柠檬酸对加氢脱硫催化剂性能的影响
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摘要
随着原油劣质化程度日益严重,环保法规对汽柴油中硫含量限制越来越严格,深度加氢脱硫使汽柴油低硫化成为一种必然趋势,而实现这一目标最重要的手段就是开发新的高性能的加氢脱硫催化剂。
本文用过量浸渍法制备了添加和不添加柠檬酸(CA)两种系列以氧化铝和氧化铝/活性炭为载体的NiMo加氢脱硫催化剂。通过N2吸附、X射线衍射(XRD)、程序升温还原(TPR)、X射线荧光(XRF)等方法对催化剂及载体进行了表征,以1wt.%二苯并噻吩(DBT)的十氢萘溶液为原料,在三相滴流床反应器上评价了催化剂的加氢脱硫活性,考察了用不同方式添加柠檬酸对催化剂活性造成的影响,探究了柠檬酸在加氢脱硫反应中所起的作用。N2吸附结果表明,添加柠檬酸制备的催化剂孔径主要集中在中孔,与未添加的催化剂相比比表面积略有下降；与添加乙酸相比,添加柠檬酸制备的氧化铝-活性炭复合载体孔径变大。活性评价结果表明,以不同方式添加柠檬酸后,催化剂的加氢脱硫活性有不同程度的提高；以氧化铝为载体制备的一系列催化剂中,柠檬酸的最佳添加量为CA/Ni=1:而CA/Mo=1为氧化铝/活性炭复合载体制备的催化剂中柠檬酸的最佳添加量。TPR和XRD结果显示添加柠檬酸后Mo物种还原峰温度有所降低,说明添加柠檬酸后催化剂中金属组分与载体间存在弱的相互作用,活性组分在载体上分散的较均匀,担载量也较高,催化剂的活性有所提高。
本文在相同的条件下考察了商业催化剂HT-2003的加氢脱硫催化性能,通过对比发现自制NiMo-CA/A系列催化剂催化活性均高于该商业催化剂。
The crude oil quality is becoming worse and worse, meanwhile the environmental legislations pay more attention to confine the content of sulfur in diesel or gas oil. Thus, the deep hydrodesulfurization processes is becoming more and more important for the low sulfur gasoline and diesel. To achieve this goal, one of the most important approachs is to develop a novel high-performance hydrodesulfurization catalyst.
Two kinds of Ni-Mo catalysts supported on alumina and alumina-activated carbons prepared by impregnation method with and without ctric acid (CA) have been compared. Catalytic activity of the the catalysts for the hydrodesulfurization of dibenzothiophene (DBT) have been studied with1.0wt.%DBT-decalin feed in a three-phase trickle bed reactor. The catalysts and supports were further characterized by N2adsorption, XRD, TPR, XRF techniques, so that the influence of adding CA through different ways on the activity of the catalysts and the role of citric acid in the catalysts preparation could be elucidated. The N2adsorption results show that the pore diameter of catalysts with CA mostly falls in mesoporous and the specific surface areas are slightly decreased compared with those without CA. The pore diameter of alumina-activated carbon support prepared with CA is larger then that with acetic acid. Adding CA during catalyst preparation by different ways has effectively increased the catalytic activity of the catalyst. The optimum catalyst activity is obtained at a CA/Ni mole ratio=1for the catalysts supported on alumina, and at a CA/Mo mole ratio=1for the catalysts supported on alumina-activated carbon. TPR and XRD results show that the presence of CA can properly weaken the metal-support interaction, increase the dispersion of NiMo and therefore the effective amount of NiMo components loaded on the surface of the supports. And so that the catalytic activity of the catalysts is increased.
Hydrodesulfurization catalytic performance of the commercial catalyst HT-2003was carried out under the same conditions. Compared with the commercial catalysts HT-2003, the catalytic activity of the self-made catalyst NiMo-CA/A is higher.
本文用过量浸渍法制备了添加和不添加柠檬酸(CA)两种系列以氧化铝和氧化铝/活性炭为载体的NiMo加氢脱硫催化剂。通过N2吸附、X射线衍射(XRD)、程序升温还原(TPR)、X射线荧光(XRF)等方法对催化剂及载体进行了表征,以1wt.%二苯并噻吩(DBT)的十氢萘溶液为原料,在三相滴流床反应器上评价了催化剂的加氢脱硫活性,考察了用不同方式添加柠檬酸对催化剂活性造成的影响,探究了柠檬酸在加氢脱硫反应中所起的作用。N2吸附结果表明,添加柠檬酸制备的催化剂孔径主要集中在中孔,与未添加的催化剂相比比表面积略有下降；与添加乙酸相比,添加柠檬酸制备的氧化铝-活性炭复合载体孔径变大。活性评价结果表明,以不同方式添加柠檬酸后,催化剂的加氢脱硫活性有不同程度的提高；以氧化铝为载体制备的一系列催化剂中,柠檬酸的最佳添加量为CA/Ni=1:而CA/Mo=1为氧化铝/活性炭复合载体制备的催化剂中柠檬酸的最佳添加量。TPR和XRD结果显示添加柠檬酸后Mo物种还原峰温度有所降低,说明添加柠檬酸后催化剂中金属组分与载体间存在弱的相互作用,活性组分在载体上分散的较均匀,担载量也较高,催化剂的活性有所提高。
本文在相同的条件下考察了商业催化剂HT-2003的加氢脱硫催化性能,通过对比发现自制NiMo-CA/A系列催化剂催化活性均高于该商业催化剂。
The crude oil quality is becoming worse and worse, meanwhile the environmental legislations pay more attention to confine the content of sulfur in diesel or gas oil. Thus, the deep hydrodesulfurization processes is becoming more and more important for the low sulfur gasoline and diesel. To achieve this goal, one of the most important approachs is to develop a novel high-performance hydrodesulfurization catalyst.
Two kinds of Ni-Mo catalysts supported on alumina and alumina-activated carbons prepared by impregnation method with and without ctric acid (CA) have been compared. Catalytic activity of the the catalysts for the hydrodesulfurization of dibenzothiophene (DBT) have been studied with1.0wt.%DBT-decalin feed in a three-phase trickle bed reactor. The catalysts and supports were further characterized by N2adsorption, XRD, TPR, XRF techniques, so that the influence of adding CA through different ways on the activity of the catalysts and the role of citric acid in the catalysts preparation could be elucidated. The N2adsorption results show that the pore diameter of catalysts with CA mostly falls in mesoporous and the specific surface areas are slightly decreased compared with those without CA. The pore diameter of alumina-activated carbon support prepared with CA is larger then that with acetic acid. Adding CA during catalyst preparation by different ways has effectively increased the catalytic activity of the catalyst. The optimum catalyst activity is obtained at a CA/Ni mole ratio=1for the catalysts supported on alumina, and at a CA/Mo mole ratio=1for the catalysts supported on alumina-activated carbon. TPR and XRD results show that the presence of CA can properly weaken the metal-support interaction, increase the dispersion of NiMo and therefore the effective amount of NiMo components loaded on the surface of the supports. And so that the catalytic activity of the catalysts is increased.
Hydrodesulfurization catalytic performance of the commercial catalyst HT-2003was carried out under the same conditions. Compared with the commercial catalysts HT-2003, the catalytic activity of the self-made catalyst NiMo-CA/A is higher.
引文
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[3]柴永明,安高军,柳云骐,等.过渡金属硫化物催化剂催化加氢作用机理[J].化学进展,2007,19(2/3)：234-242.
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[5]SHI G J, ZHAO Y, HUANG Y A, et al. Mesoporous Carbon Supported Co-Mo and Ni-Mo Catalysts for Hydrodesulfurization [J]. Chin. J. Catal.2010,26(8):961-964.
[6]林凌,伊晓东,邱波,等.免预硫化的加氢脱硫MoNiP/Al203催化剂的制备和表征[J].催化学报,2007,28(12)：1096-1100.
[7]LI H F, LIMF, CHU Y, et al. Essential role of citric acid in preparation of efficient NiW/Al2O3 HDS catalysts [J]. Applied Catalysis A:General,2011,403(1-2):75-82.
[8]BERGWERFF J A, JANSEN M, LELIVELD B (R) G, et al. Influence of the preparation method on the hydrotreating activity of MoS2/Al2O3 extrudates:A Raman microspectroscopy study on the genesis of the active phase [J]. Journal of Catalysis, 2006,243(2):292-302.
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