CN109399586A - A method of preparing carbon tungsten nitride - Google Patents
A method of preparing carbon tungsten nitride Download PDFInfo
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- CN109399586A CN109399586A CN201811411251.3A CN201811411251A CN109399586A CN 109399586 A CN109399586 A CN 109399586A CN 201811411251 A CN201811411251 A CN 201811411251A CN 109399586 A CN109399586 A CN 109399586A
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- carbon
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
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Abstract
The present invention provides a kind of methods for preparing carbon tungsten nitride, it is that the mixture of the compound or these compounds of tungsten and/or tungstenic and oxygen and organic carbon or inorganic carbon are mixed to form raw material, then directly so that it is generated heat raw material itself energization in reacting furnace and be gradually warming up to 600 DEG C or more, reduction nitridation generation carbon tungsten nitride.It is an advantage of the invention that the thermal efficiency is high, power consumption is low, good product consistency, process stabilizing, and production capacity is big.
Description
Technical field
The invention belongs to field of steel metallurgy, are related to the preparation method of carbon tungsten nitride.
Background technique
Carbon tungsten nitride (solid solution or mixed crystal of tungsten carbide, tungsten nitride or tungsten carbide and tungsten nitride, hereinafter referred to as carbon nitrogen
Change tungsten) have fusing point high, hardness is big, as superhard material, steel-making additive, wear-resistant material, catalyst etc., is widely used.One
As be used as superhard material when, be tungsten carbide.When as catalyst, can be tungsten nitride, tungsten carbide or their mixture or
The carbon tungsten nitride of person's solid solution thereof.
The preparation of carbon tungsten nitride has chemical vapour deposition technique (CVD), vacuum plasma sputtering method, and tungsten metal or tungsten close
Golden direct nitridation method, tungstic acid CRN method etc..The preparation of industrial tungsten carbide is generally with ammonium paratungstate
Beginning raw material is heated to 700 DEG C or so and is decomposed into tungsten oxide WOx (2≤x≤3), then generates gold with hydrogen reducing tungsten oxide
Belong to tungsten powder, then obtains tungsten carbide with C raw material or CO metal-carbide tungsten.Three-step reaction divides generally in two or three reactors
Duan Jinhang, that is, ammonium paratungstate raw material will could generate tungsten carbide by the heating process for the cooling that heats up twice or three times,
Energy consumption is high, long flow path.And During Hydrogen Reducing, it is easy to the biggish tungsten oxide of crystal grain is generated, so that final tungsten carbide products
Crystal grain becomes larger.
Also research generates tungsten carbide so that tungsten is white for one step of raw material carbon thermal reduction.Have using tungsten tungsten oxide as raw material, carbon heat is also
A former step generates tungsten carbide.
When preparing the carbon tungsten nitride or tungsten nitride of high nitrogen-containing, usually at 700 DEG C or so with ammonia also Yuanzhong
Perhaps then tungsten oxide generates nitride with CO or other carbon source carburizings formation carbon tungsten nitride or tungsten carbide and nitrogen to ammonium tungstate
The mixed crystal of compound.
Although thermodynamically, the generation of tungsten carbide can carry out at lower than 1000 DEG C, in order to balance reaction power
It learns, that is to say for rapid reaction within the limited time and thoroughly, often this step of carburizing reagent is generally at 1200 DEG C with enterprising
Row, some are even up to 1600 DEG C.The decomposition of ammonium paratungstate and the reduction reaction temperature of tungsten oxide are more lower, generally 900
DEG C or less.Therefore existing large-scale industrial production tungsten carbide, carburizing reagent generally carry out in molybdenum wire furnace or carbon shirt-circuiting furnace, instead
The solid material such as metal tungsten powder or tungsten oxide and/or carbon dust answered are placed in nickel boat or in the crucible of other materials,
Heat needs to be transmitted to reaction mass from heater element, and the thermal efficiency is low, and power consumption is high.Material in nickel boat and crucible, internal/external heating
The quality conformance of unevenness, product is bad, and also therefore material cannot be accumulated too thick in crucible or nickel boat, and yield is small.And nickel
Boat or crucible be easily damaged and easily with product formation adhesion.
In conclusion existing carbon tungsten nitride production process, process is complicated, and equipment capacity is low, and energy consumption is high.
Summary of the invention
The purpose of the present invention is to provide one kind, low energy consumption, equipment capacity is big, product quality consistency is good, technical process is steady
Fixed carbon tungsten nitride production technology.By in reacting furnace with power electrode to tungsten raw material and/or carbonaceous reducing agent or its
The solid material direct-electrifying generated in reaction process, then connecing between the resistance or feed particles or block of material itself
Electric shock resistance generates heat under the action of electric current and heats solid material.
The object of the present invention is achieved like this:
Tungsten raw material and/or carbonaceous reducing agent are mixed to form solid material, is then fed into reacting furnace and heats, it is heated
Tungsten raw material synthesizes carbon tungsten nitride by reduction carbon nitridation process in a reducing atmosphere in journey, it is characterised in that: the tungsten raw material
Are as follows: the mixture of the compound or these compounds of metal tungsten powder and/or tungstenic and oxygen；The heating process are as follows: anti-
Answer in furnace by power electrode to the solid material and/or its change in the heating process resulting material (with
Lower general designation material) direct-electrifying, is generated heat by the contact resistance between the resistance or material particles or block of material itself
Heated material, and the maximum temperature that the material passes through is not less than 600 DEG C, without logical inside the material in preheating section
Electricity obtains heat by the gaseous exchange heat transfer of the logistics transmission of heat by contact or the logistics by flowing through energization section with energization section
And the preheating that heats up；The solid material is by by tungsten raw material and carbonaceous reducing agent when containing the carbonaceous reducing agent
Raw material mixing, roll or squeeze, ball milling, wet-milling and/or briquetting formed；The reduction carbon nitridation process is being less than 5MPa
Reducing atmosphere under carry out.
Further, the reacting furnace is to the rotary kiln of the material direct-electrifying, the material is in institute
The bringing-up section for the rotary kiln stated forms continuous current path by random packing under gravity in the material together.Or it is described
Reacting furnace be to the material direct-electrifying vertical kiln, the material vertical kiln bringing-up section rely on gravity
It is packed together in the material and forms continuous current path.
Further, the reducing atmosphere are as follows: methanol, CO, nitrogen, ammonia, hydrocarbon, other gaseous states are carbon containing
And/or perhaps their mixture or the reducing atmosphere are the carbonaceous reducing agent to one of organic matter of nitrogen
Restore the CO that oxygen containing tungsten compound generates；The carbonaceous reducing agent are as follows: inorganic carbon, graphite, carbon black, active carbon, coke, stone
One of oil coke, pitch, starch, cellulose, organic polymer, melamine, paraffin, sugar or their mixture；Institute
State reduction carbon nitridation process are as follows: the material is between 300~1700 DEG C by the carbonaceous reducing agent and/or the reduction
It hydrogeneous and/or carbon reducing agent reduction and carbonization in atmosphere and/or is nitrogenized by the nitrogen in the reducing atmosphere, and institute
The solid material stated and/or its maximum temperature for changing resulting material process are not less than 600 DEG C；The reduction carbon nitrogenized
Reduction process, carbonization and/or nitridation process in journey complete (certainly, raw material by the movement of material in the same reacting furnace
When for metal tungsten powder, without reduction process)；Containing tungsten, carbon and/or nitrogen, on a small quantity without having reacted in the carbon tungsten nitride finished product
Oxygen element and the impurity brought into from raw material.
Further, being 10~10000 volts to the voltage of the material direct-electrifying, electric current is 10~100000
Ampere.
Further, the carbonaceous reducing agent in the reduction carbon nitridation process be raw material into before reacting furnace with
What tungstenic raw material mixed.
Further, the carbonaceous reducing agent in the reduction carbon nitridation process be CO and/or in temperature-rise period by
What organic carbonaceous reducing agent carbonization generated.
Further, iron, the iron oxide for being no more than tungsten weight 20 times (in terms of iron) are added in the solid material
One of iron content, cobalt or the carbon nitridation of more than one element is prepared in (in terms of iron), cobalt, cobalt compound (in terms of cobalt)
Tungsten alloy.
Compared with the prior art, the present invention has a characteristic that
1) apply direct current or alternating voltage directly into solid material with electrode and be passed through electric current, solid material heap puts away this
Body has certain resistance, which generates heat under the function of current, eliminates diabatic process of the heat from heater element to material,
It avoids to fire resisting material of furnace body and the nondistinctive heating of material, heat utilization ratio is high, and power consumption is low.And it avoids because of heat transfer
It is required that and cause the limitation of material accumulation thinner thickness, furnace cavity utilization rate improves, and the thermal efficiency improves, but also reacting furnace fills
Set can do it is smaller.
2) it due to carrying out heating reaction by the way of to the heating of raw material direct-electrifying, avoids having used Elema, silicon molybdenum
The heater elements such as stick or molybdenum filament and nickel boat or crucible.But also material is easier to be heated to reaction temperature, so that reaction
Rate is very fast, and the reaction time shortens, and product oxygen content is low, the product that product free carbon is low, available quality is high.
3) reduction carbon nitridation process can carry out in rotary kiln, further improve the heat and mass mistake in reaction process
Journey, so that the reaction time is short, the thermal efficiency is high, and uniform in quality is stablized, and material is movable continuously traveling inside reacting furnace, just
In large-scale industrial production, good product consistency.
Specific embodiment
Illustrate specific technical solution of the invention now in conjunction with embodiment.Following embodiment only illustrates skill of the invention
Art scheme reliable and effective can be realized, but technical solution of the invention is not limited in following embodiment.
Embodiment 1
1.5 tons of contents are greater than 88.5% and (press WO3Meter) ammonium paratungstate, 281kg pitch, roll mixing with edge runner, pressure ball,
Then it is added portionwise in the rotary kiln being powered directly to material and (is turned round using the electric heating that Chinese patent CN103335513A is disclosed
Kiln).Solid material is piled between positive and negative anodes, passes through the direct current or alternating current of 3000A between positive and negative anodes.Material successively passes through
It crosses warming-up section (namely preheating section), the high temperature section (namely bringing-up section) between rotary kiln positive and negative electrode, temperature descending section discharging.Rotary kiln
Discharge end is passed through nitrogen, nitrogen flow 80Nm3/ h, reaction end gas are withdrawn from from rotary kiln feed end.According to output demand, solids
Material is in rotary kiln internal stops 3h to 20h etc..1450 DEG C of high temperature section maximum temperature in rotary kiln.Products obtained therefrom carbon containing 6.1%,
Nitrogen content 0.1%.Product is in powdery, is further crushed to after 400 mesh as final products.Rotary kiln part carbon tungsten nitride per ton
Power consumption about 1200kWh.Because carbon tungsten nitride has the catalytic activity of similar noble metal, as carbon content is excessively high or free in fruit product
Carbon is excessively high, and the air of proper proportion can be passed through with nitrogen air inlet, the production using the oxygen in air at 400 DEG C of temperature descending section or more
Free carbon in product oxidizes away；Or the hydrogen or ammonia of proper proportion are passed through with nitrogen air inlet, using hydrogen by free carbon methane
It eliminates.Tungsten raw material ammonium paratungstate can be changed to the tungsten oxide of identical tungsten mole.
Embodiment 2
Metal tungsten powder, 100kg pitch by 1.5 tons of contents greater than 99.5% roll mixing with edge runner, and pressure ball is then continuous to add
Enter in the rotary kiln being powered directly to material (the electric heating rotary kiln disclosed using Chinese patent CN103335513A).Positive and negative anodes
Between pile with solid material, by the direct current or alternating current of 3000A between positive and negative anodes.Material successively passes through warming-up section
(namely preheating section), the high temperature section (namely bringing-up section) between rotary kiln positive and negative electrode, temperature descending section discharging.Rotary kiln discharge end is logical
Enter nitrogen, nitrogen flow 80Nm3/ h, reaction end gas are withdrawn from from rotary kiln feed end.According to output demand, solid material is being turned round
Kiln internal stops 3h to 20h etc..1350 DEG C of high temperature section maximum temperature in rotary kiln.Products obtained therefrom carbon containing 5.9%.Product is in powder
Shape is further crushed to after 400 mesh as final products.Rotary kiln part carbon tungsten nitride power consumption about 1050kWh per ton.Because of carbon
Tungsten nitride has the catalytic activity of similar noble metal, if carbon content is excessively high in fruit product or free carbon is excessively high, can with nitrogen into
Gas is passed through the air of proper proportion, using the oxygen in air 400 DEG C of temperature descending section and with upper section by the free oxidation of coal in product
Fall；Or the hydrogen or ammonia of proper proportion are passed through with nitrogen air inlet, free carbon methanation is removed using hydrogen.The secondary tungsten of tungsten raw material
Sour ammonium can be changed to the tungsten oxide of tungsten mole in proportion.
Embodiment 3
1.5 tons of contents are greater than to white (the Ca WO of tungsten of 77.0% (based on WO3)4), 140kg carbon black+140kg graphite powder, use rolling
Machine rolls mixing, then pressure ball is added portionwise in the rotary kiln being powered directly to material (using Chinese patent CN103335513A
The electric heating rotary kiln of disclosure).Solid material is piled between positive and negative anodes, passes through the direct current of 4500A or friendship between positive and negative anodes
Galvanic electricity stream.Material successively passes through warming-up section (namely preheating section), the high temperature section (namely bringing-up section) between rotary kiln positive and negative electrode,
Temperature descending section discharging.Rotary kiln discharge end is passed through nitrogen and CO, total flow 80Nm3/h, and reaction end gas is withdrawn from from rotary kiln feed end.
According to output demand, solid material is in rotary kiln internal stops 3h to 20h etc..High temperature section maximum temperature 1400 in rotary kiln
℃.Products therefrom is washed out into deoxidation calcium or calcium carbide (calcium carbide pays attention to the safety problem for the acetylene released), institute with dilute hydrochloric acid
Product carbon containing 5.8% is obtained, is crushed to after 400 mesh as final products.Rotary kiln part carbon tungsten nitride power consumption about 1700kWh per ton.
Embodiment 4
Ammonium paratungstate of 1.5 tons of contents greater than 88.5% (based on WO3) is added portionwise in the rotary kiln being powered directly to material
(the electric heating rotary kiln disclosed using Chinese patent CN103335513A).Solid material is piled between positive and negative anodes, in positive and negative anodes
Between pass through the direct current of 3000A or alternating current (nitrogenizing tungsten product with carbon when starting to be powered heating).Material is successively by rising
Temperature section (namely preheating section), the high temperature section (namely bringing-up section) between rotary kiln positive and negative electrode, temperature descending section discharging.Rotary kiln discharging
End is passed through ammonia+natural gas+CO2, total flow 80Nm3/h, reaction end gas withdraws from from rotary kiln feed end.According to output demand,
Solid material is in rotary kiln internal stops 3h to 20h etc..950 DEG C of high temperature section maximum temperature in rotary kiln.Products obtained therefrom carbon contains
Amount 1.1%, nitrogen content 5.1%.Product is in powdery, is further crushed to after 400 mesh as final products.
Claims (8)
1. a kind of method of preparation of industrialization carbon tungsten nitride, is mixed to form solid material for tungsten raw material and/or carbonaceous reducing agent, so
After be fed into reacting furnace and heat, tungsten raw material is synthesized by reduction carbon nitridation process in a reducing atmosphere in heating process
Carbon tungsten nitride, it is characterised in that: the tungsten raw material are as follows: the compound or these compounds of metal tungsten powder and/or tungstenic and oxygen
Mixture；
The heating process are as follows: in reacting furnace by power electrode to the solid material and/or its described plus
Change resulting material (hereinafter referred to as material) direct-electrifying in thermal process, by the resistance or material particles of material itself or
Contact resistance fever and heated material between person's block, and the maximum temperature that the material passes through is not less than 600 DEG C；
The solid material passes through before entering the reacting furnace by tungsten raw material when containing the carbonaceous reducing agent
With carbonaceous reducing agent mixing, roll or squeeze, ball milling, wet-milling, and/or briquetting；
The reduction carbon nitridation process carries out under the reducing atmosphere less than 5MPa.
2. the method according to claim 1 for preparing carbon tungsten nitride, it is characterised in that: the reacting furnace is to described
Material direct-electrifying rotary kiln, the material the rotary kiln bringing-up section by random packing under gravity together in institute
Continuous current path is formed in the material stated.
3. the method according to claim 1 for preparing carbon tungsten nitride, it is characterised in that: the reacting furnace is to described
Material direct-electrifying vertical kiln, the material vertical kiln bringing-up section by random packing under gravity together described
Material in form continuous current path.
4. the method as claimed in any of claims 1 to 3 for preparing carbon tungsten nitride, it is characterised in that: the reduction
Atmosphere are as follows: methanol, CO, nitrogen, ammonia, hydrocarbon, other gaseous states be carbon containing and/or one of the organic matter of nitrogen or it
Mixture or the reducing atmosphere be CO that the oxygen containing tungsten compound of the described carbonaceous reducing agent generates；
The carbonaceous reducing agent are as follows: coal, graphite, carbon black, active carbon, coke, petroleum coke, pitch, biological material, You Jigao
One of molecule, melamine, paraffin, sugar or more than one mixture；
The reduction carbon nitridation process are as follows: the material is between 300~1700 DEG C by the carbonaceous reducing agent and/or described
Reducing atmosphere in hydrogeneous and/or carbon reducing agent reduction and carbonization and/or by the reducing atmosphere nitrogen nitrogenize,
And the maximum temperature that the material passes through is not less than 600 DEG C；
Reduction process, carbonization and/or nitridation process in the reduction carbon nitridation process are by the movement of material same
It is completed in reacting furnace；
It is brought into the carbon tungsten nitride finished product containing tungsten, carbon and/or nitrogen, on a small quantity without reacted oxygen element and from raw material
Impurity.
5. the method as claimed in any of claims 1 to 4 for preparing carbon tungsten nitride, it is characterised in that: to described
The voltage of material direct-electrifying is 10~10000 volts, and electric current is 10~100000 amperes.
6. the method as claimed in any of claims 1 to 5 for preparing carbon tungsten nitride, it is characterised in that: described
Carbonaceous reducing agent in reduction carbon nitridation process is in raw material into being mixed before reacting furnace with tungsten raw material.
7. the method as claimed in any of claims 1 to 5 for preparing carbon tungsten nitride, it is characterised in that: described goes back
Carbonaceous reducing agent in former carbon nitridation process be CO and/or in temperature-rise period by organic carbonaceous in the carbonaceous reducing agent
Reducing agent carbonization generates.
8. the method as claimed in any of claims 1 to 7 for preparing carbon tungsten nitride, it is characterised in that: described
The iron for being no more than tungsten weight 20 times (in terms of iron), iron oxide (in terms of iron), cobalt, cobalt compound are added in solid material (with cobalt
Meter), one of iron content, cobalt or the carbon nitridation tungsten alloy of more than one element is prepared.
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| CN201811411251.3A CN109399586A (en) | 2018-11-24 | 2018-11-24 | A method of preparing carbon tungsten nitride |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110257646A (en) * | 2019-06-14 | 2019-09-20 | 长安大学 | A kind of process for smelting magnesium and device |
| CN110592377A (en) * | 2019-08-02 | 2019-12-20 | 长安大学 | Metal magnesium carbon thermal reduction process and device |
| CN114836729A (en) * | 2022-05-17 | 2022-08-02 | 合肥安德科铭半导体科技有限公司 | WCN film deposition method with adjustable work function |
-
2018
- 2018-11-24 CN CN201811411251.3A patent/CN109399586A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110257646A (en) * | 2019-06-14 | 2019-09-20 | 长安大学 | A kind of process for smelting magnesium and device |
| CN110592377A (en) * | 2019-08-02 | 2019-12-20 | 长安大学 | Metal magnesium carbon thermal reduction process and device |
| CN114836729A (en) * | 2022-05-17 | 2022-08-02 | 合肥安德科铭半导体科技有限公司 | WCN film deposition method with adjustable work function |
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Application publication date: 20190301 |