MgO, CaCO
3, Fe
2O
3, NiO, mica, zeolite, glass, gac, clay powders or one dimension fibre as auxiliary agent to reaction zone, or a certain amount of Duo gas of disposable feeding, CO respectively
2, CO, SO
2Gas is as assist gas, the total pressure in the control preparation room and the dividing potential drop of oxygen form different oxidizing atmosphere, guarantee that the interior total gas pressure of preparation room is less than external atmosphere pressure, utilize above-mentioned preparation method also can obtain the zinc oxide of different-shape, also can accelerate reaction process.
Embodiment 3
The preparation of zinc oxide load (intersperse or coat) silver.Measure pure water 400ml, join in the glass tubular reactor, add technical pure Silver Nitrate 5～60g again, add prepared acicular type zinc oxide 2g then.The high pressure mercury vapour lamp that is 400W with a power places in the tubular reactor, after the sealing aqueous solution is evacuated to certain vacuum tightness, gets rid of oxygen in the water and nitrogen etc.Tubular reactor is placed on the magnetic stirring apparatus, zinc oxide is suspended in the aqueous solution with certain speed.Tubular reactor is sealed to light tight with aluminium foil, and tubular reactor is linked to each other with recirculated cooling water.Open high pressure mercury vapour lamp, the argent micropartical will constantly be deposited on the surface of zinc oxide, behind illumination 1～300min, the aqueous solution be separated, will wash with zinc oxide, and drying obtains to carry the Ag-ZnO that contains of silver 0.005～5% (weight ratio).The argentiferous aqueous solution can be without any processing, returns to be used for photocatalytic deposition silver process next time.
Oxygen replenishes by certain speed and adds, and the amount of adding is and the steam output of zinc directly proportional (atomic ratio).
Claims (9)
1, the method for preparing different shape zinc oxide by vacuum limit oxygen method is characterized in that the material of metallic zinc or containing metal zinc is put into process furnace, is heated to make it fusing more than the material melting temperature, enters the vacuum-evaporation chamber, keeps melt temperature, the metallic zinc start vaporizer; Zinc fume enters the oxidation reaction chamber with certain vacuum degree because certain pressure is arranged, with the indoor oxygen reaction of feeding oxidizing reaction; In being the pressure ratio (1: 0.01～30) of 430～1200 ℃, zinc fume and oxygen, scope that the oxidizing reaction oxygen pressure is 5～101325Pa, the heating under vacuum vaporization temperature can deposit the uniform nanometer or the micron order zinc oxide product that obtain different-shapes such as amorphous, particulate state, single needle shape, four needle-likes, spininess shape, sheet respectively.
2, the method for preparing different shape zinc oxide by vacuum limit oxygen method, it is characterized in that various patterns nanometer or the micron zinc oxide corresponding processing condition as follows:
The vacuum-evaporation chambers temp (℃) Reaction chamber oxygen pressure (Pa)
5～ 9000 9000～ 17000 17000～ 23000 23000～ 101325
430～ 650 Amorphous Amorphous Amorphous Amorphous
650～ 750 Particulate state, single needle shape Particulate state, single needle shape Particulate state Particulate state
750～ 850 Single needle shape, spininess shape Four needle-likes Four needle-likes Particulate state, single needle shape
850～ 910 Spininess shape, four needle-likes Four needle-likes Four needle-likes, single needle shape Single needle shape, sheet
910～ 980 Sheet, particulate state Single needle shape, particulate state Particulate state, single needle shape Sheet, particulate state
980～ 1200 Amorphous Amorphous Particulate state, amorphous Amorphous
3,, it is characterized in that oxygen replenishes adding by certain speed, or regularly add by indirect mode by the method for claim 1 or 2 described preparing different shape zinc oxide by vacuum limit oxygen method; Zinc oxide product constantly deposits and is enriched in the feed bin, to the regular hour, with its discharge, handles accordingly after the cooling, and packing becomes the finished product; Production process is serialization production, the indirect type discharging.
4, by the method for claim 1 or 2 described preparing different shape zinc oxide by vacuum limit oxygen method, it is characterized in that adopting metal zinc ingot, industrial crude zinc, zinc alloy, zinc-containing metal waste material is raw material, but they contain cadmium, arsenic, antimony, bismuth amount of metal and can not surpass 1% respectively.
5, by the method for claim 1 or 2 described preparing different shape zinc oxide by vacuum limit oxygen method, it is characterized in that can adopt the zinc fume of drawing in pyrometallurgy of zinc factory from the zinc rectifying tower is raw material, save the vacuum-evaporation chamber, only need that zinc fume is introduced the oxidation chamber of answering with certain vacuum degree and get final product.
6,, it is characterized in that to feed rare gas element, CO by the method for claim 1 or 2 described preparing different shape zinc oxide by vacuum limit oxygen method
2, CO, SO
2Gas is as assist gas, and the total pressure in the control reaction chamber and the content and the dividing potential drop of oxygen form different oxidizing atmosphere, but the indoor total gas pressure of oxidizing reaction can obtain the zinc oxide of different-shape less than external atmosphere pressure.
7,, it is characterized in that and to spray into nano level ZrO with the oxygen discontinuous by the method for claim 1 or 2 described preparing different shape zinc oxide by vacuum limit oxygen method
2, SiO
2, Al
2O
3, TiO
2, ZnO, ZnS, CaO, ZnCO
3, MgO, CaCO
3, mica, zeolite, glass, gac, clay powders or 1-dimention nano compound fiber be as auxiliary agent, as the crystallization nucleus of zinc oxide, increases the speed of growth, the aciculiform pattern of controlled oxidation zinc.
8, by the method for claim 1 or 2 described preparing different shape zinc oxide by vacuum limit oxygen method, it is characterized in that the zinc evaporator room can merge into same preparation room with oxidation reaction chamber, preparation room is divided into two districts, and preceding is the zinc evaporating area, and the back is the oxidizing reaction negative area; The material of metallic zinc or containing metal zinc can be without fusing in advance, and is interrupted and the successive method adds in the zinc evaporating area by the mode of bulk or pulverulent material.
9, by the method for claim 1 or 2 described preparing different shape zinc oxide by vacuum limit oxygen method, it is characterized in that promptly interspersing or the clad nano argent by light-catalysed method load, its process is to fill in the reactor of certain water yield to add Silver Nitrate in one, adds zinc oxide product again; Adopt optical wavelength less than the UV-light of 400nm as light source, be raw material with pure water and Silver Nitrate, with the reactor state that is evacuated, the air scavenge in the water; With the agitator stirring zinc oxide is suspended in the aqueous solution, behind UV-irradiation 1～300min, nanometer metallic silver corpuscle will constantly be deposited on the surface of zinc oxide, and the aqueous solution is separated with zinc oxide, and drying obtains to carry the Ag-ZnO that contains of silver 0.005～2% (weight ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510039156 CN1858001A (en) | 2005-04-29 | 2005-04-29 | Method for preparing different shape zinc oxide by vacuum limit oxygen method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510039156 CN1858001A (en) | 2005-04-29 | 2005-04-29 | Method for preparing different shape zinc oxide by vacuum limit oxygen method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1858001A true CN1858001A (en) | 2006-11-08 |
Family
ID=37296963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510039156 Pending CN1858001A (en) | 2005-04-29 | 2005-04-29 | Method for preparing different shape zinc oxide by vacuum limit oxygen method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1858001A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070182B (en) * | 2007-06-11 | 2010-05-26 | 华东理工大学 | ZnO microcrystal with four-feet shape structure and its preparation method |
| CN101497127B (en) * | 2008-02-03 | 2010-12-22 | 中国科学院金属研究所 | Method for preparing zinc-zinc oxide composite nanostructure |
| CN101235538B (en) * | 2007-11-16 | 2011-07-20 | 北京矿冶研究总院 | Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization |
| CN102351239A (en) * | 2011-07-11 | 2012-02-15 | 江苏科技大学 | Device for preparing nanometer zinc oxide by vacuum limit oxygen method |
| CN102659172A (en) * | 2012-04-28 | 2012-09-12 | 江苏科技大学 | Method for preparing nano zinc oxide by vacuum oxygen limiting method |
| CN101987745B (en) * | 2009-07-29 | 2012-10-17 | 财团法人工业技术研究院 | Method for manufacturing zinc oxide and device thereof |
| RU2542245C2 (en) * | 2013-05-24 | 2015-02-20 | Алексей Иванович Гончаров | Method of obtaining dry zinc white and installation for method realisation |
| CN105200519A (en) * | 2015-10-20 | 2015-12-30 | 唐山建华科技发展有限责任公司 | Preparation method of sepiolite-tetrapod zinc oxide whisker composite material |
| CN107683852A (en) * | 2017-09-08 | 2018-02-13 | 芜湖悠派护理用品科技股份有限公司 | One kind carries Ag antibacterial zeolite particles and preparation method thereof |
| CN107720805A (en) * | 2017-10-26 | 2018-02-23 | 钢研晟华科技股份有限公司 | A kind of method that non-equilibrium oxidizing process of metallic zinc prepares nano zine oxide |
| CN109368688A (en) * | 2018-12-20 | 2019-02-22 | 兴化金孔雀实业发展有限公司 | A kind of production technology of high pure zinc oxide indirect method |
| CN109399694A (en) * | 2018-12-05 | 2019-03-01 | 马龙鹏泉环保有限公司 | A method of revolution Rotary Kiln extracts zinc oxide |
| CN109970097A (en) * | 2019-04-11 | 2019-07-05 | 唐山学院 | A kind of preparation method of nano zine oxide and prepared nano zine oxide and application thereof |
| CN111263789A (en) * | 2017-11-08 | 2020-06-09 | 乐天化学株式会社 | Thermoplastic resin composition and molded article prepared therefrom |
| CN111285395A (en) * | 2020-02-25 | 2020-06-16 | 兴化市庆丰锌品有限公司 | Production process of high-purity zinc oxide indirect method |
| CN111573711A (en) * | 2020-05-12 | 2020-08-25 | 张家港凯铭锌业有限公司 | Preparation method of zinc oxide |
| CN112299471A (en) * | 2020-11-25 | 2021-02-02 | 中南大学 | Method for synchronously preparing nano zinc oxide by efficiently separating zinc from zinc-containing electronic waste |
| CN113321235A (en) * | 2020-07-31 | 2021-08-31 | 上海交通大学 | Method for preparing zinc oxide ultrafine powder by using zinc skins of waste zinc-manganese batteries |
| CN113697845A (en) * | 2021-08-27 | 2021-11-26 | 哈尔滨工业大学 | Method for rapidly preparing high-proportion amorphous phase ZnO film |
| CN114457236A (en) * | 2021-12-16 | 2022-05-10 | 中南大学 | Separation and purification device for metal waste residues and separation and purification method for cobalt oxide residues |
| CN115346743A (en) * | 2022-08-08 | 2022-11-15 | 安徽锦华氧化锌有限公司 | Preparation method of zinc oxide of metal oxide arrester resistance card |
-
2005
- 2005-04-29 CN CN 200510039156 patent/CN1858001A/en active Pending
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070182B (en) * | 2007-06-11 | 2010-05-26 | 华东理工大学 | ZnO microcrystal with four-feet shape structure and its preparation method |
| CN101235538B (en) * | 2007-11-16 | 2011-07-20 | 北京矿冶研究总院 | Method for preparing tetrapod-like zinc oxide whisker with assistance of electric arc atomization |
| CN101497127B (en) * | 2008-02-03 | 2010-12-22 | 中国科学院金属研究所 | Method for preparing zinc-zinc oxide composite nanostructure |
| CN101987745B (en) * | 2009-07-29 | 2012-10-17 | 财团法人工业技术研究院 | Method for manufacturing zinc oxide and device thereof |
| CN102351239A (en) * | 2011-07-11 | 2012-02-15 | 江苏科技大学 | Device for preparing nanometer zinc oxide by vacuum limit oxygen method |
| CN102659172A (en) * | 2012-04-28 | 2012-09-12 | 江苏科技大学 | Method for preparing nano zinc oxide by vacuum oxygen limiting method |
| RU2542245C2 (en) * | 2013-05-24 | 2015-02-20 | Алексей Иванович Гончаров | Method of obtaining dry zinc white and installation for method realisation |
| CN105200519B (en) * | 2015-10-20 | 2017-10-31 | 唐山建华科技发展有限责任公司 | The preparation method of sepiolite four acicular type zinc oxide crystal whisker composite |
| CN105200519A (en) * | 2015-10-20 | 2015-12-30 | 唐山建华科技发展有限责任公司 | Preparation method of sepiolite-tetrapod zinc oxide whisker composite material |
| CN107683852A (en) * | 2017-09-08 | 2018-02-13 | 芜湖悠派护理用品科技股份有限公司 | One kind carries Ag antibacterial zeolite particles and preparation method thereof |
| CN107720805A (en) * | 2017-10-26 | 2018-02-23 | 钢研晟华科技股份有限公司 | A kind of method that non-equilibrium oxidizing process of metallic zinc prepares nano zine oxide |
| CN107720805B (en) * | 2017-10-26 | 2019-05-31 | 钢研晟华科技股份有限公司 | A kind of non-equilibrium oxidizing process of metallic zinc prepares the device of nano zine oxide |
| US11505674B2 (en) | 2017-11-08 | 2022-11-22 | Lotte Chemical Corporation | Thermoplastic resin composition and molded article produced from same |
| CN111263789A (en) * | 2017-11-08 | 2020-06-09 | 乐天化学株式会社 | Thermoplastic resin composition and molded article prepared therefrom |
| CN111263789B (en) * | 2017-11-08 | 2023-04-14 | 乐天化学株式会社 | Thermoplastic resin composition and molded article prepared therefrom |
| CN109399694A (en) * | 2018-12-05 | 2019-03-01 | 马龙鹏泉环保有限公司 | A method of revolution Rotary Kiln extracts zinc oxide |
| CN109368688A (en) * | 2018-12-20 | 2019-02-22 | 兴化金孔雀实业发展有限公司 | A kind of production technology of high pure zinc oxide indirect method |
| CN109970097A (en) * | 2019-04-11 | 2019-07-05 | 唐山学院 | A kind of preparation method of nano zine oxide and prepared nano zine oxide and application thereof |
| CN109970097B (en) * | 2019-04-11 | 2021-03-23 | 唐山学院 | Preparation method of nano zinc oxide, prepared nano zinc oxide and application thereof |
| CN111285395A (en) * | 2020-02-25 | 2020-06-16 | 兴化市庆丰锌品有限公司 | Production process of high-purity zinc oxide indirect method |
| CN111573711A (en) * | 2020-05-12 | 2020-08-25 | 张家港凯铭锌业有限公司 | Preparation method of zinc oxide |
| CN113321235A (en) * | 2020-07-31 | 2021-08-31 | 上海交通大学 | Method for preparing zinc oxide ultrafine powder by using zinc skins of waste zinc-manganese batteries |
| CN112299471A (en) * | 2020-11-25 | 2021-02-02 | 中南大学 | Method for synchronously preparing nano zinc oxide by efficiently separating zinc from zinc-containing electronic waste |
| CN112299471B (en) * | 2020-11-25 | 2022-02-15 | 中南大学 | Method for synchronously preparing nano zinc oxide by efficiently separating zinc from zinc-containing electronic waste |
| CN113697845A (en) * | 2021-08-27 | 2021-11-26 | 哈尔滨工业大学 | Method for rapidly preparing high-proportion amorphous phase ZnO film |
| CN114457236A (en) * | 2021-12-16 | 2022-05-10 | 中南大学 | Separation and purification device for metal waste residues and separation and purification method for cobalt oxide residues |
| CN114457236B (en) * | 2021-12-16 | 2023-01-24 | 中南大学 | Separation and purification device for metal waste residues and separation and purification method for cobalt oxide residues |
| CN115346743A (en) * | 2022-08-08 | 2022-11-15 | 安徽锦华氧化锌有限公司 | Preparation method of zinc oxide of metal oxide arrester resistance card |
| CN115346743B (en) * | 2022-08-08 | 2023-12-01 | 安徽锦华氧化锌有限公司 | Preparation method of metal oxide arrester resistor disc |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1858001A (en) | Method for preparing different shape zinc oxide by vacuum limit oxygen method | |
| Zaleska | Doped-TiO2: a review | |
| Najafian et al. | Fabrication of nanocomposite photocatalyst CuBi2O4/Bi3ClO4 for removal of acid brown 14 as water pollutant under visible light irradiation | |
| Samadi et al. | Recent progress on doped ZnO nanostructures for visible-light photocatalysis | |
| Chin et al. | Review on oxides of antimony nanoparticles: synthesis, properties, and applications | |
| CN1209482C (en) | Active raw material for thermal sprayed system, thermal sprayed electrodes of energy storage and conversion device made of it and manufacture method thereof | |
| CN100417753C (en) | Technology for preparing tetrapod-like zinc oxide whisker by normal pressure zinc vapour oxidation method | |
| CN105214709B (en) | Interlayer bimetallic ion doping carbonitride catalysis material and its preparation and application | |
| TWI245742B (en) | Method for manufacturing highly-crystallized oxide powder | |
| Uschakov et al. | The influence of oxygen concentration on the formation of CuO and Cu2O crystalline phases during the synthesis in the plasma of low pressure arc discharge | |
| Chen et al. | Photocatalytic decomposition of benzene with plasma sprayed TiO2-based coatings on foamed aluminum | |
| CN101244840B (en) | Method for manufacturing nano-oxide powder | |
| Raj et al. | Synthesis from zinc oxalate, growth mechanism and optical properties of ZnO nano/micro structures | |
| CN112191259B (en) | MXene/Au photocatalytic nitrogen fixation material, and preparation method and application thereof | |
| Aboualigaledari et al. | A review on the synthesis of the TiO2-based photocatalyst for the environmental purification | |
| Bakhtiarnia et al. | Deposition of nanoporous BiVO4 thin-film photocatalyst by reactive magnetron sputtering: Effect of total pressure and substrate | |
| CN107376905A (en) | A kind of preparation method of the Ag/ZnO composites of degradable formaldehyde | |
| CN1258009C (en) | ZnO nano crystal whisker material and its preparing method | |
| CN107163806A (en) | It is a kind of for nano-structured coating of air purifier and preparation method thereof | |
| CN102311264A (en) | Environment-protection and energy-saving nanometer zirconium oxide preparation method | |
| JP2004315356A (en) | Acicular titanium oxide particulate, method for manufacturing the same and application for the same | |
| CN1569617A (en) | Detonation method for synthesizing oxide powder | |
| Wang et al. | One-step electrospinning method to prepare gold decorated on TiO2 nanofibers with enhanced photocatalytic activity | |
| CN114618591A (en) | g-C3N4@ ZIF-8 composite photocatalyst and preparation method and application thereof | |
| Ayala-Ayala et al. | Manufacturing of Photoactive β-Bismuth Oxide by Flame Spray Oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |