CN111014248A - 一种纳米硫化镍-碳复合材料的制备方法 - Google Patents

一种纳米硫化镍-碳复合材料的制备方法 Download PDF

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CN111014248A
CN111014248A CN201911351587.XA CN201911351587A CN111014248A CN 111014248 A CN111014248 A CN 111014248A CN 201911351587 A CN201911351587 A CN 201911351587A CN 111014248 A CN111014248 A CN 111014248A
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composite material
nickel sulfide
carbon composite
nano
washing
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CN111014248B (zh
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杜辉
陈照军
段雅静
姜鹏
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Qingdao University
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Abstract

本发明公开了一种纳米硫化镍‑碳复合材料的制备方法，以含有大量石油焦微粒和分散型纳米催化剂微粒的重油悬浮床加氢尾油，和/或焦炭包裹着分散型催化剂颗粒的固体废弃物为原料，经过预处理后，在碱金属氢氧化物的作用下，采用碳化和结构活化处理工艺，然后经洗涤、干燥，制备得到具有高附加值的纳米硫化镍‑碳复合材料。具有工艺简单、原料广泛易得、成本低廉、产物附加值高、应用广泛等优点，可广泛用于储能、催化、环保等领域。

Description

一种纳米硫化镍-碳复合材料的制备方法
技术领域
本发明属于新材料领域，特别涉及一种纳米硫化镍-碳复合材料的制备方法。
背景技术
硫化镍是一种重要的金属硫化物，具有多种晶型，在催化、储能、环保等领域具有潜在的应用前景，受到研究人员的广泛关注。实际应用中，为提高硫化镍的利用率，降低使用成本，通常将硫化镍以纳米尺度分散在载体上。其中，碳材料是常用的载体材料，用于催化领域时碳材料作为一种惰性载体，能够为活性组分的分散提供丰富的比表面积；用于储能领域时，碳材料用作超级电容器电极可以提供双电层电容；用于环保领域，碳材料的丰富的孔道结构可以高效的吸附污染物。因此，纳米硫化镍-碳复合材料受到了广泛关注，可采用水热法、气相沉积法、沉淀法等方法制备得到。
中国发明专利201910308283.9公开了一种中空生物碳球基硫化镍纳米棒超级电容器及制备方法，具体是首先将生物酵母在加入戊二醛和去离子水的混合溶液中在180℃条件下水热12h，离心干燥收集棕红色样品。随后将收集到的样品在马弗炉中以1℃/min的升温速率升温至300℃并保温1h，将收集到的黑色样品置入管式炉中在惰性气体氛围下以2℃/min的升温速率升温至800℃并保温3h，既得中空氮掺杂生物炭壳。中空氮掺杂生物炭壳加入到硝酸镍、硫脲和亚磷酸钠配制的混合溶液中进行超声波和搅拌处理，然后在180℃条件下水热6h，随后离心干燥，既得中空生物碳球基硫化镍纳米棒复合样品。该方法的制备步骤繁琐，原料昂贵，制备效率低下。
中国发明专利201810189138.9公开了一种二硫化镍-碳复合材料及其制备方法和应用，具体制备步骤为：(1)通过加热将硬脂酸溶于乙醇中，加入二硫化镍纳米粒子，搅拌至混合均匀，得到混合液；其中二硫化镍纳米粒子与硬脂酸的质量比为4～7:1；(2)将步骤(1)得到的混合液冷却使硬脂酸析出，并包覆在二硫化镍纳米粒子表面，过滤，得到沉淀物；(3)将步骤(2)得到的沉淀物干燥，再在保护气氛下升温至500～600℃，使硬脂酸碳化，得到二硫化镍-碳复合材料。该方法制备得到的复合材料中二硫化镍纳米粒子的尺寸为20～100纳米，二硫化镍分散的粒径较大，分散度较低，原子利用率较低。
现有的硫化镍-碳复合材料制备方法工艺复杂、制备效率低下，制备得到的复合材料中硫化镍的分散度较低、碳材料的孔道结构不发达、比表面积低。只有通过调控碳材料的孔道结构，同时实现硫化镍的高效分散，才可以满足硫化镍-碳复合材料在催化、储能、环保等不同领域的应用。
发明内容
本发明的目的在于克服现有技术存在的不足，提供一种纳米硫化镍-碳复合材料的制备方法，以含有大量石油焦微粒和分散型纳米催化剂微粒的重油悬浮床加氢尾油，和/或焦炭包裹着分散型催化剂颗粒的固体废弃物为原料，经过预处理后，在碱金属氢氧化物的作用下，采用碳化和结构活化处理工艺，然后经洗涤、干燥，制备得到具有高附加值的纳米硫化镍-碳复合材料，该产品可广泛应用于储能、催化、环保等领域。
本发明是采用以下的技术方案实现的：
一种纳米硫化镍-碳复合材料的制备方法，制备过程包括以下步骤：
(1)尾油和/或固体废弃物预处理；
(2)与碱金属氢氧化物混合均匀，在H2/He混合气氛下，升温进行结构活化；
(3)冷却后经洗涤、干燥得到纳米硫化镍-碳复合材料。
进一步，所述尾油和/或固体废弃物来自重质原料油经过悬浮床加氢工艺后的产物，所述重质原料油包括重质原油、常压渣油、减压渣油、煤焦油、沥青；
所述悬浮床加氢工艺采用分散型纳米催化剂，所述分散型纳米催化剂为硫化镍纳米催化剂。
进一步，所述尾油中含有大量石油焦微粒和分散型纳米催化剂微粒，所述固体废弃物中焦炭包裹着的分散型催化剂颗粒，而且分散型纳米催化剂微粒以小于20纳米的尺度分散在尾油和/或固体废弃物中。
进一步，所述步骤(1)中尾油的预处理过程为：首先通过减压蒸馏去除尾油中沸点小于550℃的馏分；将剩余部分使用糠醛萃取，将萃余物冷却后粉碎、研磨至35～400目；所述萃取条件为：温度为60℃，剂油比为0.7，萃取时间为30min；
所述步骤(1)中固体废弃物的预处理过程为：使用甲苯或溶剂油洗涤固体废弃物，然后使用糠醛萃取，洗净干燥后粉碎、研磨至50～400目；优选的，研磨至50～300目；所述萃取条件为：温度为70℃，糠醛/固体废弃物质量比为1.0，萃取时间为40min。
进一步，所述步骤(2)中预处理后的尾油和/或固体废弃物与碱金属氢氧化物的质量比为1：0.2～12；
所述碱金属氢氧化物为氢氧化钾或氢氧化钠；
所述H2与He的体积比1:9；
所述结构活化过程中，升温速率为2～20℃/min，活化温度为700～1200℃，处理时间为0.5～10小时。
进一步，所述步骤(3)中洗涤过程包括依次采用蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤三个步骤。
进一步，所述复合材料的比表面积为2000～3200m2/g，所述复合材料中硫化镍含量为3～35wt％。
本发明的另一目的在于提供一种纳米硫化镍-碳复合材料，采用上述制备方法制备得到。
本发明还提供了上述纳米硫化镍-碳复合材料应用于锂离子电池负极材料、超级电容器电极材料、水电解制氢催化材料、汞吸附材料领域。
本发明采用重油悬浮床加氢工艺的尾油和固体废弃物这一低附加值、极难处理的复杂体系为原料；对于尾油，首先通过减压蒸馏去除其中沸点小于550℃的馏分，然后通过糠醛萃取除去其中的强极性组分；对于固体废弃物，首先通过预处理洗涤清洗去除其中残留的石油烃分子，然后通过糠醛萃取除去其中的强极性组分；最后经过破碎后在高温和混合气氛下采用碱金属氢氧化物对其进行碳化和结构活化，处理过程中尾油大分子或缩合度较低的焦炭分子在分散型纳米催化剂和氢气的作用下能够部分发生加氢裂化反应，生成的小分子烃类物质逃逸离开反应体系使尾油颗粒内部形成孔隙，从而使碱金属氢氧化物能够通过孔隙进入尾油颗粒内部发生活化反应，最终制备得到具有高比表面积和高分散度的纳米硫化镍-碳复合材料。
与现有技术相比，本发明的技术方案具有以下优点和进步：
本发明提供的纳米硫化镍-碳复合材料的制备方法具有工艺简单、原料广泛易得、成本低廉、产物附加值高、产物应用广泛等优点，同时还解决了重油悬浮床加氢工艺中低附加值、难处理的副产物问题。
附图说明
图1为实施例1所制备纳米硫化镍-碳复合材料的透射电镜照片。
图2为实施例2所制备纳米硫化镍-碳复合材料的透射电镜照片。
图3为对比例1所制备硫化镍-碳复合材料的透射电镜照片。
图4为对比例2所制备硫化镍-碳复合材料的透射电镜照片。
具体实施方式
下面结合附图对本发明的实施方案进行详细描述，实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器均为可以通过市售购买获得的常规产品。
实施例1
以克拉玛依减压渣油在分散型硫化镍纳米催化剂的作用下经过悬浮床加氢反应工艺得到的尾油为原料，首先通过减压蒸馏去除尾油中沸点小于550℃的馏分，在温度为60℃，剂油比为0.7，萃取时间为30min的条件下使用糠醛萃取，将处理后剩余部分冷却后粉碎、研磨至35～200目，然后将其与氢氧化钾按质量比1：10混合均匀，在H2/He(体积比1:9)混合气氛下，以5℃/min速率升温至700℃进行结构活化，活化时间2小时，冷却后先后经蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤，最终干燥得到纳米硫化镍-碳复合材料，所述复合材料的比表面积为3126m2/g，所述复合材料中硫化镍含量为17.5wt％，硫化镍以粒径小于20纳米的颗粒均匀分散在复合材料中。
实施例2
以委内瑞拉超稠油在分散型硫化镍纳米催化剂的作用下经过悬浮床加氢反应工艺得到的固体废弃物为原料，首先使用甲苯洗涤固体废弃物去除其中残留的石油烃分子，在温度为70℃，糠醛/固体废弃物质量比为1.0，萃取时间为40min的条件下使用糠醛萃取，干燥后粉碎、研磨至50～200目，然后将其与氢氧化钾按质量比1：12混合均匀，在H2/He(体积比1:9)混合气氛下，以2℃/min速率升温至900℃进行结构活化，活化时间6小时，冷却后先后经蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤，最终干燥得到纳米硫化镍-碳复合材料，所述复合材料的比表面积为2955m2/g，所述复合材料中硫化镍含量为23wt％，硫化镍以粒径小于20纳米的颗粒均匀分散在复合材料中。
实施例3
以克拉玛依减压渣油在分散型硫化镍纳米催化剂的作用下经过悬浮床加氢反应工艺得到的尾油为原料，首先通过减压蒸馏去除尾油中沸点小于550℃的馏分，在温度为60℃，剂油比为0.7，萃取时间为30min的条件下使用糠醛萃取，将处理后剩余部分冷却后粉碎、研磨至35～200目，然后将其与氢氧化钾按质量比1：2混合均匀，在H2/He(体积比1:9)混合气氛下，以16℃/min速率升温至1200℃进行结构活化，活化时间8小时，冷却后先后经蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤，最终干燥得到纳米硫化镍-碳复合材料，所述复合材料的比表面积为2253m2/g，所述复合材料中硫化镍含量为12.8wt％，硫化镍以粒径小于20纳米的颗粒均匀分散在复合材料中。
对比例1
以克拉玛依减压渣油在水溶性镍催化剂的作用下经过悬浮床加氢反应工艺得到的尾油为原料，首先通过减压蒸馏去除尾油中沸点小于550℃的馏分，将剩余部分冷却后粉碎、研磨至35～200目，然后将其与氢氧化钾按质量比1：10混合均匀，在H2/He(体积比1:9)混合气氛下，以5℃/min速率升温至700℃进行结构活化，活化时间2小时，冷却后先后经蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤，最终干燥得到硫化镍-碳复合材料，所述复合材料的比表面积为879m2/g，所述复合材料中硫化镍含量为1.3wt％，分散的硫化镍粒径大于100纳米。
对比例2
以委内瑞拉超稠油在油溶性镍催化剂的作用下经过悬浮床加氢反应工艺得到的固体废弃物为原料，首先使用甲苯洗涤固体废弃物去除其中残留的石油烃分子，在温度为70℃，糠醛/固体废弃物质量比为1.0，萃取时间为40min的条件下使用糠醛萃取，干燥后粉碎、研磨至50～200目，然后将其与氢氧化钾按质量比1：12混合均匀，在H2/He(体积比1:9)混合气氛下，以2℃/min速率升温至900℃进行结构活化，活化时间6小时，冷却后先后经蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤，最终干燥得到硫化镍-碳复合材料，所述复合材料的比表面积为378m2/g，所述复合材料中硫化镍含量为2.3wt％，分散的硫化镍粒径大于100纳米。
对比例3
以克拉玛依减压渣油在分散型硫化镍纳米催化剂的作用下经过悬浮床加氢反应工艺得到的尾油为原料，首先通过减压蒸馏去除尾油中沸点小于550℃的馏分，将处理后剩余部分冷却后粉碎、研磨至35～200目，然后将其与氢氧化钾按质量比1：10混合均匀，在H2/He(体积比1:9)混合气氛下，以5℃/min速率升温至700℃进行结构活化，活化时间2小时，冷却后先后经蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤，最终干燥得到纳米硫化镍-碳复合材料，所述复合材料的比表面积为1068m2/g，所述复合材料中硫化镍含量为8.2wt％，氧化镍含量为3.3wt％，硫化镍和氧化镍的粒径大于60纳米。

Claims (9)

1.一种纳米硫化镍-碳复合材料的制备方法，其特征在于，制备过程包括以下步骤：
(1)尾油和/或固体废弃物预处理；
(2)与碱金属氢氧化物混合均匀，在H2/He混合气氛下，升温进行结构活化；
(3)冷却后经洗涤、干燥得到纳米硫化镍-碳复合材料；
所述尾油和/或固体废弃物来自重质原料油经过悬浮床加氢工艺后的产物；
所述悬浮床加氢工艺采用分散型纳米催化剂，所述分散型纳米催化剂为硫化镍纳米催化剂。
2.根据权利要求1所述的一种纳米硫化镍-碳复合材料的制备方法，其特征在于，所述重质原料油包括重质原油、常压渣油、减压渣油、煤焦油、沥青；所述尾油中含有大量石油焦微粒和分散型纳米催化剂微粒，所述固体废弃物中焦炭包裹着分散型催化剂颗粒，而且分散型纳米催化剂微粒以小于20纳米的尺度分散在尾油和/或固体废弃物中。
3.根据权利要求1所述的一种纳米硫化镍-碳复合材料的制备方法，其特征在于，所述步骤(1)中尾油的预处理过程为：首先通过减压蒸馏去除尾油中沸点小于550℃的馏分；将剩余部分使用糠醛萃取，将萃余物冷却后粉碎、研磨至35～400目；所述萃取条件为：温度为60℃，剂油比为0.7，萃取时间为30min；
所述步骤(1)中固体废弃物的预处理过程为：使用甲苯或溶剂油洗涤固体废弃物，然后使用糠醛萃取，洗净干燥后粉碎、研磨至50～400目；优选的，研磨至50～300目；所述萃取条件为：温度为70℃，糠醛/固体废弃物质量比为1.0，萃取时间为40min。
4.根据权利要求1所述的一种纳米硫化镍-碳复合材料的制备方法，其特征在于，所述步骤(2)中预处理后的尾油和/或固体废弃物与碱金属氢氧化物的质量比为1：0.2～12；
所述碱金属氢氧化物为氢氧化钾或氢氧化钠。
5.根据权利要求1所述的一种纳米硫化镍-碳复合材料及其制备方法，其特征在于，所述H2与He的体积比1:9；
所述结构活化过程中，升温速率为2～20℃/min，活化温度为700～1200℃，处理时间为0.5～10小时。
6.根据权利要求1所述的一种纳米硫化镍-碳复合材料的制备方法，其特征在于，所述步骤(3)中洗涤过程包括依次采用蒸馏水洗涤、稀盐酸溶液酸洗、蒸馏水洗涤三个步骤。
7.根据权利要求1所述的一种纳米硫化镍-碳复合材料的制备方法，其特征在于，所述复合材料的比表面积为2000～3200m2/g，所述复合材料中硫化镍含量为3～35wt％。
8.一种纳米硫化镍-碳复合材料，采用权利要求1-7任一项所述的一种纳米硫化镍-碳复合材料的制备方法制备得到。
9.权利要求8所述纳米硫化镍-碳复合材料应用于锂离子电池负极材料、超级电容器电极材料、水电解制氢催化材料、汞吸附材料领域。
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CN115463617B (zh) * 2022-09-26 2024-04-19 矿业大学(北京)内蒙古研究院 一种磁铁矿/焦炭复合电磁波吸波材料及其制备方法

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