CN1660530A - Method for preparing material of Nano metal powder - Google Patents
Method for preparing material of Nano metal powder Download PDFInfo
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- CN1660530A CN1660530A CN 200410022918 CN200410022918A CN1660530A CN 1660530 A CN1660530 A CN 1660530A CN 200410022918 CN200410022918 CN 200410022918 CN 200410022918 A CN200410022918 A CN 200410022918A CN 1660530 A CN1660530 A CN 1660530A
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Abstract
A process for preparing the metallic nanoparticles is based on the low-heat solid-phase replacement reaction and the sublimation-coagulation principle, and features that the ammonium chloride is used as the paragenetic substance of target nanoparticles, and it is heated to sublimake it for separating and purifying the product.
Description
Technical field
The present invention relates to a kind of nano metal powder preparation methods.
Background technology
The preparation of nano material has by physical method by the procedural nature branch and obtains the physics method of nanometer system and prepare the chemical method of nanometer system by the chemical reaction of molecule or ion from the body material.Chemical method comprises coprecipitation, reversed micelle (capsule) method, hydro-thermal method, chemical heat solution, ion sputtering method, electrochemical process, chemical gaseous phase deposition method, phonochemistry dissociate method, forced hydrolysis method, sol-gel processing, Subjective and Objective growth method and organic chemical reactions method etc.The chemical preparation process that adopts includes wet process mostly at present, and raw material availability is not high, and preparation flow length, complex process and washing difficulty, and causes environmental pollution.
In chemical method preparation, solid state reaction becomes the important component part of material preparation because it has energy-conservation, green production characteristics efficiently.High temperature solid state reaction (＞600 ℃) has been set up leading position in the synthetic field of material at present, and along with the development of material science and the continuous appearance of new material, middle heat (100～600 ℃), low-heat solid phase synthesis process (＜600 ℃) more and more come into one's own; Heat (as: pyrolysis), low-heat (as: solid phase metathesis reaction) solid state reaction in synthetic then most employing of nano material.
In the chemical heat decomposition reaction, the primitive reaction thing that employing can be decomposed at a certain temperature generates solid-state material and gas by decomposition reaction, and product gas is evaporated in course of reaction or after the reaction and removes, and can obtain desirable solid material; To the preparation process of this traditional chemical thermal decomposition and adjustment and the modification that condition meets the requirements, can make specific nano material.
In the low-heat solid state reaction, adopt solid-state reactants, be in contact with one another under certain condition and react; After reaction is finished, remove the symbiosis product that is soluble in cleaning solution, promptly get product by washing.Although this method just is used to prepare nano material in the recent period, caused numerous researchers' attention; The powder body material of having studied at present and having expected, can directly prepare with low-heat solid phase metathesis reaction has: oxide, hydroxide, carbonate, oxalates, citrate, tartrate, sulfide etc.
Metal carbonate, oxalates, citrate etc. are the important presomas of preparation magnesium-yttrium-transition metal nano material.Nano metal carbonate, oxalates, citrate can obtain nano-metal-oxide by pyrolysis and suitable condition control; Nano-metal-oxide can make nano metal by hot hydrogen reduction.In above-mentioned solid state reaction preparation process, all include liquid phase process.In order to remove the symbiosis product of low fever solid phase reaction, must be by the mode of washing; Thermolysis process then must have analyte makes dispersion treatment to prevent the product cohesion in the liquid phase.
The employing pyrolysis prepares nano-metal-oxide and hydrogen reduction prepares nano metal, must make pure presoma---nano metal carbonate, oxalates, citrate etc.; The preparation of presoma has liquid-phase precipitation method, sol-gel processing, low fever solid phase reaction method etc., must be through complicated washing process, and technological operation difficulty height, investment are greatly restricting the large-scale production and the industrialization of nano-metal-oxide greatly.
Summary of the invention
Prepare shortcoming in the nano metal in order to overcome pyrolysis, the present invention according to low-heat solid phase metathesis reaction prepare powder, the ammonium chloride distillation---the principle and the characteristics of the process of sublimating provide a kind of method for preparing nano metal.
The present invention prepares powder, ammonium chloride distillation---the principle and the characteristics of the process of sublimating according to low-heat solid phase metathesis reaction, the symbiosis product of the target powder that generates in the metathesis reaction process is set at the ammonium chloride that can distil, reach the separation and the purifying of product by distillation ammonium chloride, obtain target powder.
The present invention is that the metal-precipitator of aqueous phase is a raw material with stable, solid metal chloride and stable, solid ammonium salt, adopts temperature rise China preparation target powder in solid salt normal temperature solid phase reaction, the ammonium chloride.Specific embodiment is:
(1) adopt abrading type to mix method, the solid-phase reactant of micron order particle diameter fully mixed, reaction at normal temperatures, the reaction time is 0.2～3.0 hour, ammonium chloride and target nano-powder;
(2) product is dried down at 60～150 ℃;
(3) dried ammonium chloride and target nano-powder thing are placed the stove that can ventilate, under by carrier band gas, 200 ℃～1200 ℃ conditions of temperature, heat-treat, 0.5～5 hour time, make the ammonium chloride distillation, get the target nano-powder.
One of described raw material is a metal chloride; Another reactant is the ammonium salt precipitating reagent of respective metal in the aqueous solution, as ammonium sulfide, carbonic hydroammonium, ammonium oxalate, ammonium citrate.
Described heat treatment process is the sublimation process of ammonium chloride; In this process, the target nano-powder obtains separating and purifying; Described carrier band gas according to the requirement of target nanometer product property, may be air, nitrogen, argon gas etc. as the load of distillation ammonium chloride.
The target nano-powder material of indication of the present invention mainly is water-fast precipitated metal things such as the sulfide, carbonate, oxalates, citrate of metal.Nano metal carbonate, oxalates, citrate etc. can be used as the presoma of preparation nano-metal-oxide or nano metal, particle diameter＜100nm (controlled), material content 〉=99.5%.
According to the requirement of target product, the heat treatment process described in the said method comprises three classes:
(1) only there is the sublimation process of ammonium chloride;
The decomposable process that another nano-substance is arranged when (2) the ammonium chloride distillation being arranged is as the thermal decomposition of metal carbonate, oxalates, citrate etc.;
(3) two step heat treatments: after treating that the ammonium chloride distillation is finished, carry out the thermal decomposition of nano-substance.
The present invention utilizes the low-heat solid state reaction, and solid phase reaction is not used solvent, has high selectivity, high yield, simple technological process and other advantages; To be appointed as ammonium chloride with the product of object symbiosis, by the mode of heating sublimation, the purification of target product has solved the difficulty that the low-temperature solid phase reaction product is difficult to separation and purification preferably; Low-heat solid state reaction and ammonium chloride distillation are combined, reach the solid phase method preparation and the purifying of nanometer product, avoid chemical method to prepare the wet scrubbing process of nano material, reach the clean certainly of nano material preparation, the absolutely dry method of process, technology is simple, and energy consumption is low, pollution-free, and industrialized implementation is convenient.Utilize materials such as gained metal sulfide of the present invention, metal oxide and metal carbonate, oxalates, citrate, be crystal perfection, pattern nano-solid powder clearly.
The specific embodiment
It below is part specific embodiment of the present invention.Providing of these embodiment limits the present invention anything but.
Embodiment 1
To contain crystallization water cobalt chloride solid and ammonium oxalate solid (slightly excessive), mix 0.2～3.0 hour by lapping mode by stoichiometry; Above-mentioned product is dried down at 60～150 ℃; With the heat treatment under oxygen atmosphere, 200 ℃～600 ℃ conditions of temperature of above-mentioned dry thing, 0.5～5 hour time; The product that obtains by said process is nano level Co
3O
4, particle diameter is 30～70nm.
Embodiment 2
To contain crystallization water neodymium chloride solid and carbonic hydroammonium solid (slightly excessive), mix 0.2～3.0 hour by lapping mode by stoichiometry; Above-mentioned product is dried down at 60～150 ℃; In oxygen atmosphere, ammonium chloride, 0.5～2 hour time are removed in distillation under 200 ℃～500 ℃ conditions with above-mentioned dry thing; Again in 400 ℃～900 ℃ its products of thermal decomposition, 0.5～5 hour time; The product that obtains by said process is nano level Nd
2O
3, particle diameter is 30～80nm.
Embodiment 3
To contain crystallization water zinc chloride solid and ammonium sulfide solid (slightly excessive), mix 0.2～3.0 hour by lapping mode by stoichiometry; Above-mentioned product is dried down at 60～150 ℃; Above-mentioned dry thing distilled under 200 ℃～500 ℃ conditions remove ammonium chloride, 0.5～2 hour time; The product that obtains by said process is nano level ZnS, and particle diameter is 30～100nm.
Embodiment 4
With calcium chloride dihydrate solid and carbonic hydroammonium solid (slightly excessive), mixed 0.2～3.0 hour by lapping mode by stoichiometry; Above-mentioned product is dried down at 60～150 ℃; Above-mentioned dry thing distilled under 200 ℃～500 ℃ conditions remove ammonium chloride, 0.5～2 hour time; The product that obtains by said process is nano level CaCO
3, particle diameter is 20～70nm.
Embodiment 5
Barium chloride, ammonium sulfide (by slightly excessive with the zinc sulfate complete reaction) with water-containing crystal thing zinc sulfate and equivalent mixed 0.2～3.0 hour by lapping mode; Above-mentioned product is dried down at 60～150 ℃; Above-mentioned dry thing distilled under 200 ℃～800 ℃ conditions remove ammonium chloride, 0.5～2 hour time; The product that obtains by said process is nanoscale lithopone (ZnSBaSO
4), particle diameter is 20～100nm.
Claims (4)
1. nano metal powder preparation methods, prepare powder, ammonium chloride distillation---the principle and the characteristics of the process of sublimating according to low-heat solid phase metathesis reaction, the symbiosis product of the target powder that generates in the metathesis reaction process is set at the ammonium chloride that can distil, reach the separation and the purifying of product by distillation ammonium chloride, obtain target powder, it is characterized in that: with stable, solid metal chloride and stable, solid ammonium salt is that the metal-precipitator of aqueous phase is a raw material, adopts temperature rise China preparation target powder in solid salt normal temperature solid phase reaction, the ammonium chloride; Specific embodiment is:
(1) adopt abrading type to mix method, the solid-phase reactant of micron order particle diameter fully mixed, reaction at normal temperatures, the reaction time is 0.2～3.0 hour, ammonium chloride and target nano-powder;
(2) product is dried down at 60～150 ℃;
(3) dried ammonium chloride and target nano-powder thing are placed the stove that can ventilate, under by carrier band gas, 200 ℃～1200 ℃ conditions of temperature, heat-treat, 0.5～5 hour time, make the ammonium chloride distillation, get the target nano-powder.
2. method according to claim 1 is characterized in that: one of described raw material is a metal chloride; Another reactant is the ammonium salt precipitating reagent of respective metal in the aqueous solution, as ammonium sulfide, carbonic hydroammonium, ammonium oxalate, ammonium citrate.
3. method according to claim 1 is characterized in that: described heat treatment process is the sublimation process of ammonium chloride; Described carrier band gas according to the requirement of target nanometer product property, may be air, nitrogen, argon gas etc. as the load of distillation ammonium chloride.
4. method according to claim 1 is characterized in that: the target nano-powder material of indication mainly is water-fast precipitated metal things such as the sulfide of metal, carbonate, oxalates, citrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410022918 CN1660530A (en) | 2004-02-25 | 2004-02-25 | Method for preparing material of Nano metal powder |
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| CN 200410022918 CN1660530A (en) | 2004-02-25 | 2004-02-25 | Method for preparing material of Nano metal powder |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9079164B2 (en) | 2012-03-26 | 2015-07-14 | Brigham Young University | Single reaction synthesis of texturized catalysts |
| US9114378B2 (en) | 2012-03-26 | 2015-08-25 | Brigham Young University | Iron and cobalt based fischer-tropsch pre-catalysts and catalysts |
| US9289750B2 (en) | 2013-03-09 | 2016-03-22 | Brigham Young University | Method of making highly porous, stable aluminum oxides doped with silicon |
| CN105834455A (en) * | 2016-05-03 | 2016-08-10 | 陕西理工学院 | Simple preparation method for zero-valent alpha-Fe particles with high stability |
-
2004
- 2004-02-25 CN CN 200410022918 patent/CN1660530A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9079164B2 (en) | 2012-03-26 | 2015-07-14 | Brigham Young University | Single reaction synthesis of texturized catalysts |
| US9114378B2 (en) | 2012-03-26 | 2015-08-25 | Brigham Young University | Iron and cobalt based fischer-tropsch pre-catalysts and catalysts |
| US9289750B2 (en) | 2013-03-09 | 2016-03-22 | Brigham Young University | Method of making highly porous, stable aluminum oxides doped with silicon |
| CN105834455A (en) * | 2016-05-03 | 2016-08-10 | 陕西理工学院 | Simple preparation method for zero-valent alpha-Fe particles with high stability |
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