CN100584763C - Method for preparing nano bismuth oxide - Google Patents

Method for preparing nano bismuth oxide Download PDF

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CN100584763C
CN100584763C CN200610118215A CN200610118215A CN100584763C CN 100584763 C CN100584763 C CN 100584763C CN 200610118215 A CN200610118215 A CN 200610118215A CN 200610118215 A CN200610118215 A CN 200610118215A CN 100584763 C CN100584763 C CN 100584763C
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preparation
heating
bismuth
microwave oven
microwave
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CN101177302A (en
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李咸伟
杨华明
俞勇梅
苏晓晖
石洪志
何晓蕾
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Baoshan Iron and Steel Co Ltd
Central South University
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Baoshan Iron and Steel Co Ltd
Central South University
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Abstract

The invention provides a preparation method of bismuth oxide. Both bismuth salt compound and alcohol are available and taken as reaction materials. The bismuth oxide product is prepared through microwave radiation. The preparation method provided by the invention has the advantages of environmental friendliness, simple technology, low production cost, narrow distribution of the particle size of the product, strong oxidation, high catalysis activity, non-toxicity and good chemical stability; the invention can be used in the treatment of wastewater, sewage and exhaust gas and the field of energy material; the invention can also be used to reduce the emission of industrial pollutants and can be popularized and applied in the treatment of exhaust gas for waste incineration industry, such as the iron and steel enterprises in China.

Description

The preparation method of bismuthous oxide bismuth trioxide
Technical field
The present invention relates to the oxide powder preparation field, be specifically related to a kind of preparation technology of bismuthous oxide bismuth trioxide.
Background technology
Bismuth oxide (Bi 2O 3) as a kind of semiconductor catalyst, in the existing application widely of catalytic field, and the research in photocatalysis field is also less relatively.Semi-conductor Bi 2O 3Band-gap energy be 2.8eV (and traditional photocatalyst TiO 2Band-gap energy be 3.2eV), its energy gap and TiO 2Approaching, and because its good stability has good photochemical catalysis development prospect.Nanometer Bi 2O 3Because its specific surface area is big, surfactivity point is many, thereby can show more excellent photocatalysis activity.Have and report the experimental study that contains nitrite waste water and degradating organic dye with the bismuth oxide photochemical catalysis, the result shows, Bi 2O 3Has good photocatalytic activity.People such as Anthony have studied semi-conductor Bi 2O 3Catalyzed degradation organochlorine contamination thing.The fourth roc of Jilin University has been studied Bi 2O 3Photochemical catalytic oxidation character to gaseous-phase organic pollutant has obtained certain achievement.
The nanometer Bi of present report 2O 3The preparation method mainly contain chemical precipitation method, hydrolysis method, sol-gel method, molten atomizing oxidation style, microemulsion method, chemical gas phase coacervation, plasma method etc., the whole bag of tricks all has its characteristics.The precipitator method are simple to operate, the Bi for preparing 2O 3The product purity height, production cost is low.People such as Li Wei (CN1544337A) disclose a kind of preparation nanometer Bi 2O 3Method, this method adopts pearl white concentrate as raw material, and it is leached, and obtains the nano bismuth oxide product with the sodium hydroxide solution precipitation after the removal of impurities.People such as Patil (Materials letters, 2005,59:2523-2525) obtain bismuth hydroxide by the ammonia precipitation process bismuth nitrate solution, obtain nano bismuth oxide through after the roasting.Hydrolysis method is come the synthesis oxide particle by the control hydrolysis condition, is a kind of method commonly used, very easily generates than coarse particles but use this method.Adopt the raw materials cost of sol-gel method preparation higher, but this method raw material mixes on the molecular level level, mixes highly evenly, the synthesis temperature of material is low, and material is formed easily and controlled, and equipment is simple.(journal of Shandong university (natural science edition) 1997,32 (1): such as Chen Dairong 88-93) with Bi (OR) 3(R:CH 2CH 2OCH 3, Cme 2Et) make presoma, synthesized Bi by the Sol-Gel method 2O 3It is spherical that polycrystal powder, the bismuth oxide micro-powder that obtains at last are approximately, and size range is 60-120nm.Adopt the technical process of molten atomizing oxidation style short, product purity is high, fine size, pollution-free, cost is low, but requires degree higher to equipment and processing parameter.(Wuhan University of Technology's journal, 2006,28 (2): 10-13) adopt bismuth vapor-phase oxidation method to make median size is the bismuth oxide powder of 33.7nm to Hu Hanxiang.The experimental installation of microemulsion method is simple, and energy consumption is low, strong operability, and powder monodispersity, interface property and the good stability of gained are compared with additive method, and particle diameter is easy to control, adapts to wide.But this method production cost is higher, needs to consume a large amount of organic solvent and tensio-active agent.There is report to be equipped with nanometer Bi with the polyhydroxy-alcohol legal system 2O 3, adopt this method effectively to stop particulate to be grown up, the Bi for preparing through this method 2O 3Grain diameter is 70-90nm (Joumnal of MaterialsScience 36 (2001) 297-299).More than several preparation methods relative merits are respectively arranged, and seek simple to operately, with low cost, monodispersity is good, the nanometer Bi that purity is high 2O 3The preparation method improve the key that it uses the width and the degree of depth.Trade effluent and waste gas are the serious organic pollutants of a kind of environmental pollution, and selecting a kind of catalytic activity height, cheap catalyzer is the key that realizes trade effluent and off gas treatment.
In order to overcome the deficiencies in the prior art, the present inventor utilizes the starting material that are easy to get, and adopts the microwave radiation mode of non-environmental-pollution, obtains the bismuth oxide product, thereby has finished the present invention.
Therefore, the preparation method who the purpose of this invention is to provide a kind of bismuthous oxide bismuth trioxide.
Summary of the invention
The preparation method of bismuthous oxide bismuth trioxide provided by the invention is called normal pressure liquid phase microwave method, may further comprise the steps:
1) dissolving step: the bismuth salt compound is dissolved in a small amount of organic solvent;
2) microwave irradiation step: carry out in the instrument of microwave transmissive member is housed, the reaction times is 3-60 minute, and reaction power is 180-900 watt:
3) washing step: with step 2) products therefrom water and dehydrated alcohol wash respectively;
4) drying step: drying temperature is 70-100 ℃;
5) calcination steps: maturing temperature is 500-700 ℃, and roasting time is 2-4 hour.
In dissolving step, the bismuth salt compound is selected from five nitric hydrate bismuths, bismuth acetate; Organic solvent is selected from ethylene glycol, propylene glycol; This step also can be used ultrasonic dispersing, and the time is 15-30 minute.
In microwave irradiation step, instrument can adopt household microwave oven, experiment with microwave oven, industrial microwave oven, preferably adopts the household microwave oven of being furnished with the water-cooled reflux after reequiping.Reactive mode can adopt continuous type of heating or be interrupted type of heating, wherein is interrupted type of heating and can adopts every heating in 0-15 minute once, and heating repeatedly repeatedly.
In drying step, its dry atmosphere is air atmosphere.
In calcination steps, preferred 600 ℃ of temperature; Preferred 2 hours of time.
Beneficial effect of the present invention is:
1) prior art for preparing technology relative complex, production cost is higher relatively and time-consuming; The present invention be with the bismuth salt compound that is easy to get and alcohols as the reaction starting material, technology is simple, easy to operate, raw material is easy to get, production cost is low, the synthetic condition is comparatively loose, can produce high value-added product.
2) instrument that microwave transmissive member is housed that the present invention is used can adopt the household microwave oven of being furnished with the water-cooled reflux, and this instrument is easy, be easy to get.The present invention adopts microwave radiation, and non-environmental-pollution is a kind of green synthesis process, is fit to the preparation method of the bismuthous oxide bismuth trioxide of Small Scale Industry production.
3) the product particle size distribution of the present invention's preparation is narrower, and oxidation capacity is strong, and the catalytic activity height is nontoxic, and chemical stability is good.The present invention is prepared the experiment (experimental result as shown in Figure 3) that products therefrom carries out photochemical catalytic oxidation nitrite trade effluent, prove that this product is fit to waste gas pollution control and treatment (as the catalytic decomposition of Dioxins etc.), also can be applicable to environmental protection fields such as wastewater treatment, sewage disposal, energy and material.The reduction of discharging that also can be applicable to industrial pollutants is handled, and can be applied to the off gas treatment of domestic iron and steel enterprise, waste incineration industry.
Description of drawings
Fig. 1 is the process flow diagram of preparation bismuthous oxide bismuth trioxide;
Fig. 2 is the XRD figure of presoma and product of roasting;
Fig. 3 is the time-efficiency curve diagram of 0.4g bismuth oxide photochemical catalytic oxidation 10mg/L nitrite trade effluent, and solution system pH value is 2.3.
Embodiment
The present invention is further elaborated with embodiment below, but these embodiment have any restriction to the present invention absolutely not.Any change that those skilled in the art are done in to the invention process under the enlightenment of this specification sheets all will drop in the scope of claims.
Embodiment 1 prepares the method for bismuth oxide
Accurately take by weighing 3.65g five nitric hydrate bismuths, measure the 50ml propylene glycol, both are mixed in beaker, ultra-sonic dispersion 30min dissolves fully to Bismuth trinitrate.Then above-mentioned mixed solution is transferred in the 250ml round-bottomed flask, places in the microwave oven that is connected to reflux and react, microwave power is 360W, microwave radiation 6 minutes (each 2 minutes, midfeather 1 minute, totally 3 times).After reaction finishes, collect product, carry out centrifugation, and respectively wash 3 times with deionized water and dehydrated alcohol.Dry 6h under 80 ℃.Obtain the bismuth oxide product at 600 ℃ of following roasting 2h.
Preparation technology's flow process of this method is seen Fig. 1.
The XRD spectra of products therefrom is seen Fig. 2.As can be seen, microwave product major part is unbodied non-crystalline state from b.As can be seen, sharp-pointed from a through the product X RD peak shape after the roasting, do not have assorted peak and exist, with α-Bi 2O 3Standard x RD spectrogram in full accord.
Embodiment 2
Accurately take by weighing the 1.66g bismuth acetate, measure 50ml ethylene glycol, both are mixed in beaker, ultra-sonic dispersion 20min dissolves fully to bismuth acetate.Then above-mentioned mixed solution is transferred in the 250ml round-bottomed flask, places in the microwave oven that is connected to reflux and react, microwave power is 180W, microwave radiation 20 minutes (each 4 minutes, midfeather 2 minutes, totally 5 times).After reaction finishes, collect product, carry out centrifugation, and respectively wash 3 times with deionized water and dehydrated alcohol.Dry 12h under 60 ℃.Obtain the bismuth oxide product at 550 ℃ of following roasting 2h.
The XRD spectra of products therefrom and Fig. 2 basically identical.
Embodiment 3
Accurately take by weighing the 1.66g bismuth acetate, measure the 50ml propylene glycol, both are mixed in beaker, ultra-sonic dispersion 20min dissolves fully to bismuth acetate.Then above-mentioned mixed solution is transferred in the 250ml round-bottomed flask, places in the microwave oven that is connected to reflux and react, microwave power is 540W, microwave radiation 16 minutes (each 4 minutes, midfeather 2 minutes, totally 4 times).After reaction finishes, collect product, carry out centrifugation, and respectively wash 3 times with deionized water and dehydrated alcohol.Dry 12h under 60 ℃.Obtain the bismuth oxide product at 650 ℃ of following roasting 2h.
The XRD spectra of products therefrom and Fig. 2 basically identical.

Claims (9)

1. the preparation method of a bismuthous oxide bismuth trioxide is characterized in that may further comprise the steps:
1) dissolving step: five nitric hydrate bismuths or bismuth acetate are dissolved in a small amount of ethylene glycol or the propylene glycol organic solvent;
2) microwave irradiation step: carry out in the instrument of microwave transmissive member is housed, the reaction times is 3-60 minute, and reaction power is 180-900 watt;
3) washing step: with step 2) products therefrom water and dehydrated alcohol wash respectively;
4) drying step: drying temperature is 70-100 ℃;
5) calcination steps: maturing temperature is 500-700 ℃, and roasting time is 2-4 hour.
2. preparation method as claimed in claim 1, wherein said dissolving step is used ultrasonic dispersing, and the time is 15-30 minute.
3. preparation method as claimed in claim 1, wherein said instrument is selected from household microwave oven, experiment microwave oven, industrial microwave oven.
4. preparation method as claimed in claim 3, wherein said household microwave oven is furnished with the water-cooled reflux.
5. preparation method as claimed in claim 1, wherein said microwave irradiation step adopt continuous type of heating or are interrupted type of heating.
6. preparation method as claimed in claim 5, wherein said interruption type of heating adopts every heating in 0-15 minute once, and heating is repeatedly repeatedly.
7. preparation method as claimed in claim 1, in the wherein said drying step, dry atmosphere is air atmosphere.
8. preparation method as claimed in claim 1, in the wherein said calcination steps, maturing temperature is 600 ℃.
9. preparation method as claimed in claim 1, in the wherein said calcination steps, roasting time is 2 hours.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11276533B2 (en) 2017-11-24 2022-03-15 Lg Chem, Ltd. Process for preparing anode active material for pseudocapacitor

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CN101824625B (en) * 2009-03-05 2012-05-16 南京理工大学 Method for controllably synthesizing bismuth-based nano-material by directly electrolyzing metal bismuth
CN104400003A (en) * 2014-12-04 2015-03-11 孚派特环境科技(苏州)有限公司 Bismuth metal nanorod and preparation method thereof
CN109759096B (en) * 2019-01-21 2021-06-29 陕西科技大学 BiOBr nanosphere, preparation method and application of BiOBr nanosphere as photocatalyst in photodegradation of dye
CN110961158B (en) * 2019-11-19 2023-03-21 江苏大学 Environment response type PNIPAM/Bi 2 O 3 Preparation method and application thereof
CN114097826B (en) * 2022-01-25 2022-04-08 中科优品(天津)科技发展有限公司 Application of bismuth trioxide as bactericide
CN115140769B (en) * 2022-06-27 2023-07-21 南京大学 Bismuth dioxide material, preparation method thereof and application thereof in preparing formic acid by electrochemical reduction of carbon dioxide
CN115382555B (en) * 2022-09-26 2023-11-03 青岛理工大学 Bi (Bi) 2 O 3 Foam Ni and microwave radiation preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11276533B2 (en) 2017-11-24 2022-03-15 Lg Chem, Ltd. Process for preparing anode active material for pseudocapacitor

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