CN108993522A - 一种镍基多金属复合型催化剂及其制备方法和应用 - Google Patents
一种镍基多金属复合型催化剂及其制备方法和应用 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 30
- 241000983344 Trachelospermum jasminoides Species 0.000 claims abstract description 28
- 239000002028 Biomass Substances 0.000 claims abstract description 16
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 238000005235 decoking Methods 0.000 claims abstract description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 230000009849 deactivation Effects 0.000 abstract description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
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- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明公开了一种镍基多金属复合型催化剂及其制备方法和应用。该制备方法包括:将埃络石纳米棒、硝酸镍、硝酸铁、硝酸铈、尿素和去离子水混合加热搅拌,再经陈化、抽滤、烘干、碾碎、煅烧后,得到所述镍基多金属复合型催化剂。经实验验证,本发明的催化剂催化裂解焦油的转换率可达到95%以上,显著净化了生物质燃气,提升了燃气品质,而且抗积碳能力强,抗失活能力佳,使用寿命长。本发明制备方法简单、流程易操作。用于秸秆生物质催化热解除焦具有极高的催化活性,寿命时间长,分离回收简单。
Description
技术领域
本发明属于催化剂制备领域,更具体地,涉及一种镍基多金属复合型催化剂及其制备方法和应用。
背景技术
随着经济的快速发展,能源资源的消耗速度也迅速增长,而煤、石油、天然气等传统化石能源资源日益枯竭,人类迫切需要开发替代能源和可再生能源去满足能源需求,以补充和替代现有的化石能源。生物质被视为继煤炭、石油和天然气之后的第四大能源,生物质转化成为燃料的整个链条中最有效的手段就是热转化,生物质热转化技术是以生物质为原料,在高温条件下通过热化学反应将生物质转化为可燃性气体的过程。生物质热转化可将生物质原料转化为以CO和H2为主的气体燃料,可直接转换实现燃气、热能和电能的供给。我国农业秸秆生物质储量丰富,一方面可将可再生的农业生物质转化为燃料或工业原料,供工农业使用;另一方面可避免大量的生物质资源被废弃或随意焚烧而造成环境污染,变废为宝。
近年来对生物质能的研究和应用愈来愈引起人们的关注,开发新能源和可再生能源特别是把它们转化为高品位能源,因地制宜,多种能源互补,以逐步减少和替代化石能源的使用,是保护生态环境,走经济社会可持续发展之路的重大措施。
在生物质热转化的过程中,所产生的燃气含有大量的焦油,焦油的形成不仅导致设备腐蚀堵塞,造成设备损坏,而且降低燃气热值和品质。因此除去和减少燃气中的焦油含量势在必行。传统的除焦的方法有物理喷淋、织网过滤、超高温裂解等,虽然有一定的效果,但也存在使用周期短、造价成本高等问题逐渐被取代。目前,催化热解重整是被认为除去生产过程种的焦油含量、净化燃气、提升燃气品质最有潜力的方法。而物质燃气的催化重整技术关键在于高效催化剂的制备。因此开发出一种制备方法简单、具有高气体产率及焦油转化率的催化剂势在必行。
发明内容
本发明的目的在于解决上述问题,提供一种制备方法简单、具有高气体产率及焦油转化率的催化剂。
为了实现上述目的,本发明的第一方面提供一种镍基多金属复合型催化剂的制备方法,该制备方法包括:
将埃络石纳米棒、硝酸镍、硝酸铁、硝酸铈、尿素和去离子水混合加热搅拌,再经陈化、抽滤、烘干、碾碎、煅烧后,得到所述镍基多金属复合型催化剂。
作为本发明优选的实施方式,以埃络石纳米棒的重量为基准,硝酸镍的用量为埃络石纳米棒的20~25wt%,硝酸铁的用量为埃络石纳米棒的10~15wt%,硝酸铈的用量为埃络石纳米棒的10~15wt%,尿素的用量为埃络石纳米棒的400~500wt%。
作为本发明优选的实施方式,搅拌的转速为10~30r/s,在该转速下,制备得到的镍基多金属复合型催化剂可获得目标的均匀度;更优选为18~22r/s,在该转速下,制备得到的镍基多金属复合型催化剂的均匀度更加优异。
作为本发明优选的实施方式,煅烧的温度为600~800℃,煅烧的时间为2~2.5h。
作为本发明优选的实施方式,煅烧的温度为650~750℃。在此温度下制备得到的镍基多金属复合型催化剂具有更优异的催化性能。
作为本发明优选的实施方式,加热的温度为110~120℃,加热的时间为2~3h;陈化的时间为10~14h;烘干的温度为115~130℃。
本发明的第二方面提供由上述的制备方法制得的镍基多金属复合型催化剂。
作为本发明优选的实施方式,所述镍基多金属复合型催化剂的孔径为12.85~76.01nm,比表面积为12.65~84.00m2/g。
本发明的第三方面提供上述的镍基多金属复合型催化剂在生物质热解除焦中的应用。
作为本发明优选的实施方式,所述催化剂在生物质热解除焦中的应用时的温度为700~900℃。
根据本发明,优选地,所述硝酸镍的纯度≥98%,所述硝酸铁的纯度≥98%,所述硝酸铈的纯度≥99%。
本发明的优点和积极效果:
与传统的催化剂相比,本发明以价廉易得、表面积大、活性中心多、负载效果好的埃络石纳米棒为载体,以硝酸镍为主活性组分,硝酸铁、硝酸铈为助活性组分,通过均匀沉淀法,得到的多金属复合型催化剂呈中空棒状,不仅具备了大比表面积的特性,且所制备的催化剂达到了纳米级的粒度,可与焦油分子更好地接触,进行催化,而且利用硝酸镍、硝酸铁、硝酸铈按一定比例进行负载,可使得催化剂的稳定性更好,负载能力更强。负载多金属活性组分,可使得各金属活性组分之间生成金属合金,产生更好的催化效果。经实验验证,本发明的催化剂催化裂解焦油的转换率可达到95%以上,显著净化了生物质燃气,提升了燃气品质,而且抗积碳能力强,抗失活能力佳,使用寿命长。
本发明制备方法简单、流程易操作。用于秸秆生物质催化热解除焦具有极高的催化活性,寿命时间长,分离回收简单。
本发明的其它特征和优点将在随后具体实施方式部分予以详细说明。
附图说明
图1示出了本发明一个实施例的镍基多金属复合型催化剂的制备方法的简易流程图。
具体实施方式
下面将更详细地描述本发明的优选实施方式。虽然以下描述了本发明的优选实施方式,然而应该理解,可以以各种形式实现本发明而不应被这里阐述的实施方式所限制。相反,提供这些实施方式是为了使本发明更加透彻和完整,并且能够将本发明的范围完整地传达给本领域的技术人员。
本发明实施例中,硝酸镍的纯度≥98%,硝酸铁的纯度≥98%,硝酸铈的纯度≥99%。
实施例1:
本实施例提供一种镍基多金属复合型催化剂。该镍基多金属复合型催化剂的制备方法为:将埃络石纳米棒、硝酸镍、硝酸铁、硝酸铈、尿素和去离子水置于油浴锅内混合加热搅拌,加热的温度为115℃,加热的时间为2.5h,搅拌的转速为20r/s,再经12h陈化、抽滤、恒温干燥箱120℃烘干后,碾碎,在700℃下煅烧2h,得到孔径为21.66nm~31.12nm,比表面积为33.95m2/g~42.80m2/g的镍基多金属复合型催化剂。其中,以埃络石纳米棒的重量为基准,硝酸镍的用量为埃络石纳米棒的23wt%,硝酸铁的用量为埃络石纳米棒的12wt%,硝酸铈的用量为埃络石纳米棒的12wt%,尿素的用量为埃络石纳米棒的400~500wt%。
实施例2:
与实施例1的不用之处在于,煅烧的温度为750℃。
实施例3:
与实施例1的不用之处在于,煅烧的温度为800℃。
对比例1:
与实施例1的不用之处在于,仅采用硝酸镍,不采用硝酸铁、硝酸铈,以埃络石纳米棒的重量为基准,硝酸镍的用量为埃络石纳米棒的23wt%。
对比例2:
与实施例1的不用之处在于,仅采用硝酸铁,不采用硝酸镍、硝酸铈,以埃络石纳米棒的重量为基准,硝酸铁的用量为埃络石纳米棒的12wt%。
对比例3:
与实施例1的不用之处在于,仅采用硝酸铈,不采用硝酸镍、硝酸铁,以埃络石纳米棒的重量为基准,硝酸铈的用量为埃络石纳米棒的12wt%。
对实施例1-3及对比例1-3制备得到的催化剂的气体产率及焦油转化率进行测试,结果如表1所示,其中,所述催化剂在使用时的温度为700~900℃。
表1
图1示出了本发明一个实施例的镍基多金属复合型催化剂的制备方法的简易流程图。先称取一定量埃络石(即埃络石纳米棒)、尿素以及硝酸镍、硝酸铁、硝酸铈,加入一定量去离子水,于三井烧瓶中油浴加热搅拌,加热的温度为115℃,加热的时间为2.5h,然后抽滤、烘干碾碎,再经马弗炉煅烧得到成品。
以上已经描述了本发明的各实施例,上述说明是示例性的,并非穷尽性的,并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下,对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。
Claims (9)
1.一种镍基多金属复合型催化剂的制备方法,其特征在于,该制备方法包括:
将埃络石纳米棒、硝酸镍、硝酸铁、硝酸铈、尿素和去离子水混合加热搅拌,再经陈化、抽滤、烘干、碾碎、煅烧后,得到所述镍基多金属复合型催化剂。
2.根据权利要求1所述的制备方法,其中,以埃络石纳米棒的重量为基准,硝酸镍的用量为埃络石纳米棒的20~25wt%,硝酸铁的用量为埃络石纳米棒的10~15wt%,硝酸铈的用量为埃络石纳米棒的10~15wt%,尿素的用量为埃络石纳米棒的400~500wt%。
3.根据权利要求1所述的制备方法,其中,搅拌的转速为10~30r/s。
4.根据权利要求1所述的制备方法,其中,煅烧的温度为600~800℃,煅烧的时间为2~2.5h。
5.根据权利要求4所述的制备方法,其中,煅烧的温度为650~750℃。
6.根据权利要求1所述的制备方法,其中,加热的温度为110~120℃,加热的时间为2~3h;陈化的时间为10~14h;烘干的温度为115~130℃。
7.由权利要求1-6中任意一项所述的制备方法制得的镍基多金属复合型催化剂。
8.根据权利要求7所述的镍基多金属复合型催化剂,其中,所述镍基多金属复合型催化剂的孔径为12.85~76.01nm,比表面积为12.65~84.00m2/g。
9.权利要求7所述的镍基多金属复合型催化剂在生物质热解除焦中的应用。
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