Investigation of Selectivity over HDS Catalysts by in situ IR Spectra of Adsorbed CO and Molecular Simulation Calculation

doi:10.3969/j.issn.0251-0790.2012.02.030

Abstract

Abstract: Two CoMo/Al₂O₃ catalysts with different supports(Al₂O₃-A and Al₂O₃-B) were prepared by pore-filling impregnation. Active phases of the sulfided CoMo/Al₂O₃ catalysts were identified and analyzed quantitatively by means of in situ FTIR spectrum of adsorbed CO. The charge distribution, adsorption energy and activation energies of hydrotreating reaction of thiophene and 1-hexene on the MoS₂ surface before and after adding Co were calculated by molecular simulation, respectively. The results reveal that the increase of CoMoS phase on the catalyst surface improves the HDS/HYD selectivity. Compared with HYD site of 1-hexene, the electron accepting ability of thiophene HDS site can be improved significantly by the adding of Co support, which benefits to improve the adsorptions of thiophene on the surface over catalyst and decrease the activation energy barrier of HDS for thiophene. This fact also points out that the CoMoS phase is the active site of high HDS and HDS/HYD selectivity.

Key words: Adsorption of CO, In situ FTIR spectrum, Quantum chemical calculation, Fluid catalytic cracking(FCC) gasoline, Hydrode-sulfurization selectivity

CLC Number:

O643.3

TrendMD:

QIHE Ri-Ma, ZHAO Xiao-Guang, ZHANG Yun-Hong, YUAN Hui, XU Guang-Tong. Investigation of Selectivity over HDS Catalysts by in situ IR Spectra of Adsorbed CO and Molecular Simulation Calculation[J]. Chem. J. Chinese Universities, 2012, 33(02): 383.

References

[1] SUN Ai-Guo(孙爱国), WANG Dao-Ming(汪道明). Petro. Ref. Engin.(炼油设计)[J], 2002, 32(10): 4-9 [2] LI Da-Dong(李大东). Acta Petrolei Sinica(石油学报)[J], 2005, 21(3): 17-24 [3] LI M. F., LI H. F., Jiang F., Chu Y., Nie H.. Catal. Today [J], 2010, 149(1/2): 35-39 [4] QI Xing-Yi(齐兴义), GUO Lin(郭林), LI Wen-Zhao(李文钊), Michel Lacroix, Michel Vrinat, Francoise Mauge. Chem. J. Chinese Universities(高等学校化学学报)[J], 2002, 23(2): 296-297 [5] Cristol S., Paul J. F., Payen E., Bougeard D., Hutschka F., Clemendot S.. J. Catal.[J], 2004, 224: 138-147 [6] Cristol S., Paul J. F., Schovsbo C., Veilly E., Payen E.. J. Catal.[J], 2006, 239: 145-153 [7] Paul J. F., Cristol S.. Catal. Today[J], 2008, 130: 139-148 [8] Raybaud P., Hafner J., Kresse G., Toulhoat H.. Phys. Rev. Lett.[J], 1998, 80: 1481-1484 [9] Todorova T., Prins R., Weber T.. J. Catal.[J], 2005, 236: 190-204 [10] Moses P. G., Hinnemann B., Topsoe H., Norskov J.. J. Catal.[J], 2007, 248: 188-203 [11] Bruneta S., Meya D., Perot G., Christophe B., Fabrice D.. Appl. Catal. A: Gen.[J], 2005, 278: 143-172 [12] Mochizuki T., Itou H., Toba M., Miki Y., Yoshimura Y.. Energ. Fuel[J], 2008, 22: 1456-1462 [13] Shi G. J., Zhao H. Y., Song L. G., Shen J. Y.. Energ. Fuel[J], 2008, 22: 2450-2454 [14] Toba M., Miki Y., Matsui T., Harada M., Yoshimura Y.. Appl. Catal. B: Environ.[J], 2007, 70: 542-547 [15] Fan Y., Lu J., Shi G., Liu H. Y., Bao X. J.. Catal. Today[J], 2007, 125: 220-228 [16] Toba M., Miki Y., Kanda Y., Harada M., Yoshimura Y.. Catal. Today[J], 2005, 104: 64-69 [17] Hatanaka S.,Yamada M.. Ind. Eng. Chem. Res.[J], 1997, 36: 5110-5117 [18] Hatanaka S.,Yamada M.. Ind. Eng. Chem. Res.[J], 1998, 37: 1748-1754 [19] Lélias M. A., Kooyman P. J., Mariey L., Olivieroa L., Traverta A., van Gestel J.. J. Catal.[J], 2009, 267: 14-23 [20] Travert A., Dujardin C., Maug F., Veilly E., Cristol S., Paul J. F., Payen E.. J. Phys. Chem. B[J], 2006, 110: 1261-1270 [21] Lélias M. A.,Guludec E. Le., Mariey L., van Gestel J., Travert A., Oliviero L., Mauge F.. Catal. Today[J], 2010, 150(3/4): 179-185 [22] Dujardin C., Lelias M. A., Gestel J. van, Travert A., Duchet J. C., Mauge F.. Appl. Catal. A: Gen.[J], 2007, 322: 46-57 [23] Sundaramurthy V., Dalai A. K., Adjaye J.. Catal. Lett.[J], 2005, 102(3/4): 299-306 [24] CHEN Wen-Bin(陈文斌). Influence of Acid-base Properties of Support on the Properties of Sulfided Mo and CoMo/Al₂O₃ Hydrotreating Catalysts(载体酸碱性质对硫化态钼和钴钼催化剂性质的影响)[D], Beijing: Research Institute of Petroleum Processing, 2009 [25] Mueller B., van Langeveld A. D., Moulijn J. A., Knoezinger H.. J. Phys. Chem.[J], 1993, 97(35): 9028-9033 [26] Lélias M. A., Gestel J van., Maug F., van Veen J. A. R.. Catal. Today[J], 2008, 130: 109-116 [27] Sorescu D. C., Cugini A. V., Sholl D. S.. Fuel Chemistry Division Preprints[J], 2002, 47(1): 226-227 [28] Qiu L. M., Xu G. T.. Appl. Surf . Sci.[J], 2010, 256: 3413-3417