CN107265417A - 一种硼缺陷氮化硼纳米片及其制备方法和用途 - Google Patents
一种硼缺陷氮化硼纳米片及其制备方法和用途 Download PDFInfo
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Abstract
本发明涉及吸附脱硫的非金属吸附剂,特指一种硼缺陷氮化硼纳米片及其制备方法和在吸附降低燃油中芳香硫化物的用途。将硼酸和氮源溶解到超纯水中,然后加入共反应源,上述溶液在80~90℃下搅拌蒸发。(2)待溶液全部蒸发完后,所得固体放入管式炉中在氮气或氨气的气氛下700~1000℃煅烧5h,得到硼缺陷氮化硼纳米片;由于部分硼原子的缺失,导致氮化硼化学硬度降低,能与软碱的二苯并噻吩形成很好的相互作用,从而除去燃油中的二苯并噻吩。
Description
技术领域
本发明涉及吸附脱硫的非金属吸附剂,特指一种硼缺陷氮化硼纳米片及其制备方法和在吸附降低燃油中芳香硫化物的用途。
背景技术
随着世界经济的发展,清洁燃料的开发越来越迫切。到目前为止,化石燃料仍是世界上的主要能源之一。然而,燃料中普遍存在的硫化合物燃烧后会释放SOx气体。这些气体不仅会导致酸雨,而且还会对人体造成伤害。因此,实现高效清洁燃料变得越来越重要。由于温和的操作条件和高选择性,吸附脱硫(ADS)受到越来越多的关注。
最近,层状六方氮化硼(BN)已经被广泛的研究兴趣。在我们以前的报告中,BN材料已被证明能够用作吸附脱硫的非金属吸附剂(Green Chem.,2015,17,1647-1656)。尽管BN材料展现出一定的吸附脱硫能力,但其性能仍未达到工业应用潜力的要求。据以前的报道,软硬酸碱度(HSAB)理论在对ADS的作用中起着非常重要的作用(Energy Fuels,2008,22,3858-3863)。众所周知,软酸易与软碱反应,硬酸易发生与硬碱相互作用。由于硼原子存在空轨道,电子缺陷特征使其具有一定的吸电子能力,因此BN可以显示出一些路易斯酸度。以广泛研究的芳香族硫化合物二苯并噻吩(DBT)为例,实验结果表明DBT是软碱。为了进一步提高吸附脱硫性能,应通过适当的策略调整BN样品的硬度达到DBT的硬度。
发明内容
本发明的目的在于提供一种硼缺陷氮化硼纳米片的吸附剂。
本发明另一个目的在于提供上述吸附剂的制备方法。
本发明还提供了上述吸附剂的应用。
为实现上述目的,制备方法包括,(1)将硼酸和氮源溶解到超纯水中,然后加入共反应源,上述溶液在80~90℃下搅拌蒸发。(2)待溶液全部蒸发完后,所得固体放入管式炉中在氮气或氨气的气氛下700~1000℃煅烧5h,得到硼缺陷氮化硼纳米片。
所述的氮源是二氰二胺;所述硼酸和氮源的摩尔比是1:6~1:12,优选1:10。
所述的共反应源是指巴比妥酸。
所述的巴比妥酸与硼酸的摩尔比为0.1:1~2:1,优选1:1。
上述方法得到的硼缺陷氮化硼纳米片吸附剂,根据紫外漫反射光表征发现因为巴比妥酸的加入,氮化硼的禁带宽度变小;而X-射线光电子价带谱确定巴比妥酸的加入不会影响氮化硼的价带,因此可以得出巴比妥酸的加入,氮化硼的导带降低。由于B 2p决定了氮化硼的导带,导带的降低意味着吸电子能力降低,化学硬度的降低。
上述硼缺陷氮化硼纳米片有吸附降低燃油中芳香硫化物的用途。
本发明吸附降低燃油中芳香硫化物在常温,常压下进行,反应条件温和。
本发明提供了一种新型的硼缺陷氮化硼纳米片吸附剂,由于部分硼原子的缺失,导致氮化硼化学硬度降低,能与软碱的二苯并噻吩形成很好的相互作用,从而除去燃油中的二苯并噻吩。
本发明具有以下优点:
1、制备方法简单,成本低。
2、所筛选的硼缺陷氮化硼纳米片吸附剂具有高吸附活性,高选择性。
具体实施方式
下面通过实例对本发明给予进一步的说明。
实施例1
0.01mol硼酸,0.06mol二氰二胺,0.001mol巴比妥酸溶解在40ml的超纯水中,在80℃下搅拌,待溶剂水完全蒸发完后,将得到的白色固体在氮气气氛下700℃煅烧5小时,所得产物用BN-0.001表示。
实施例2
0.01mol硼酸,0.08mol二氰二胺,0.005mol巴比妥酸溶解在40ml的超纯水中,在80℃下搅拌,待溶剂水完全蒸发完后,将得到的白色固体在氮气气氛下800℃煅烧5小时,所得产物用BN-0.005表示。
实施例3
0.01mol硼酸,0.1mol二氰二胺,0.01mol巴比妥酸溶解在40ml的超纯水中,在90℃下搅拌,待溶剂水完全蒸发完后,将得到的白色固体在氮气气氛下900℃煅烧5小时,所得产物用BN-0.01表示。
实施例4
0.01mol硼酸,0.12mol二氰二胺,0.015mol巴比妥酸溶解在40ml的超纯水中,在90℃下搅拌,待溶剂水完全蒸发完后,将得到的白色固体在氮气气氛下1000℃煅烧5小时,所得产物用BN-0.015表示。
实施例5
将实施例1~4所得的硼缺陷氮化硼纳米片吸附剂用于降低燃油中芳香硫化物。
燃油类型:(1)模拟油是将二苯并噻吩溶解在正辛烷中,配成硫含量为500ppm模型油;(2)柴油为加氢处理后柴油,硫含量为600ppm;(3)FCC汽油,硫含量为150ppm。
在100ml震荡瓶中加入0.05g活性氮化硼和20ml模拟油或真实油。将震荡瓶放入震荡器中,常温常压下进行吸附反应。油品采用荧光测硫仪检测油中硫化物的含量,计算吸附容量。结果显示,硼缺陷氮化硼纳米片有较高的吸附容量。
序号 | 油品 | 活性氮化硼 | 时间/小时 | 吸附容量mg/g |
5 | 模拟油 | BN-0.001 | 5 | 28.4 |
6 | 模拟油 | BN-0.005 | 5 | 32.8 |
7 | 模拟油 | BN-0.01 | 5 | 43.6 |
8 | 模拟油 | BN-0.015 | 5 | 31.2 |
9 | 柴油 | BN-0.01 | 5 | 35.2 |
10 | 汽油 | BN-0.01 | 5 | 28.6 |
Claims (7)
1.一种硼缺陷氮化硼纳米片,其特征在于,采用如下方法制备:
(1)将硼酸和氮源溶解到超纯水中,然后加入共反应源,上述溶液在80~90℃下搅拌蒸发;
(2)待溶液全部蒸发完后,所得固体放入管式炉中在氮气或氨气的气氛下700~1000℃煅烧5h,得到硼缺陷氮化硼纳米片。
2.如权利要求1所述的一种硼缺陷氮化硼纳米片,其特征在于,所述的氮源是二氰二胺;所述硼酸和氮源的摩尔比是1:6~1:12。
3.如权利要求2所述的一种硼缺陷氮化硼纳米片,其特征在于,所述硼酸和氮源的摩尔比是1:10。
4.如权利要求1所述的一种硼缺陷氮化硼纳米片,其特征在于,所述的共反应源是指巴比妥酸,所述的巴比妥酸与硼酸的摩尔比为0.1:1~2:1。
5.如权利要求4所述的一种硼缺陷氮化硼纳米片,其特征在于,所述的巴比妥酸与硼酸的摩尔比为1:1。
6.如权利要求1所述的一种硼缺陷氮化硼纳米片,其特征在于,价带不变,导带降低,氮化硼的化学硬度降低。
7.如权利要求1-6任一所述的一种硼缺陷氮化硼纳米片在吸附降低燃油中芳香类硫化物的用途。
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