采用共浸渍法制备了P/Ni摩尔比为2的Ni_2P/SBA-15,再通过二次浸渍引入助剂Mo制得Mo-Ni_2P/SBA-15,将它调制成活件胶后均匀涂敷于预处理后的载体表面,干燥焙烧后在氢气流中采用程序升温还原法,制备了一系列Mo-Ni_2P/SBA-15/堇青石整体式催化剂.采用X射线衍射、N_2吸附-脱附和X射线光电子能谱对催化剂结构进行了表征,以二苯并噻吩为模型含硫化合物,考察了催化剂的加氢脱硫件能.结果表明,Mo的加入增大了催化剂的比表面积,在催化剂表面形成了MoNiP_2,且Ni_2P为主要活性物相.Mo在催化剂表而主要以Mo~(6+)和Mo~(δ+)形式存在;当w(Mo)=4.2%时,n(Mo)/n(Ni+Mo)=0.18的整体式催化剂上二苯并噻吩的转化率最高,且在较低反应温度时以直接脱硫机理为主,而较高反应温度时以加氢脱硫机理为主.
A series of Mo-Ni_2P/SBA-15/cordierite monolithic catalysts with different Mo contents were prepared by dipping a sol containing nickel phosphide precursors (prepared by impregnating nickel nitrate, diammonium hydrogen phosphate, and ammonium into SBA-15) on a pretreated cordierite support followed by temperature-programmed reduction in a H2 flow. The structure of the catalysts was characterized by N2 adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The catalytic performance of the catalysts for hydrode-sulfurization (HDS) was evaluated in a fixed-bed microreactor using dibenzothiophene as the model compound. The results indicated that the addition of Mo increased the surface area of the catalysts. Ni_2P particles were the active phase, and there was the MoNiP_2 phase when Mo was added. The valence states of Mo were mainly Mo~(6+) and Mo~(δ+). The Mo-NiEP/SBA-15/cordierite monolithic catalysts with w(Mo) = 4.2%and n(Mo)/n(Ni+Mo)= 0.18 had perfect HDS catalytic performance. When Mo was added, the hydrodesulfurization route was the dominant path at high temperature, and direct desulfurization route at low temperature.
参考文献
| [1] | Shu Y Y;Oyama S T .[J].Carbon,2005,43:1517. |
| [2] | 王洪学,李翠清,徐景峰,孙桂大,李凤艳.一种新型加氢精制磷化钨催化剂的研究[J].分子催化,2004(04):271-274. |
| [3] | Abu II;Smith KJ .HDN and HDS of model compounds and light gas oil derived from Athabasca bitumen using supported metal phosphide catalysts[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2007(1):58-67. |
| [4] | Brock, SL;Senevirathne, K .Recent developments in synthetic approaches to transition metal phosphide nanoparticles for magnetic and catalytic applications[J].Journal of Solid State Chemistry,2008(7):1552-1559. |
| [5] | Burns A W;Layman K A;Bale D H;Bussell M E .[J].Applied Catalysis A:General,2008,343:68. |
| [6] | Oyama ST. .Novel catalysts for advanced hydroprocessing: transition metal phosphides[J].Journal of Catalysis,2003(1/2):343-352. |
| [7] | 宋立民,李伟,张明慧,陶克毅.Ni2P/SiO2-Al2O3催化剂的制备、表征及其对4,6-二甲基二苯并噻吩加氢脱硫反应的催化性能[J].催化学报,2007(02):143-147. |
| [8] | Lee Y K;Shu Y Y;Oyama S T .[J].Applied Catalysis A:General,2007,322:1914. |
| [9] | Lee Y K;Oyama S T .[J].Journal of Catalysis,2006,239:376. |
| [10] | Yang Sh F;Liang Ch H;Prins R .[J].Journal of Catalysis,2006,237:118. |
| [11] | 吴平易,季生福,胡林华,李成岳.介孔分子筛孔中过渡金属的组装及其催化应用[J].化学进展,2007(04):437-443. |
| [12] | 黄晓凡,季生福,吴平易,刘倩倩,刘辉,朱吉钦,李成岳.Ni2P/SBA-15催化剂的结构及加氢脱硫性能[J].物理化学学报,2008(10):1773-1779. |
| [13] | Wang A J;Ruan L F;Teng Y;Li X Lu M H Ren J Wang Y Hu Y K .[J].Journal of Catalysis,2005,229:314. |
| [14] | Kreutzer M T;Kapteijn F;Moulijn J A .[J].Catalysis Today,2006,111:111. |
| [15] | Centi G;Perathoner S .[J].Catalysis Today,2003,79-80:3. |
| [16] | Wei N;Ji Sh F;Wu P Y;Guo Y N Liu H Zhu J Q Li Ch Y .[J].Catalysis Today,2009,147:s66. |
| [17] | Zholobenko V L;Khodakov A Y;Durand D .[J].Microporous and Mesoporous Materials,2003,66:297. |
| [18] | Rayo P;Rana M S;Ramirez J;Ancheyta J Agui lar-Elguezabal A .[J].Catalysis Today,2008,130:283. |
| [19] | 温钦武,沈健,李会鹏,赵昕,李春晶.介孔分子筛催化剂Co-Mo/SBA-15的制备及其加氢脱硫性能[J].石油学报(石油加工),2009(01):42-47. |
| [20] | Koranyi T I;Vit Z;Poduval D G;Ryoo R Kim H S Hensen E J .[J].Journal of Catalysis,2008,253:119. |
| [21] | Sun FX;Wu WC;Wu ZL;Guo J;Wei ZB;Yang YX;Jiang ZX;Tian FP;Li C .Dibenzothiophene hydrodesulfurization activity and surface sites of silica-supported MoP, Ni2P, and Ni-Mo-P catalysts[J].Journal of Catalysis,2004(2):298-310. |
| [22] | Abu II;Smith KJ .The effect of cobalt addition to bulk MoP and Ni2P catalysts for the hydrodesulfurization of 4,6-dimethyldibenzothiophene[J].Journal of Catalysis,2006(2):356-366. |
| [23] | Cecilia, J.A.;Infantes-Molina, A.;Rodríguez-Castellón, E.;Jiménez-López, A. .A novel method for preparing an active nickel phosphide catalyst for HDS of dibenzothiophene[J].Journal of Catalysis,2009(1):4-15. |
| [24] | 李彦鹏,刘大鹏,刘晓,柴永明,刘晨光.器外预硫化型MoNiP/γ-Al2O3催化剂的二苯并噻吩加氢脱硫活性[J].催化学报,2006(07):624-630. |
| [25] | Teng, Y.;Wang, A.;Li, X.;Xie, J.;Wang, Y.;Hu, Y. .Preparation of high-performance MoP hydrodesulfurization catalysts via a sulfidation-reduction procedure[J].Journal of Catalysis,2009(2):369-379. |
- 下载量()
- 访问量()
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%