CN103771512A - Preparation method of metallic oxide nanometer powder - Google Patents
Preparation method of metallic oxide nanometer powder Download PDFInfo
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- CN103771512A CN103771512A CN201410016778.1A CN201410016778A CN103771512A CN 103771512 A CN103771512 A CN 103771512A CN 201410016778 A CN201410016778 A CN 201410016778A CN 103771512 A CN103771512 A CN 103771512A
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Abstract
The invention discloses a preparation method of metallic oxide nanometer powder. The preparation method is simple in process, convenient to operate, universal for equipment and suitable for industrial production of nanometer powder. The preparation method comprises the following steps: dissolving metal salt by using water (or partially adding ethyl alcohol) so as to obtain a stable metal ion solution A, stirring the metal ion solution A and an alkaline precipitant solution B at a certain speed, mixing and reacting so as to obtain a precipitation precursor; putting the precipitation precursor in a double-tapered rotary vacuum drier, adding n-amyl alcohol to a tank of the double-tapered rotary vacuum drier, controlling heating temperature, drying till no liquid outflows, and halting the machine; and taking out dried metal hydroxide, and roasting so as to obtain the metallic oxide nanometer powder with good dispersity and uniform particle size distribution. The preparation method is simple to operate and has an industrial quantity production advantage; azeotropic alcohols can be recycled.
Description
Technical field
The present invention relates to liquid-phase precipitation method and prepare nano-powder method, particularly a kind of metallic oxide nano powder preparation method
Background technology
At present, while adopting liquid-phase precipitation method to prepare nanometer metal oxide powder, metal oxide precursor (coprecipitate) is easy to when dry produce reunite, and causes presoma powder in roasting process to occur hard aggregation, and size distribution is wider.The reason that produces this phenomenon is: metal oxide precursor is after filtering, between particle, contain large water gaging, while drying evaporation drying at a certain temperature, because water molecules capillary contraction in the time evaporating is pressed together particle, especially, the free water molecule of wet granular Adsorption on Surface and free hydroxyl (being non-bridge formation hydroxyl) form hydrogen bond, in drying process, the bridging effect that this hydrogen bond produces causes particle further to approach and the hydrogen bond action of the hydroxyl on adjacent particle surface occurs, further dehydration (as calcining) will make particle produce real chemical bond and forms the coacervate that is difficult to dispersion, size distribution is wider.
For addressing the above problem, adopt vacuum component distillation to obtain certain effect, the principle of vacuum component distillation is: in the time that organic solvent and water vapour air pressure sum equal normal atmosphere, biphasic mixture starts azeotropic, along with the carrying out of distillation, in mixture, the content of water constantly reduces; Along with the variation of this component of mixture, the azeotropic point of mixture constantly raises, until equal the boiling point of organic solvent; The object of vacuum component distillation is: reduce the boiling point of azeotropic liquid by vacuum, reduce capillary force action, also can eliminate the bridge formation effect of water molecules hydrogen bond simultaneously, thereby reduce congregation; The moisture of parcel in throw out is removed to greatest extent with the form of azeotrope, thereby prevents the formation of hard aggregation.Because the surface tension of organic solvent is lower, on the other hand due to some organic molecule can with the hydroxyl reaction of microparticle surfaces, organic group replaces surperficial oh group, can eliminate the possibility that forms chemical bond between particle, stops the generation of congregation.
Open (bulletin) number: the CN1611448 of Chinese patent, discloses the method that the direct liquid-phase precipitation method of a kind of use is prepared nano-metal-oxide.The method adopts ethanol as principal reaction medium and washings, has effectively eliminated the agglomeration producing in preparation process, makes final nanometer metal oxide powder favorable dispersity.
Chinese patent is (bulletin) number: CN101723319A openly, discloses a kind of method of preparing nanometer hypovanadic oxide doped powder by azeotropic distillation.The method adopts this colloidal sol is dissolved in azeotropic solvent and carries out component distillation, and the powder obtaining transforms adulterated powder through reduction constant temperature crystalline phase.The hypovanadic oxide doped powder size homogeneous of preparing, favorable dispersity.
Above-mentioned disclosed method main drawback is: the method for preparing nano-metal-oxide with direct liquid-phase precipitation method adopts ethanol as principal reaction medium and washings, because ethanol is volatile, flammable and explosive substance, has aborning very large danger; Use in addition ethanol as washings, can not be thoroughly the chlorion in throw out or the complete wash clean of other negatively charged ion owing to not using in a large number, the nano-powder of producing may residual impurity.A kind of method of preparing nanometer hypovanadic oxide doped powder by azeotropic distillation, although adopt component distillation mode, but owing to not adopting vacuum mode, in azeotropic process, environment is also under normal atmosphere or higher than normal atmosphere, also may produce capillary force action, weaken the bridge formation effect of eliminating water molecules hydrogen bond, do not reach the best congregation that reduces.And after azeotropic, also need further vacuum-drying, increase production link and equipment.
Summary of the invention
The invention provides a kind of metallic oxide nano powder preparation method, method technique is simple, easy to operate, and Device-General is applicable to suitability for industrialized production nano-powder.
The preparation method of a kind of metallic oxide nano powder provided by the invention comprises the following steps:
One. metal-salt is put into container, and water and dehydrated alcohol preparation, obtain stable metal ion solution, and the amount that adds dehydrated alcohol is 20% of metal ion solution cumulative volume, and metal ion solution concentration is 0.5～1.2mol/L, is called precursor solution A; Getting alkaline precipitating agent is dissolved in redistilled water, be mixed with stable alkaline precipitating agent, its concentration is 0.5～2.0mol/L, is called precursor solution B, precursor solution A is reacted and is precipitated presoma with B short mix in reactor, pass through deionized water filtration washing, drain;
Two. the above-mentioned precipitation presoma of draining is put into DoubletaperedVacuumdrier, pass into a liquid-inlet pipe from dryer outer in parallel with vapour outlet, the other end of liquid-inlet pipe connects azeotropic liquid alcohols container for storing liquid, drying machine vapour outlet connects condenser, its phlegma enters separatory container for storing liquid, the outlet of separatory container for storing liquid upper end is communicated with azeotropic liquid alcohols container for storing liquid, has valve control between container for storing liquid.Open DoubletaperedVacuumdrier, vacuumize and heat, opening azeotropic liquid alcohols container for storing liquid and drying machine communicating valve simultaneously, in DoubletaperedVacuumdrier tank body, adding Pentyl alcohol, add-on is greater than drains presoma volume, control Heating temperature, be initially controlled at 40-50 ℃, remain on-0.1Mpa of tank internal pressure, tank body rotating speed 8-12 rev/min, progressively heat to 120 ℃, azeotropic temperature is finally added to 150 ℃, continues to be dried to absence of liquid and flows out shutdown;
Three. take out dried metal hydroxides, at 450 ℃～1000 ℃, roasting 0.5～2 hour, obtains loose metallic oxide nano powder.
Described in step 1, metal-salt comprises: chlorate, vitriol, nitrate and phosphoric acid salt; Alkaline precipitating agent comprises: sodium hydroxide, potassium hydroxide, ammoniacal liquor and ammonium chloride; Azeotropic alcohols comprises: Pentyl alcohol, propyl carbinol and with the immiscible alcohols of water.
The present invention is compared with existing same class methods, and its significant beneficial effect is: the method is simple to operate, and azeotropic alcohols can recycle, and has industrialization lot production advantage.
Accompanying drawing explanation
Fig. 1 is a kind of preparation method's process flow diagram of metallic oxide nano powder.
Fig. 2 is the ZrO of particle diameter 15～20nm
2powder transmission electron microscope photo.
Fig. 3 is particle diameter 8～10nmFe
2o
3powder transmission electron microscope photo.
Fig. 4 is the CeO of particle diameter 10～15nm
2powder transmission electron microscope photo.
Fig. 5 is the TiO of particle diameter 8～10nm
2powder transmission electron microscope photo.
Embodiment
Below in conjunction with accompanying drawing, take laboratory room small-sized production as example, describe the present invention in detail.
Embodiment 1
As shown in Figure 1, a kind of preparation method of metallic oxide nano powder, the operation steps of the method is as follows:
One. take 2493 grams of ZrOCI
2, the YCl that 480ml concentration is 0.8mol
3solution, 11.79 grams of AlCl
36H
2o, all puts into container, is mixed with stable precursor solution A with 8L water and 2L dehydrated alcohol; Get 1800mlNH
3h
2o, is dissolved in water and 2L dehydrated alcohol, is mixed with 10L precursor solution B; By precursor solution A and B, short mix reaction in reactor is precipitated presoma, uses deionized water filtering stock extremely without CI
-and drain slurry moisture as far as possible;
Two. the above-mentioned precipitation presoma of draining is put into 20L rotatory evaporator material container, put into azeotropic liquid alcohol class I liquid I Pentyl alcohol simultaneously, add-on is greater than drains presoma volume, control Heating temperature, initially be controlled at 40-50 ℃, remain on-0.1Mpa of tank internal pressure, tank body rotating speed 8-12 rev/min, progressively heat to 50 ℃ and stop, azeotropic 1-5 hour, if reducing, liquid outflow amount improves temperature to 80 ℃ left and right, continue azeotropic for some time, increase temperature according to flowing liquid speed, observe at any time flowing liquid and whether contain moisture content, final flowing liquid is that continuous liq proves that moisture content is except clean, azeotropic temperature is finally added to 99 ℃, continue to be dried to absence of liquid and flow out shutdown, take out azeotropic drying thing,
Three. azeotropic drying thing is placed in stoving oven through 980 ℃, and 30min roasting, obtains the ZrO of particle diameter 15～20nm
2powder, as shown in Figure 2.
Embodiment 2
As shown in Figure 1, a kind of preparation method of metallic oxide nano powder, the operation steps of the method is as follows:
One. take 1692 grams of FeCl
36H2O puts into container, is mixed with stable precursor solution A with 8L water and 2L dehydrated alcohol; Get 751.47 grams of sodium hydroxide, be dissolved in and in 10L redistilled water, be mixed with stable precursor solution B; Precursor solution A, B short mix reaction in reactor is precipitated to presoma, uses deionized water filtering stock extremely without CI
-, and drain slurry moisture as far as possible;
Two. with the step 2 of embodiment 1;
Three. azeotropic drying thing is placed in stoving oven through 450 ℃, and 30min roasting, obtains particle diameter 8～10nmFe
2o
3powder, as shown in Figure 3.
Embodiment 3
As shown in Figure 1, a kind of preparation method of metallic oxide nano powder, the operation steps of the method is as follows:
One. take 2234 grams of CeCl
37H
2o puts into container, is mixed with stable precursor solution A with 8L water and 2L dehydrated alcohol; Get 2000mlNH
3h
2o, is dissolved in water and 2L dehydrated alcohol, is mixed with the precursor solution B that 10L is stable; Precursor solution A, B short mix reaction in reactor is precipitated to presoma, uses deionized water filtering stock extremely without CI
-, and drain slurry moisture as far as possible.
Two. with the step 2 of embodiment 1;
Three. azeotropic drying thing is placed in stoving oven through 600 ℃, and 30min roasting, obtains the CeO of particle diameter 10～15nm
2powder, as shown in Figure 4.
Embodiment 4
As shown in Figure 1, a kind of preparation method of metallic oxide nano powder, the operation steps of the method is as follows:
One. take 539mlTiCl
4-ethanolic soln is put into container, is diluted with water to 2L and is mixed with stable precursor solution A; Get 502mlNH
3h
2o, is dissolved in water to 2L, is mixed with stable precursor solution B; Precursor solution A, B short mix reaction in reactor is precipitated to presoma, uses deionized water filtering stock extremely without CI
-, and drain slurry moisture as far as possible;
Two. with the step 2 of embodiment 1;
Three. azeotropic drying thing is placed in stoving oven through 500 ℃, and 30min roasting, obtains the TiO of particle diameter 8～10nm
2powder, as shown in Figure 5.
Claims (2)
1. a preparation method for metallic oxide nano powder, is characterized in that the method comprises the following steps:
One. metal-salt is put into container, and water and dehydrated alcohol preparation, obtain stable metal ion solution, and the amount that adds dehydrated alcohol is 20% of metal ion solution cumulative volume, and metal ion solution concentration is 0.5～1.2mol/L, is called precursor solution A; Getting alkaline precipitating agent is dissolved in redistilled water, be mixed with stable alkaline precipitating agent, its concentration is 0.5～2.0mol/L, is called precursor solution B, precursor solution A is reacted and is precipitated presoma with B short mix in reactor, pass through deionized water filtration washing, drain;
Two. the above-mentioned precipitation presoma of draining is put into DoubletaperedVacuumdrier, pass into a liquid-inlet pipe from dryer outer in parallel with vapour outlet, the other end of liquid-inlet pipe connects azeotropic liquid alcohols container for storing liquid, drying machine vapour outlet connects condenser, its phlegma enters separatory container for storing liquid, the outlet of separatory container for storing liquid upper end is communicated with azeotropic liquid alcohols container for storing liquid, between container for storing liquid, there is valve control, open DoubletaperedVacuumdrier, vacuumize and heat, open azeotropic liquid alcohols container for storing liquid and drying machine communicating valve simultaneously, in DoubletaperedVacuumdrier tank body, add Pentyl alcohol, add-on is greater than drains presoma volume, control Heating temperature, initially be controlled at 40-50 ℃, remain on-0.1Mpa of tank internal pressure, tank body rotating speed 8-12 rev/min, progressively heat to 120 ℃, azeotropic temperature is finally added to 150 ℃, continue to be dried to absence of liquid and flow out shutdown,
Three. take out dried metal hydroxides, at 450 ℃～1000 ℃, roasting 0.5～2 hour, obtains loose metallic oxide nano powder.
2. the preparation method of a kind of metallic oxide nano powder according to claim 1, is characterized in that the said metal-salt of step 1 comprises: chlorate, vitriol, nitrate and phosphoric acid salt; Alkaline precipitating agent comprises: sodium hydroxide, potassium hydroxide, ammoniacal liquor and ammonium chloride; Azeotropic alcohols comprises: Pentyl alcohol, propyl carbinol and with the immiscible alcohols of water.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529690A (en) * | 2018-04-17 | 2018-09-14 | 广东普加福光电科技有限公司 | A kind of preparation method and applications of nickel oxide nano crystal |
| CN110482501A (en) * | 2019-09-12 | 2019-11-22 | 辽宁科技大学 | A kind of method of reaction in-situ preparation carbon coating nitrided iron nano-powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611448A (en) * | 2004-01-06 | 2005-05-04 | 鞍山科技大学 | Method for preparing nano metal oxide using direct liquid phase precipitation process |
| CN101104524A (en) * | 2006-07-14 | 2008-01-16 | 中南大学 | Process for preparing nanometer cerium dioxide |
| CN102718485A (en) * | 2012-06-27 | 2012-10-10 | 中国地质大学（武汉） | Cerium-doped lanthanum zirconate nano powder and preparation method thereof |
| CN103212718A (en) * | 2013-04-18 | 2013-07-24 | 辽宁科技大学 | Preparation method of over-spreading pre-dispersion molten iron attached nanometer oxide powder |
| CN103411401A (en) * | 2013-07-15 | 2013-11-27 | 南京腾飞干燥设备有限公司 | Bipyramid rotation vacuum drier |
-
2014
- 2014-01-14 CN CN201410016778.1A patent/CN103771512B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611448A (en) * | 2004-01-06 | 2005-05-04 | 鞍山科技大学 | Method for preparing nano metal oxide using direct liquid phase precipitation process |
| CN101104524A (en) * | 2006-07-14 | 2008-01-16 | 中南大学 | Process for preparing nanometer cerium dioxide |
| CN102718485A (en) * | 2012-06-27 | 2012-10-10 | 中国地质大学（武汉） | Cerium-doped lanthanum zirconate nano powder and preparation method thereof |
| CN103212718A (en) * | 2013-04-18 | 2013-07-24 | 辽宁科技大学 | Preparation method of over-spreading pre-dispersion molten iron attached nanometer oxide powder |
| CN103411401A (en) * | 2013-07-15 | 2013-11-27 | 南京腾飞干燥设备有限公司 | Bipyramid rotation vacuum drier |
Non-Patent Citations (4)
| Title |
|---|
| 潘勇等: ""共沸蒸馏法制备纳米Fe2O3粉体及表征"", 《2005年（第四届）中国纳米科技西安研讨会论文集》 * |
| 玉占君等: ""干燥条件对合成超微粉体Y2O3粒径的影响"", 《辽宁师范大学学报（自然科学版）》 * |
| 王喜忠: ""干燥设备化工选型"", 《干燥刊中刊》 * |
| 王宝和等: ""共沸蒸馏置换干燥法制备纳米氧化镁粉体的研究"", 《盐湖研究》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108529690A (en) * | 2018-04-17 | 2018-09-14 | 广东普加福光电科技有限公司 | A kind of preparation method and applications of nickel oxide nano crystal |
| CN110482501A (en) * | 2019-09-12 | 2019-11-22 | 辽宁科技大学 | A kind of method of reaction in-situ preparation carbon coating nitrided iron nano-powder |
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