CN101905881B - 一种石墨化程度高的纳米碳材料制备方法 - Google Patents

一种石墨化程度高的纳米碳材料制备方法 Download PDF

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CN101905881B
CN101905881B CN 201010250457 CN201010250457A CN101905881B CN 101905881 B CN101905881 B CN 101905881B CN 201010250457 CN201010250457 CN 201010250457 CN 201010250457 A CN201010250457 A CN 201010250457A CN 101905881 B CN101905881 B CN 101905881B
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CN101905881A (zh
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高利珍
张卫珂
张敏
梁翼红
田晓峰
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Shanxi Dinuo Technology Co.,Ltd.
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WUXI CHENGXIN CARBON MATERIALS TECHNOLOGY Co Ltd
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Abstract

本发明专利公开了一种石墨化程度高的纳米碳材料制备方法，以天然气、煤层气、沼气、乙炔等烷烃气体为原料气，加入不同的催化剂在600～800℃温度和1～8bar的压力下，将含有碳氢化合物的原料气体通入催化裂解反应器进行催化裂解反应，制备出不同形貌的纳米碳材料，本发明利用甲烷在催化剂上裂解机理为：CH4可以在一定条件下发生如下裂解反应：CH4→C+2H2甲烷催化裂解，能耗低，通过改变反应条件，尤其是催化剂的结构和种类，这一反应可生产纳米碳材料，如优良结构的碳纳米管、碳纳米纤维和碳纳米颗粒，可以广泛应用于催化剂载体、储氢材料和增强材料，同时可以零排放制氢气。

Description

一种石墨化程度高的纳米碳材料制备方法
技术领域：
本发明涉及一种高石墨化碳材料的制备方法，特别是提供了一种低成本、批量化气相分解碳氢化合物生产一种形貌可控的石墨化程度高的纳米碳管、纳米碳球、纳米洋葱碳等纳米碳材料的制备方法。
技术背景：
高度石墨化的碳材料，如碳球、纳米碳管、碳纤维、洋葱碳等，由于其良好的电子、机械性能，化学惰性，生物相容性，正在被广泛地应用于工程、电子、化工、生物等领域。其中，石墨化的洋葱碳，在超电容、催化剂负载、药物缓释等方面有广阔的应用前景。而碳包裹的磁性金属离子(催化剂)由于石墨化外壳优异的物理化学性质，保护了其中活泼的磁性金属，在电磁、光学性质的研究以及核磁共振成像、磁性悬浮密封液等领域有着重要的应用。
迄今为止，科学家们探索了多种制备石墨化碳材料的方法，如化学气相沉积(CVD)、电弧放电、激光蒸发、溶剂热解等方法。但是大部分方法都需要昂贵的特殊设备，以及大量的能源输入，且不利于工业化批量生产。采用催化热解法制备一维纳米碳材料，一般采用碳氢化合物气体作为碳源，氢气、氩气或者氮气作为稀释气和载气。稀释气和载气的作用主要是夹带碳源进入反应，调节反应过程中碳氢比。在实际的应用中，为了获得较高质量一维纳米碳材料，过程的关键是要研发出高活性(甲烷有高的单程转化率)、高稳定性和高选择性的催化剂。
发明内容：
本发明针对现有技术的不足，提供了一种零排放、批量化制备石墨化程度高的纳米碳材料制备方法。
为实现以上目的，本发明专利采用的制作过程为：
一种石墨化程度高的纳米碳材料制备方法，以天然气、煤层气、沼气、乙炔等烷烃气体为原料气，加入不同的催化剂在600～800℃温度和1～8bar的压力下，将含有碳氢化合物的原料气体通入催化裂解反应器进行催化裂解反应，制备出不同形貌的纳米碳材料。
所述的催化剂为不同Mo、Ni(Fe，Co)和Mg含量的Mox-Ni(Fe，Co)y-MgOz固溶体催化剂、Ni/Y-型沸石结构催化剂、La2NiO4催化剂、Ni/MCM-41催化剂、Fe-Cr合金催化剂和LaNi0.9Co0.1O3催化剂。
所述的催化剂为不同Mo、Ni(Fe，Co)和Mg含量的Mox-Ni(Fe，Co)y-MgOz固溶体，则催化裂解后所得到的石墨化碳材料为单壁碳纳米管(SWCNT)。
所述的催化剂为La2NiO4，则催化裂解后所得到的碳材料为多壁碳纳米管(MWCNT)，所得多壁碳纳米管内径为15nm左右，壁层40曾左右。
所述的原料气中同时通入苯(体积分数为100ppm)，催化剂为Ni/MCM-41，催化裂解后所得到的碳材料为直径在500纳米左右的微米级圆盘碳(MCD)。
所述的催化剂为Fe-Cr合金催化剂，催化裂解后所得到的碳材料为纳米洋葱碳(CNO)，且该纳米洋葱碳碳层在50层左右，直径在100nm左右。
所述的催化剂为LaNi0.9Co0.1O3，催化裂解后所得到的碳材料为微米级碳纤维。
本发明利用甲烷在催化剂上裂解机理为：CH4可以在一定条件下发生如下裂解反应：CH4→C+2H2甲烷催化裂解，能耗低，通过改变反应条件，尤其是催化剂的结构和种类，这一反应可生产纳米碳材料，如优良结构的碳纳米管、碳纳米纤维和碳纳米颗粒，可以广泛应用于催化剂载体、储氢材料和增强材料，同时可以零排放制氢气。
具体实施方式：
本发明以天然气、煤层气、沼气等烷烃气体为原料气，在催化剂存在下，在600～800℃温度和1～8bar的压力下，将原料气体通入反应器进行催化裂解反应制备纳米碳材料，当所选用催化剂分别为不同Mo、Ni(Fe，Co)和Mg含量的Mox-Ni(Fe，Co)y-MgOz固溶体催化剂、Ni/Y-型沸石结构催化剂、La2NiO4催化剂、Ni/MCM-41催化剂、Fe-Cr合金催化剂和LaNi0.9Co0.1O3催化剂时，裂解原料气制备的碳材料相应为石墨化程度高的单壁纳米碳管、纳米碳球、纳米洋葱碳、微米碳盘、微米碳纤维等。
下面结合实施列对本发明作进一步说明，但不限于此。
实施例1：
以不同Mo、Ni(Fe，Co)和Mg含量的Mox-Ni(Fe，Co)y-MgOz固溶体为催化剂，裂解温度为800℃，常压下催化裂解后所得碳材料为单壁碳纳米管(SWCNT)；以Mo0.1Fe0.05Mg0.85Ox、Mo0.105Co0.045Mg0.85Ox和Mo0.2Ni0.1Mg0.7Ox固体氧化物为催化剂，则催化裂解后所得到的碳材料为薄壁碳纳米管(TWCNT)，管径顺序为：TWCNTFe＜TWCNTCo＜TWCNTNi，且TWCNTFe和TWCNTCo为闭合薄壁碳纳米管，TWCNTNi为端口敞开式碳纳米管；以La2NiO4为催化剂，催化裂解后所得到的碳材料为多壁碳纳米管(MWCNT)，所得多壁碳纳米管内径为15nm左右，壁层40曾左右。
实施例2：
原料气中同时通入苯(体积分数为100ppm)以Ni/MCM-41为催化剂，催化裂解后所得到的碳材料为直径在500纳米左右的微米级圆盘碳(MCD)；以Fe-Cr合金为催化剂，催化裂解后所得到的碳材料为纳米洋葱碳(CNO)，800℃下，该反应转化率为90％左右，接近理论转化率(92.9％)，且所产纳米洋葱碳在50层左右，直径在100nm左右；以LaNi0.9Co0.1O3为催化剂，催化裂解后所得到的碳材料为微米级碳纤维。

Claims (1)

1.一种石墨化程度高的纳米碳材料制备方法，以天然气、煤层气、沼气、乙炔，烷烃气体为原料气，加入不同的催化剂在600～800℃温度和1～8bar的压力下，将含有碳氢化合物的原料气体通入催化裂解反应器进行催化裂解反应，制备出不同形貌的纳米碳材料；其特征在于：所述的原料气中同时通入苯，体积分数为100ppm，催化剂为Ni/MCM-41，催化裂解后所得到的碳材料为直径500纳米的微米级圆盘碳MCD。
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