CN102502598A - Catalytic graphitization method for wood powder - Google Patents
Catalytic graphitization method for wood powder Download PDFInfo
- Publication number
- CN102502598A CN102502598A CN2011103269285A CN201110326928A CN102502598A CN 102502598 A CN102502598 A CN 102502598A CN 2011103269285 A CN2011103269285 A CN 2011103269285A CN 201110326928 A CN201110326928 A CN 201110326928A CN 102502598 A CN102502598 A CN 102502598A
- Authority
- CN
- China
- Prior art keywords
- graphitization
- wood powder
- nanometer
- temperature
- nickel
- 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
Images
Abstract
The invention discloses a catalytic graphitization method for wood powder. The wood powder is subjected to catalytic graphitization in the presence of nanometer ferric oxide or nanometer nickel serving as a catalyst. The method comprises the following steps of: adding the nanometer ferric oxide or nanometer nickel into the wood powder, and uniformly mixing to obtain premix; and raising the temperature of the premix to graphitization temperature under the protection of nitrogen, and preserving heat for 2 hours, wherein the graphitization temperature is between 900 and 1,600 DEG C, and the addition amount of the nanometer ferric oxide or nanometer nickel is 3 to 15 percent of the mass of the wood powder based on iron or nickel. A graphitized material prepared by the method is prepared by a simple process, low in graphitization temperature and high in graphitization degree which is 100 percent.
Description
One, technical field
The present invention relates to a kind of biomass catalyzing graphitizing method, specifically a kind of method of wood powder catalyzed graphitization.
Two, background technology
Domestic fewer about the catalyzed graphitization of biomass such as timber is studied, mainly contain the Dalian materialization doing relevant research work with Shenyang metal grade, external Japan and the research of Hispanic seminar many.Nagle in 1997 etc. studied for the first time turmeric tree in carbonization process density, dimensional contraction, the velocity of sound, carbon yield and percent crystallinity with temperature variations; And pass through XRD test confirmation 2500 ℃ of following charings; It is main that material component is still with amorphous carbon; Only along with the increase of temperature, the ordering degree of carbon structure increases.Cheng in 1999 etc. have studied the greying behavior of stupalith under 1300-3000 ℃ that timber, bamboo and corresponding resin impregnating are crossed, even the result finds charcoal and resin charcoal its d at high temperature
002Also have only 0.341nm and 9nm with the Lc value, confirmed that further resin charcoal and charcoal belong to non-graphitized raw material of wood-charcoal material.Further further investigation along with charing; On the basis that people such as calendar year 2001 Kim study in front; Adopting tunicin, phycophyta, flax respectively is raw material, with the raw material of wood-charcoal material 500 ℃ of following charings, 2000 ℃ of following greyings; The result finds in carbonization process, to have only tunicin to present 100 and 101 diffraction peaks of graphite-structure, and major part is the amorphous carbon structure.It is that catalyzer is being lower than 1000 ℃ of xylogen in the following catalysis birch that Uraki in 2003 adopts nickelous acetate first.The adding of discovering catalyzer can effectively reduce graphitization temperature, realizes the catalyzed graphitization of biomass, but because temperature is not very high (1000 ℃), the d of the graphite carbon under this temperature
002Has only 0.339nm.Hata seminar and Sevilla seminar use different metallic catalyzer (Al, Fe, Ni, Mn, Fe (NO respectively subsequently
3)
3, Ni (NO
3)
2, Al
2O
3) realized the low temperature graphitization of biomass at low temperatures.The Dalian materialization Wang etc. the conductive polymers pyrroles is joined (fibrous paper, cotton, timber) in the biomass, use FeCl
3Make catalyzer, absorb heat by microwave heating and polymkeric substance and realize the low-temperature catalyzed graphitization of biomass.But the aforesaid method thermal treatment temp is higher, and technology is complicated.
Three, summary of the invention
The present invention is the weak point for fear of above-mentioned prior art, and the method for the wood powder catalyzed graphitization that a kind of graphitization temperature is low, degree of graphitization is high is provided.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of the method for wood powder catalyzed graphitization of the present invention are: with nanometer red oxide of iron or nanometer nickel is that catalyzer is to the wood powder catalyzed graphitization; Said wood powder is with obtaining behind the China fir powder crushing screening, and the particle diameter of said wood powder is less than 38 μ m.
The characteristics of the method for wood powder catalyzed graphitization of the present invention also are to operate according to the following steps: with mixing in nanometer red oxide of iron or the nanometer nickel adding wood powder, obtain Preblend; Under nitrogen protection, said Preblend is warming up to the graphitization temperature insulation got final product in 2 hours; Said graphitization temperature is 900-1600 ℃; The addition of said nanometer red oxide of iron or nanometer nickel is the 3-15% of wood powder quality in iron or nickel.
The characteristics of the method for wood powder catalyzed graphitization of the present invention also are: the temperature rise rate that is warming up to graphitization temperature is 3 ℃/min.
The characteristics of the method for wood powder catalyzed graphitization of the present invention also are: preferred 1600 ℃ of graphitization temperature.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the catalyzer red oxide of iron or the nickel powder of the present invention's use obtain easily, and cheap;
2, the graphitized material technology of the inventive method preparation is simple, and graphitization temperature is low, and the degree of graphitization of the graphitized material of preparation is high, and degree of graphitization can reach 100%.
Four, description of drawings
Fig. 1 is the XRD figure of 1600 ℃ of graphitized material when adding down different nanometer red oxide of iron catalyst content.
The XRD figure of graphitized material when Fig. 2 is 1600 ℃ of down different nano nickel catalyst content.
Fig. 3 is that nanometer red oxide of iron addition is the XRD figure of graphitized material under 6% o'clock different graphitization degree temperature.
Fig. 4 is that nanometer nickel addition is the XRD figure of graphitized material under 6% o'clock different graphitization degree temperature.
Five, embodiment
Below in conjunction with embodiment the present invention is done further description.
Embodiment 1:
China fir powder crushing screening is obtained the wood powder of particle diameter less than 38 μ m,, obtain Preblend mixing in the nanometer red oxide of iron adding wood powder; Under nitrogen protection, said Preblend is warming up to 1600 ℃ and be incubated 2h and promptly obtain graphitized material with the temperature rise rate of 3 ℃/min; The addition of nanometer red oxide of iron is respectively 0wt%, 3wt%, 6wt%, 10wt%, the 15wt% of wood powder quality.
(Fig. 1) discovers through X-ray diffraction: 2 θ of the graphitized material of present embodiment preparation are respectively 26.04 °, 26.34 °, 26.51 °, 26.5 °, 26.56 °, corresponding d
002Value respectively is 0.3419nm, 0.3381nm, 0.3354nm, 0.3361nm, 0.3353nm.This shows that along with the catalyzer addition is increased to 15% from 0%, the graphite spacing is reduced to 0.3353nm from 0.3419nm, the spacing of ideal graphite is 0.3354nm, and (002) diffraction angle is 26.56 °.When the addition of nanometer red oxide of iron is 15%, be optimum concn, the degree of graphitization of raw material of wood-charcoal material is 100% under this catalyst concn.
Embodiment 2:
China fir powder crushing screening is obtained the wood powder of particle diameter less than 38 μ m,, obtain Preblend mixing in the nanometer nickel adding wood powder; Under nitrogen protection, said Preblend is warming up to 1600 ℃ and be incubated 2h and promptly obtain graphitized material with the temperature rise rate of 3 ℃/min; The addition of nanometer red oxide of iron is respectively 0wt%, 3wt%, 6wt%, 10wt%, the 15wt% of wood powder quality.
Find through X-ray diffraction (Fig. 2): 2 θ of the graphitized material of present embodiment preparation are respectively 26.04 °, 26.24 °, 26.5 °, 26.48 °, 26.52 °, corresponding d
002Value is respectively 0.3419nm, 0.3394nm, 0.3359nm, 0.3361nm, 0.3358nm.This shows that along with the catalyzer addition is increased to 15% from 0%, the graphite spacing is reduced to 0.3358nm respectively from 0.3394nm, the spacing of ideal graphite is 0.3354nm, and (002) diffraction angle is 26.56 °.When the addition of nano-nickel powder is 15%, be optimum concn, the degree of graphitization of raw material of wood-charcoal material is 95.3% under this catalyst concn.
Embodiment 3:
China fir powder crushing screening is obtained the wood powder of particle diameter less than 38 μ m, and with mixing in the nanometer red oxide of iron adding wood powder, the addition of nanometer red oxide of iron is the 6wt% of wood powder quality, obtains Preblend; Under nitrogen protection, said Preblend is warming up to 900 ℃, 1200 ℃, 1400 ℃ and 1600 ℃ successively with the temperature rise rate of 3 ℃/min and is incubated 2h respectively and promptly obtain the graphitized material for preparing under the different graphitization degree temperature.
(Fig. 3) discovers through X-ray diffraction: 2 θ of the graphitized material of present embodiment preparation are respectively 26.06 °, 26.14 °, 26.34 ° and 26.56 °, corresponding d
002Value is respectively 0.3415nm, 0.3406nm, 0.3381nm and 0.3353nm.This shows that along with graphitization temperature is increased to 1600 ℃ from 900 ℃, the graphite spacing is reduced to 0.3353nm from 0.3415nm, the spacing of ideal graphite is 0.3354nm, and (002) diffraction angle is 26.56 °.When graphitization temperature is 1600 ℃, be optimum temps, the degree of graphitization of raw material of wood-charcoal material is 100% under this temperature.
Embodiment 4:
China fir powder crushing screening is obtained the wood powder of particle diameter less than 38 μ m, and with mixing in the nanometer nickel adding wood powder, the addition of nanometer nickel is the 6wt% of wood powder quality, obtains Preblend; Under nitrogen protection, said Preblend is warming up to 900 ℃, 1200 ℃, 1400 ℃ and 1600 ℃ successively with the temperature rise rate of 3 ℃/min and is incubated 2h respectively and promptly obtain the graphitized material for preparing under the different graphitization degree temperature.
(Fig. 4) discovers through X-ray diffraction: 2 θ of the graphitized material of present embodiment preparation are respectively 26.13 °, 26.26 °, 26.48 ° and 26.50 °, corresponding d
002Value is respectively 0.3406nm, 0.3391nm, 0.3363nm and 0.3361nm.This shows that along with graphitization temperature is increased to 1600 ℃ from 900 ℃, the graphite spacing is reduced to 0.3361nm from 0.3406nm, the spacing of ideal graphite is 0.3354nm, and (002) diffraction angle is 26.56 °.And diffraction angle arrives 1400 ℃ in carbonization temperature; Angle has just reached 26.48 °; Near the diffraction angle of ideal graphite, this shows that nickel powder catalysis China fir powder can realize the conversion of decolorizing carbon to graphite under lower temperature, when graphitization temperature is 1600 ℃; Be optimum temps, the degree of graphitization of raw material of wood-charcoal material is 93% under this temperature.
Claims (4)
1. the method for a wood powder catalyzed graphitization, it is characterized in that: with nanometer red oxide of iron or nanometer nickel is that catalyzer is to the wood powder catalyzed graphitization; Said wood powder is with obtaining behind the China fir powder crushing screening, and the particle diameter of said wood powder is less than 38 μ m.
2. the method for wood powder catalyzed graphitization according to claim 1 is characterized in that operating according to the following steps: with mixing in nanometer red oxide of iron or the nanometer nickel adding wood powder, obtain Preblend; Under nitrogen protection, said Preblend is warming up to the graphitization temperature insulation got final product in 2 hours; Said graphitization temperature is 900-1600 ℃; The addition of said nanometer red oxide of iron or nanometer nickel is the 3-15% of wood powder quality in iron or nickel.
3. method according to claim 2 is characterized in that: the temperature rise rate that is warming up to graphitization temperature is 3 ℃/min.
4. method according to claim 2 is characterized in that: graphitization temperature is 1600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103269285A CN102502598B (en) | 2011-10-25 | 2011-10-25 | Catalytic graphitization method for wood powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103269285A CN102502598B (en) | 2011-10-25 | 2011-10-25 | Catalytic graphitization method for wood powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102502598A true CN102502598A (en) | 2012-06-20 |
| CN102502598B CN102502598B (en) | 2013-07-31 |
Family
ID=46214749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103269285A Expired - Fee Related CN102502598B (en) | 2011-10-25 | 2011-10-25 | Catalytic graphitization method for wood powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102502598B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745677A (en) * | 2012-07-06 | 2012-10-24 | 同济大学 | Collaborative graphitization method for amorphous carbon material |
| CN103466606A (en) * | 2013-08-23 | 2013-12-25 | 安徽理工大学 | Effect of particle size of catalyst on catalytic graphitization of resin material |
| CN104058391A (en) * | 2013-03-20 | 2014-09-24 | 常州碳宇纳米科技有限公司 | Method for wood powder graphitization by catalyst at low temperature |
| WO2015034670A1 (en) * | 2013-09-05 | 2015-03-12 | Graftech International Holdings Inc. | Carbon products derived from lignin/carbon residue |
| CN104891479A (en) * | 2015-05-26 | 2015-09-09 | 中国林业科学研究院林产化学工业研究所 | Plant-based graphene and preparation method thereof |
| WO2016130026A1 (en) * | 2015-02-13 | 2016-08-18 | Carbonscape Limited | Graphite production from biomass |
| CN106744915A (en) * | 2016-12-16 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of cellulose base graphitized material and preparation method thereof |
| CN110255552A (en) * | 2019-07-01 | 2019-09-20 | 武汉科技大学 | A kind of wooden calcium sulfonate's graphitizing method |
| CN110407204A (en) * | 2019-09-04 | 2019-11-05 | 内蒙古奥原新材料有限公司 | A kind of Preparation method and use of coke low temperature graphitization |
| CN111987289A (en) * | 2020-09-01 | 2020-11-24 | 侯梦斌 | Preparation method of storage battery negative electrode material |
| CN112788934A (en) * | 2020-12-18 | 2021-05-11 | 中国林业科学研究院林产化学工业研究所 | Preparation method of wood fiber-based electromagnetic shielding carbon material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445234A (en) * | 2009-01-06 | 2009-06-03 | 黑龙江大学 | A preparation method of graphitized carbon nano material |
-
2011
- 2011-10-25 CN CN2011103269285A patent/CN102502598B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445234A (en) * | 2009-01-06 | 2009-06-03 | 黑龙江大学 | A preparation method of graphitized carbon nano material |
Non-Patent Citations (2)
| Title |
|---|
| M.SEVILLA ET AL.: "Synthesis of Graphitic Carbon Nanostructures from Sawdust and Their Application as Electrocatalyst Supports", 《J. PHYS. CHEM.》 * |
| 王于刚 等: "聚芳基乙炔树脂/杉木粉木材陶瓷的制备与表征", 《应用化学》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745677A (en) * | 2012-07-06 | 2012-10-24 | 同济大学 | Collaborative graphitization method for amorphous carbon material |
| CN104058391A (en) * | 2013-03-20 | 2014-09-24 | 常州碳宇纳米科技有限公司 | Method for wood powder graphitization by catalyst at low temperature |
| CN103466606B (en) * | 2013-08-23 | 2015-09-02 | 安徽理工大学 | The catalyst particle of different size is adopted PDVB resin material to be carried out to the method for catalyzed graphitization |
| CN103466606A (en) * | 2013-08-23 | 2013-12-25 | 安徽理工大学 | Effect of particle size of catalyst on catalytic graphitization of resin material |
| US10011492B2 (en) | 2013-09-05 | 2018-07-03 | Graftech International Holdings Inc. | Carbon products derived from lignin/carbon residue |
| CN105121386A (en) * | 2013-09-05 | 2015-12-02 | 格拉弗技术国际控股有限公司 | Carbon products derived from lignin/carbon residue |
| WO2015034670A1 (en) * | 2013-09-05 | 2015-03-12 | Graftech International Holdings Inc. | Carbon products derived from lignin/carbon residue |
| CN105121386B (en) * | 2013-09-05 | 2018-06-01 | 格拉弗技术国际控股有限公司 | The carbon product obtained from lignin/breeze |
| JP2018511553A (en) * | 2015-02-13 | 2018-04-26 | カーボンスケイプ リミテッド | Graphite production from biomass |
| WO2016130026A1 (en) * | 2015-02-13 | 2016-08-18 | Carbonscape Limited | Graphite production from biomass |
| CN104891479B (en) * | 2015-05-26 | 2017-02-01 | 中国林业科学研究院林产化学工业研究所 | Plant-based graphene and preparation method thereof |
| CN104891479A (en) * | 2015-05-26 | 2015-09-09 | 中国林业科学研究院林产化学工业研究所 | Plant-based graphene and preparation method thereof |
| CN106744915A (en) * | 2016-12-16 | 2017-05-31 | 中国林业科学研究院林产化学工业研究所 | A kind of cellulose base graphitized material and preparation method thereof |
| CN110255552A (en) * | 2019-07-01 | 2019-09-20 | 武汉科技大学 | A kind of wooden calcium sulfonate's graphitizing method |
| CN110407204A (en) * | 2019-09-04 | 2019-11-05 | 内蒙古奥原新材料有限公司 | A kind of Preparation method and use of coke low temperature graphitization |
| CN110407204B (en) * | 2019-09-04 | 2023-07-28 | 内蒙古奥原新材料有限公司 | Preparation method and application of coke low-temperature graphitization |
| CN111987289A (en) * | 2020-09-01 | 2020-11-24 | 侯梦斌 | Preparation method of storage battery negative electrode material |
| CN112788934A (en) * | 2020-12-18 | 2021-05-11 | 中国林业科学研究院林产化学工业研究所 | Preparation method of wood fiber-based electromagnetic shielding carbon material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102502598B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102502598B (en) | Catalytic graphitization method for wood powder | |
| AU2016339389B2 (en) | Composite containing carbon nanostructure, high molecular material using same and preparation method | |
| CN105772708B (en) | A kind of method that nitrogen-doped carbon nanometer pipe coated metal oxide particulate composite is prepared using biomass castoff | |
| CN103568385B (en) | Heat-preservation hard composite carbon fiber felt and preparation method thereof | |
| Li et al. | From starch to carbon materials: insight into the cross-linking reaction and its influence on the carbonization process | |
| CN104118874B (en) | A kind of preparation method of gac/graphene complex | |
| CN102515146B (en) | Catalytic graphitization method of polyvinyl tri(phenylethynyl)silane | |
| CA3055280A1 (en) | Method for producing activated carbon | |
| CN101245128B (en) | Modified phenolic resin for fire resistive material and preparation method thereof | |
| CN101780955A (en) | Chitosan activated carbon and preparation method thereof | |
| CN101254911A (en) | Method for preparing carbon nano-tube and carbon nano-fibre by using phenol resin as carbon source | |
| CN104004150B (en) | Phenolic resin of energy in-situ preparation Graphene and preparation method thereof | |
| CN101886332A (en) | Preparation method of polyacrylonitrile base preoxidized fiber felt and graphite carbon felt | |
| CN105502330A (en) | Carbon nanostructure composite and preparation method thereof | |
| CN106433807B (en) | The method that biomass fast pyrogenation gas catalyzed conversion prepares high-grade liquid fuel | |
| CN102689899B (en) | A preparation method for improving specific surface area of activated carbon | |
| CN102383224B (en) | Method of preparing carbon fibers through crosslinked reaction of boron trichloride and polyacrylonitrile precursors | |
| CN101982409B (en) | Method for catalyzing and graphitizing polyaryl acetylene resin | |
| Xie et al. | Thermal degradation and conversion of plant biomass into high value carbon products | |
| CN103342357B (en) | Low temperature catalytic graphitization method for polydivinylbenzene resin | |
| CN103289034B (en) | Transition metal compound composite lignin modified phenolic resin and preparation method thereof | |
| CN103265025A (en) | Method for preparing biomass conductive charcoal electromagnetic shielding material | |
| CN100588457C (en) | Shaping method for super absorbent charcoal powder body for adsorbing CO2 | |
| CN104058391A (en) | Method for wood powder graphitization by catalyst at low temperature | |
| CN106976855A (en) | A kind of preparation method of holocellulose hydro-thermal charcoal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130731 Termination date: 20161025 |