CN107737943A - A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder - Google Patents
A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder Download PDFInfo
- Publication number
- CN107737943A CN107737943A CN201711069845.6A CN201711069845A CN107737943A CN 107737943 A CN107737943 A CN 107737943A CN 201711069845 A CN201711069845 A CN 201711069845A CN 107737943 A CN107737943 A CN 107737943A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- methanol
- reduction
- powder
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
Abstract
The invention provides a kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder, it is used as reduction raw material by the use of the cheap methanol of cost price, methanol steam using argon gas as carrier at relatively low 800 ~ 1100 DEG C of temperature directly with tungsten oxide powder haptoreaction, produce tungsten carbide or/and tungsten powder product, greatly improve the efficiency of reduction, it is carbonized simultaneously, compared with traditional handicraft, significantly reduced on its energy consumption cost, and accelerate reaction rate, shorten technological process, also reduce cost of material, the purpose of high efficiency, low cost production tungsten carbide or/and tungsten powder is reached, it is high to solve preparation temperature in existing tungsten carbide/tungsten powder production technology well, low production efficiency, a series of problems, such as with high costs, with good industrial application value.
Description
Technical field
The present invention relates to chemical metallurgy technical field, especially designs a kind of Reduction of methanol and prepares tungsten carbide or/and tungsten powder
Method.
Background technology
Diamondite has a special corrosion resistance, high-melting-point, high rigidity, excellent fracture toughness and compression strength,
There is the title of modern industry tooth, be widely used in manufacturing cutting element, wear parts, cermet material, thermal jet paint material
Deng.
Domestic production at present prepares tungsten carbide and is mainly reduced directly carbonizatin method, using tungsten and carbon as raw material, by product
The carbon black ball mill of amount of the tungsten powder of required average particle diameter size with waiting material is dry-mixed, after being sufficiently mixed extrusion forming, is put into
Graphite boat, 1400 DEG C ~ 1700 DEG C are heated in the hydrogen gas stream with graphite resistor furnace or induction furnace, be allowed to carburizing generation tungsten carbide,
Obtain tungsten carbide or tungsten carbide and tungsten powder blended product.But this method reaction temperature is high, Ball-milling Time length, comprehensive energy
Consumption and cost are higher, and Intensive ball mill break process easily causes tungsten powder to participate in impurity with carbon black powders raw material, is also easy to lead
Cause powder activity increase and produce the danger of vigorous oxidation or blast.
Therefore, tungsten carbide/tungsten powder production that a kind of new cost and energy consumption are relatively low, production efficiency is high, security is good is needed badly
Product preparation technology.
The content of the invention
For above shortcomings in the prior art, prepare and be carbonized it is an object of the invention to provide a kind of Reduction of methanol
The method of tungsten or/and tungsten powder, a kind of new method is provided for the preparation of tungsten carbide or/and tungsten powder product, to solve existing carbon
A series of problems, such as changing the cost and high energy consumption, low production efficiency, security deficiency of tungsten production technology.
To achieve the above object, present invention employs following technical scheme：
A kind of Reduction of methanol prepares tungsten carbide or/and the method for tungsten powder comprises the following steps：
Step 1：It is put into using tungstic acid or tungsten dioxide powder as tungsten oxide raw material in reacting furnace, into reacting furnace
Argon gas is continually fed into, control reacting furnace begins to warm up heating after excluding furnace air；
Step 2：After reaction in-furnace temperature reaches specified reaction temperature, control reacting furnace keeps constant temperature, continues into reacting furnace
It is passed through the mixed gas of methanol steam and argon gas so that tungsten oxide raw material enters in the mixed-gas environment for specifying reaction temperature
The processing of row reduction and carbonization；The specified reaction temperature is 800 ~ 1100 DEG C；
Step 3：Reduction and carbonization processing is completed to continue to be passed through argon gas in backward reacting furnace so that the carbonization of gained after reduction and carbonization
Tungsten or/and tungsten powder take out after being cooled to room temperature, obtain tungsten carbide or/and the cold product of tungsten powder.
Above-mentioned Reduction of methanol is prepared in the method for tungsten carbide or/and tungsten powder, preferably, in the step 1,
Reach more than 99.9% as the tungsten trioxide powder of tungsten oxide raw material or the purity of tungsten dioxide powder.
Above-mentioned Reduction of methanol is prepared in the method for tungsten carbide or/and tungsten powder, preferably, in the step 2 to
The concrete mode that the mixed gas of methanol steam and argon gas is passed through in reacting furnace is：
（1）It is by thermostat water bath that the temperature of methanol is constant by the obturator equipped with liquid methanol as thermostat water bath
At 30 ~ 60 DEG C；
（2）Argon gas, which is passed through in the liquid methanol of the obturator splendid attire, makes it be mixed with methanol, forms methanol steam and argon
The mixed gas of gas, and by gas flowmeter control methanol steam and the output flow of the mixed gas of argon gas, methanol is steamed
The mixed gas of vapour and argon gas is passed through in reacting furnace.
Above-mentioned Reduction of methanol is prepared in the method for tungsten carbide or/and tungsten powder, preferably, institute in the step 2
The methanol steam and the mixed gas of argon gas used, percent by volume shared by methanol steam are 20% ~ 30%, volume ratio shared by argon gas
For 70% ~ 80%.
Above-mentioned Reduction of methanol is prepared in the method for tungsten carbide or/and tungsten powder, specifically, in the step 2, if control
The specified reaction temperature that reacting furnace internal standard temperature processed reaches is 800 ~ 880 DEG C, and tungsten oxide raw material is specifying reaction temperature
The reaction time that reduction and carbonization processing is carried out in mixed-gas environment is 8 ~ 12 hours, then reduction and carbonization processing products therefrom is carbon
Change the mixed-powder of tungsten powder or tungsten carbide and simple substance tungsten.
Above-mentioned Reduction of methanol is prepared in the method for tungsten carbide or/and tungsten powder, specifically, in the step 2, if control
The specified reaction temperature that reacting furnace internal standard temperature processed reaches is 900 ~ 1100 DEG C, and tungsten oxide raw material is specifying reaction temperature
The reaction time that reduction and carbonization processing is carried out in mixed-gas environment is 1 ~ 2 hour, then reduction and carbonization processing products therefrom is single
Matter tungsten powder.
Compared to prior art, the present invention has the advantages that：
1st, in the inventive method, the methanol cheap by the use of cost price steams as reduction raw material using argon gas as the methanol of carrier
Vapour, directly with tungsten oxide powder haptoreaction, produces tungsten carbide or/and tungsten powder product at relatively low 800 ~ 1100 DEG C of temperature,
The efficiency of reduction is greatly improved, while is carbonized, compared with traditional handicraft, the inventive method carburizing temperature is low, and
Reaction rate is accelerated, shortens technological process, reduces raw material and energy consumption cost, has reached high efficiency, low cost production tungsten carbide
Or/and the purpose of tungsten powder.
2nd, the inventive method provides a kind of new technology for the production of tungsten carbide/tungsten powder, reduces production cost, accelerates anti-
Speed is answered, it is high to solve in existing tungsten carbide/tungsten powder production technology preparation temperature well, low production efficiency, with high costs etc.
A series of problems.
Brief description of the drawings
Fig. 1 is the method flow diagram that Reduction of methanol of the present invention prepares tungsten carbide or/and tungsten powder.
Fig. 2 is the XRD thing phasors of products therefrom in the embodiment of the present invention one.
Fig. 3 is the XRD thing phasors of products therefrom in the embodiment of the present invention two.
Fig. 4 is the XRD thing phasors of products therefrom in the embodiment of the present invention three.
Embodiment
It is directed to existing tungsten carbide production technology in the prior art and cost and high energy consumption, low production efficiency, security is present
The problems such as insufficient, the invention provides a kind of new technology for producing tungsten carbide or/and tungsten powder, i.e., a kind of Reduction of methanol prepares carbon
Change the method for tungsten or/and tungsten powder.
The tungsten carbide of the present invention or/and the technological process of tungsten powder preparation method are as shown in figure 1, it comprises the following steps：
Step 1：It is put into using tungstic acid or tungsten dioxide powder as tungsten oxide raw material in reacting furnace, into reacting furnace
Argon gas is continually fed into, control reacting furnace begins to warm up heating after excluding furnace air.
In the step, in order to ensure the purity of prepared tungsten carbide or/and tungsten powder product, as tungsten oxide raw material
The purity of tungsten trioxide powder or tungsten dioxide powder is preferably able to reach more than 99.9%.As for used anhydrous wolframic acid powder
End or the average grain diameter of tungsten dioxide powder, then average particle diameter size can be selected according to needed for product, certainly, three oxidations
The average particle diameter size of tungsten powder or tungsten dioxide powder is smaller, then the time required for later stage reduction and carbonization is handled can accordingly get over
It is long.
Reacting furnace can use tube furnace, fixed bed or fluid bed.Excluded to being first passed through argon gas before reaction stove heat in stove
Air, tungsten oxide raw material can be avoided to be heated and aoxidize in aerobic environment.Reach in in-furnace temperature and specify reaction temperature
Before degree, the lasting lower argon gas that is passed through into stove is to play a part of protection against oxidation to tungsten oxide raw material.
Step 2：After reaction in-furnace temperature reaches specified reaction temperature, control reacting furnace keeps constant temperature, into reacting furnace
It is continually fed into the mixed gas of methanol steam and argon gas so that tungsten oxide raw material is specifying the mixed-gas environment of reaction temperature
Middle progress reduction and carbonization processing.
In the step, it is 800 ~ 1100 DEG C to specify reaction temperature.When reaction in-furnace temperature reach more than 800 DEG C it is specified instead
After answering temperature, tungsten oxide raw material possesses reactivity, and the mixed of methanol steam and argon gas is now continually fed into reacting furnace
Close gas so that the methanol steam using argon gas as carrier directly contacts progress in the case where specifying reaction temperature with tungsten oxide raw material
Reduction and carbonization reacts, and course of reaction is as follows：
CH3OH + WO2 = W + 2H2O + CO；
3CH3OH + 2WO3 = 2W + 6H2O + 3CO；
4CO + WO2 = WC + 3CO2；
5CO + WO3 = WC + 4CO2；
2CO + W = WC + CO2。
Methanol steam is the faster gas-solid reaction of reaction rate with the course of reaction that tungsten oxide raw material contacts, therefore its is whole
Precursor reactant efficiency high, course of reaction are stablized easily-controllable.Process is it can also be seen that reduction and carbonization reaction product mainly has from the reactions above
Simple substance tungsten（W）And tungsten carbide（WC）.Herein, at the specified reaction temperature and reduction and carbonization maintained in the step in reacting furnace
In the reaction time of reason, certain influence into branch be present for product.What if control reacting furnace internal standard temperature reached specifies
Reaction temperature is 800 ~ 880 DEG C, and the simple substance tungsten for reducing to obtain under 800 ~ 880 DEG C of temperature environment can be by further carbon
Change, and the reaction time of progress reduction and carbonization processing can in the mixed-gas environment for specifying reaction temperature for tungsten oxide raw material
Reach sufficiently long 8 ~ 12 hours, to be then tungsten-carbide powder or tungsten carbide mixed with simple substance tungsten for reduction and carbonization processing products therefrom
Close powder；And if the specified reaction temperature for controlling reacting furnace internal standard temperature to reach is 900 ~ 1100 DEG C, at 900 ~ 1100 DEG C
The carbonization that continues of simple substance tungsten is suppressed under temperature environment, it is difficult to is continued to be carbonized as tungsten carbide, therefore tungsten oxide raw material exists
The reaction time for carrying out reduction and carbonization processing in the mixed-gas environment of reaction temperature is specified only to need 1 ~ 2 hour, reduction and carbonization
Processing products therefrom is simple substance tungsten powder.
Meanwhile in order to cause tungsten oxide raw material to obtain more sufficiently reacting, the methanol used in the step
In the mixed gas of steam and argon gas, percent by volume shared by methanol steam is preferably up to 20% ~ 30%, and volume ratio shared by argon gas is then
For 70% ~ 80%, to ensure to possess in reacting furnace good, sufficient reduction and carbonization environment.
In addition, by above-mentioned course of reaction it can also be seen that the main component of tail gas is caused by reduction and carbonization process
Vapor, CO2With the complete CO of unreacted, therefore tail gas can be recycled；And as preferable recycling side
Formula, can be by tail gas to carry out separating treatment, by vapor, CO2Separate and obtain CO gas, it is isolated
CO gas to the fuel as heating reaction furnace, reaction can also be participated in reacting furnace to rejoin,
Help reduces the consumption of energy consumption and methanol feedstock, so as to further reduce production cost.
Step 3：Reduction and carbonization processing is completed to continue to be passed through argon gas in backward reacting furnace so that gained after reduction and carbonization
Tungsten carbide or/and tungsten powder take out after being cooled to room temperature, obtain tungsten carbide or/and the cold product of tungsten powder.
Product in reacting furnace after reduction and carbonization is simple substance tungsten powder, tungsten-carbide powder or tungsten carbide and simple substance tungsten
Mixed-powder, the step makes it be cooled under argon gas protection environment to room temperature, to prevent being oxidized in its cooling procedure.By
Do not handled in the inventive method using ball mill crushing, while simple substance will not be also produced in reduction and carbonization processing course of reaction
Solid matter outside tungsten, tungsten carbide, therefore impurity will not be introduced, thus taken out from reacting furnace the tungsten carbide after cooling or/
And tungsten powder, you can as tungsten carbide or/and tungsten powder product.
It can see by above-mentioned handling process, the inventive method uses the methanol steam using argon gas as carrier to reduce carbon
Change tungsten oxide to prepare tungsten carbide or/and tungsten powder, reaction temperature need to only reach relatively low 800 ~ 1100 DEG C, and this is due to first
Alcohol steam and the course of reaction that tungsten oxide raw material contacts are the faster gas-solid reactions of reaction rate, W-response efficiency high, together
When reagency in the lasting mixed gas for being passed through methanol steam and argon gas take away the vapor and CO of reaction generation2, reduce
Partial pressure of oxygen in reacting furnace, the further reduction of tungsten oxide raw material is helped lend some impetus to, realizes and reduces carbon at a lower temperature
Change the purpose of tungsten oxide raw material, save energy consumption cost；In addition, the CO compositions in the tail gas product of reduction and carbonization reaction can return
Receive and utilize, production cost can be helped further reduce.It can be seen that Reduction of methanol of the present invention prepares tungsten carbide or/and tungsten powder
Method reduces production cost and energy consumption, improves production efficiency, and avoids because Intensive ball mill break process causes powder
Activity increases and produces vigorous oxidation or the risk of blast, the cost and energy consumption for solving existing tungsten carbide production technology well
A series of problems, such as height, low production efficiency, security deficiency.
The present invention is described in further detail with instantiation below in conjunction with the accompanying drawings.
Embodiment one：
The present embodiment use purity for 99.99% WO3Powder is as tungsten oxide raw material, WO3The average grain diameter of powder is 3 μm,
Tungsten carbide or/and tungsten powder are prepared using the inventive method, comprised the following steps that：
（1）By the WO that purity is 99.99%3Powder is put into reacting furnace as tungsten oxide raw material, is continually fed into reacting furnace
Argon gas, control reacting furnace is begun to warm up after excluding furnace air, and controls heating target temperature in reacting furnace to reach specified reaction
Temperature.In the present embodiment, specified reaction temperature is set as 800 DEG C.
（2）After reaction in-furnace temperature reaches specified 800 DEG C of reaction temperature and controls reacting furnace constant temperature 1min, to reacting furnace
Inside it is continually fed into the mixed gas of methanol steam and argon gas so that tungsten oxide raw material is specifying the mixed gas ring of reaction temperature
Reduction and carbonization processing is carried out in border.In the present embodiment, be passed through into reacting furnace methanol steam and argon gas mixed gas it is specific
Mode is：It is by thermostat water bath that the temperature of methanol is permanent first by the obturator equipped with liquid methanol as thermostat water bath
It is scheduled on 60 DEG C；Then argon gas is passed through in the liquid methanol of the obturator splendid attire makes it be mixed with methanol, forms methanol and steams
The mixed gas of vapour and argon gas, and by gas flowmeter control methanol steam and the output flow of the mixed gas of argon gas, will
The mixed gas of methanol steam and argon gas is passed through in reacting furnace；Adopt be passed through in such a way into reacting furnace mixed gas be because
For in practical operation, because methanol steam is the volatile matter of liquid methanol, it is difficult to which independent is subject to traffic organising and flow control
System, and argon gas, which is passed through in the liquid methanol of obturator splendid attire, makes it be output to after being mixed with methanol in reacting furnace, just quite
Traffic organising is carried out to serve as the carrier of methanol steam in by means of the argon gas as protection against oxidation gas, and causes argon gas band
Dynamic methanol steam flows in reacting furnace participates in reduction and carbonization reaction, and the steam volatile quantity of liquid methanol is easily by temperature
Influence, therefore by control the water bath with thermostatic control temperature of warm water bath with, it becomes possible to methanol in convenient regulation and control mixed gas,
Argon gas volume accounting, to realize the control to gaseous environment state in reacting furnace.
In the present embodiment, in the mixed gas for adjusting methanol steam and argon gas, percent by volume is shared by methanol steam
30%, volume ratio shared by argon gas is 70%.In the present embodiment, the reaction time that reduction and carbonization processing is carried out to tungsten oxide raw material is
12 hours.
（3）Reduction and carbonization processing is completed to continue to be passed through argon gas in backward reacting furnace so that the carbonization of gained after reduction and carbonization
Tungsten or/and tungsten powder take out after being cooled to room temperature, obtain tungsten carbide or/and the cold product of tungsten powder.Mutually detected through thing, this example system
The items testing result of standby products obtained therefrom is as shown in Fig. 2 in fig. 2, WC thing phases are represented marked as 1, it can thus be appreciated that in this example
Product is tungsten carbide.
Embodiment two：
The present embodiment use purity for 99.99% WO3Powder is as tungsten oxide raw material, WO3The average grain diameter of powder is 4 μm,
Tungsten carbide or/and tungsten powder are prepared using the inventive method, comprised the following steps that：
（1）By 99.99% WO3Powder is put into reacting furnace as tungsten oxide raw material, and argon gas is continually fed into reacting furnace,
Control reacting furnace is begun to warm up after excluding furnace air, and controls heating target temperature in reacting furnace to reach specified reaction temperature.
In the present embodiment, specified reaction temperature is set as 850 DEG C.
（2）After reaction in-furnace temperature reaches specified 850 DEG C of reaction temperature and controls reacting furnace constant temperature 10min, to reaction
The mixed gas of methanol steam and argon gas is continually fed into stove so that tungsten oxide raw material is specifying the mixed gas of reaction temperature
Reduction and carbonization processing is carried out in environment.In the present embodiment, the tool of the mixed gas of methanol steam and argon gas is passed through into reacting furnace
Body mode is：First by the obturator equipped with liquid methanol as thermostat water bath, by thermostat water bath by the temperature of methanol
It is constant at 30 DEG C；Then argon gas is passed through in the liquid methanol of the obturator splendid attire makes it be mixed with methanol, forms methanol
The mixed gas of steam and argon gas, and the output flow of the mixed gas of methanol steam and argon gas is controlled by gas flowmeter,
The mixed gas of methanol steam and argon gas is passed through in reacting furnace.Thus mode is passed through mixed gas into reacting furnace, passes through control
The water bath with thermostatic control temperature of warm water bath processed and the output flow of mixed gas, it becomes possible to the first in convenient regulation and control mixed gas
Alcohol, argon gas volume accounting.In the present embodiment, in the mixed gas for adjusting methanol steam and argon gas, volume hundred shared by methanol steam
Divide than being 20%, volume ratio shared by argon gas is 80%.In the present embodiment, the reaction of reduction and carbonization processing is carried out to tungsten oxide raw material
Time is 9 hours.
（3）Reduction and carbonization processing is completed to continue to be passed through argon gas in backward reacting furnace so that the carbonization of gained after reduction and carbonization
Tungsten or/and tungsten powder take out after being cooled to room temperature, obtain tungsten carbide or/and the cold product of tungsten powder.Mutually detected through thing, this example system
The items testing result of standby products obtained therefrom is as shown in figure 3, in figure 3, WC thing phases are represented marked as 1, it can thus be appreciated that in this example
Product is tungsten-carbide powder.
Embodiment three：
The present embodiment use purity for 99.99% WO3Powder is as tungsten oxide raw material, WO3The average grain diameter of powder is 5 μm,
Tungsten carbide or/and tungsten powder are prepared using the inventive method, comprised the following steps that：
（1）By 99.99% WO3Powder is put into reacting furnace as tungsten oxide raw material, and argon gas is continually fed into reacting furnace,
Control reacting furnace is begun to warm up after excluding furnace air, and controls heating target temperature in reacting furnace to reach specified reaction temperature.
In the present embodiment, specified reaction temperature is set as 950 DEG C.
（2）After reaction in-furnace temperature reaches specified 950 DEG C of reaction temperature and controls reacting furnace constant temperature 10min, to reaction
The mixed gas of methanol steam and argon gas is continually fed into stove so that tungsten oxide raw material is specifying the mixed gas of reaction temperature
Reduction and carbonization processing is carried out in environment.In the present embodiment, the tool of the mixed gas of methanol steam and argon gas is passed through into reacting furnace
Body mode is：First by the obturator equipped with liquid methanol as thermostat water bath, by thermostat water bath by the temperature of methanol
It is constant at 30 DEG C；Then argon gas is passed through in the liquid methanol of the obturator splendid attire makes it be mixed with methanol, forms methanol
The mixed gas of steam and argon gas, and the output flow of the mixed gas of methanol steam and argon gas is controlled by gas flowmeter,
The mixed gas of methanol steam and argon gas is passed through in reacting furnace.Thus mode is passed through mixed gas into reacting furnace, passes through control
The water bath with thermostatic control temperature of warm water bath processed and the output flow of mixed gas, it becomes possible to the first in convenient regulation and control mixed gas
Alcohol, argon gas volume accounting.In the present embodiment, in the mixed gas for adjusting methanol steam and argon gas, volume hundred shared by methanol steam
Divide than being 20%, volume ratio shared by argon gas is 80%.In the present embodiment, the reaction of reduction and carbonization processing is carried out to tungsten oxide raw material
Time is 1.8 hours.
（3）Reduction and carbonization processing is completed to continue to be passed through argon gas in backward reacting furnace so that the carbonization of gained after reduction and carbonization
Tungsten or/and tungsten powder take out after being cooled to room temperature, obtain tungsten carbide or/and the cold product of tungsten powder.Mutually detected through thing, this example system
The items testing result of standby products obtained therefrom is as shown in figure 4, in Fig. 4, W thing phases are represented marked as 2, it can thus be appreciated that being produced in this example
Thing is simple substance tungsten powder.
In addition, embodiment three times, respectively example IV, embodiment five and embodiment are also carried out using the inventive method
Six.The major parameter and products therefrom of each secondary embodiment are as shown in the table.
The contrast of above-described embodiment is also demonstrated, and Reduction of methanol of the present invention is prepared in the method for tungsten carbide or/and tungsten powder, if
The specified reaction temperature for controlling reacting furnace internal standard temperature to reach is 800 ~ 880 DEG C, and reduction and carbonization processing products therefrom is tungsten carbide
The mixed-powder of powder or tungsten carbide and simple substance tungsten；If control specified reaction temperature that reacting furnace internal standard temperature reaches for 900 ~
1100 DEG C, reduction and carbonization processing products therefrom is simple substance tungsten powder.
It can see by above-mentioned each embodiment, the method that Reduction of methanol of the present invention prepares tungsten carbide or/and tungsten powder,
The methanol cheap by the use of cost price as reduction raw material, methanol steam using argon gas as carrier temperature it is relatively low 800 ~
Directly tungsten carbide or/and tungsten powder product are produced, greatly improves reduction with tungsten oxide powder haptoreaction at 1100 DEG C
Efficiency, while be carbonized, compared with traditional handicraft, significantly reduced on its energy consumption cost, and accelerate reaction speed
Rate, technological process is shortened, also reduce cost of material, reached the mesh of high efficiency, low cost production tungsten carbide or/and tungsten powder
, solve preparation temperature height, low production efficiency, the system of grade one with high costs in existing tungsten carbide/tungsten powder production technology well
Row problem, there is good industrial application value.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (6)
1. a kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder, it is characterised in that comprise the following steps：
Step 1：It is put into using tungstic acid or tungsten dioxide powder as tungsten oxide raw material in reacting furnace, into reacting furnace
Argon gas is continually fed into, control reacting furnace begins to warm up heating after excluding furnace air；
Step 2：After reaction in-furnace temperature reaches specified reaction temperature, control reacting furnace keeps constant temperature, continues into reacting furnace
It is passed through the mixed gas of methanol steam and argon gas so that tungsten oxide raw material enters in the mixed-gas environment for specifying reaction temperature
The processing of row reduction and carbonization；The specified reaction temperature is 800 ~ 1100 DEG C；
Step 3：Reduction and carbonization processing is completed to continue to be passed through argon gas in backward reacting furnace so that the carbonization of gained after reduction and carbonization
Tungsten or/and tungsten powder take out after being cooled to room temperature, obtain tungsten carbide or/and the cold product of tungsten powder.
2. the method that Reduction of methanol prepares tungsten carbide or/and tungsten powder according to claim 1, it is characterised in that the step
In rapid one, reach more than 99.9% as the tungsten trioxide powder of tungsten oxide raw material or the purity of tungsten dioxide powder.
3. the method that Reduction of methanol prepares tungsten carbide or/and tungsten powder according to claim 1, it is characterised in that the step
The concrete mode for being passed through the mixed gas of methanol steam and argon gas in rapid two into reacting furnace is：
（1）It is by thermostat water bath that the temperature of methanol is constant by the obturator equipped with liquid methanol as thermostat water bath
At 30 ~ 60 DEG C；
（2）Argon gas, which is passed through in the liquid methanol of the obturator splendid attire, makes it be mixed with methanol, forms methanol steam and argon
The mixed gas of gas, and by gas flowmeter control methanol steam and the output flow of the mixed gas of argon gas, methanol is steamed
The mixed gas of vapour and argon gas is passed through in reacting furnace.
4. the method that Reduction of methanol prepares tungsten carbide or/and tungsten powder according to claim 1, it is characterised in that the step
The mixed gas of methanol steam and argon gas used in rapid two, percent by volume shared by methanol steam are 20% ~ 30%, argon gas institute
Volume ratio is accounted for as 70% ~ 80%.
5. the method that Reduction of methanol prepares tungsten carbide or/and tungsten powder according to claim 1, it is characterised in that the step
In rapid two, if the specified reaction temperature for controlling reacting furnace internal standard temperature to reach is 800 ~ 880 DEG C, and tungsten oxide raw material is being specified
The reaction time that reduction and carbonization processing is carried out in the mixed-gas environment of reaction temperature is 8 ~ 12 hours, then reduction and carbonization processing institute
Obtain the mixed-powder that product is tungsten-carbide powder or tungsten carbide and simple substance tungsten.
6. the method that Reduction of methanol prepares tungsten carbide or/and tungsten powder according to claim 1, it is characterised in that the step
In rapid two, if the specified reaction temperature for controlling reacting furnace internal standard temperature to reach is 900 ~ 1100 DEG C, and tungsten oxide raw material is referring to
The reaction time for determining to carry out reduction and carbonization processing in the mixed-gas environment of reaction temperature is 1 ~ 2 hour, then reduction and carbonization is handled
Products therefrom is simple substance tungsten powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711069845.6A CN107737943B (en) | 2017-11-03 | 2017-11-03 | A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711069845.6A CN107737943B (en) | 2017-11-03 | 2017-11-03 | A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107737943A true CN107737943A (en) | 2018-02-27 |
| CN107737943B CN107737943B (en) | 2019-08-02 |
Family
ID=61233930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711069845.6A Active CN107737943B (en) | 2017-11-03 | 2017-11-03 | A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107737943B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026184A (en) * | 2019-04-16 | 2019-07-19 | 北京科技大学 | A kind of method of controllable preparation nano material@mesoporous carbon heterojunction structure |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122768A (en) * | 1995-09-29 | 1996-05-22 | 中国科学院固体物理研究所 | Dimension controllable method for prepn. of Nanometre grade tungsten carbide |
| CN1654322A (en) * | 2005-02-01 | 2005-08-17 | 北京科技大学 | Method for preparing nanometer tungsten carbide powder by methyl alcohol cracking |
| CN101579744A (en) * | 2009-06-24 | 2009-11-18 | 中北大学 | Preparation method of nanometer zinc powder based on reducing atmosphere produced by methanol catalytic pyrolysis |
| CN105586463A (en) * | 2016-03-22 | 2016-05-18 | 北京科技大学 | Technique for directly reducing pellet ore by means of methanol |
| CN106744960A (en) * | 2016-11-15 | 2017-05-31 | 重庆大学 | A kind of method that oxidation of coal titanium or/and titanium carbide are prepared with carburetted hydrogen gas reduction |
| CN106944628A (en) * | 2016-10-06 | 2017-07-14 | 江西理工大学 | A kind of scrap hard alloy, which is reclaimed, prepares ultrafine WC Co composite powder methods |
| CN107200331A (en) * | 2017-07-07 | 2017-09-26 | 浙江理工大学 | A kind of preparation method of open system SiC nanowire |
-
2017
- 2017-11-03 CN CN201711069845.6A patent/CN107737943B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122768A (en) * | 1995-09-29 | 1996-05-22 | 中国科学院固体物理研究所 | Dimension controllable method for prepn. of Nanometre grade tungsten carbide |
| CN1654322A (en) * | 2005-02-01 | 2005-08-17 | 北京科技大学 | Method for preparing nanometer tungsten carbide powder by methyl alcohol cracking |
| CN101579744A (en) * | 2009-06-24 | 2009-11-18 | 中北大学 | Preparation method of nanometer zinc powder based on reducing atmosphere produced by methanol catalytic pyrolysis |
| CN105586463A (en) * | 2016-03-22 | 2016-05-18 | 北京科技大学 | Technique for directly reducing pellet ore by means of methanol |
| CN106944628A (en) * | 2016-10-06 | 2017-07-14 | 江西理工大学 | A kind of scrap hard alloy, which is reclaimed, prepares ultrafine WC Co composite powder methods |
| CN106744960A (en) * | 2016-11-15 | 2017-05-31 | 重庆大学 | A kind of method that oxidation of coal titanium or/and titanium carbide are prepared with carburetted hydrogen gas reduction |
| CN107200331A (en) * | 2017-07-07 | 2017-09-26 | 浙江理工大学 | A kind of preparation method of open system SiC nanowire |
Non-Patent Citations (1)
| Title |
|---|
| YIJIE WU 等: "The preparation of tungsten carbides and tungsten powders by reaction of tungsten trioxide with methanol", 《INTERNATIONAL JOURNAL OF REFRACTORY METALS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026184A (en) * | 2019-04-16 | 2019-07-19 | 北京科技大学 | A kind of method of controllable preparation nano material@mesoporous carbon heterojunction structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107737943B (en) | 2019-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106103746B (en) | The operating method of oxygen blast furnace | |
| JP5498494B2 (en) | Carbide manufacturing method and system | |
| CN106834775B (en) | A kind of method of carbon thermal reduction and Nitration synthesis ferrovanadium nitride | |
| CN101337689B (en) | Method for producing titanium tetrachloride using low grade titan raw material | |
| CN102796561B (en) | Anaerobic gasification method and device for biomass fuels by carbon dioxide circulation | |
| CN102304599A (en) | Method and device for producing direct reduced iron by using gas-based reduction shaft furnace | |
| CN107052357A (en) | A kind of preparation method of high-purity rhenium powder | |
| CN105176594B (en) | A kind of device and method for brown coal hydrogasification system also Primordial Qi | |
| CN102212706A (en) | Method for extracting arsenic metal from arsenic trioxide material by two-stage carbon reduction | |
| CN114729409B (en) | Method for direct reduction of iron ore | |
| CN101921941A (en) | Method for producing vanadium-nitrogen alloy | |
| CN105960469A (en) | Combined system for producing steel and method for operating the combined system | |
| CN114737051B (en) | Iron-containing pellet direct reduction process and system based on hot air external circulation of rotary kiln-melting furnace | |
| CN106044771B (en) | A kind of titanium carbide preparation method that titanium processing is proposed based on titanium-containing blast furnace slag carbonization | |
| CN104087700A (en) | Method and system for preparing sponge iron by using gas-based shaft furnace | |
| CN100439014C (en) | Preparation method and equipment for nano-grade superfine cobalt powder | |
| CN107737943A (en) | A kind of method that Reduction of methanol prepares tungsten carbide or/and tungsten powder | |
| CN106744960A (en) | A kind of method that oxidation of coal titanium or/and titanium carbide are prepared with carburetted hydrogen gas reduction | |
| CN100410170C (en) | Method for preparing iron carbide using iron ore concentrate powder | |
| CN108018474A (en) | A kind of method that vanadium nitride is prepared with ammonium metavanadate serialization | |
| CN107758669A (en) | A kind of method that propyl alcohol reduction prepares Molybdenum carbide powders | |
| CN102173418A (en) | Metallic carbide superfine powder used for preparing superfine crystalline cemented hard alloy and preparation process thereof | |
| JP6777894B2 (en) | Oxygen blast furnace equipment and method of manufacturing pig iron using the oxygen blast furnace equipment | |
| CN109052476B (en) | Method for preparing molybdenum dioxide in short process | |
| CN103896210A (en) | CH4-CO2 catalytic reforming reaction device and process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |