CN110310844A - Sludge utilizes method and the nickel foam-nitrogen-doped nanometer carbon composite prepared by this method - Google Patents
Sludge utilizes method and the nickel foam-nitrogen-doped nanometer carbon composite prepared by this method Download PDFInfo
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- CN110310844A CN110310844A CN201910578922.3A CN201910578922A CN110310844A CN 110310844 A CN110310844 A CN 110310844A CN 201910578922 A CN201910578922 A CN 201910578922A CN 110310844 A CN110310844 A CN 110310844A
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- nitrogen
- nickel foam
- sludge
- doped nanometer
- nanometer carbon
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 90
- 239000010802 sludge Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000006260 foam Substances 0.000 claims abstract description 77
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000005336 cracking Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 17
- 238000010348 incorporation Methods 0.000 description 10
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of sludge using method and the nickel foam-nitrogen-doped nanometer carbon composite prepared by this method, and the utilization method of the sludge includes the following steps: that nickel foam is placed in reactor first, and will be replaced into protective atmosphere in reactor；Sludge is passed through into reactor again, 500~900 DEG C are heated to the heating rate of 15~100 DEG C/s, make sludge that pyrolytic reaction occur in reactor and generates sludge tar, and make the sludge tar generated that cracking reaction occur under the catalysis of nickel foam, and form nitrogen-doped nanometer carbon material in the porous surface growth in situ of nickel foam.Nickel foam-nitrogen-doped nanometer carbon composite of this method preparation, including nickel foam substrate and the nitrogen-doped nanometer carbon material being grown on nickel foam substrate.The present invention is effectively utilized the high nitrogen attribute in sludge, prepared nickel foam-nitrogen-doped nanometer carbon composite, and charge/discharge capacity promotes 5~20 times relative to simple nickel foam, has good chemical property.
Description
Technical field
The present invention relates to a kind of utilization method of sludge, particularly relates to a kind of utilization method of sludge and prepared by this method
Nickel foam-nitrogen-doped carbon nano carbon composite material.
Background technique
With the quickening of Development of China's Urbanization, municipal sludge yield is risen year by year.Contain a large amount of poisonous and harmful substances in sludge
And organic matter, caused by secondary pollution seriously threaten the production and living of the mankind.Pyrolyzing sludge technology receives extensive pass in recent years
Note, pyrolyzing sludge are heated under anaerobic to it using the thermal instability of organic matter in sludge, and organic cracking shape is made
At substances such as the higher pyrolysis gas of utility value, sludge tar and coke.
Sludge tar, also known as pyrolysis oil are a kind of major products that pyrolyzing sludge generates, and complicated component, component is up to
Hundreds of, including carbonaceous materials such as alcohols, phenols, carboxylic acids, aldehydes and furans, also include nitrogenous hydridization class, amides and
The nitrogen substances such as nitrile.How rationally using the sludge tar generated during pyrolyzing sludge, to solving the problems, such as that sludge pollution has
Significance.
Sludge tar can be applied to burning boiler and thermoelectric power generation mainly as the substitute of fossil fuel in a short time at present,
It is long-term to consider to can be applied to turbine and diesel engine.However, some problems of pyrolysis oil diesel oil substitute are there are also to be solved, especially its
Acid (pH=3), is also easy to produce NOxAnd oil smoke, and the problems such as polymerize again.Also have and sludge tar is further refined and spread out
It is raw, to obtain the chemical substance of more value, such as using sludge tar as raw material production synthesis gas, further combine FT synthesis life
Hydrocarbon is produced, however, the method process is complicated, processing cost is high, can not efficiently use sludge tar high nitrogen-containing
Feature.
Summary of the invention
The purpose of the present invention is to provide a kind of sludge to be received using method and by nickel foam-N doping prepared by this method
Rice carbon composite, can be realized the effective use of sludge.
To achieve the above object, the utilization method of sludge provided by the present invention includes the following steps: nickel foam first
It is placed in reactor, and protective atmosphere will be replaced into reactor；It is passed through sludge, into reactor again with 15~100 DEG C/s's
Heating rate is heated to 500~900 DEG C and is maintained at the temperature (until reaction terminates), is pyrolyzed sludge in reactor
Reaction generates sludge tar, and makes the sludge tar generated that cracking reaction occur under the catalysis of nickel foam, and pyrolysis product is steeping
The porous surface growth in situ of foam nickel forms nitrogen-doped nanometer carbon material.
Preferably, the total reaction time of the pyrolytic reaction and cracking reaction is 10~90min, and more excellent is 30~60min.
Total reaction time is too short, and sludge tar yield is few, and total reaction time is too long, and second pyrolysis reaction easily occurs for sludge tar, influences
The shape characteristic of nano-carbon material.
Preferably, the heating rate is 30~80 DEG C/s, is heated to 600~800 DEG C.Heating rate is faster, and sludge is burnt
Oil yield is higher, and the growth of nano-carbon material is more.
Preferably, the total carbon content of the sludge is 20~45wt%, and total nitrogen content is 3~10wt%, and water content does not surpass
Cross 30wt%.
Preferably, this method further includes pre-processing to nickel foam, the steps include: successively to utilize acetone, hydrochloric acid, ethyl alcohol
It is cleaned by ultrasonic with deionized water, is then dried and calcined, then is restored in a hydrogen atmosphere.Preprocessing process can
To effectively remove the impurity of foam nickel surface attachment, be conducive to the activity for improving foamed nickel catalyst agent and selectivity.
Preferably, the temperature of ultrasonic cleaning is 20~50 DEG C, cleans 10~30min every time；The temperature of calcining be 600~
900 DEG C, calcination time is 30~90min；The temperature restored is 600~800 DEG C, and the reaction time is 50~70min.
Preferably, the protective atmosphere is formed by one of nitrogen, helium and argon gas, can not also be participated in using other
The protective gas of catalytic cracking reaction.
Invention also provides nickel foam-nitrogen-doped nanometer carbon composites using preceding method preparation, including bubble
Foam Ni substrate and the nitrogen-doped nanometer carbon material being grown on nickel foam substrate, the nitrogen-doped nanometer carbon material includes carbon nanometer
Pipe and carbon nano-fiber.
Preferably, the diameter of the nitrogen-doped nanometer carbon composite is between 5~100nm, wherein the nitrogen adulterated
Quality be nitrogen-doped nanometer carbon material quality 4%~12%；The quality of the nitrogen-doped nanometer carbon material is nickel foam matter
The 30%~75% of amount.
Invention also provides foregoing foams nickel-application of the nitrogen-doped nanometer carbon composite on electrode material, examples
Such as the electrodes conduct base material of good supercapacitor.
Compared with prior art, the beneficial effects of the present invention are: the present invention to utilize catalytic cracking and chemical deposition pair
Sludge is handled, and prepares nitrogen-doped nanometer carbon material in foam nickel surface, the high nitrogen attribute being effectively utilized in sludge；It should
Method is environmentally protective, simple process, low cost, and prepared nitrogen-doped nanometer carbon material can be by adjusting reaction temperature and anti-
Effective Regulation is carried out to the diameter and length of nano material between seasonable；Nickel foam-nitrogen-doped nanometer carbon of this method preparation is compound
Material, charge/discharge capacity promote 5~20 times relative to simple nickel foam, have good chemical property, after being conducive to
Continuous industrial application.
Detailed description of the invention
Fig. 1 is the SEM scanning electron microscope (SEM) photograph of the nitrogen-doped nanometer carbon material of nickel foam Surface Creation in the embodiment of the present invention 1,
The diameter that nitrogen-doped nanometer carbon material can be observed is 20nm.
Fig. 2 is that figure is swept in the face SEM-EDS for the nitrogen-doped nanometer carbon material that nickel foam face generates in the embodiment of the present invention 1, can
Observing has the incorporation of apparent nitrogen by the nano-carbon material of foam nickel surface (real image is colour, a large amount of small green spots thereon
For the nitrogen of incorporation).
Fig. 3 is the chemical property CV curve of 1 Central Plains nickel foam of the embodiment of the present invention.
Fig. 4 is that the chemical property CV in the embodiment of the present invention 1 after nickel foam Surface Creation nitrogen-doped nanometer carbon material is bent
Line.
Fig. 5 is the chemical property CV curve in the embodiment of the present invention 6 after nickel foam Surface Creation nano-carbon material.
Specific embodiment
The following further describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
Embodiment 1
Sludge provided in this embodiment utilizes method, the specific steps of which are as follows:
Under the conditions of 30 DEG C, by nickel foam in ultrasonic washing instrument successively with 3mol/L hydrochloric acid, dehydrated alcohol and go from
Sub- water cleans 15min, and drying is simultaneously put into reactor after calcining 1 hour at 700 DEG C and carries out reduction treatment, in 700 DEG C of items
Reduction treatment 60min under part.Catalyst of the nickel foam as growth nitrogen-doped nanometer carbon material after reduction, makees in protective atmosphere
Be passed through under carbon content 35wt%, nitrogen content 5wt%, water content 15wt% sludge (present invention in, all not specified contains
Amount is mass content), 50 DEG C/s of heating rate obtains nickel foam-nitrogen-doped nanometer carbon composite wood in 700 DEG C of reaction 60min
Material.
Nickel foam-nitrogen-doped nanometer carbon composite is observed by SEM scanning electron microscope, obtains Fig. 1, it can be seen that
Nano-carbon material is generated in nickel foam hole.It is observed again by SEM-EDS, obtains Fig. 2, it can be seen that foam nickel surface
Nano-carbon material there is apparent nitrogen to mix, the mass content of the nitrogen of incorporation is the 8.7% of nano-carbon material (including nitrogen).Into one
Step carries out TEM transmissioning electric mirror test, it is known that the nano-carbon material on nickel foam substrate surface is multi-walled carbon nanotube, and caliber is about
For 20nm, content is the 45% of nickel foam quality.
As electrochemical workstation to former nickel foam and through nickel foam made from the present embodiment-nitrogen-doped nanometer carbon composite wood
The electrochemistry of material can be carried out test, obtain the chemical property CV curve (Fig. 3) and nickel foam Surface Creation nitrogen of former nickel foam
The chemical property CV curve (Fig. 4) of dopen Nano carbon material.CV curve is integrated, and passes through formula charge/discharge capacity C
=A/ (2 × s × △ V), wherein A is integral area, and s is scanning speed, and △ V is scanning voltage range, calculates and knows this implementation
The more former nickel foam of nickel foam-nitrogen-doped nanometer carbon composite charge/discharge capacity made from example promotes 15 times.
Can be seen that nickel foam prepared by the present embodiment-nitrogen-doped nanometer carbon composite by above-mentioned test has
Good chemical property, has a good application prospect on electrode material.
Embodiment 2
Sludge provided in this embodiment utilizes method, the specific steps of which are as follows:
Under the conditions of 40 DEG C, by nickel foam in ultrasonic washing instrument successively with 3mol/L hydrochloric acid, dehydrated alcohol and go from
Sub- water cleans 15min, and drying is simultaneously put into reactor after calcining 1 hour at 700 DEG C and carries out reduction treatment, in 700 DEG C of items
Reduction treatment 60min under part.Catalyst of the nickel foam as growth nitrogen-doped nanometer carbon material after reduction, makees in protective atmosphere
The sludge of carbon content 38wt%, nitrogen content 6wt%, water content 25wt% are passed through under, 80 DEG C/s of heating rate is reacted at 600 DEG C
90min, foam nickel surface have the generation of nitrogen-doped nanometer carbon material, obtain nickel foam-nitrogen-doped nanometer carbon composite.
It is tested using method in embodiment 1, it is known that nano-carbon material of the present embodiment on nickel foam substrate surface be
Multi-walled carbon nanotube, caliber are about 10nm, and content is the 75% of nickel foam quality；Meanwhile having in nano-carbon material obvious
Nitrogen incorporation, the mass content of the nitrogen of incorporation is the 7.9% of nano-carbon material (including nitrogen)；Foam obtained by the present embodiment
The more former nickel foam of nickel-nitrogen-doped nanometer carbon composite charge/discharge capacity promotes 18 times, has good chemical property,
It is had a good application prospect on electrode material.
Embodiment 3
Sludge provided in this embodiment utilizes method, the specific steps of which are as follows:
Under the conditions of 30 DEG C, by nickel foam in ultrasonic washing instrument successively with 3mol/L hydrochloric acid, dehydrated alcohol and go from
Sub- water cleans 15min, and drying is simultaneously put into reactor after calcining 1 hour at 700 DEG C and carries out reduction treatment, in 700 DEG C of items
Reduction treatment 60min under part.Catalyst of the nickel foam as growth nitrogen-doped nanometer carbon material after reduction, makees in protective atmosphere
The sludge tar of carbon content 32wt%, nitrogen content 4wt%, water content 10wt%, 40 DEG C/s of heating rate, 800 are passed through under
DEG C reaction 30min, foam nickel surface has the generation of nitrogen-doped nanometer carbon material, obtains nickel foam-nitrogen-doped nanometer carbon composite wood
Material.
It is tested using method in embodiment 1, it is known that nano-carbon material of the present embodiment on nickel foam substrate surface be
Multi-walled carbon nanotube and carbon nano-fiber, for the diameter of the two in 30~80nm, content is the 20% of nickel foam quality；Meanwhile
There is apparent nitrogen to mix in nano-carbon material, the mass content of the nitrogen of incorporation is the 4.3% of nano-carbon material (including nitrogen)；This reality
It applies the more former nickel foam of nickel foam obtained by example-nitrogen-doped nanometer carbon composite charge/discharge capacity and promotes 7 times.
Embodiment 4
Sludge provided in this embodiment utilizes method, the specific steps of which are as follows:
Under the conditions of 30 DEG C, by nickel foam in ultrasonic washing instrument successively with 3mol/L hydrochloric acid, dehydrated alcohol and go from
Sub- water cleans 15min, and drying is simultaneously put into reactor after calcining 1 hour at 700 DEG C and carries out reduction treatment, in 700 DEG C of items
Reduction treatment 60min under part.Catalyst of the nickel foam as growth nitrogen-doped nanometer carbon material after reduction, makees in protective atmosphere
The sludge of carbon content 42wt%, nitrogen content 8wt%, water content 5wt% are passed through under, 30 DEG C/s of heating rate is reacted at 600 DEG C
90min, foam nickel surface have the generation of nitrogen-doped nanometer carbon material, obtain nickel foam-nitrogen-doped nanometer carbon composite.
It is tested using method in embodiment 1, it is known that nano-carbon material of the present embodiment on nickel foam substrate surface be
Multi-walled carbon nanotube, caliber are about 15nm, and content is the 40% of nickel foam quality；Meanwhile having in nano-carbon material obvious
Nitrogen incorporation, the mass content of the nitrogen of incorporation is the 9.3% of nano-carbon material (including nitrogen)；Foam obtained by the present embodiment
The more former nickel foam of nickel-nitrogen-doped nanometer carbon composite charge/discharge capacity promotes 20 times, has good chemical property,
It is had a good application prospect on electrode material.
Embodiment 5
Sludge provided in this embodiment utilizes method, the specific steps of which are as follows:
Under the conditions of 40 DEG C, by nickel foam in ultrasonic washing instrument successively with 3mol/L hydrochloric acid, dehydrated alcohol and go from
Sub- water cleans 20min, and drying is simultaneously put into reactor after calcining 1 hour at 700 DEG C and carries out reduction treatment, in 700 DEG C of items
Reduction treatment 60min under part.Catalyst of the nickel foam as growth nitrogen-doped nanometer carbon material after reduction, makees in protective atmosphere
The sludge of carbon content 45wt%, nitrogen content 10wt%, water content 2wt% are passed through under, 25 DEG C/s of heating rate is reacted at 600 DEG C
90min, foam nickel surface have the generation of nitrogen-doped nanometer carbon material, obtain nickel foam-nitrogen-doped nanometer carbon composite.
It is tested using method in embodiment 1, it is known that nano-carbon material of the present embodiment on nickel foam substrate surface be
Multi-walled carbon nanotube, caliber are 18nm or so, and content is the 65% of nickel foam quality；Meanwhile having in nano-carbon material bright
Aobvious nitrogen incorporation, the mass content of the nitrogen of incorporation are the 10.2% of nano-carbon material (including nitrogen), bubble obtained by the present embodiment
The more former nickel foam of foam nickel-nitrogen-doped nanometer carbon composite charge/discharge capacity promotes 12 times, has good chemical property,
It is had a good application prospect on electrode material.
Embodiment 6
The present embodiment is substantially completely identical as the preparation step of embodiment 1, and difference is only that the substance being passed through is nitrogen content
Biomass less than 1%.
Perspective Electronic Speculum TEM test is carried out to obtained nickel foam-nitrogen-doped nanometer carbon composite, it is known that Ni-based in foam
The nano-carbon material in body surface face includes multi-walled carbon nanotube and carbon nano-fiber, and for diameter for 15~95nm, content is bubble
The 15% of foam nickel quality.
As electrochemical workstation to nickel foam made from the present embodiment-nitrogen-doped nanometer carbon composite electrochemistry
It can be carried out test, obtain the chemical property CV curve (Fig. 5) of the composite material.CV curve is integrated, it is known that this implementation
The more former nickel foam of nickel foam-nitrogen-doped nanometer carbon composite charge/discharge capacity (see Fig. 3) made from example promotes 5 times.
The present embodiment due in raw material nitrogen content it is very low, nitrogen is substantially free of in obtained nano-carbon material, and (nitrogen content is
0.8%), the more former nickel foam of gained nickel foam-nano carbon composite material charge/discharge capacity only promotes 5 times.
Claims (10)
1. a kind of utilization method of sludge, characterized by the following steps: nickel foam is placed in reactor first, and
Protective atmosphere will be replaced into reactor；Sludge is passed through into reactor again, is heated to the heating rate of 15~100 DEG C/s
500~900 DEG C and it is maintained at the temperature, makes sludge that pyrolytic reaction occur in reactor and generate sludge tar, and make to generate
Cracking reaction occurs under the catalysis of nickel foam for sludge tar, and pyrolysis product forms nitrogen in the porous surface growth in situ of nickel foam
Dopen Nano carbon material.
2. the utilization method of sludge according to claim 1, it is characterised in that: the pyrolytic reaction and cracking reaction it is total
Reaction time is 10~90min.
3. the utilization method of sludge according to claim 1 or 2, it is characterised in that: the heating rate be 30~80 DEG C/
S is heated to 600~800 DEG C.
4. the utilization method of sludge according to claim 1 or 2, it is characterised in that: the total carbon content of the sludge is 20
~45wt%, total nitrogen content are 3~10wt%, and water content is no more than 30wt%.
5. the utilization method of sludge according to claim 1 or 2, it is characterised in that: further include being located in advance to nickel foam
Reason, the steps include: successively to be cleaned by ultrasonic using acetone, hydrochloric acid, ethyl alcohol and deionized water, is then dried and calcined,
It is restored in a hydrogen atmosphere again.
6. the utilization method of sludge according to claim 5, it is characterised in that: the temperature of ultrasonic cleaning is 20~50 DEG C,
10~30min of cleaning every time；The temperature of calcining is 600~900 DEG C, and calcination time is 30~90min；The temperature restored is
600~800 DEG C, the reaction time is 50~70min.
7. the utilization method of sludge described in any one of claim 1 to 3, it is characterised in that: the protective atmosphere by
The formation of one of nitrogen, helium and argon gas.
8. a kind of nickel foam-nitrogen-doped nanometer carbon composite wood using such as the method preparation of any one of claim 1~7
Material, it is characterised in that: including nickel foam substrate and the nitrogen-doped nanometer carbon material being grown on nickel foam substrate, the N doping
Nano-carbon material includes carbon nanotube and carbon nano-fiber.
9. nickel foam according to claim 8-nitrogen-doped nanometer carbon composite, it is characterised in that: the N doping is received
The diameter of rice carbon material is between 5~100nm, wherein the quality for the nitrogen adulterated is nitrogen-doped nanometer carbon material quality
4%~12%；The quality of the nitrogen-doped nanometer carbon material is the 30%~75% of nickel foam quality.
10. a kind of nickel foam as claimed in claim 8 or 9-application of the nitrogen-doped nanometer carbon composite on electrode material.
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