CN116216713B - 一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法及应用 - Google Patents
一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法及应用 Download PDFInfo
- Publication number
- CN116216713B CN116216713B CN202310034366.XA CN202310034366A CN116216713B CN 116216713 B CN116216713 B CN 116216713B CN 202310034366 A CN202310034366 A CN 202310034366A CN 116216713 B CN116216713 B CN 116216713B
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- graphite alkyne
- graphite
- magnetic
- uniformly distributed
- 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.)
- Active
Links
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 67
- 239000010439 graphite Substances 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- -1 graphite alkyne Chemical class 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 239000006249 magnetic particle Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical group COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 102000020897 Formins Human genes 0.000 claims description 4
- 108091022623 Formins Proteins 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011301 petroleum pitch Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002699 waste material Substances 0.000 claims description 2
- 239000011300 coal pitch Substances 0.000 claims 1
- 239000011280 coal tar Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 28
- 239000012298 atmosphere Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Analytical Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法及应用。所述的石墨炔掺杂磁性多孔炭由有机无机复合物经炭化或炭化‑活化制备，包括如下步骤：将重质有机物、石墨炔和混有无水金属氯化物的抑石墨化剂加入分散剂中，在一定条件处理后，经过滤，干燥后得到有机无机复合物；有机无机复合物在惰性气氛下炭化得到可磁分离的多孔炭材料或者在活化剂存在下进行活化得到可磁分离的高比表多孔炭材料。本发明优点在于重质有机物通过简单复合后热处理即可得到可磁分离石墨炔掺杂多孔炭，石墨炔的加入使得金属分布更均匀以及孔隙更发达，所得多孔炭在使用后可以通过外磁场进行分离并回收。
Description
技术领域
本发明属于材料技术领域，具体涉及一种利用重质有机物与石墨炔和无机物复合、炭化或炭化-活化制备磁性多孔炭的方法。
背景技术
重质有机物富含芳烃结构单元，是一种富碳的混合物，其高附加值利用一直是业界关注的研究方向。在众多的高附加值产品中，多孔炭在气态污染物、液态污染物处理以及催化剂载体方面拥有良好的表现，但粉状活性炭在使用过程中再生以及难分离等问题是制约其应用的瓶颈。通过在吸附材料上负载磁纳米物质以改善材料的吸附性能及通过其磁分离特性与反应物分离是解决这一问题的途径之一，常用的磁性多孔碳的合成方法包括化学共沉淀法、热解法、溶剂热合成法和微乳液法。中国专利CN101497028A公开了一种热解法制备磁性活性炭的方法，将煤质原料、磁性添加剂、粘结剂和表面活性剂充分混合成混合物、加压成型以及干燥后，经过热处理和活化制成磁性活性炭，制得的磁性活性炭最高比表面积可达953.1m2/g，总孔容为1.28cm3/g。中国专利CN102078797A公开了一种改性磁性催化剂的制备方法及其应用，采用大表面积的活性炭，利用溶剂热合成法制得具有磁性的活性炭，然后对磁性活性炭进行载硫或载溴改性，制得的改性磁性活性炭可用于烟气脱汞，当比表面积为548.3m2/g时，磁力为39J/(T kg)。但上述方法获得的磁性活性炭磁性颗粒在炭基体上分散不均匀且容易脱落，同时这些方法存在制备条件苛刻、工艺流程较长、成本较高以及孔隙不发达等问题。
石墨炔(graphdiyne，GDY)，是由sp和sp2杂化形成的一种新型碳的同素异形体，它是由1,3-二炔键将苯环共轭连接形成二维平面网络结构的全碳分子，具有丰富的碳化学键，大的共轭体系、宽面间距、优良的化学和热稳定性等，是继富勒烯、碳纳米管、石墨烯之后，一种新的全碳二维平面结构材料。石墨炔中的碳碳三键具有良好的化学活性，易吸附氢，氟，氧等原子，这为制备掺杂的碳材料提供了良好的环境。
因此，针对于现有技术，本发明利用石墨炔特殊结构带来的诸多优异性质，提出一种操作简单、快速制备一种磁性粒子均匀分散在多孔碳体相的磁性多孔炭材料的方法。
发明内容
本发明的目的是提供了一种磁性颗粒均匀分布的石墨炔掺杂磁性多孔炭或磁性颗粒均匀分布的石墨炔掺杂高比表磁性多孔炭的制备方法及其应用。
本发明目的是通过以下方式实现：
一种石墨炔掺杂磁性多孔炭材料的制备方法，，其主要包括以下步骤：
将重质有机物、石墨炔和混有无水金属氯化物的抑石墨化剂加入分散剂中，反应完成后，经过滤，干燥后得到有机无机复合物。有机无机复合物在惰性气体存在条件下经热处理后得到磁性颗粒均匀分布的石墨炔掺杂磁性多孔炭；或者有机无机复合物在气态活化剂存在条件下经活化处理后得到磁性颗粒均匀分布的石墨炔掺杂的高比表磁性多孔炭。
进一步的，所述的重质有机物选自废聚苯乙烯、煤焦油、煤沥青、石油沥青、煤直接液化残渣或煤液化沥青，较优的为煤液化沥青。
进一步的，所述的石墨炔选自石墨炔(GDY)、α-石墨炔(α-GY)、β-石墨炔(β-GY)、γ-石墨炔(γ-GY)、δ-石墨炔(δ-GY)、6,6,12-石墨炔(6,6,12-GY)中的一种或两种以上。
进一步的，所述分散剂为二硫化碳、硝基苯、1,2-二氯乙烷、二氯甲烷、氯仿或四氯化碳中的一种或两种以上，较优的为二硫化碳。
进一步的，所述抑石墨化剂为甲缩醛、氯仿、四氯化碳或1,2-二氯乙烷中的一种或两种以上，较优的为甲缩醛。
进一步的，所述无水金属氯化物为无水三氯化铁、无水氯化钴或无水氯化镍中的一种或两种以上，较优的为无水三氯化铁。
进一步的，所述重质有机物与抑石墨化剂的质量比为5:1～40。
进一步的，所述重质有机物与石墨炔的质量比为5:1～40。
进一步的，所述抑石墨化剂与无水金属氯化物的质量比为5:1～40。
进一步的，所述重质有机物与分散剂的质量比为5:1～200。
进一步的，所述反应温度为20～300℃，反应时间为0.1～48h。
进一步的，所述干燥条件为：60～150℃下干燥2～24h。
进一步的，所述惰性气体为氮气、氩气或氦气中的一种或两种以上；所述气态活化剂为水蒸气、二氧化碳、氧气、空气中的一种或两种以上混合，较优的为二氧化碳。
进一步的，所述惰性气体流量为20～2000mL min-1。
进一步的，所述热处理温度为400～1600℃，升温速率为1～20℃min-1。
进一步的，所述炭化时间为0.2～20h。
进一步的，所述气态活化剂流量为40～2000mL min-1。
进一步的，所述活化条件为：活化温度为500～1300℃，升温速率为1～20℃min-1，活化时间为0.1～20h。
本发明另一方面在于提供由上述方法制备得到磁性颗粒均匀分布的磁性多孔炭材料，所述的磁性多孔炭材料具有高比表面积，比表面积大于300m2/g。
本发明另一方面的在于提供上述多孔炭材料的应用。
进一步的，上述多孔炭材料可应用于吸附材料、超级电容器电极材料和催化剂载体等领域。
本发明的有益效果：本发明提供了一种以重质有机物为原料，与石墨炔充分混合后，在无水金属氯化物的作用下与抑石墨化剂作用来制备有机无机复合物，经过炭化制备磁性多孔炭材料或经过炭化-活化制备高比表磁性多孔炭材料。该制备方法耗时短，操作简单，生产成本低，收率高，制备得到的有机无机复合物具有良好的热稳定性；制备得到的磁性多孔炭材料可以进行磁分离以及具有良好的吸附性能。
附图说明
为了更清楚地说明本发明实施例，下面将对实施例涉及的附图进行简单地介绍。
图1为实施例6制得的磁性多孔炭材料的XRD谱图。
图2为实施例6制得的磁性多孔炭材料的扫描电镜和元素分布图，(a)为扫描电镜，(b)为元素分布图。
图3为实施例6制得的磁性多孔炭材料的磁滞回线图。
图4为实施例6制得的r-CLA-24h-900-T-2h和r-CLA-24h-N-900-T-2h磁性多孔炭材料的氮气吸-脱附曲线。
图5为应用例1的r-CLA-24h-900-T-2h和r-CLA-24h-N-900-T-2h碘蒸气吸附曲线。
图6为实施例6制得的磁性多孔炭材料的在5mL 0.1000mol/L的(1/2I2)溶液中吸附前后对比图。
具体实施方式
下面结合实施例对本发明进行详细的说明，但本发明的实施方式不限于此，显而易见地，下面描述中的实施例仅是本发明的部分实施例，对于本领域技术人员来讲，在不付出创造性劳动性的前提下，获得其他的类似的实施例均落入本发明的保护范围。
实施例1
在室温下，将3g煤液化沥青重质有机组分溶解在100mL的1,2-二氯乙烷中，然后加入1g石墨炔(GDY)，最后加入3g甲缩醛和13g无水三氯化铁形成均匀的混合物置于250mL三口烧瓶中，在80℃、氮气气氛下搅拌反应0.5h、1h、2h、4h、16h和24h，过滤后得到固体产物A；在120℃真空烘箱中干燥12h，得到产物B分别标记为r-CLA-0.5h、r-CLA-1h、r-CLA-2h、r-CLA-4h、r-CLA-16h、r-CLA-24h以及未加石墨炔样品r-CLA-24h-N。
实施例2
在室温下，将3g煤液化沥青重质有机组分溶解在100mL的1,2-二氯乙烷中，然后加入1g石墨炔(GDY)，最后加入3g甲缩醛和13g无水氯化钴形成均匀的混合物置于250mL三口烧瓶中，在80℃、氮气气氛下搅拌反应24h，过滤后得到固体产物C；在120℃真空烘箱中干燥12h，得到产物D标记为r-CLA-Co-24h。
实施例3
在室温下，将3g煤液化沥青重质有机组分溶解在100mL的二硫化碳，然后加入1g石墨炔(GDY)，最后加入3g甲缩醛和13g无水氯化镍形成均匀的混合物置于250mL三口烧瓶中，在80℃、氮气气氛下搅拌反应24h，过滤后得到固体产物E；在120℃真空烘箱中干燥12h，得到产物F标记为r-CLA-Ni-24h。
实施例4
在室温下，将3g煤液化沥青重质有机组分溶解在100mL的二硫化碳，然后加入1g石墨炔(GDY)，最后加入3g甲缩醛与6.5g无水三氯化铁和6.5g无水氯化镍形成均匀的混合物置于250mL三口烧瓶中，在80℃、氮气气氛下搅拌反应24h，过滤后得到固体产物G；在120℃真空烘箱中干燥12h，得到产物H标记为r-CLA-Fe-Ni-24h。
实施例5
在室温下，将3g煤液化沥青重质有机组分溶解在100mL的1,2-二氯乙烷中，然后加入1g石墨炔(GDY)，最后加入3g甲缩醛与6.5g无水三氯化铁和6.5g无水氯化钴形成均匀的混合物置于250mL三口烧瓶中，在80℃、氮气气氛下搅拌反应24h，过滤后得到固体产物I；在120℃真空烘箱中干燥12h，得到产物J标记为r-CLA-Fe-Co-24h。
实施例6
取交联反应24h后的产物r-CLA-24h或未掺杂石墨炔样品r-CLA-24h-N 1.0g，将其置于管式炉中，在60mL min-1的Ar气氛下，以10℃min-1的升温速率升温至900℃，保持2h后自然降温。即得到磁性颗粒均匀分布的石墨炔掺杂磁性多孔炭，标记为r-CLA-24h-900-T-2h和r-CLA-24h-N-900-T-2h，磁性多孔炭材料r-CLA-24h-900-T-2h的XRD谱图如附图1所示，可以看出磁性多孔炭材料是由碳和多种晶相的Fe2O3组成。由附图2扫描电镜图和元素分布图可知，石墨炔掺杂磁性颗粒分布均匀。该石墨炔掺杂磁性多孔炭材料的磁滞回线如附图3所示。磁性多孔炭材料r-CLA-24h-900-T-2h和r-CLA-24h-N-900-T-2h的氮气吸脱附曲线如附图4所示，可知石墨炔掺杂后使得材料的孔隙变得更加丰富。由附图6可知，磁性多孔炭材料r-CLA-24h-900-T-2h可以对碘离子进行吸附并且可进行磁分离。
表1、实施例6制得的磁性多孔炭材料的孔结构参数
实施例7
取交联反应24h后的产物r-CLA-24h 1.0g，将其置于管式炉中，在60mL min-1的Ar气氛下，以10℃min-1的升温速率升温至900℃，切换流速为80mL min-1的CO2，活化4h，完成后，切换为60mL min-1的Ar气氛，冷却至室温，即得到磁性颗粒均匀分布的石墨炔掺杂高比表磁性多孔炭材料，标记为r-CLA-24h-900-4h。
实施例8
取实施例2～5交联反应后的产物1.0g，将其置于管式炉中，在60mL min-1的Ar气氛下，以10℃min-1的升温速率升温至900℃，保持2h后自然降温。即得到磁性颗粒均匀分布的石墨炔掺杂磁性多孔炭材料。
实施例9
取实施例2～5交联反应后的产物1.0g，将其置于管式炉中，在60mL min-1的Ar气氛下，以10℃min-1的升温速率升温至900℃，切换流速为80mL min-1的CO2，依次活化4h，完成后，切换为60mL min-1的Ar气氛，冷却至室温，即得到磁性颗粒均匀分布的石墨炔掺杂高比表磁性多孔炭材料。
应用例1
将实施例6的样品进行碘蒸气吸附实验；其方法为将过量的碘单质放入干燥器中，取100mg样品放于20ml样品瓶底部，样品瓶开盖放入干燥器中，盖紧干燥器，并将其放入75℃烘箱中，不同时间间隔内，最长40小时后从烘箱中取出，冷却到室温，根据重量法测定样品吸附碘蒸气的含量。在测试过程中，放入一个同规格的空样品瓶作为参考。计算公式如下：Q＝(m2-m1-M2+M1)/m1，其中Q(mg/g)为碘的吸附量，m1(mg)和m2(mg)分别为样品吸附碘之前和之后的重量，M1(mg)和M2(mg)为对应参考瓶质量。
Claims (10)
1.一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，包括以下步骤：将重质有机物、石墨炔和混有无水金属氯化物的抑石墨化剂加入分散剂中，反应完成后，经过滤，干燥后得到有机无机复合物；有机无机复合物在惰性气体存在条件下经热处理后得到磁性颗粒均匀分布的石墨炔掺杂磁性多孔炭；或者有机无机复合物在气态活化剂存在条件下经活化处理后得到磁性颗粒均匀分布的石墨炔掺杂的高比表磁性多孔炭；
所述分散剂为二硫化碳、硝基苯、1,2-二氯乙烷、二氯甲烷、氯仿或四氯化碳中的一种或两种以上；所述抑石墨化剂为甲缩醛。
2.根据权利要求1所述的一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，所述的重质有机物选自废聚苯乙烯、煤焦油、煤沥青、石油沥青、煤直接液化残渣；所述的石墨炔选自α-石墨炔、β-石墨炔、γ-石墨炔、δ-石墨炔、6,6,12-石墨炔中的一种或两种以上；所述无水金属氯化物为无水三氯化铁、无水氯化钴或无水氯化镍中的一种或两种以上。
3.根据权利要求1所述的一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，所述重质有机物与抑石墨化剂的质量比为5:1～40；所述重质有机物与石墨炔的质量比为5:1～40；所述抑石墨化剂与无水金属氯化物的质量比为5:1～40；所述重质有机物与分散剂的质量比为5:1～200。
4.根据权利要求1所述的一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，所述反应温度为20～300℃，反应时间为0.1～48h；所述干燥条件为：60～150℃下干燥2～24h。
5.根据权利要求1所述的一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，所述惰性气体为氮气、氩气或氦气中的一种或两种以上。
6.根据权利要求1所述的一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，所述惰性气体流量为20～2000mL min-1；所述热处理温度为400～1600℃，升温速率为1～20℃min-1；所述热处理时间为0.2～20h。
7.根据权利要求1所述的一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，所述气态活化剂为水蒸气、二氧化碳、氧气、空气中的一种或两种以上混合。
8.根据权利要求1所述的一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法，其特征在于，所述气态活化剂流量为40～2000mL min-1；所述活化条件为：活化温度为500～1300℃，升温速率为1～20℃min-1，活化时间为0.1～20h。
9.权利要求1-8任一所述的制备方法制得的磁性多孔炭。
10.一种如权利要求9所述的磁性多孔炭的应用，所述磁性多孔炭材料应用于吸附材料、超级电容器电极材料和催化剂载体领域。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310034366.XA CN116216713B (zh) | 2023-01-10 | 2023-01-10 | 一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法及应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310034366.XA CN116216713B (zh) | 2023-01-10 | 2023-01-10 | 一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法及应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116216713A CN116216713A (zh) | 2023-06-06 |
| CN116216713B true CN116216713B (zh) | 2024-06-18 |
Family
ID=86581740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310034366.XA Active CN116216713B (zh) | 2023-01-10 | 2023-01-10 | 一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法及应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116216713B (zh) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407204A (zh) * | 2019-09-04 | 2019-11-05 | 内蒙古奥原新材料有限公司 | 一种焦炭低温石墨化的制备方法及用途 |
-
2023
- 2023-01-10 CN CN202310034366.XA patent/CN116216713B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110407204A (zh) * | 2019-09-04 | 2019-11-05 | 内蒙古奥原新材料有限公司 | 一种焦炭低温石墨化的制备方法及用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116216713A (zh) | 2023-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kang et al. | Hydrogen adsorption on nitrogen-doped carbon xerogels | |
| Liang et al. | Synthesis of Sargassum char-supported Ni-Fe nanoparticles and its application in tar cracking during biomass pyrolysis | |
| Mei et al. | N-doped activated carbon from used dyeing wastewater adsorbent as a metal-free catalyst for acetylene hydrochlorination | |
| Perez-Cabero et al. | Characterization of carbon nanotubes and carbon nanofibers prepared by catalytic decomposition of acetylene in a fluidized bed reactor | |
| Ghosh et al. | Green synthesis of transition metal nanocrystals encapsulated into nitrogen-doped carbon nanotubes for efficient carbon dioxide capture | |
| Liu et al. | One‐Pot Synthesis of a Nitrogen‐Doped Carbon Composite by Electrospinning as a Metal‐Free Catalyst for Oxidation of H2S to Sulfur | |
| Bai et al. | In situ preparation of nitrogen-rich and functional ultramicroporous carbonaceous COFs by “segregated” microwave irradiation | |
| Dong et al. | Ultramicroporous carbon granules with narrow pore size distribution for efficient CH4 separation from coal‐bed gases | |
| CN106564868A (zh) | 一种氮掺杂多孔碳材料的制备方法 | |
| Zhang et al. | Hollow BCN microrods with hierarchical multichannel structure as a multifunctional material: Synergistic effects of structural topology and composition | |
| Habimana et al. | Synthesis of Cu-BTC/Mt composites porous materials and their performance in adsorptive desulfurization process | |
| EP3085666A1 (en) | Method for repairing reduced graphene oxide | |
| Zhang et al. | N-doped porous carbocatalyst engineering via modulating the crystalline size of ZIF-8 for continuous H2S selective oxidation | |
| Gao et al. | Enhanced carbon dioxide adsorption performance and kinetic study of K and Al co-doped Li4SiO4 | |
| Wang et al. | Catalytic toluene steam reforming using Ni supported catalyst from pyrolytic peat | |
| Lu et al. | Nitrogen-modified metal-free carbon materials for acetylene hydrochlorination | |
| Wang et al. | Steam reforming of biomass tar model compound over two waste char-based Ni catalysts for syngas production | |
| Wang et al. | Conversion of coal into N-doped porous carbon for high-performance SO 2 adsorption | |
| Lei et al. | Facile template-free synthesis of 3D cluster-like nitrogen-doped mesoporous carbon as metal-free catalyst for selective oxidation of H2S | |
| Yuwen et al. | Mechanism of microwave-assisted iron-based catalyst pyrolysis of discarded COVID-19 masks | |
| Gou et al. | Densification and pelletization of porous boron nitride fibers for effective CO2 adsorption | |
| CN103846101A (zh) | 一种C-SiC催化剂及其制备和应用 | |
| Zhao et al. | ZIF-derived hierarchical pore carbons as high-performance catalyst for methane decomposition | |
| Tehrani et al. | Seed-mediated synthesis of a modified micro-mesoporous MIL-101 (Cr) for improved benzene and toluene adsorption at room conditions | |
| CN116216713B (zh) | 一种通过石墨炔掺杂制备磁性颗粒均匀分布的磁性多孔炭的方法及应用 |
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 |