CN100457605C - Process for preparing nano vanadium nitride and nano vanadium carbonitride powder - Google Patents
Process for preparing nano vanadium nitride and nano vanadium carbonitride powder Download PDFInfo
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- CN100457605C CN100457605C CNB2006100213287A CN200610021328A CN100457605C CN 100457605 C CN100457605 C CN 100457605C CN B2006100213287 A CNB2006100213287 A CN B2006100213287A CN 200610021328 A CN200610021328 A CN 200610021328A CN 100457605 C CN100457605 C CN 100457605C
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Abstract
The preparation process of nanometer vanadium nitride powder and nanometer vanadium carbo-nitride powder with the material including powdered ammonium vanadate, carbon reductant and small amount of RE catalyst includes the following steps: dissolving in deionized water or distilled water through stirring to prepare solution; heating the solution and drying to obtain precursor powder containing vanadium source and carbon source; reacting the precursor powder with introduced reducing gas inside a high temperature reaction furnace at 800-950 deg.c for 30-60 min to obtain nanometer vanadium nitride powder and nanometer vanadium carbo-nitride powder of size smaller than 100nm and with homogeneous size distribution. The process of the present invention has the features of low reaction temperature, short reaction time, low production cost, etc and is suitable for industrial production.
Description
Technical field
The invention provides the preparation method of a kind of nano level vanadium nitride and nano-scale carbon vanadium nitride powder-body, belong to nanometer scale ceramics powder preparing field.
Background technology
Vanadium nitride relative density big (6.04), fusing point height (2350 ℃), hardness big (Mohs' hardness 9～10) have higher heat, chemical stability and strong mechanical property, and vanadium nitride is widely used in extremely hard cutting tool, grinding tool and structured material.Vanadium nitride has supraconductivity, is the main composition of many magneticss and electronic component.Vanadium nitride still is a kind of catalyzer of brilliance, and its catalysis behavior is similar to precious metals such as platinum, palladium, rhodium, has high catalytic activity and selectivity, and good stability and anti-poisoning performance, is the surrogate of the economy of these precious metal materials.
Nano vanadium nitride is compared with the micron order vanadium nitride, has the following advantages: 1. can reduce the sintering temperature of some materials, improve sintering character; With it as wild phase, can effectively improve the intensity and the wear resistance of metal, ceramic matrix; 3. as catalyzer, has higher catalytic activity; 4. as superconducting material, has higher superconductivity.Therefore, nano vanadium nitride has broad application prospects.
The nitridation process of conventional metals vanadium is extremely complicated, metal powder need be milled to less than 300 orders and reaction for a long time at high temperature, even the method for applied microwave plasma body associating is reacted after 3 hours, need reactant to react again 3 hours after levigate, just can obtain mutually pure level vanadium nitride.Industrial, vanadium nitride adopts V usually
2O
5With charcoal be raw material, in nitrogen atmosphere, carry out reduction nitridation reaction in 1250 ℃, just can obtain the micron order vanadium nitride.Applied metal vanadium powder and Li
3N, Ca
3N
2Or Mg
3N
2Reaction only can obtain impure vanadium nitride in nitrogen atmosphere.Use above-mentioned basic metal or alkaline-earth metal nitridizing agent and VCl
2Or VCl
3Under vacuum condition, consolidate replacement(metathesis)reaction, or use VCl
4Carry out liquid-solid replacement(metathesis)reaction, can under the condition of gentleness, (400～900 ℃) prepare VN, but reaction raw materials costs an arm and a leg, and also only can obtain the micron order vanadium nitride.
J.G.Choi etc. have reported with V at Applied Catalysis A:Gerneral Vol.168 (1998) pp.47-56
2O
5Be raw material, ammonia is a nitridizing agent, adopts the temperature programming reaction method to prepare vanadium nitride powder-body, but temperature of reaction height, the product granularity that makes are big.
People such as Zheng Chen scheme in 2002 propose the preparation method of vanadium nitride powder-body in patent CN 1233549C: use technical grade V
2O
5Reduction preparation VOCl
2Solution is again with (NH
4)
2CO
3Or NH
4HCO
3Reaction, synthetic vanadyl (IV) basic carbonate ammonium presoma.Presoma is at NH
3In the atmosphere under relatively mild condition ammonia separate nitrogenize, can obtain particle diameter is the vanadium nitride powder-body of 95-98% at 20nm to 1 μ m, even particle size distribution, vanadium nitride content.Technology was complicated when the subject matter that this method exists was the preparation presoma; Reaction times is very long, causes the production cycle longer, and production cost is higher.
People such as high Lian in 2003 propose the preparation method of cubic-phase nano vanadium nitride powder-body in patent CN 1187261C: with a hydration Vanadium Pentoxide in FLAKES (V of precipitator method preparation
2O
5H
2O) powder is a raw material, in ammonia atmosphere hydration Vanadium Pentoxide in FLAKES powder high-temperature ammonolysis in tubular react furnace is made the cubic-phase nano vanadium nitride powder-body.By changing processing condition such as nitriding temperature, nitridation time, can obtain nano vanadium nitride powder-body less than the various grain sizes of 50nm.The nitrogenizing reaction temperature is controlled at 500～800 ℃, and temperature retention time of nitrogenization 3～5 hours, nitrogenize temperature rise rate are 5～10 ℃/minute.Under optimal conditions, can obtain the cubic-phase nano vanadium nitride powder-body.This method is compared with previous methods has lot of advantages, low as temperature of reaction, can make nano level vanadium nitride powder-body etc., but also come with some shortcomings: technology is complicated when preparation one hydration Vanadium Pentoxide in FLAKES powder, and the cycle is longer; Nitridation time 3-5 hour, the reaction times was longer.
Therefore, be necessary to explore the preparation method of a kind of low cost, the simple nano vanadium nitride powder-body of technology, so that satisfy the application of vanadium nitride powder-body better in fields such as cutting tool, superconducting material, catalyzer.
The carbon vanadium nitride is the compound solid solution body of vanadium carbide and vanadium nitride, and characteristics such as the relative density that it combines the crystal grain thinning of vanadium carbide and vanadium nitride is big, fusing point is high, hardness is big have the performance of a lot of excellences.At present, the research report of nano-scale carbon vanadium nitride powder-body is not arranged also, estimate that the nano-sized carbon vanadium nitride can have broad application prospects in fields such as high-performance steel, ultra-fine cemented carbide, catalyzer, superconducting materials.
Therefore, the nano-sized carbon vanadium nitride powder-body is worth development research, has better market application.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of nano vanadium nitride and nano-sized carbon vanadium nitride powder-body.Present method adopts the source to enrich cheap ammonium vanadate and carbonaceous reducing agent is a raw material, and preparation precursor powder earlier reduces, nitrogenizing reaction again, it is low to have temperature of reaction, and soaking time is short, and technology is simple, characteristics such as production cost is low are easy to realize suitability for industrialized production.
Embodiment of the present invention are: with powdery ammonium vanadate, carbonaceous reducing agent and catalyzer is raw material, wherein catalyzer is a kind of in Calcium Fluoride (Fluorspan) or the rare earth class catalyzer, according to a certain ratio above-mentioned raw materials is dissolved in deionized water or the distilled water, and stirs, make solution.With this solution heating, drying, obtain containing the precursor powder of vanadium source and carbon source at last then.Precursor powder is placed high temperature reaction stove, N
2Or NH
3Or their mixed gas reduced under the condition in 800～950 ℃, 30～60 minutes, nitrogenizing reaction as reduction and protective atmosphere, made the nano vanadium nitride and the nano-sized carbon vanadium nitride powder-body of median size＜100nm, even particle size distribution.
Further be that described powdery ammonium vanadate is ammonium meta-vanadate, poly ammonium vanadate or their mixture.
Further be that described carbonaceous reducing agent is nanometer carbon black, nano active charcoal, glucose or sucrose.
Further be, described catalyzer is Calcium Fluoride (Fluorspan), rare earth simple substance, rare earth compound or back two kinds mixture, and addition is 0.01%～2%.
Further be, described being dissolved in deionized water or the distilled water, temperature is 50 ℃～100 ℃.
Further be, described Heating temperature is 100 ℃～300 ℃ with this solution heating, drying, and the time is 1～2h; Drying temperature is 50 ℃～100 ℃, and the time is 1～5h.
Further be that described high temperature reaction stove is carbon tube furnace, tube furnace, induction furnace, microwave agglomerating furnace, rotary kiln, shaft furnace, grate, pushed bat kiln or tunnel furnace.
Compare with the existing method for preparing vanadium nitride and carbon vanadium nitride powder-body, the invention has the advantages that:
(1) abundant raw material, cheap.The present invention is a raw material with ammonium vanadate and carbonaceous reducing agent, and the source is abundant, and is cheap, saves cost.
(2) temperature of reaction is low, and the reaction times is short, save energy.The present invention adopts trace catalysts such as adding rare earth first, greatly reduces temperature of reaction, has shortened the reaction times, can save the energy greatly at preparation nano vanadium nitride and nano-sized carbon vanadium nitride powder-body under 800～950 ℃, 30～60min condition.
(3) technology is simple.The present invention can once finish reduction, nitrogenizing reaction, and is easy to operate, is fit to suitability for industrialized production.
(4) composition is single, epigranular, tiny.Vanadium nitride and carbon vanadium nitride powder-body median size＜100nm that reaction generates, even particle size distribution, foreign matter content is few.
Embodiment
Embodiment 1:
Catalyzer (CaF with 7.6g powdery ammonium meta-vanadate, 2.4g nanometer carbon black and 0.01%～2%
2, LaCl
3Or CeCl
3) be dissolved in the 50ml deionized water (50 ℃～100 ℃), obtain the solution that mixes after the stirring, solution is placed loft drier, heat 1～2h under 100～300 ℃ of conditions, dry 1～5h under 50～100 ℃ of conditions obtains containing the precursor powder of vanadium source and carbon source at last.Precursor powder is placed high temperature reaction stove, insulation 30～60min in the time of 600 ℃, and the N of feeding 0.02MPa
2, under 800～950 ℃, 30～60min condition, make the nano vanadium nitride powder-body of median size＜100nm, even particle size distribution.
Embodiment 2:
Catalyzer (CaF with 6.8g powdery ammonium meta-vanadate, 9.0g powdery glucose and 0.01%～2%
2, YCl
3Or NdCl
3) be dissolved in the 50ml distilled water (50 ℃～100 ℃), obtain the solution that mixes after the stirring, solution is placed loft drier, heat 1～2h under 100～300 ℃ of conditions, in dry 1～5h, obtain containing the precursor powder of vanadium source and carbon source at last under 50～100 ℃ of conditions.Precursor powder is placed high temperature reaction stove, insulation 30～60min in the time of 600 ℃, and the N of feeding 0.02MPa
2, under 800～900 ℃, 30～60min condition, make the nano vanadium nitride powder-body of mean particle size＜100nm, even particle size distribution.
Embodiment 3:
Catalyzer (CaF with 7.4g powdery ammonium meta-vanadate, 2.6g nanometer carbon black and 0.01%～2%
2, LaCl
3Or CeCl
3) be dissolved in the 50ml deionized water (50 ℃～100 ℃), obtain the solution that mixes after the stirring, solution is placed loft drier, heat 1～2h under 100～300 ℃ of conditions, dry 1～5h under 50～100 ℃ of conditions obtains containing the precursor powder of vanadium source and carbon source at last.Precursor powder is placed high temperature reaction stove, insulation 30～60min in the time of 600 ℃, and the N of feeding 0.01MPa
2, under 800～950 ℃, 30～60min condition, make the nano-sized carbon vanadium nitride powder-body of median size＜100nm, even particle size distribution.
Embodiment 4:
Catalyzer (CaF with 6.6g powdery ammonium meta-vanadate, 9.5g powdery glucose and 0.01%～2%
2, YCl
3Or NdCl
3) be dissolved in the 50ml distilled water (50 ℃～100 ℃), obtain the solution that mixes after the stirring, solution is placed loft drier, heat 1～2h under 100～300 ℃ of conditions, dry 1～5h under 50～100 ℃ of conditions obtains containing the precursor powder of vanadium source and carbon source at last.Precursor powder is placed high temperature reaction stove, insulation 30～60min in the time of 600 ℃, and the N of feeding 0.01MPa
2, under 800～900 ℃, 30～60min condition, make the nano-sized carbon vanadium nitride powder-body of median size＜100nm, even particle size distribution.
Claims (7)
1, the preparation method of a kind of nano vanadium nitride and nano-sized carbon vanadium nitride powder-body, it is characterized in that: with powdery ammonium vanadate, carbonaceous reducing agent and catalyzer is raw material, wherein catalyzer is a kind of in Calcium Fluoride (Fluorspan) or the rare earth class catalyzer, according to a certain ratio above-mentioned raw materials is dissolved in deionized water or the distilled water, and stirs, make solution, then with this solution heating, drying, obtain containing the precursor powder of vanadium source and carbon source at last, precursor powder is placed high temperature reaction stove, and feed N
2Or NH
3Or their mixed gas reduced under the condition in 800～950 ℃, 30～60 minutes, nitrogenizing reaction as reduction and protective atmosphere, made the nano vanadium nitride and the nano-sized carbon vanadium nitride powder-body of median size＜100nm, even particle size distribution.
2,, it is characterized in that described powdery ammonium vanadate is ammonium meta-vanadate, poly ammonium vanadate or their mixture according to the described method for preparing nano vanadium nitride and nano-sized carbon vanadium nitride powder-body of claim 1.
3,, it is characterized in that described carbonaceous reducing agent is nanometer carbon black, nano active charcoal, glucose or sucrose according to the described method for preparing nano vanadium nitride and nano-sized carbon vanadium nitride powder-body of claim 1.
4, according to the described method for preparing nano vanadium nitride and nano-sized carbon vanadium nitride powder-body of claim 1, it is characterized in that described rare earth class catalyzer is rare earth simple substance, rare earth compound or both mixtures, addition is 0.01%～2%.
5, according to the described method for preparing nano vanadium nitride and nano-sized carbon vanadium nitride powder-body of claim 1, it is characterized in that raw material is dissolved in deionized water or the distilled water, temperature is 50 ℃～100 ℃.
6, according to the described method for preparing nano vanadium nitride and nano-sized carbon vanadium nitride powder-body of claim 1, it is characterized in that Heating temperature is 100 ℃～300 ℃ with this solution heating, drying, the time is 1～2 hour; Drying temperature is 50 ℃～100 ℃, and the time is 1～5 hour.
7,, it is characterized in that described high temperature reaction stove is carbon tube furnace, tube furnace, microwave agglomerating furnace, induction furnace, rotary kiln, shaft furnace, grate, pushed bat kiln or tunnel furnace according to the described method for preparing nano vanadium nitride and nano-sized carbon vanadium nitride powder-body of claim 1.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101411986B (en) * | 2007-10-19 | 2010-09-15 | 中国科学院大连化学物理研究所 | Carbon-supported transitional metal carbon nitride compound as well as preparation and application thereof |
| CN103526153B (en) * | 2012-07-03 | 2017-10-24 | 山东科技大学 | A kind of nitriding method |
| CN103343257A (en) * | 2013-07-18 | 2013-10-09 | 四川大学 | Preparation method of multi-component nanograin growth inhibitor |
| CN103626140B (en) * | 2013-12-12 | 2015-06-10 | 河南工业大学 | Method for synthesizing nanometer vanadium nitride/chromium nitride composite powder by carbon-thermal reduction and nitridation process |
| CN103708429B (en) * | 2013-12-19 | 2015-08-19 | 河南工业大学 | A kind of preparation method of nano vanadium nitride/chromium nitride composite powder |
| CN106591688B (en) * | 2016-12-01 | 2018-05-11 | 武汉科技大学 | A kind of method for preparing VN alloy with extracting vanadium from stone coal richness vanadium liquid |
| CN107058855B (en) * | 2017-04-12 | 2018-08-21 | 武汉科技大学 | A method of preparing VN alloy with containing vanadium solution |
| CN109280934A (en) * | 2018-09-28 | 2019-01-29 | 陕西科技大学 | A kind of carbon-coated vanadium nitride elctro-catalyst, preparation method and application |
| CN110681409A (en) * | 2019-10-23 | 2020-01-14 | 陕西科技大学 | Carbon tube supported ultra-small VN hydrogen production electrocatalyst, synthesis method and application |
| CN112919429B (en) * | 2019-12-06 | 2023-03-28 | 中国科学院过程工程研究所 | Preparation method of vanadium nitride, vanadium nitride prepared by preparation method and application of vanadium nitride |
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| CN1587064A (en) * | 2004-08-05 | 2005-03-02 | 常州市茂盛特合金制品厂 | Process for producing vanadium nitrate |
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