CN108264048A - A kind of method of free carbon in removing transition metal carbides - Google Patents
A kind of method of free carbon in removing transition metal carbides Download PDFInfo
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- CN108264048A CN108264048A CN201810037914.3A CN201810037914A CN108264048A CN 108264048 A CN108264048 A CN 108264048A CN 201810037914 A CN201810037914 A CN 201810037914A CN 108264048 A CN108264048 A CN 108264048A
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- carbide
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention provides a kind of method for removing free carbon in transition metal carbides, and the method is with Ca CaCl2Molten salt system is decarburization medicament, at 800 ~ 1100 DEG C, chemism calcium is made to react generation calcium carbide with free carbon, passes through CaCl2Increase kinetics and protect the volatilization loss of Ca, remove decarburization product CaC by way of acidleach later2And excessive Ca, achieve the purpose that remove free carbon, present invention removing free carbon is more thorough, and technological process is simple, and is easy to industrialized production；The secondary oxidation of carbide in itself is avoided, new impurity will not be introduced to carbide in process of production, while the purity of carbide can be further improved；Using Ca CaCl2Molten salt system, chemism Ca can be dissolved in the CaCl of molten condition2, with CaCl2For medium, the contact between Ca and free carbon is increased, accelerates reaction rate.
Description
Technical field
The invention belongs to field of metallurgy, and in particular to a kind of method for removing free carbon in transition metal carbides.
Background technology
Transition metal carbides are because of its high-melting-point, high rigidity, excellent heat conductivity in recent years, elevated temperature strength, wearability, resist
Outstanding advantages of corrosivity, high thermal stability, is used widely, such as resistance on mechanical component in industry and technology
Mill, anti-corrosion coating, contact material, the diffusion barrier of electronic device and metal matrix composite material etc..In addition, they also have
Similar electricity, magnetism with its base metal so that they can apply to the fields such as nuclear reactor and similar to noble metal
The fields such as catalysis cause the great interest of researchers.
It is carbonized between titanium atom with very strong Covalent bonding together, there are several characteristics of metalloid, such as high fusing point, boiling point
And hardness, hardness are only second to diamond, there is good heat conduction and electric conductivity, and superconductivity is even shown when temperature is extremely low.Cause
This, titanium carbide be widely used in manufacture cermet, heat-resisting alloy, hard alloy, anti-friction material, high-temperature radiation material and its
Its high-temperature vacuum device has extensively with the composite diphase material of its preparation in fields such as mechanical processing, metallurgical mineral products, space flight and fusion reactors
General application.Zirconium carbide is a kind of big materials with high melting point of hardness and fabulous high-temperature refractory.It is used as in rocket engine
A kind of raw material of solid propellant or for producing steel alloy and production metal zirconium and zirconium chloride raw material, be have it is a kind of very
Promising fine ceramics material.Hafnium carbide is highly suitable for rocket nozzle, the nose cone portion for the cosmic rocket that can reentry
Position is for industries such as ceramics.Vanadium carbide can be used as Cutanit additive mainly for the manufacture of vanadium steel.Niobium carbide is hard
Degree is big, fusing point is high, high-temperature behavior is good, therefore it has important purposes in surface peening and modification technology.It is used for example as
The coating of jet engine turbo blade and rocket nozzle can significantly improve its service life.And it is also applied to electron emission pipe
Production, substantially reduce the heat emission of grid, extend the service life of electron emission pipe, have important push away to producing high-power transmitting tube
Action is used.The dosage of niobium carbide is increased in hard alloy, it can be with partial substitution resource rareness, expensive tantalum source.Carbonization
Tantalum does sintering cemented carbide grain growth inhibitor use, has positive effect to crystal grain is inhibited to grow up.For powder metallurgy, skiver
Tool, fine ceramics, chemical vapor deposition, hard, wear-resistant alloy cutter, tool, mold and wear-and corrosion-resistant structure member additive,
Improve the toughness of alloy.Chromium carbide is a kind of under high temperature environment with good wear-resisting, corrosion-resistant, oxidation resistant dystectic
Material, with nichrome made from hard alloy particle, using plasma spraying method, can be used as high temperature resistant, wear-resisting, resistance to oxidation with
Acid-proof coating is widely used on aircraft engine and Petro-Chemical Machinery device, is greatly improved the service life of machinery.Molybdenum carbide by
In having the characteristics that higher melt and hardness, good thermal stability and mechanical stability, fabulous anticorrosion properties, in material modification
Aspect, it can be used as coating material, can also be used as added material use.Molybdenum carbide is used for usually as coating material
The fields such as some high rigidity, abrasion-resistant and high temperature resistant.Molybdenum carbide has certain properties of noble metal, for dehydrogenation of hydrocarbons, hydrogenolysis
It with the catalytic activity of isomerization reaction, can compare favourably, be known as " quasi- platinum catalyst " with noble metal platinum, iridium.
The mainstream synthetic method of transition metal carbides has two classes at present：Be respectively metal direct carborization and carbon heat also
Former method.Wherein metal direct carborization is that magnesium-yttrium-transition metal simple substance is directly obtained by the reaction its carbide, such raw material with carbon
Method is of high cost, and product purity is determined by material purity.Carbothermic method is by transition group metallic oxide and carbonaceous reducing agent
Reaction, reduction and carbonization obtain its carbide.This method is at low cost, and simple process.However, this method needs excessive carbon ability
The product for ensureing to obtain restores completely, has extra free carbon to be present in product after reaction, reduces the purity of product.For removing
Free carbon in this method product, the technique of two kinds of removing free carbons have been suggested：Flotation decarbonization and oxidation decarbonization.Flotation removes
Carbon method is the hydrophobicity using carbon, by way of ventilating into water, carbon is made to float, and carbide is sunken to the bottom and reaches separation
Purpose, however program decarburization is not thorough enough, can only carry out preliminary decarburization.Oxidation decarbonization is the side by heating in air
Formula makes carbon be reacted with oxygen, achievees the purpose that except carbon, but the program can make carbide that secondary oxidation occur, and reduce product purity.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of method for removing free carbon in transition metal carbides, institute
Method is stated with Ca-CaCl2Molten salt system is decarburization medicament, at 800 ~ 1100 DEG C, chemism calcium is made to react life with free carbon
Into calcium carbide, pass through CaCl2Increase kinetics and protect the volatilization loss of Ca, remove decarburization by way of acidleach later
Product CaC2And excessive Ca, achieve the purpose that remove free carbon；
Further, it the described method comprises the following steps：
Step 1：It is considered to be worth doing using calcium, anhydrous calcium chloride and carbide carry out batch mixing as raw material；
Step 2：Raw material is put into high temperature furnace, under an argon atmosphere, 1-2h is kept the temperature in 800 ~ 1100 DEG C；
Step 3：The product obtained in step 2 is leached with hydrochloric acid solution；
Step 4：The filter residue obtained in step 3 is obtained into the higher carbide of purity after drying；
Step 5：It calcines the filtrate obtained in step 3 drying and under high temperature, recycling obtains anhydrous calcium chloride；
Further, the transiting group metal elements are VIB, VB or group vib element, and carbide is titanium carbide, zirconium carbide, carbon
Change hafnium, vanadium carbide, niobium carbide, ramet, chromium carbide or molybdenum carbide；
Further, processing need to be dried in anhydrous calcium chloride in advance in the step 1；
Further, mixing method is stirring in the step 1；
Further, calcium chloride dosage described in the step 1 is 0.5 ~ 2g/g carbide, and calcium bits dosage is 0.02 ~ 0.1g/g
Carbide；
Further, other a small amount of salt of addition are calcined through in the step 5, reduce CaCl2Molten salt system fusing point；
Beneficial effects of the present invention are as follows：
1）：Compared to traditional flotation decarbonization, this programme removing free carbon is more thorough, and technological process is simple, and is easy to industry
Metaplasia is produced；
2）：Compared to oxidation decarbonization, this programme avoids the secondary oxidation of carbide in itself, will not give carbon in process of production
Compound introduces new impurity, while this programme has both deep deoxidation function, can further improve the purity of carbide；
3）：Using Ca-CaCl2Molten salt system, chemism Ca can be dissolved in the CaCl of molten condition2, with CaCl2For medium, increase
Big contact between Ca and free carbon, accelerates reaction rate.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, it is not used to
Limit the present invention.On the contrary, the present invention cover it is any be defined by the claims the present invention spirit and scope on do replacement,
Modification, equivalent method and scheme.Further, in order to which the public is made to have a better understanding the present invention, below to the present invention's
It is detailed to describe some specific detail sections in datail description.Part without these details for a person skilled in the art
Description can also understand the present invention completely.
With reference to specific embodiment, the invention will be further described, but not as a limitation of the invention.Here is
The present invention's enumerates most preferred embodiment：
The present invention provides a kind of method for removing free carbon in transition metal carbides, and the method is with Ca-CaCl2Molten salt body
It is for decarburization medicament, at 800 ~ 1100 DEG C, chemism calcium is made to react generation calcium carbide with free carbon, passes through CaCl2Increase
The volatilization loss of kinetics and protection Ca, removes decarburization product CaC by way of acidleach later2And excessive Ca,
Achieve the purpose that remove free carbon.
It the described method comprises the following steps：
Step 1：It is considered to be worth doing using calcium, anhydrous calcium chloride and carbide carry out batch mixing as raw material；
Step 2：Raw material is put into high temperature furnace, under an argon atmosphere, 1-2h is kept the temperature in 800 ~ 1100 DEG C；
Step 3：The product obtained in step 2 is leached with hydrochloric acid solution；
Step 4：The filter residue obtained in step 3 is obtained into the higher carbide of purity after drying；
Step 5：It calcines the filtrate obtained in step 3 drying and under high temperature, recycling obtains anhydrous calcium chloride.
Wherein described transiting group metal elements are VIB, VB or group vib element, and carbide is titanium carbide, zirconium carbide, carbon
Change hafnium, vanadium carbide, niobium carbide, ramet, chromium carbide or molybdenum carbide, anhydrous calcium chloride need to be dried in advance in the step 1
Processing, mixing method are stirring, and the calcium chloride dosage is 0.5 ~ 2g/g carbide, and calcium considers dosage to be worth doing and is carbonized for 0.02 ~ 0.1g/g
Object is calcined through other a small amount of salt of addition in the step 5, reduces CaCl2Molten salt system fusing point.
Embodiment 1
Pure TiO will be analyzed2, graphite in mass ratio 20:9.1 mixings keep the temperature 2 hours under 1500 DEG C of argon gas atmospheres, obtain containing trip
Titanium carbide powder from carbon, by this powder and calcium bits, anhydrous calcium chloride in mass ratio 1：0.02：0.5 ratio mixing, 850
DEG C, 2 hours are kept the temperature under argon gas atmosphere, obtains the titanium carbide powder of removing free carbon.Through Electronic Speculum (SEM) and transmission electron microscope (TEM)
Analysis shows free carbon is successfully separated from product, and the phenomenon that without secondary oxidation.After testing, free carbon in product
Content ＜ 0.1wt%.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference lies in：
Pure V will be analyzed2O3, graphite in mass ratio 20:12.2 mixings obtain the vanadium carbide powder containing free carbon, by this powder with
Calcium bits, anhydrous calcium chloride in mass ratio 1：0.05：1 ratio mixing, at 1050 DEG C, keeps the temperature 1 hour under argon gas atmosphere, is taken off
Except the vanadium carbide powder of free carbon.Through Electronic Speculum (SEM) and transmission electron microscope (TEM), analysis shows, free carbon is successfully from product
It separates, and the phenomenon that without secondary oxidation.After testing, in product free carbon content ＜ 0.1wt%.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference lies in：
Pure ZrO will be analyzed2, graphite in mass ratio 20:6.0 mixings obtain the Zirconium carbide powder containing free carbon, by this powder and calcium
Bits, anhydrous calcium chloride in mass ratio 1：0.1：2 ratio mixing, at 950 DEG C, 1 hour is kept the temperature under argon gas atmosphere, obtains removing trip
Zirconium carbide powder from carbon.Through Electronic Speculum (SEM) and transmission electron microscope (TEM), analysis shows, free carbon is successfully detached from product
Out, the phenomenon that and without secondary oxidation.After testing, in product free carbon content ＜ 0.1wt%.
One kind of embodiment described above, only more preferably specific embodiment of the invention, those skilled in the art
The usual variations and alternatives that member carries out in the range of technical solution of the present invention should all include within the scope of the present invention.
Claims (7)
- A kind of 1. method for removing free carbon in transition metal carbides, which is characterized in that the method is with Ca-CaCl2Fused salt System is decarburization medicament, at 800 ~ 1100 DEG C, chemism calcium is made to react generation calcium carbide with free carbon, passes through CaCl2Increase Add kinetics and protect the volatilization loss of Ca, remove decarburization product CaC by way of acidleach later2And excessive Ca achievees the purpose that remove free carbon.
- 2. it according to the method described in claim 1, it is characterized in that, the described method comprises the following steps：Step 1：It is considered to be worth doing using calcium, anhydrous calcium chloride and carbide carry out batch mixing as raw material；Step 2：Raw material is put into high temperature furnace, under an argon atmosphere, 1-2h is kept the temperature in 800 ~ 1100 DEG C；Step 3：The product obtained in step 2 is leached with hydrochloric acid solution；Step 4：The filter residue obtained in step 3 is obtained into the higher carbide of purity after drying；Step 5：It calcines the filtrate obtained in step 3 drying and under high temperature, recycling obtains anhydrous calcium chloride.
- 3. according to the method described in claim 2, it is characterized in that, the transiting group metal elements are VIB, VB or group vib member Element, carbide are titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, niobium carbide, ramet, chromium carbide or molybdenum carbide.
- 4. according to the method described in claim 2, it is characterized in that, anhydrous calcium chloride need to be dried in advance in the step 1 Processing.
- 5. according to the method described in claim 2, it is characterized in that, mixing method is stirring in the step 1.
- 6. according to the method described in claim 2, it is characterized in that, calcium chloride dosage described in the step 1 is 0.5 ~ 2g/g Carbide, calcium bits dosage is 0.02 ~ 0.1g/g carbide.
- 7. according to the method described in claim 2, it is characterized in that, be calcined through other a small amount of salt of addition in the step 5, Reduce CaCl2Molten salt system fusing point.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231208A (en) * | 2018-11-30 | 2019-01-18 | 长江师范学院 | A kind of preparation method of transition metal carbide |
| WO2020213033A1 (en) * | 2019-04-15 | 2020-10-22 | 中部電力株式会社 | Hafnium carbide powder for plasma electrodes, method for producing same, hafnium carbide sintered body, and plasma electrode |
| CN115818646A (en) * | 2022-12-14 | 2023-03-21 | 昆明理工大学 | Preparation method of titanium carbide powder |
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| CN108439366A (en) * | 2013-03-15 | 2018-08-24 | 西弗吉尼亚大学研究公司 | Technique, composition and its method generated for pure carbon |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109231208A (en) * | 2018-11-30 | 2019-01-18 | 长江师范学院 | A kind of preparation method of transition metal carbide |
| WO2020213033A1 (en) * | 2019-04-15 | 2020-10-22 | 中部電力株式会社 | Hafnium carbide powder for plasma electrodes, method for producing same, hafnium carbide sintered body, and plasma electrode |
| CN115818646A (en) * | 2022-12-14 | 2023-03-21 | 昆明理工大学 | Preparation method of titanium carbide powder |
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