Na_2O，K_2O及其引入顺序对过渡金属催化剂HDS的影响
摘要
环境问题已经成为世界范围关注的焦点,环保法规中越来越严格的气体排放标准使炼油企业面临深度脱硫的压力。而柴油中的含硫化合物如二苯并噻吩(DBT)以及其衍生物等,由于取代基空间位阻效应,导致反应活性低,使深度脱硫问题近年来变得更加棘手。在加氢脱硫过程中,DBT通过两条平行反应途径进行脱硫。预加氢脱硫途径是先将DBT的一个苯环加氢后再脱去硫原子,进而生成苯基环己烷(CHB)。在直接脱硫途径中,硫原子的脱除是通过直接断裂C-S键而生成联苯(BP)。两条路径对比不难看出,预加氢脱硫途径伴随着氢气的高消耗,从而降低了加氢脱硫过程中的经济性。因此,在研发催化剂过程中加氢脱硫(HDS)活性以及直接脱硫产物BP选择性应该得到均衡考虑。
通过不同的引入顺序将碱金属组分Na2O和K20引入到NiMo和NiW催化剂前躯体中,并以质量分数0.8%DBT的十氢萘溶液作模型化合物,考察了硫化物催化剂的HDS反应性能。对于NiMo体系的催化剂,XRD和TPR结果表明,引入Na2O和K20促进了过渡金属硫化物催化剂前驱体中β-NiMoO4物种的生成,不利于活性组分的分散,同时还抑制了其还原。UV-Vis结果则表明引入Na2O和K20对催化剂中物种的分布和配位状态有一定的影响。反应结果表明,Na20和K20引入以后DBT在硫化物催化剂上主要是以直接脱硫途径进行反应的。
Na20引入顺序对NiMo/MCM-41催化剂活性有较大影响。共浸渍法引入Na20时,同时抑制了催化剂加氢反应路径(HYD)和直接脱硫反应路径(DDS)活性,因此其HDS活性最低。而在活性组分之前引入Na2O,对催化剂HYD活性影响最小,但DDS活性显著增加,提高了NiMo/MCM-41总的HDS反应活性,降低了氢耗。
K20的引入顺序的影响与Na20基本一致,但是由于其碱性更强,因此更加抑制了催化剂HYD活性,使其BP选择性更高。同时对于加氢活性更强的NiW体系催化剂,Na2O,K20的引入造成HDS反应活性的下降。
以上结果也说明可以通过控制碱金属氧化物的引入顺序,调变催化剂活性和选择性,是一种对硫化物催化剂有效的改性方法。
In recent years, much attention has been paid to air pollution and production of clean diesel by deep hydrodesulfurization(HDS) has attracted increasing attention due to the implemen-tation of more stringent specifications in many countries. Among all sulfur-containing compounds present in diesel, dibenzothiophene(DBT) and its alkylated derivatives are the most refractory compounds to desulfurize due to steric hindrance. The HDS of DBT proceeds through two parallel pathways. In the hydrogenation (HYD) pathway, the aromatic ring is hydrogenated and the sulfur is removed subsequently to form cyclohexylbenzene (CHB), while in the so-called hydrogenolysis (HYG) pathway, the sulfur atom is directly removed from the molecule via C-S bond cleavage, leading to the formation of biphenyl (BP). We can conclude that the HYD pathway needs more hydrogen consumption from the contrast. Hence, studies on both the activity and the BP selectivity of HDS catalysts are needed for developing better deep HDS catalysts.
Na2O and K2O was introduced to transitional metal sulfide catalysts precursor by different sequences, and the hydrodesulfurization (HDS) performances of the prepared catalysts were studied using a model fuel containing 0.8 wt% DBT in decalin. The hydrodesulfurization (HDS) performances of the transitional metal sulfide catalysts were studied using a model fuel containing 0.8 wt% DBT in decalin. As to NiMo catalysts, the XRD and TPR results indicated that introduction of Na2O and K2O not only facilitated the formation ofβ-NiMoO4, leading to decrease in dispersion of active species, but also hindered the reducibility of NiMo/MCM-41 catalyst precursor. The UV-Vis results indicated that both the distributions and the coordination states of the active species were affected by introduction of Na2O and K2O to NiMo/MCM-41. The results show that the HDS of DBT predominately takes the route of direct desulfurization (DDS) over the transitional metal sulfide catalysts when K2O and Na2O were introduced.
The HDS activity of NiMo/MCM-41 was strongly affected by the Na2O introduction sequence. For the catalyst in which Na2O was introduced by the co-impregnation method, both the activities of the hydrogenation pathway (HYD) and direct desulfurization pathway (DDS) were inhibited, resulting in a decrease in the overall HDS activity. The addition of Na2O before the loading of the active components showed a minimum influence on the HYD activity of NiMo/MCM-41, but significantly enhanced its DDS activity, leading to the improvement in the overall HDS activity and decrease in the H2 consumption.
The K2O introduction sequence has the same effect as Na2O, a decrease in the catalyst hydrogenation activity and increase the BP selectivity are caused by increase the alkaline of catalyst. Nevertheless, neither the Na20 nor K2O can play positive effects on the HDS activity for NiW catalysts.
The results suggested that both the activity and selectivity of the sulfide catalysts can be modified by controlling the addition sequence of the alkali-metal oxides, which is showed to be an effective way for the modification of the catalysts.
通过不同的引入顺序将碱金属组分Na2O和K20引入到NiMo和NiW催化剂前躯体中,并以质量分数0.8%DBT的十氢萘溶液作模型化合物,考察了硫化物催化剂的HDS反应性能。对于NiMo体系的催化剂,XRD和TPR结果表明,引入Na2O和K20促进了过渡金属硫化物催化剂前驱体中β-NiMoO4物种的生成,不利于活性组分的分散,同时还抑制了其还原。UV-Vis结果则表明引入Na2O和K20对催化剂中物种的分布和配位状态有一定的影响。反应结果表明,Na20和K20引入以后DBT在硫化物催化剂上主要是以直接脱硫途径进行反应的。
Na20引入顺序对NiMo/MCM-41催化剂活性有较大影响。共浸渍法引入Na20时,同时抑制了催化剂加氢反应路径(HYD)和直接脱硫反应路径(DDS)活性,因此其HDS活性最低。而在活性组分之前引入Na2O,对催化剂HYD活性影响最小,但DDS活性显著增加,提高了NiMo/MCM-41总的HDS反应活性,降低了氢耗。
K20的引入顺序的影响与Na20基本一致,但是由于其碱性更强,因此更加抑制了催化剂HYD活性,使其BP选择性更高。同时对于加氢活性更强的NiW体系催化剂,Na2O,K20的引入造成HDS反应活性的下降。
以上结果也说明可以通过控制碱金属氧化物的引入顺序,调变催化剂活性和选择性,是一种对硫化物催化剂有效的改性方法。
In recent years, much attention has been paid to air pollution and production of clean diesel by deep hydrodesulfurization(HDS) has attracted increasing attention due to the implemen-tation of more stringent specifications in many countries. Among all sulfur-containing compounds present in diesel, dibenzothiophene(DBT) and its alkylated derivatives are the most refractory compounds to desulfurize due to steric hindrance. The HDS of DBT proceeds through two parallel pathways. In the hydrogenation (HYD) pathway, the aromatic ring is hydrogenated and the sulfur is removed subsequently to form cyclohexylbenzene (CHB), while in the so-called hydrogenolysis (HYG) pathway, the sulfur atom is directly removed from the molecule via C-S bond cleavage, leading to the formation of biphenyl (BP). We can conclude that the HYD pathway needs more hydrogen consumption from the contrast. Hence, studies on both the activity and the BP selectivity of HDS catalysts are needed for developing better deep HDS catalysts.
Na2O and K2O was introduced to transitional metal sulfide catalysts precursor by different sequences, and the hydrodesulfurization (HDS) performances of the prepared catalysts were studied using a model fuel containing 0.8 wt% DBT in decalin. The hydrodesulfurization (HDS) performances of the transitional metal sulfide catalysts were studied using a model fuel containing 0.8 wt% DBT in decalin. As to NiMo catalysts, the XRD and TPR results indicated that introduction of Na2O and K2O not only facilitated the formation ofβ-NiMoO4, leading to decrease in dispersion of active species, but also hindered the reducibility of NiMo/MCM-41 catalyst precursor. The UV-Vis results indicated that both the distributions and the coordination states of the active species were affected by introduction of Na2O and K2O to NiMo/MCM-41. The results show that the HDS of DBT predominately takes the route of direct desulfurization (DDS) over the transitional metal sulfide catalysts when K2O and Na2O were introduced.
The HDS activity of NiMo/MCM-41 was strongly affected by the Na2O introduction sequence. For the catalyst in which Na2O was introduced by the co-impregnation method, both the activities of the hydrogenation pathway (HYD) and direct desulfurization pathway (DDS) were inhibited, resulting in a decrease in the overall HDS activity. The addition of Na2O before the loading of the active components showed a minimum influence on the HYD activity of NiMo/MCM-41, but significantly enhanced its DDS activity, leading to the improvement in the overall HDS activity and decrease in the H2 consumption.
The K2O introduction sequence has the same effect as Na2O, a decrease in the catalyst hydrogenation activity and increase the BP selectivity are caused by increase the alkaline of catalyst. Nevertheless, neither the Na20 nor K2O can play positive effects on the HDS activity for NiW catalysts.
The results suggested that both the activity and selectivity of the sulfide catalysts can be modified by controlling the addition sequence of the alkali-metal oxides, which is showed to be an effective way for the modification of the catalysts.
引文
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