CN114471604A - 一种提高碳纳米管生长倍率的催化剂及其制备方法和应用 - Google Patents
一种提高碳纳米管生长倍率的催化剂及其制备方法和应用 Download PDFInfo
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及制备碳纳米管的催化剂技术领域,特别涉及一种提高碳纳米管生长倍率的催化剂及其制备方法和应用。该催化剂为钴、锰、镁和铝的复合氧化物,所述钴、锰、镁和铝的摩尔比为(1.5~5.5):(1~4.5):(0.5~2):1。本发明将钴、锰、镁和铝四种金属按照特定比例进行复合,可作为生产碳纳米管的催化剂。将该催化剂用于生产碳纳米管时,可显著提高碳纳米管的生长倍率。
Description
技术领域
本发明涉及制备碳纳米管的催化剂技术领域,特别涉及一种提高碳纳米管生长倍率的催化剂及其制备方法和应用。
背景技术
碳纳米管是一种结构特殊的新型碳材料,具有优异的力学性能和理化性能,在锂离子电池导电剂、催化剂载体、药物载体、增强共混材料、电子器件等领域具有广泛的应用前景。碳纳米管具有非常优良的导电性能,同时又具有极高的长径比,在锂离子电池的正极材料中可以有效地形成导电网络,提升电极导电性能,具体表现在电池容量大、循环寿命长,适合高端数码类电池及新能源汽车动力电池。
目前,已报道的碳纳米管生长倍率一般不超过55倍。如相关技术公开了活性金属负载于皂石或者水滑石上的碳纳米管催化剂,其制备方法为:首先采用水热法制备皂石或水滑石载体,在超声作用下使载体负载活性金属,再经干燥、500℃~900℃煅烧后得到所需催化剂。利用该催化剂生产碳纳米管的倍率为25~35倍。相关技术公开了活性金属负载于氧化铝上的石墨化金属催化剂,其制备方法为:先在100℃至500℃的初次煅烧温度下煅烧氢氧化铝来形成载体,在所述载体上负载催化金属前体,然后在100℃至800℃的二次煅烧温度下煅烧在所述载体上负载的所述催化金属前体,利用该催化剂生产碳纳米管的倍率最高为22.7倍。相关技术公开了一种二段法制备高倍率超细管径的碳纳米管及其催化剂和制备方法,将活性金属和载体金属的混合盐溶液经过二段焙烧,碳纳米管生长倍率为45~55倍。
开发工艺流程简便、低成本、超高倍率的碳纳米管催化剂,有利于降低碳纳米管的生产成本,降低碳纳米管的灰分从而减少酸洗提纯带来的污染,符合技术发展和环境保护的需求,有利于推动碳纳米管在更多的领域得到应用。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此,本发明提出一种催化剂,可显著提高碳纳米管的生长倍率。
同时,本发明还提供该催化剂的制备方法,以及制备碳纳米管的方法。
具体地,本发明涉及如下的技术方案:
本发明的第一方面是提供一种催化剂,所述催化剂为钴、锰、镁和铝的复合氧化物,所述钴、锰、镁和铝的摩尔比为(1.5~5.5):(1~4.5):(0.5~2):1。
本发明将钴、锰、镁和铝四种金属按照特定比例进行复合,可作为生产碳纳米管的催化剂。将该催化剂用于生产碳纳米管时,可显著提高碳纳米管的生长倍率。
在本发明的一些实例中,所述钴、锰、镁和铝的摩尔比为(1.8~5.3):(1~4):(0.9~1.7):1,优选(1.8~3):(1~4):(0.9~1.7):1,更优选(2.5~3):(2.2~4):(1~1.6):1,进一步优选(2.5~2.8):(2.2~2.5):1:1。
在本发明的一些实例中,所述钴、锰、镁和铝的复合氧化物以聚集体的形式存在,所述聚集体的当量粒径为0.5~5μm。
本发明的第二方面是提供所述催化剂的制备方法,包括如下步骤:将钴盐、锰盐、镁盐、铝盐与络合剂混合后进行焙烧,得到所述催化剂。
在本发明的一些实例中,所述钴盐、锰盐、镁盐、铝盐包括钴、锰、镁和铝的硝酸盐、氯化盐、硫酸盐中的至少一种。例如,钴盐包括硝酸钴、氯化钴、硫酸钴中的至少一种,锰盐包括硝酸锰、氯化锰、硫酸锰中的至少一种。
在本发明的一些实例中,所述络合剂包括柠檬酸、乙二胺四乙酸(EDTA)、羟基乙酸、氨基磺酸中的至少一种。此类络合剂含有羧基或磺酸基,能够提供孤电子对给各金属离子,形成溶解性良好的金属络合物,能够促进金属盐的完全溶解和不同金属在催化剂中的均匀分布,同时在催化剂焙烧过程能够充分燃烧,起到造孔作用,使催化剂疏松多孔。
在本发明的一些实例中,各组分占钴盐、锰盐、镁盐、铝盐与络合剂总质量的质量百分比为:
钴盐20%~50%
锰盐12%~32%
镁盐5%~20%
铝盐5%~25%
络合剂10%~40%。
在本发明的一些实例中,各组分占钴盐、锰盐、镁盐、铝盐与络合剂总质量的质量百分比为:
钴盐21.4%~49.6%
锰盐12.6%~31.5%
镁盐5.3%~18.7%
铝盐6.7%~22.3%
络合剂11.1%~38.9%。
在本发明的一些实例中,各组分占钴盐、锰盐、镁盐、铝盐与络合剂总质量的质量百分比为:
钴盐22%~46%
锰盐13%~30%
镁盐7.5%~15%
铝盐8.5%~19.5%
络合剂17%~29.5%。
在本发明的一些实例中,各组分占钴盐、锰盐、镁盐、铝盐与络合剂总质量的质量百分比为:
钴盐22%~40%
锰盐16%~30%
镁盐8.5%~15%
铝盐8.5%~19.5%
络合剂17%~29.5%。
在本发明的一些实例中,各组分占钴盐、锰盐、镁盐、铝盐与络合剂总质量的质量百分比为:
钴盐22.5%~26.5%
锰盐23%~30%
镁盐8.5%~10.5%
铝盐8.5%~12.5%
络合剂28%~29.5%。
在本发明的一些实例中,所述催化剂的制备方法更具体包括如下步骤:将钴盐、锰盐、镁盐、铝盐与络合剂制成混合溶液,对所述混合溶液进行焙烧,得到所述催化剂。
在本发明的一些实例中,所述焙烧的温度为400~800℃,焙烧的时间为10~60min。所述焙烧在空气中进行。
在本发明的一些实例中,所述混合溶液中,水量为钴盐、锰盐、镁盐、铝盐与络合剂总质量的1~2倍。在钴盐、锰盐、镁盐、铝盐与络合剂中加入水后进行充分搅拌,搅拌时间为30~60min,直至固体颗粒完全溶解。接着将混合溶液加热至40~80℃,继续搅拌3~6小时,搅拌转速为80~100r/min。
在本发明的一些实例中,所述焙烧后还包括粉碎、过筛的步骤,通过粉碎、过筛,制得粒径不大于1000μm的复合金属催化剂。
本发明的第三方面是提供上述催化剂在制备碳纳米管中的应用,所述应用中,碳纳米管的生长倍率≥80倍,优选80~120倍,更优选85~120倍。所述生长倍率为单位质量的催化剂所能制备的碳纳米管的质量。
在本发明的一些实例中,所述碳纳米管的比表面积为120~160m2/g,电阻率为50~100mΩ·cm。
在本发明的一些实例中,所述碳纳米管的直径为15~30nm。
在本发明的一些实例中,所述碳纳米管的灰分含量为0.5%~1.5%,优选0.8%~1.25%。
本发明的第四方面是提供一种碳纳米管的制备方法,包括如下步骤:使用所述催化剂对碳源反应气进行催化裂解,得到碳纳米管。
在碳源反应气的作用下,催化剂中的钴、锰金属氧化物被还原成活性金属单质,然后催化碳源反应气裂解,在催化剂表面生长碳纳米管。
在本发明的一些实例中,所述碳源反应气包括丙烯、乙烯、丙烷、乙烷中的至少一种。
在本发明的一些实例中,所述碳源反应气的流量、催化裂解温度和时间、金属复合材料的用量可按本领域通用技术确定,同时,在催化裂解过程中碳源反应气与保护气体(如氮气、氩气)共同通入反应器中,同时保护气体的流量也可按本领域通用技术确定。作为示例,所述碳源反应气的流量、保护气体的流量和催化剂用量的比例为2~6L/min:5~9L/min:5~7g,催化裂解温度为600~700℃,优选620~690℃,催化裂解时间为45~90min。
相对于现有技术,本发明具有如下有益效果:
本发明将钴、锰、镁和铝四种金属按照特定比例进行复合,可作为生产碳纳米管的催化剂。将该催化剂用于生产碳纳米管时,催化活性极高,并且能持久保持较高的催化活性,可显著提高碳纳米管的生长倍率,碳纳米管的生长倍率高达80~120倍,有利于提高碳纳米管的生产效率,降低碳纳米管的生产成本。
另外,生产的碳纳米管原粉中灰分含量更低,可减少酸洗提纯的成本,并且减少酸洗提纯所带来的环境污染。
附图说明
图1为实施例1中催化剂的SEM图。
图2为实施例1中碳纳米管的TEM图。
具体实施方式
以下结合具体的实施例进一步说明本发明的技术方案。以下实施例中所用的原料,如无特殊说明,均可从常规商业途径得到;所采用的工艺,如无特殊说明,均采用本领域的常规工艺。
一种碳纳米管的制备方法,包括如下步骤:
步骤一:按如下表1的比例准确称量制备催化剂的原料硝酸钴、硝酸锰、硝酸镁、硝酸铝和柠檬酸,并将原料放入密闭搅拌容器内,再加入去离子水启动搅拌,去离子水的质量约为原料总质量的2倍,搅拌转速为100r/min,搅拌30分钟,直至固体颗粒完全溶解,得到混合溶液;
步骤二:将混合溶液加热至80℃,继续搅拌3小时,搅拌转速为100r/min;
步骤三:将步骤二的溶液等量倒入坩埚中,并置于焙烧炉中焙烧,温度控制在800℃作用,焙烧时间为30min;
步骤四:用粉碎机将焙烧后得到的固体样品粉碎,全部过20目筛,制得超高倍率碳纳米管的催化剂。实施例1的催化剂SEM如图1所示。图1显示,该催化剂呈现聚集体状态,聚集体大小主要集中在0.5~5μm。
步骤五:将筛分好的催化剂投入流化床反应炉中,通入含有碳源的反应气和载气的混合气,反应充分后,停止反应并继续在保护气氛下冷却,得到黑色蓬松的碳纳米管。碳源反应气流量为6L/min,保护气体流量为9L/min,催化裂解温度为650℃,催化裂解时间为60min,催化剂单次用量为6g。
其中,实施例1的碳源反应气为丙烯,实施例2的为乙烯,实施例3的为丙烷,实施例4的为乙烷,实施例5的为丙烯和丙烷的混合气,载体均为氮气。
表1.催化剂原料组成(质量百分比%)
各实施例制备的碳纳米管的性能参数见下表2,其中实施例1的碳纳米管的TEM图如图2所示。
表2.碳纳米管的性能参数
结果显示,采用由钴、锰、镁和铝组成的复合氧化物催化剂可有效催化碳纳米管的生长,且实施例1~5中碳纳米管的生长倍率达到85~115倍,且碳纳米管具有高比表面积和良好的电性能,灰分低。同时,图2显示,所得碳纳米管的直径主要集中在16~28nm。
催化剂的催化活性越高,在相同条件下,碳纳米管的生长时间就越长,倍率也会越高。只要催化裂解反应在持续进行,碳源反应气就会不断裂解出氢气并进入尾气中,并最终会达到平衡,即尾气中氢气的体积百分比会稳定在一定范围之内,一旦催化剂逐渐失活,则催化裂解反应会减缓,氢气的体积百分比也会逐渐下降。因此,通过检测尾气中氢气的体积百分比的变化,即可知道催化剂的催化活性可持续多久。表2中氢气的体积百分比指的是同样反应至60min时尾气中氢气的体积百分比。使用实施例1~5的催化剂制备碳纳米管过程中,尾气中氢气的体积百分比较高,说明这些催化剂具有持久的催化活性。
相比之下,对比例1采用了不恰当的金属比例后,虽然所得碳纳米管的比表面积未发生明显变化,但是生长倍率明显降低;电阻率升高,导电性变差;同时灰分增高,杂质变多;尾气中氢气的体积百分比降低,催化活性降低。上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种催化剂,其特征在于:所述催化剂为钴、锰、镁和铝的复合氧化物,所述钴、锰、镁和铝的摩尔比为(1.5~5.5):(1~4.5):(0.5~2):1。
2.根据权利要求1所述催化剂,其特征在于:所述钴、锰、镁和铝的摩尔比为(1.8~5.3):(1~4):(0.9~1.7):1。
3.根据权利要求2所述催化剂,其特征在于:所述钴、锰、镁和铝的摩尔比为(1.8~3):(1~4):(0.9~1.7):1。
4.权利要求1~3任一项所述催化剂的制备方法,其特征在于:包括如下步骤:将钴盐、锰盐、镁盐、铝盐与络合剂混合后进行焙烧,得到所述催化剂。
5.根据权利要求4所述制备方法,其特征在于:各组分占钴盐、锰盐、镁盐、铝盐与络合剂总质量的质量百分比为:
钴盐20%~50%
锰盐12%~32%
镁盐5%~20%
铝盐5%~25%
络合剂10%~40%。
6.根据权利要求4所述制备方法,其特征在于:所述焙烧的温度为400~800℃。
7.权利要求1~3任一项所述催化剂在制备碳纳米管中的应用,所述应用中,碳纳米管的生长倍率≥80。
8.根据权利要求7所述应用,其特征在于:所述碳纳米管的比表面积为120~160m2/g。
9.根据权利要求7所述应用,其特征在于:所述碳纳米管的灰分含量为0.5%~1.5%。
10.一种碳纳米管的制备方法,其特征在于:包括如下步骤:使用权利要求1~3任一项所述催化剂对碳源反应气进行催化裂解,得到碳纳米管。
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