CN109368613A - A method of porous carbon is prepared using hard alloy scraps - Google Patents
A method of porous carbon is prepared using hard alloy scraps Download PDFInfo
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- CN109368613A CN109368613A CN201811208985.1A CN201811208985A CN109368613A CN 109368613 A CN109368613 A CN 109368613A CN 201811208985 A CN201811208985 A CN 201811208985A CN 109368613 A CN109368613 A CN 109368613A
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The present invention provides a kind of method for preparing porous carbon using hard alloy scraps, the described method includes: the hard alloy scraps using cobalt content higher than 10% carry out molten-salt electrolysis as electrolytic anode, after the tungsten in the hard alloy scraps and the anode after cobalt dissolves out completely, after clean and reuse electrolysis.The method provided by the invention for preparing porous carbon using hard alloy scraps; using fused salt electrolysis process; hard alloy scraps using cobalt content higher than 10% is anodes; by being electrolysed the tungsten and cobalt all dissolutions that make in hard alloy scraps, so that anode becomes the carbon material with porous structure, filled at high temperature by fused salt; protect its architectural characteristic; it need to only be cooled to room temperature, impregnated by simple deionized water and dry to get the porous carbon of complete hole configurations is arrived.This method is at low cost and process route is simple, again recycles the carbon in hard alloy scraps in the form of porous carbon while recycling non-ferrous metal, is suitable for promoting and applying.
Description
Technical field
The present invention relates to porous carbon materials preparation field more particularly to a kind of sides that porous carbon is prepared using hard alloy scraps
Method.
Background technique
Porous carbon materials not only have many advantages, such as carbon material chemical stability height, good conductivity, due to drawing for porous structure
Enter, also have the characteristics that specific surface area is high, cellular structure is abundant, catalysis, absorption and in terms of all obtain
It is widely applied.
The common synthetic method of porous carbon materials mainly has activation method and two kinds of template, wherein activation method be prepare it is porous
The conventional method of carbon material, including chemical activation, physically activated, physical chemistry activation combination, carbon matrix precursor catalytic activation, can
Carbonization and pyrolysis high molecular polymer mixing carbonization, the carbonization of polymer aerogel, biomass carbonization-activation；Template is
Pore structure effectively is controlled using template, thus the method for preparing material structurally ordered, that aperture is uniform.According to the mould used
The difference of plate, template can be divided into: soft template method, a kind of method of direct synthesizing ordered mesoporous carbon, (such as by carbon matrix precursor
Phenolic resin) interacting with soft template (mainly surfactant) carries out self assembly, then carbon matrix precursor is carbonized to obtain
Porous material；Hard template method introduces forerunner in its duct using a kind of material with special pore structure as hard template
Body obtains the porous carbon materials with special pore structure by being carbonized and removing hard template；Double-template method, (such as using hard template
Porous anodic aluminium oxide and PS bead) come control carbon material pattern or macropore formation, while being controlled using soft template
The formation of ordered mesoporous pore canals, to obtain the porous carbon materials with grade cellular structure.
But these existing methods often have that at high cost, synthesis technology is complicated or purity is relatively low, hinder more
Hole carbon material is widely applied.
Therefore, it is necessary to research and develop a kind of method that at low cost and process route simply prepares porous carbon.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of method for preparing porous carbon using hard alloy scraps.
The present invention provides a kind of method for preparing porous carbon using hard alloy scraps, comprising: with cobalt content higher than 10%
Hard alloy scraps are that electrolytic anode carries out molten-salt electrolysis, after the tungsten in the hard alloy scraps and after cobalt dissolves out completely, are cleaned back
Anode after receiving electrolysis.
The hard alloy scraps are preferably tungsten-cobalt series hard alloy, such as YG3, YG6, YG8, YG10, YG16, YG20.
Hard alloy is a kind of composite material being made of hard phase WC and Binder Phase (the usually metals such as Co, Ni),
There is no chemical reactions for middle hard phase WC and Binder Phase.Carbon atom accounting 40%~50% in hard alloy, this part carbon exist
It is often ignored in the removal process of hard alloy.In above-mentioned technical proposal, use fused salt electrolysis process with hard alloy scraps for electricity
Solution anode prepares porous carbon, belongs to one kind of hard template method, while recycling tungsten, cobalt metal powder, has obtained having complete
The porous carbon of hole configurations, compares conventional method low in raw material price and process route is simple.
Preferably, the above method the following steps are included:
(1) hard alloy scraps by cobalt content higher than 10% carry out classification cleaning by cobalt content；
(2) will classification cleaning after hard alloy scraps as anode, inert electrode as cathode, in molten salt electrolyte into
Row electrolysis makes tungsten and cobalt dissolution in hard alloy scraps；
(3) after in hard alloy scraps tungsten and cobalt dissolve out completely and cathode precipitation after, stop electrolysis, take out electrolysis after
Anode is drying to obtain porous carbon after cleaning.
Preferably, molten salt electrolyte described in step (2) is NaCl-KCl molten salt system, more preferably equimolar ratio
NaCl-KCl molten salt system.
Further, it is electrolysed by the way of controlling electric current in step (2), current density is 60~100mA/cm2。
Preferably, when being electrolysed by the way of controlling electric current, first with current density for 60~65mA/cm2Constant Electric Current
2.5~4h is solved, cobalt is made to dissolve out and deposit completely in cathode；Again with current density for 90~100mA/cm2Constant-current electrolysis 4.5~
6h makes tungsten dissolve out and deposit completely in cathode.
Alternatively, being electrolysed by the way of controlling voltage in step (2), tank voltage is 2.0~3.0V.
Preferably, when being electrolysed by the way of controlling voltage, first with tank voltage be 2.0~2.2V constant-potential electrolysis extremely
Galvanic current disappears, and cobalt is made to dissolve out and deposit completely in cathode；It is again that 2.8~3.0V constant-potential electrolysis to polarization current disappears with tank voltage
It loses, tungsten is made to dissolve out and deposit completely in cathode.
Preferably, it when being electrolysed in step (2), is protected using inert gas, electrolysis temperature is 600~900 DEG C,
More preferably 750 DEG C.
Preferably, inert electrode described in step (2) is tungsten bar, graphite rod, stud or stainless steel plate.
Specific embodiment as one preferred, the method for preparing porous carbon using hard alloy scraps includes following
Step:
(1) hard alloy scraps by cobalt content higher than 10% carry out classification cleaning by cobalt content；
(2) using the hard alloy scraps after classification cleaning as anode, inert electrode is as cathode, at 600~900 DEG C
In NaCl-KCl molten salt system, control current density is 60~100mA/cm2Or control tank voltage is that 2.0~3.0V carries out electricity
Solution makes tungsten and cobalt dissolution in hard alloy scraps；
(3) after in hard alloy scraps tungsten and cobalt dissolve out completely and cathode precipitation after, stop electrolysis, take out electrolysis after
Anode is drying to obtain porous carbon after cleaning.
The method provided by the invention for preparing porous carbon using hard alloy scraps, using fused salt electrolysis process, with cobalt content height
It is anode in 10% hard alloy scraps, dissolves out tungsten in hard alloy scraps and cobalt all by being electrolysed, so that anode becomes
Carbon material with porous structure, is filled by fused salt at high temperature, protects its architectural characteristic, need to be only cooled to room temperature,
It is impregnated and is dried to get the porous carbon of complete hole configurations is arrived by simple deionized water.This method is at low cost and technique road
Line is simple, again recycles the carbon in hard alloy scraps in the form of porous carbon while recycling non-ferrous metal, is suitable for promoting and applying.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the XRD diagram of gained porous carbon in the embodiment of the present invention 1；
Fig. 2 is the SEM figure of gained porous carbon in the embodiment of the present invention 1；
Fig. 3 is the EDX figure of gained porous carbon in the embodiment of the present invention 1；
Fig. 4 is the SEM figure and XRD diagram of the cobalt dust of cathode deposition in the embodiment of the present invention 1；
Fig. 5 is the SEM figure and XRD diagram of the tungsten powder of cathode deposition in the embodiment of the present invention 1；
Fig. 6 is the SEM figure of gained porous carbon in the embodiment of the present invention 2.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
Embodiment 1
The present embodiment provides a kind of methods for preparing porous carbon using hard alloy scraps, comprising the following steps:
(1) one piece of WC-15wt%Co hard alloy scraps is taken, 3 × 3 × 15mm fritter is cut into and is cleaned in acetone soln
Surface grease is removed, the hard alloy scraps fritter after cleaning is tied up in stainless steel electrode bar front end as anode；Take diameter 3mm tungsten
Stick is as cathode；By the sodium chloride of equimolar ratio and the dry fritting of potassium chloride, it is stand-by that molten salt system is made；
(2) under argon atmosphere, the molten salt system that heats up is close with electric current by the way of constant-current electrolysis to 750 DEG C
Spend 60mA/cm2Electrolysis 3 hours makes cobalt be completely dissolved and deposit in cathode；An other cathode is replaced, with current density
100mA/cm2Electrolysis 5 hours makes tungsten be completely dissolved and deposit in cathode, stops electrolysis；
(3) it is cooled to room temperature to molten salt system, takes out anode, impregnated 24 hours in deionized water, and in 50 DEG C of air blast
It dries in drying box to get porous carbon.
XRD test is carried out after gained porous carbon is ground, as a result as shown in Figure 1, it can be seen that occur at 25 degree and 45 degree
Two apparent amorphous packets illustrate that the porous carbon of preparation exists in the form of agraphitic carbon；A small amount of unreacted WC is shown strongly
Diffraction maximum, this is because WC have crystal structure.
The SEM of gained porous carbon schemes and EDX figure is as shown in Figures 2 and 3, the porous carbon hole as can be seen from the figure prepared
Size is uniform, and gamma-spectrometric data shows that the element in scanning range is carbon.
It is 1093.68m using the porous carbon specific surface area that specific surface porosity tester measures preparation2/ g, porosity are
50.35%.
SEM figure and the XRD diagram that the cobalt dust of cathode is deposited in the present embodiment are as shown in Figure 4, it can be seen that powder is in ball
Shape graininess, average grain diameter are less than 100nm.
SEM figure and the XRD diagram that the tungsten powder of cathode is deposited in the present embodiment are as shown in Figure 5, it can be seen that powder is in ball
Shape graininess, average grain diameter are less than 200nm.
Embodiment 2
The present embodiment provides a kind of methods for preparing porous carbon using hard alloy scraps, comprising the following steps:
(1) WC-15wt%Co hard alloy scraps fragment muti-piece is taken, cleaning removes surface grease in acetone soln, dry
Afterwards in graphite anode basket；Take diameter 6mm graphite rod as cathode；The sodium chloride of equimolar ratio and potassium chloride is dry pre-
It is molten, it is stand-by that molten salt system is made；
(2) under argon atmosphere, the molten salt system that heats up is to 750 DEG C, by the way of constant-potential electrolysis, control flume electricity
Pressure is that 2.0V is electrolysed to polarization current disappearance, it was demonstrated that cobalt has been completely dissolved；An other cathode is replaced, control tank voltage is 3.0V
Electrolysis to polarization current disappears, it was demonstrated that tungsten has been completely dissolved, and stops electrolysis；
(3) it is cooled to room temperature to molten salt system, takes out anode, impregnated 24 hours in deionized water, and in 50 DEG C of air blast
It dries in drying box to get porous carbon, microscopic appearance is as shown in Figure 6.
Comparative example 1
(1) WC-10wt%Co hard alloy 3 × 3 × 15mm fritter is taken, cleaning removes surface grease in acetone soln,
Hard alloy scraps fritter after cleaning is tied up in stainless steel electrode bar front end as anode；Take diameter 3mm tungsten bar as cathode；It will
The dry fritting of the sodium chloride and potassium chloride of equimolar ratio, it is stand-by to be made molten salt system；
(2) under argon atmosphere, the molten salt system that heats up is close with electric current by the way of constant-current electrolysis to 750 DEG C
Spend 100mA/cm2Electrolysis 5 hours, dissolves out tungsten, cobalt completely.
(3) it is cooled to room temperature to molten salt system, takes out anode, discovery anode fragmentation is peeled off.This is because cobalt content exists
The more dispersed not connection of Binder Phase cobalt in 10% hard alloy below forms the carbon skeleton of porous structure after can not dissolving out.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of method for preparing porous carbon using hard alloy scraps characterized by comprising useless higher than 10% with cobalt content
Hard alloy is that electrolytic anode carries out molten-salt electrolysis, after the tungsten in the hard alloy scraps and after cobalt dissolves out completely, clean and reuse
Anode after electrolysis.
2. the method according to claim 1, wherein the following steps are included:
(1) hard alloy scraps by cobalt content higher than 10% carry out classification cleaning by cobalt content；
(2) using the hard alloy scraps after classification cleaning as anode, inert electrode carries out electricity as cathode in molten salt electrolyte
Solution makes tungsten and cobalt dissolution in hard alloy scraps；
(3) after in hard alloy scraps tungsten and cobalt dissolve out completely and cathode precipitation after, stop electrolysis, take out electrolysis after sun
Pole is drying to obtain porous carbon after cleaning.
3. according to the method described in claim 2, it is characterized in that, molten salt electrolyte described in step (2) is molten for NaCl-KCl
The NaCl-KCl molten salt system of salt system, preferably equimolar ratio.
4. according to the method described in claim 2, it is characterized in that, step (2) in be electrolysed by the way of controlling electric current,
Current density is 60~100mA/cm2。
5. according to the method described in claim 4, it is characterized in that, elder generation is when being electrolysed by the way of controlling electric current with electricity
Current density is 60~65mA/cm22.5~4h of constant-current electrolysis, then with current density for 90~100mA/cm2Constant-current electrolysis 4.5~
6h。
6. according to the method described in claim 2, it is characterized in that, step (2) in be electrolysed by the way of controlling voltage,
Tank voltage is 2.0~3.0V.
7. according to the method described in claim 6, it is characterized in that, elder generation is when being electrolysed by the way of controlling voltage with slot
Voltage is that 2.0~2.2V constant-potential electrolysis to polarization current disappears, then with tank voltage is 2.8~3.0V constant-potential electrolysis to polarization current
It disappears.
8. according to the described in any item methods of claim 2~7, which is characterized in that when being electrolysed in step (2), use is lazy
Property gas protected, electrolysis temperature be 600~900 DEG C, preferably 750 DEG C.
9. according to the described in any item methods of claim 2~7, which is characterized in that inert electrode described in step (2) is tungsten
Stick, graphite rod, stud or stainless steel plate.
10. according to the method described in claim 2, characterized by comprising the following steps:
(1) hard alloy scraps by cobalt content higher than 10% carry out classification cleaning by cobalt content；
(2) using the hard alloy scraps after classification cleaning as anode, inert electrode is as cathode, in 600~900 DEG C of NaCl-
In KCl molten salt system, control current density is 60~100mA/cm2Or control tank voltage is that 2.0~3.0V is electrolysed, and makes to give up
Tungsten and cobalt dissolution in hard alloy；
(3) after in hard alloy scraps tungsten and cobalt dissolve out completely and cathode precipitation after, stop electrolysis, take out electrolysis after sun
Pole is drying to obtain porous carbon after cleaning.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114934296A (en) * | 2022-04-21 | 2022-08-23 | 湖北绿钨资源循环有限公司 | Method for recycling tungsten carbide by electrolyzing waste hard alloy under assistance of aeration |
| CN115125587A (en) * | 2022-07-22 | 2022-09-30 | 中南大学 | Device and method for low-carbon separation of tungsten, cobalt and carbon through fused salt electrolysis of hard alloy |
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| CN104018190A (en) * | 2014-06-17 | 2014-09-03 | 北京工业大学 | Method for recovering waste hard alloy |
| CN106222703A (en) * | 2016-08-25 | 2016-12-14 | 北京工业大学 | Multistep selective electrolysis reclaims the method for metal in hard alloy scraps |
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2018
- 2018-10-17 CN CN201811208985.1A patent/CN109368613A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018190A (en) * | 2014-06-17 | 2014-09-03 | 北京工业大学 | Method for recovering waste hard alloy |
| CN106222703A (en) * | 2016-08-25 | 2016-12-14 | 北京工业大学 | Multistep selective electrolysis reclaims the method for metal in hard alloy scraps |
Non-Patent Citations (1)
| Title |
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| LIWEN ZHANG ET AL.: "Electrochemical separation and extraction of cobalt and tungsten from cemented scrap", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114934296A (en) * | 2022-04-21 | 2022-08-23 | 湖北绿钨资源循环有限公司 | Method for recycling tungsten carbide by electrolyzing waste hard alloy under assistance of aeration |
| CN115125587A (en) * | 2022-07-22 | 2022-09-30 | 中南大学 | Device and method for low-carbon separation of tungsten, cobalt and carbon through fused salt electrolysis of hard alloy |
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