介孔分子筛SBA-15负载Ni-B非晶态合金催化噻吩加氢脱硫性能的研究
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摘要
本文采用化学还原法制备了Ni-B/SBA-15非晶态合金催化剂,以噻吩加氢脱硫为探针反应,研究了不同的SBA-15改性方法对Ni-B/SBA-15催化加氢脱硫性能的影响。采用等离子发射光谱法(ICP)、小角X衍射(小角XRD)、程序升温还原(TPR)、程序升温脱附(TPD)等方法考察了载体和催化剂的结构及表面性能。
本文第一部分分别采用原位合成和后处理改性的方法将磺酸基团引入介孔分子筛SBA-15,以增强SBA-15表面酸性,提高催化剂加氢脱硫反应的活性。结果表明,与未改性SBA-15为载体相比,对甲苯磺酸原位加入及对甲苯磺酸后处理改性SBA-15负载的Ni-B非晶态合金催化剂具有较多的酸量和吸附中心,有利于硫化物分子中的C-S键断裂,从而提高催化剂脱硫的效率。
本文第二部分采用共价接枝法制备APTS改性SBA-15,将氨基官能团引入SBA-15改善其化学环境,其负载的Ni-B催化剂噻吩转化率达到50.8%。由于氨基与Ni2+的络合作用,有助于Ni在催化剂中的分散,因而更容易被还原。ICP结果表明,在相同的制备条件下,相比未改性的SBA-15,APTS改性SBA-15使其催化剂中Ni的负载量增加,并且非晶态合金组成中Ni的含量也增大,B的含量降低,有利于提高催化剂的活性。
本文第三部分采用燃烧法制备得到SBA-15-ZnO复合载体,并以其为载体制备了Ni-B非晶态合金催化剂。结果表明,随着ZnO在复合载体中的含量增大,其负载的催化剂加氢脱硫反应活性有所降低。然而,由于ZnO制备成本大大地低于SBA-15,且其制备工艺远比SBA-15合成简单。因此,可选择添加少量ZnO与SBA-15制备复合载体用于加氢脱硫反应。
In this paper, with chemical reduction method Ni-B/SBA-15 amorphous alloy catalyst was prepared using different modified SBA-15 as surpports. The catalytic activity of catalysts was characterized with thiophene hydrodesulfurization reaction. Moreover, supports and catalysts were characterized by ICP, small-angle XRD, TPR, TPD, SEM and TEM.
In the first part of this thesis, SBA-15 was modified with TsOH by in situ synthesis and post treatment modification method respectively. It was found that the catalyst performance of Ni-B catalysts supported by SBA-15 containing TsOH was better than the one supported by pure SBA-15. SBA-15 modified with TsOH by both two kinds of methods has more acid sites and harder acid ability, which would benefit for breaking C-S bond and then improving efficiency of catalyst.
In the second part, Ni-B/SBA-15-APTS which has higher catalytic activity was prepared. The complexation between -NH2 and Ni2+ was benefit for the good dispersion of Ni-B alloy particles and more Ni2+ could be reduced. ICP results also show that quantity of Ni supported in SBA-15-APTS was bigger than pure SBA-15, and the content of Ni in Ni-B amorphous alloy was increased.
Finaly, Ni-B amorphous alloy was prepared with ZnO-SBA-15 composite support was prepared. It was discovered that the hydrodesulfurization poperty of catalyst with ZnO-SBA-15 composite support was decreased with the introduction of ZnO. While the preparation process was much easier than the one of SBA-15, and the cost of the former also was lower than the latter. So ZnO-SBA-15 composite support with certain quantity of ZnO was considerable for hydrodesulfurization.
本文第一部分分别采用原位合成和后处理改性的方法将磺酸基团引入介孔分子筛SBA-15,以增强SBA-15表面酸性,提高催化剂加氢脱硫反应的活性。结果表明,与未改性SBA-15为载体相比,对甲苯磺酸原位加入及对甲苯磺酸后处理改性SBA-15负载的Ni-B非晶态合金催化剂具有较多的酸量和吸附中心,有利于硫化物分子中的C-S键断裂,从而提高催化剂脱硫的效率。
本文第二部分采用共价接枝法制备APTS改性SBA-15,将氨基官能团引入SBA-15改善其化学环境,其负载的Ni-B催化剂噻吩转化率达到50.8%。由于氨基与Ni2+的络合作用,有助于Ni在催化剂中的分散,因而更容易被还原。ICP结果表明,在相同的制备条件下,相比未改性的SBA-15,APTS改性SBA-15使其催化剂中Ni的负载量增加,并且非晶态合金组成中Ni的含量也增大,B的含量降低,有利于提高催化剂的活性。
本文第三部分采用燃烧法制备得到SBA-15-ZnO复合载体,并以其为载体制备了Ni-B非晶态合金催化剂。结果表明,随着ZnO在复合载体中的含量增大,其负载的催化剂加氢脱硫反应活性有所降低。然而,由于ZnO制备成本大大地低于SBA-15,且其制备工艺远比SBA-15合成简单。因此,可选择添加少量ZnO与SBA-15制备复合载体用于加氢脱硫反应。
In this paper, with chemical reduction method Ni-B/SBA-15 amorphous alloy catalyst was prepared using different modified SBA-15 as surpports. The catalytic activity of catalysts was characterized with thiophene hydrodesulfurization reaction. Moreover, supports and catalysts were characterized by ICP, small-angle XRD, TPR, TPD, SEM and TEM.
In the first part of this thesis, SBA-15 was modified with TsOH by in situ synthesis and post treatment modification method respectively. It was found that the catalyst performance of Ni-B catalysts supported by SBA-15 containing TsOH was better than the one supported by pure SBA-15. SBA-15 modified with TsOH by both two kinds of methods has more acid sites and harder acid ability, which would benefit for breaking C-S bond and then improving efficiency of catalyst.
In the second part, Ni-B/SBA-15-APTS which has higher catalytic activity was prepared. The complexation between -NH2 and Ni2+ was benefit for the good dispersion of Ni-B alloy particles and more Ni2+ could be reduced. ICP results also show that quantity of Ni supported in SBA-15-APTS was bigger than pure SBA-15, and the content of Ni in Ni-B amorphous alloy was increased.
Finaly, Ni-B amorphous alloy was prepared with ZnO-SBA-15 composite support was prepared. It was discovered that the hydrodesulfurization poperty of catalyst with ZnO-SBA-15 composite support was decreased with the introduction of ZnO. While the preparation process was much easier than the one of SBA-15, and the cost of the former also was lower than the latter. So ZnO-SBA-15 composite support with certain quantity of ZnO was considerable for hydrodesulfurization.
引文
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