Influence of Ni on the active phase and hydrodenitrogenation and hydrodesulfurization activities of MoS2 catalysts
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摘要: 为了获得较多高活性II型MoS2活性相,采用四硫代钼酸铵原位热分解法制备了MoS2基催化剂,对比分析了Ni源引入方式和热分解气氛对MoS2活性相微观结构、表面元素化学状态和加氢脱氮脱硫性能等的影响。结果表明,同时引入Mo源和Ni源原位沉淀生成无定形NiMoS4后,再热分解有利于Ni取代MoS2片晶边缘的Mo原子,被修饰后的MoS2片晶保持较高的分散度、适宜的长度(3−5 nm)和堆叠层数(2−4层),从而在边缘暴露较多具有加氢和氢解活性的rim和corner活性位点。热分解气氛H2比N2更有利于Ni在热分解过程中取代MoS2边缘的Mo原子,形成更多II型Ni-Mo-S活性结构,有利于喹啉和二苯并噻吩的吸附活化和加氢反应。当加氢反应温度340 ℃、氢压3 MPa、重时空速23.4 h−1、氢油比为600和使用0.1 g NMS-H2催化剂时,喹啉加氢脱氮转化率达23.8%,二苯并噻吩加氢脱硫转化率达93.3%。Abstract: To obtain type II active phase with higher activity, MoS2-based catalysts were prepared by thermal decomposition of ammonium tetrathiomolybdate. The influence of Ni adding way and decomposition atmosphere on the microstructures of MoS2 slabs, chemical state of surface elements, as well as hydrodesulfurization and hydrodenitrogenation activities were investigated. Results indicated that simultaneous impregnation of Mo and Ni precursors caused in situ deposition of amorphous NiMoS4 over the support surface, which subsequently facilitated the substitution of Mo atoms by Ni atoms at MoS2 edges. Accordingly, these decorated catalysts exhibited higher dispersion of MoS2 slabs with more suitable slab length (3–5 nm) and stacking number (2–4), which attributed to larger numbers of rim and corner active sites exposed at the edges. These active sites were essential in hydrogenation and hydrogenolysis reactions. In comparison with N2 atmosphere, thermal decomposition in H2 atmosphere was more conducive to the substitution of Mo atoms by Ni atoms at MoS2 edges, which provided more active Ni-Mo-S structures for the adsorption, activation and hydrogenolysis of quinoline and dibenzothiophene molecules. The catalyst prepared by thermal decomposition of NiMoS4 in H2 atmosphere showed superior activities in the quinoline hydrodenitrogenation with 23.8% conversion and in the dibenzothiophene hydrodesulfurization with 93.3% conversion, under the conditions of 340 °C, 3 MPa, a weight hourly space velocity of 23.4 h–1, H2/oil volume ratio of 600 and 0.1 g of NMS-H2 catalysts.
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Key words:
- NiMo sulfide /
- quinoline /
- dibenzothiophene /
- hydrogenation reaction
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表 1 样品的物理结构性质
Table 1 Physical structure properties of sample
Sample Specific surface area/(m2·g−1) Total pore volume/(cm3·g−1) Most probable pore size/nm γ-Al2O3 288 1.03 14.3 NMS-N2 204 0.57 11.3 NMS-H2 206 0.60 11.7 NMS-T-N2 198 0.62 12.6 表 2 MoS2片晶平均长度LA、平均堆叠层数NA、分散度fMo和不同活性位点的比例
Table 2 Average length LA, stack number NA, Mo atoms dispersion and fraction of different active sites
Catalyst LA/nm NA fMo R fe fr fc NMS-N2 3.9 4.2 0.28 1.09 0.248 0.228 0.059 NMS-H2 3.7 3.4 0.29 0.58 0.257 0.443 0.073 NMS-T-N2 4.9 6.6 0.23 1.33 0.213 0.160 0.038 表 3 Mo 3d和Ni 2p信号的分峰拟合
Table 3 Deconvolution results of Mo 3d and Ni 2p signals
Sample Mosulf/
%Mo distribution/
%Nisulf/
%Ni distribution/
%Mo4+ Mo5+ Mo6+ NiSx NiMoS Ni2+ NMS-N2 40 40 13 47 71 15 56 29 NMS-H2 47 47 14 39 87 16 71 13 NMS-T-N2 39 39 17 44 66 11 55 34 表 4 不同催化剂的喹啉HDN性能和选择性
Table 4 Quinoline HDN activity and selectivity over different catalysts
Catalyst xHDN/% Product selectivity/% Route ratio PCH PCHE PB DHQ 58THQ OPA 14THQ (PCH + PCHE)/PB NMS-N2 12.8 9.7 1.4 3.8 9.6 25.7 3.5 46.2 2.92 NMS-H2 23.8 17.8 2.2 6.5 10.3 24.9 4.7 33.4 3.07 NMS-T-N2 8.6 6.3 1.3 2.9 8.2 20.4 3.3 57.5 2.62 表 5 不同催化剂的二苯并噻吩HDS性能和选择性
Table 5 Dibenzothiophene HDS activity and selectivity over different catalyst
Catalyst xHDS/% Product selectivity/% Route ratio BP CHB BCH BP/(CHB + BCH) NMS-N2 91.6 74.8 24.0 1.2 2.96 NMS-H2 93.3 65.3 30.8 3.9 1.88 NMS-T-N2 81.9 80.5 19.1 0.4 4.12 -
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