CN115074092A - 含氮含硫碳纳米管及其制备方法和应用 - Google Patents
含氮含硫碳纳米管及其制备方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 105
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 105
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000011593 sulfur Substances 0.000 title claims abstract description 77
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 109
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 91
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 55
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 23
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000009471 action Effects 0.000 claims abstract description 9
- 238000005336 cracking Methods 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 239000012752 auxiliary agent Substances 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- 239000011733 molybdenum Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003990 capacitor Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- -1 nitrogen doping Chemical compound 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种含氮含硫碳纳米管及其制备方法和应用。其中制备方法,通过以含硫氮的烃类混合物为碳源,在纳米金属催化剂的作用下进行裂解,从而制备得到含氮含硫碳纳米管。本发明通过以含硫氮的烃类混合物为碳源,在纳米金属催化剂的作用下进行裂解,实现了原位掺杂制备含氮含硫碳纳米管,实现了含氮含硫碳纳米管的高效制备。
Description
技术领域
本发明涉及碳纳米管制备技术领域,特别是涉及一种含氮含硫碳纳米管及其制备方法和应用。
背景技术
碳纳米管是一种新兴的低维纳米材料,主要由SP2杂化碳卷曲而成,具有化学稳定性高,强度高,比表面积大,导电性与半导体性可调,从而具有多种应用前景。
碳纳米管可由化学气相沉积法制备,该方法主要是采用催化剂高温下裂解碳源而得,其中,碳源通常为烃类、含碳氧化物(如CO)、塑料等,催化剂一般采用由过渡金属Fe、Cu、Ni、Co、Cr等构成的普通催化剂。但目前上述碳纳米管的制备存在以下问题:1)制备反应常常生成甲烷,氢气等副产物,基于碳源质量的碳纳米管收率大部分限制在50%~70%。2)目前碳纳米管主要采用碳数低8的有机物为原料,缺少采用碳源质量高于80%的原料的制备方法。3)制备规模越大,需要处理的低价值尾气就越大,导致经济性不佳。
另一方面现有技术中对于碳纳米管的掺杂也多有报道,比如掺氮,掺硼,掺硫,掺磷等,通过掺杂来改变碳纳米管的各种性能。但是,目前的掺杂方法,大多是先制备碳纳米管,然后进行专门掺杂。即只能采用两步法制备,其主要原因是催化剂不能耐氮或硫,易失活,因而采用间接方法;而这种间接方法,会造成资源浪费程度高,导致制备成本较高。
发明内容
基于上述问题,本发明的一个实施方式中的目的在于提供一种含氮含硫碳纳米管及其制备方法和应用,以实现碳纳米管的原位掺杂,实现含氮含硫碳纳米管高效制备。本发明的上述目的可以通过以下技术方案实现的:
根据本发明的一个方面,本发明提供的一种含氮含硫碳纳米管的制备方法,是通过以含硫氮的烃类混合物为碳源,在纳米金属催化剂的作用下进行裂解,得到所述含氮含硫碳纳米管。
可选地,所述烃类混合物,其硫含量为0.02%~4%,氮含量为0.02%~5%。可选地,所述烃类混合物富含芳烃和/或环烷烃,其中,芳烃与环烷烃总含量为40%~80%。可选地,所述烃类混合物为含硫氮的C10-C20的富含芳烃和/或环烷烃的烃类混合物。
可选地,所述纳米金属催化剂包括主活性相金属、助剂和载体,其中,所述主活性相金属和助剂形成的复合纳米颗粒镶嵌于所述载体的孔中。
可选地,所述复合纳米颗粒的尺寸为0.1nm~10nm。
可选地,所述复合纳米颗粒中有1/4~1/3的体积镶嵌于所述载体的孔中。
可选地,所述复合纳米颗粒与载体的结合力为1000N~5000N。
可选地,所述纳米金属催化剂,按照质量百分比计,主活性相金属为5%~20%,所述助剂为3%~10%,其余为载体。
可选地,所述主活性相金属为铁、镍、钴中的一种或多种。所述助剂为钼、铜、锰、锌、钨中的一种或多种。所述载体为氧化铝、氧化硅、氧化镁、氧化锆、氧化钙中的一种或多种。
可选地,裂解时,温度为700℃~950℃,制备压力为0.01MPa~2MPa,基于碳源的质量空速为0.01h-1~2h-1,裂解时间为0.5h~240h。进一步地,烃类碳源分压为10%~100%,其余为载体。
可选地,所述含氮含硫碳纳米管基于碳源的收率为90%~95%。
根据本发明的另一个方面,本发明提供的一种含氮含硫碳纳米管,采用所述的含氮含硫碳纳米管的制备方法制备得到。其中,所述含氮含硫碳纳米管中,碳含量为93%~99.95%,硫含量为0.02%~4%,氮含量为0.03%~3%。进一步地,所述含氮含硫碳纳米管中,碳层晶面内长度为17nm~100nm,碳纳米管的直径为0.5nm~100nm。
根据本发明的还一个方面,本发明提供的一种含氮含硫碳纳米管在导电材料、导热材料或吸附材料中的应用,所述含氮含硫碳纳米管采用所述的含氮含硫碳纳米管的制备方法制备得到。可选地,所述含氮含硫碳纳米管作为超级电容器的电极材料、高分子的导电增强与导热材料、陶瓷材料的导电增强与导热材料、锂离子电池中的导电剂、或有机物的吸附剂。
有益效果:本发明以含硫氮的烃类混合物为碳源,在纳米金属催化剂的作用下进行裂解,实现了原位掺杂制备含氮含硫碳纳米管,实现了含氮含硫碳纳米管的高效制备。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的,决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明提供的一种含氮含硫碳纳米管的制备方法,是以含硫氮的烃类混合物为碳源,在纳米金属催化剂的作用下进行裂解,从而实现了原位掺杂且高效的含氮含硫碳纳米管的制备。
本发明中,采用含硫氮的烃类混合物为碳源,经纳米金属催化剂作用下裂解,实现了碳纳米管氮硫原位掺杂。优选地,采用含硫氮的富含芳烃和/或环烷烃的烃类混合物为碳源,芳烃与环烷烃总含量为40%~80%,采用该碳源实现了氮硫原位掺杂,并且提高了碳纳米管基于碳源的收率,还使碳纳米管生长时,微观上碳的自组装更加快速与结构完美,进而提高了碳纳米管性能。进一步地优选地,采用含硫氮的C10-C20的富含芳烃和/或环烷烃的烃类混合物为碳源,例如柴油、石脑油等,传统制备碳纳米管的原料通常为小分子有机物(如丙烯、乙烯、乙醇等),本发明的原料常是制备这些小分子的原料,相比目前先制备小分子再将小分子作为碳源来制备碳纳米管的繁琐程序,本发明直接采用C10-C20原料作为碳源,简化制备过程,降低了成本,提供可一种碳数C10-C20制备碳纳米管制备方法。
本发明中,碳源在纳米金属催化剂作用下裂解,实现了含氮含硫碳纳米管的原位且高效制备。进一步地,所述纳米金属催化剂包括主活性相金属、助剂和载体;其中,所述主活性相金属和助剂形成的复合纳米颗粒镶嵌于所述载体的孔中。更进一步地,所述复合纳米颗粒的尺寸为0.1nm~10nm。所述复合纳米颗粒中有1/4~1/3的体积镶嵌于所述载体的孔中。所述复合纳米颗粒与载体的结合力为1000N~5000N。优选地,所述纳米金属催化剂,按照质量百分比计,主活性相金属为5%~20%,所述助剂为3%~10%,其余为载体。其中,所述主活性相金属为铁、镍、钴中的一种或多种;所述助剂为钼、铜、锰、锌、钨中的一种或多种;所述载体为氧化铝、氧化硅、氧化镁、氧化锆、氧化钙中的一种或多种。采用上述的纳米金属催化剂,利用高芳烃含量或高环烷烃含量的烃类原料,如柴油或石脑油,直接制备基于碳源的高收率的碳纳米管;同时,又能够耐受这些原来常含有硫氮等有机杂质,从而一起原位、高效地实现含氮含硫碳纳米管的制备。
本发明中,所述碳源是在反应器中的纳米金属催化剂的作用下,经高温裂解,得到所述含氮含硫碳纳米管。其中,使用的反应器包括固定床和流化床等。裂解时,温度为700℃~950℃,制备压力为0.01MPa~2MPa,基于碳源的质量空速为0.01h-1~2h-1,裂解时间为0.5h~240h;其中,烃类分压为10%~100%,其余为载体,所述载体可以为氮气、氩气、氦气等。采用上述制备条件可以更高效地制备含氮含硫碳纳米管,所得到的碳纳米管具有碳基收率高,基于碳源的收率为90%~95%,掺氮掺硫便捷,导电性与半导体性可调,微观碳层排列整齐的优点。
本发明提供的所述含氮含硫碳纳米管中,其碳含量为93%~99.95%,硫含量为0.02%~4%,氮含量为0.03%~3%。进一步地,所述含氮含硫碳纳米管中,碳纳米管的直径为0.5nm~100nm;碳层晶面内长度(carbon in plane length)17nm~100nm(传统碳层晶面内长度仅为6nm~13nm),粉体状产品的导电性增加2~4倍。氮硫的掺杂调节了碳层的能带结构,提高了导电性,使碳纳米管表面具有亲水和疏水特性,从而在各类吸附或脱附及反应中具有很大的调变可能,具有了显著的反应扩散优势,具有更广更高应用价值。
本发明所述含氮含硫碳纳米管可以应用在导电、导热或吸附等材料中,且具有优异性能。例如,可以作为超级电容器的电极材料、高分子的导电增强与导热材料、陶瓷材料的导电增强与导热材料、锂离子电池中的导电剂、或有机物的吸附剂。
下面结合具体实施例对本申请的实施方式做更进一步说明:
实施例1
纳米金属催化剂:其主活性相为20%铁,助剂为10%钼,其余70%为载体(载体中含有质量分数为30%氧化铝),铁及钼的复合纳米颗粒的尺寸为5nm;该复合纳米颗粒有28%的体积镶嵌于载体的孔中;纳米颗粒与载体的结合力在3000N。碳源:富含芳环的柴油,芳烃含量在60%,硫含量为0.2%,氮含量为0.2%。
将纳米金属催化剂放置于固定床中,通入载气(氩气),加热到950℃,通入碳源,烃类的分压为10%,在0.01MPa绝对压力下,基于碳源的空速为0.01h-1,碳源在催化剂上裂解0.5小时。
所得的碳纳米管,碳含量为99.5%,硫含量为0.2%,氮含量为0.3%。碳层晶面内(carbon in plane length)长度为100nm,碳纳米管的直径为0.5nm。该实施例,基于烃类原料的碳纳米管收率为90%。
该实施例制备得到的碳纳米管的用途为超级电容器的电极材料。
实施例2
纳米金属催化剂:主活性相为15%镍,助剂为5%钨与2%锌,其余为氧化硅载体,铁及钼的复合纳米颗粒的尺寸为10nm;该复合纳米颗粒有1/3的体积镶嵌于载体的孔中;纳米颗粒与载体的结合力在1000N。碳源:富含芳环的C10-C20烃,芳烃含量在80%,硫含量为4%,氮含量为5%。
将纳米金属催化剂放置于固定床中,通入载气(氩气),加热到750℃,通入碳源,烃类的分压为30%,在0.2MPa绝对压力下,基于碳源的空速为0.05h-1,碳源在催化剂上裂解240小时。
所得的碳纳米管中,碳含量为95%,硫含量为4%,氮含量为1%。碳层晶面内长度为17nm,碳纳米管的直径为100nm。该实施例,基于烃类原料的碳纳米管收率为92.5%。
该实施例制备得到的碳纳米管的用途为高分子复合材料中的导电材料或有机物的吸附剂。
实施例3
纳米金属催化剂:主活性相为15%铁,助剂为5%钼,其余为载体(含20%氧化镁与60%氧化钙);铁及钼的复合纳米颗粒的尺寸为1nm;该复合纳米颗粒有1/4的体积镶嵌于载体的孔中;纳米颗粒与载体的结合力在5000N。碳源:富含芳环的C10-C20烃,芳烃含量在50%,硫含量为0.4%,氮含量为0.5%。
将纳米金属催化剂放置于流化床中,通入载气(氮气),加热到850℃,通入碳源,烃类的分压为70%,在2MPa绝对压力下,基于碳源的空速为2h-1,碳源在催化剂上裂解10.5小时。
所得的碳纳米管中,碳含量为99.95%,硫含量为0.02%,氮含量为0.03%。碳层晶面内长度为40nm,碳纳米管的直径为2.5nm。该实施例,基于烃类原料的碳纳米管收率为91%。
该实施例制备得到的碳纳米管的用途为超级电容器的电极材料或锂电池的导电剂。
实施例4
纳米金属催化剂:主活性相为2%铁和8%Co,助剂为5%钼和2%Mn,其余为载体(含50%氧化锆和33%氧化钙),铁及钼的复合纳米颗粒的尺寸为2-4nm;该复合纳米颗粒有28%的体积镶嵌于载体的孔中;纳米颗粒与载体的结合力在2500N。碳源:富含环烷烃的柴油,环烷烃含量在40%,硫含量为4%,氮含量为3.5%。
将纳米金属催化剂放置于固定床中,通入载气(氦气),加热到800℃,通入碳源,烃类的分压为80%,在1MPa绝对压力下,基于碳源的空速为2h-1,碳源在催化剂上裂解24小时。
所得的碳纳米管中,碳含量为93%,硫含量为4%,氮含量为3%;碳层晶面内长度为50nm,碳纳米管的直径为5nm。该实施例,基于烃类原料的碳纳米管收率为90%。
该实施例制备得到的碳纳米管的用途为超级电容器的电极材料,高分子或陶瓷材料的导电增强与导热材料。
实施例5
纳米金属催化剂:主活性相为2%钴,3%Ni,助剂为1.5%钼,1.5%W,其余为载体(含46%氧化镁和46%氧化硅),钴及钼的复合纳米颗粒的尺寸为0.1nm;该复合纳米颗粒有30%的体积镶嵌于载体的孔中;纳米颗粒与载体的结合力在2000N。碳源:富含芳烃的C10-C20,芳烃含量在80%,硫含量为2.4%,氮含量为5%。
将纳米金属催化剂放置于流化床中,加热到700℃,通入碳源,烃类的分压为100%,在1.2MPa绝对压力下,基于碳源的空速为1.2h-1,碳源在催化剂上裂解150小时。
所得的碳纳米管中,碳含量为93%,硫含量为2%,氮含量为5%。碳层晶面内长度为70nm,碳纳米管的直径为25nm。该实施例,基于烃类原料的碳纳米管收率为93%。
该实施例制备得到的碳纳米管的用途为超级电容器的电极材料,高分子或陶瓷材料的导电增强与导热材料,或有机物的吸附材料。
实施例6
纳米金属催化剂:主活性含相为1.5%钴,1.5%Fe和2%Ni,助剂为1.5%钼及8.5%Cu,其余为载体(含85%氧化镁)。钴、铁、镍及钼、铜的复合纳米颗粒的尺寸为6-12nm;该复合纳米颗粒有32%的体积镶嵌于载体的孔中;纳米颗粒与载体的结合力在2000N。碳源:富含环烷烃的C10-C20,环烷烃含量在80%,硫含量为2.4%,氮含量为5%。
将纳米金属催化剂放置于流化床中,加热到700℃,通入碳源,烃类的分压为100%,在1.2MPa绝对压力下,基于碳源的空速为1.2h-1,碳源在催化剂上裂解150小时。
所得的碳纳米管中,碳含量为93%,硫含量为2%,氮含量为5%。碳层晶面内长度为70nm;碳纳米管的直径为25nm。该实施例,基于烃类原料的碳纳米管收率为95%。
该实施例制备得到的碳纳米管的用途为超级电容器的电极材料,高分子或陶瓷材料的导电增强与导热材料,有机物的吸附材料。
本发明上述实施例中,与现有技术相比还具有如下优点和有益效果:
1)相比间接掺氮/掺硫的间接方法,本发明采用含硫氮的烃类混合物为碳源,例如柴油或烃类混合物等含硫氮有机物杂质的原料,克服了催化剂不耐氮和硫的缺陷,直接实现了碳纳米管的原位掺杂,原料便宜,制备步骤少,比传统两步法掺杂,成本降低50%~80%。
2)本发明采用了富含芳烃和/或环烷烃的烃类混合物为碳源,直接制备高收率的碳纳米管(基于碳源),其收率达到了90%及以上,比传统使用小分子碳源时的碳纳米管收率提高了20%~35%,本发明制备过程中副产物少,处理简单,碳纳米管的制备成本降低约50%。
3)本发明采用富含芳烃和/或环烷烃的烃类混合物为碳源,使碳纳米管生长时,微观上碳的自组装更加快速与结构完美,提高了碳纳米管性能;例如,使碳层内晶内长度(carbon in plane length)由传统的6nm~13nm增加到17nm~100nm,使产品(粉体状)的导电性增加2~4倍,在用于复合导电场景时,可使碳纳米管的用量降低20%~30%,使复合物的成本降低30%~40%。
4)与目前使用的高纯度、小分子碳源(如丙烯、乙醇、乙烯)等相比,本发明的原料采用含硫氮的C10-C20的富含芳烃和/或环烷烃的烃类混合物,例如柴油、石脑油等,这些通常是制备上述小分子的原料,使得本发明制备过程简单,步骤少,原料更加便宜,可使制备成本降低10%~20%。采用上述原料既实现了氮硫原位掺杂,又提高了碳纳米管基于碳源的收率。
5)本发明得到的含氮含硫碳纳米管产品,同时具有亲油性与亲水性,具有更广的应用范围,且在吸附/脱附反应中具有显著的反应扩散优势,可使碳纳米管用量降低50%,使吸附剂或催化剂的成本降低50%~60%。
本发明的描述是为了示例和描述起见而给出的,而并不是无遗漏的或者将本发明限于所公开的形式。很多修改和变化对于本领域的普通技术人员而言是显然的。选择和描述实施例是为了更好说明本发明的原理和实际应用,并且使本领域的普通技术人员能够理解本发明从而设计适于特定用途的带有各种修改的各种实施例。
Claims (13)
1.一种含氮含硫碳纳米管的制备方法,其特征在于,以含硫氮的烃类混合物为碳源,在纳米金属催化剂的作用下进行裂解,得到所述含氮含硫碳纳米管。
2.根据权利要求1所述的含氮含硫碳纳米管的制备方法,其特征在于,所述烃类混合物富含芳烃和/或环烷烃,其中,芳烃与环烷烃总含量为40%~80%。
3.根据权利要求2所述的含氮含硫碳纳米管的制备方法,其特征在于,
所述烃类混合物为含硫氮的C10-C20的富含芳烃和/或环烷烃的烃类混合物;
所述烃类混合物,其硫含量为0.02%~4%,氮含量为0.02%~5%。
4.根据权利要求1所述的含氮含硫碳纳米管的制备方法,其特征在于,所述纳米金属催化剂包括主活性相金属、助剂和载体,其中,所述主活性相金属和助剂形成的复合纳米颗粒镶嵌于所述载体的孔中。
5.根据权利要求4所述的含氮含硫碳纳米管的制备方法,其特征在于,
所述复合纳米颗粒的尺寸为0.1nm~10nm;
所述复合纳米颗粒中有1/4~1/3的体积镶嵌于所述载体的孔中;
所述复合纳米颗粒与载体的结合力为1000N~5000N。
6.根据权利要求4所述的含氮含硫碳纳米管的制备方法,其特征在于,
所述纳米金属催化剂,按照质量百分比计,主活性相金属为5%~20%,所述助剂为3%~10%,其余为载体;
其中,所述主活性相金属为铁、镍、钴中的一种或多种;所述助剂为钼、铜、锰、锌、钨中的一种或多种;所述载体为氧化铝、氧化硅、氧化镁、氧化锆、氧化钙中的一种或多种。
7.根据权利要求1所述的含氮含硫碳纳米管的制备方法,其特征在于,裂解时,温度为700℃~950℃,制备压力为0.01MPa~2MPa,基于碳源的质量空速为0.01h-1~2h-1,裂解时间为0.5h~240h;其中,烃类分压为10%~100%,其余为载体。
8.根据权利要求1所述的含氮含硫碳纳米管的制备方法,其特征在于,所述含氮含硫碳纳米管,基于碳源的收率为90%~95%。
9.一种含氮含硫碳纳米管,其特征在于,采用权利要求1-8任一项所述的含氮含硫碳纳米管的制备方法制备得到。
10.根据权利要求9所述的一种含氮含硫碳纳米管,其特征在于,所述含氮含硫碳纳米管中,碳含量为93%~99.95%,硫含量为0.02%~4%,氮含量为0.03%~3%。
11.根据权利要求9所述的一种含氮含硫碳纳米管,其特征在于,所述含氮含硫碳纳米管中,碳层晶面内长度为17nm~100nm,碳纳米管的直径为0.5nm~100nm。
12.一种含氮含硫碳纳米管在导电材料、导热材料或吸附材料中的应用,其特征在于,所述含氮含硫碳纳米管采用权利要求1-8任一项所述的含氮含硫碳纳米管的制备方法制备得到。
13.根据权利要求12所述的含氮含硫碳纳米管在导电材料、导热材料或吸附材料中的应用,其特征在于,所述含氮含硫碳纳米管作为超级电容器的电极材料、高分子的导电增强与导热材料、陶瓷材料的导电增强与导热材料、锂离子电池中的导电剂、或有机物的吸附剂。
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