尖晶石型衍生的Ni/Al<sub>2</sub>O<sub>3</sub>催化剂低温催化顺酐加氢合成丁二酸酐

引用本文: 李杰, 任远航, 岳斌, 贺鹤勇. 尖晶石型衍生的Ni/Al₂O₃催化剂低温催化顺酐加氢合成丁二酸酐[J]. 催化学报, 2017, 38(7): 1166-1173. doi: 10.1016/S1872-2067(17)62844-4 shu

Citation: Jie Li, Yuanhang Ren, Bin Yue, Heyong He. Ni/Al₂O₃ catalysts derived from spinel NiAl₂O₄ for low-temperature hydrogenation of maleic anhydride to succinic anhydride[J]. Chinese Journal of Catalysis, 2017, 38(7): 1166-1173. doi: 10.1016/S1872-2067(17)62844-4 shu

尖晶石型衍生的Ni/Al₂O₃催化剂低温催化顺酐加氢合成丁二酸酐

复旦大学化学系, 上海市分子催化与功能材料重点实验室, 上海 200433
基金项目:
国家自然科学基金（21173050，21371035）；中石化基金（X514005）.

摘要: 开发高活性的顺酐加氢制丁二酸酐和γ-丁内酯催化剂具有重要的工业意义.顺酐加氢多采用Cu基和Ni基催化剂，但一般Cu基和Ni基催化剂存在反应温度高（170-260℃）和稳定性差等缺点，很有必要开发高活性的顺酐加氢催化剂.我们以拟薄水铝石作为Al₂O₃载体的前驱体，采用浸渍法制备了一系列镍铝尖晶石型衍生的不同Ni含量的Ni/Al₂O₃催化剂，并研究了它们在顺酐加氢反应中的催化性能.
还原前Ni/Al₂O₃催化剂的X射线衍射结果表明，催化剂含有NiAl₂O₄物种.氮吸附结果显示，不同Ni含量的催化剂均具有介孔结构.氢-程序升温还原研究发现，Ni/Al₂O₃催化剂经750℃还原2 h后，其表面上NiAl₂O₄物种能被高效还原.X射线粉末衍射结果表明，750℃还原的Ni/Al₂O₃催化剂中金属Ni颗粒尺寸随着Ni负载量升高而增大.利用一氧化碳-程序升温脱附对750℃还原的Ni/Al₂O₃催化剂进行研究，发现750℃还原的催化剂上金属Ni物种含量从高到低依次为：Ni （7.5%）/Al₂O₃ > Ni （5%）/Al₂O₃ > Ni （2.5%）/Al₂O₃.采用CO化学吸附获得的Ni （2.5%）/Al₂O₃，Ni （5%）/Al₂O₃和Ni （7.5%）/Al₂O₃催化剂上金属Ni颗粒尺度分别为8.0，12.8和15.7 nm.活性研究结果表明，750℃还原的Ni （5%）/Al₂O₃催化剂具有最高的催化活性，这可能是由于Ni （5%）/Al₂O₃催化剂具有较多的Ni活性位点和较合适的Ni颗粒粒度所致.进一步研究发现，在650-750℃还原温度下，Ni （5%）/Al₂O₃催化剂的还原度随着还原温度的升高而升高，Ni分散度随着还原温度的升高而降低.活性结果研究表明，700℃还原的Ni （5%）/Al₂O₃催化剂具有较多的Ni活性位点和较合适的Ni颗粒粒度，具有最高的加氢催化活性，其在120℃，H₂压力为0.5 MPa和质量空速为2 h^-1的反应条件下，能获得近100%的顺酐转化率和90%的丁二酸酐选择性，同时该催化剂具有优良的稳定性.以上结果表明，尖晶石型衍生的Ni/Al₂O₃催化剂是一个十分有应用前景的顺酐加氢催化剂.

关键词:

顺酐
/ 丁二酸酐
/ 加氢
/ 镍
/ 尖晶石

English

Ni/Al₂O₃ catalysts derived from spinel NiAl₂O₄ for low-temperature hydrogenation of maleic anhydride to succinic anhydride

Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, Shanghai 200433, China
Received Date: 22 February 2017
Revised Date: 19 April 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21173050, 21371035) and SINOPEC (X514005).

Abstract: Ni/Al₂O₃ catalysts were derived from spinel NiAl₂O₄ with different Ni content ((2.5, 5 and 7.5) wt%). The catalysts were obtained by H₂ reduction and were investigated for the low-temperature hydro-genation of maleic anhydride (MA) to produce succinic anhydride (SA). The characterization results showed that Ni⁰ active sites were mainly derived during the H₂ reduction from spinel NiAl₂O₄. Among the catalysts studied, employing the optimum preparation and reaction conditions with Ni(5%)/Al₂O₃ yielded the highest catalytic performance. A near-100% conversion of MA and~90% selectivity to SA were achieved at 120℃ and 0.5 MPa of H₂ with a weighted hourly space velocity (MA) of 2 h^-1.

Key words:

1. [1] C. I. Meyer, A. J. Marchi, A. Monzon, T. F. Garetto, Appl. Catal. A, 2009, 367, 122-129.
2. [2] R. C. Zhang, H. B. Yin, D. Z. Zhang, L. Qi, H. H. Lu, Y. T. Shen, T. S. Jiang, Chem. Eng. J., 2008, 140, 488-496.
3. [3] D. Z. Gao, Y. H. Feng, H. B. Yin, A. L. Wang, T. S. Jiang, Chem. Eng. J., 2013, 233, 349-359.
4. [4] X. Liao, Y. Zhang, M. Hill, X. Xia, Y. X. Zhao, Z. Jiang, Appl. Catal. A, 2014, 488, 256-264.
5. [5] J. Li, L. P. Qian, L. Y. Hu, B. Yue, H. Y. He, Chin. Chem. Lett., 2016, 27, 1004-1008.
6. [6] H. J. Yuan, C. L. Zhang, W. T. Huo, C. L. Ning, Y. Tang, Y. Zhang, D. Q. Cong, W. X. Zhang, J. H. Luo, S. Li, Z. L. Wang, J. Chem. Sci., 2014, 126, 141-145.
7. [7] Y. Hara, H. Kusaka, H. Inagaki, K. Takahashi, K. Wada, J. Catal., 2000, 194, 188-197.
8. [8] Y. Q. Huang, Y. Ma, Y. W. Cheng, L. J. Wang, X. Li, Appl. Catal. A, 2015, 495, 124-130.
9. [9] G. Budroni, A. Corma, J. Catal., 2008, 257, 403-408.
10. [10] J. Li, W. P. Tian, L. Shi, Ind. Eng. Chem. Res., 2010, 49, 11837-11840.
11. [11] Y. Yu, Y. L. Guo, W. C. Zhan, Y. Guo, Y. S. Wang, G. Z. Lu, J. Mol. Catal. A, 2014, 392, 1-7.
12. [12] Y. Yu, W. C. Zhan, Y. Guo, G. Z. Lu, S. Adjimi, Y. L. Guo, J. Mol. Catal. A, 2014, 395, 392-397.
13. [13] C. I. Meyer, S. A. Regenhardt, A. J. Marchi, T. F. Garetto, Appl. Catal. A, 2012, 417-418, 59-65.
14. [14] S. A. Regenhardt, C. I. Meyer, T. F. Garetto, A. J. Marchi, Appl. Catal. A, 2012, 449, 81-87.
15. [15] W. T. Huo, C. L. Zhang, H. J. Yuan, M. J. Jia, C. L. Ning, Y. Tang, Y. Zhang, J. H. Luo, Z. L. Wang, W. X. Zhang, J. Ind. Eng. Chem., 2014, 20, 4140-4145.
16. [16] Y. Zhang, L. L. Zhao, H. X. Zhang, H. T. Li, P. P. Liu, Y. Y. Gai, Y. X. Zhao, CIESC., 2015, 66, 2505-2513.
17. [17] C. I. Meyer, S. A. Regenhardt, M. E. Bertone, A. J. Marchi, T. F. Garetto, Catal. Lett., 2013, 143, 1067-1073.
18. [18] J. Li, W. P. Tian, X. Wang, L. Shi, Chem. Eng. J., 2011, 175, 417-422.
19. [19] W. P. Tian, S. F. Guo, L. Shi, Pet. Sci. Technol., 2014, 32, 1784-1790.
20. [20] S. F. Guo, L. Shi, Catal. Today, 2013, 212, 137-141.
21. [21] M. E. Bertone, S. A. Regenhardt, C. I. Meyer, V. Sebastian, T. F. Garetto, A. J. Marchi, Top. Catal., 2016, 59, 159-167.
22. [22] P. G. Savva, K. Goundani, J. Vakros, K. Bourikas, C. Fountzoula, D. Vattis, A. Lycourghiotis, C. Kordulis, Appl. Catal. B, 2008, 79, 199-207.
23. [23] A. L. Alberton, M. M. V. M Souza, M. Schmal, Catal. Today, 2007, 123, 257-264.
24. [24] B. C. Lippens, J. H. de Boer, Acta Crystal, 1964, 17, 1312-1321.
25. [25] H. T. Li, Y. L. Xu, C. G. Gao, Y. X. Zhao, Catal. Today, 2010, 158,475-480.
26. [26] G. Paglia, C. E. Buckley, A. L. Rohl, R. D. Hart, K. Winter, A. J. Studer, B. A. Hunter, J. V. Hanna, Chem. Mater., 2004, 16, 220-236.
27. [27] Z. G. Hao, Q. S. Zhu, Z. Jiang, B. L. Hou, H. Z. Li, Fuel Process. Technol., 2009, 90, 113-121.
28. [28] G. H. Li, L. J. Hu, J. M. Hill, Appl. Catal. A, 2006, 301, 16-24.
29. [29] Z. Ma, Q. Z. Jiang, X. Wang, W. G. Zhang, Z. F. Ma, Catal. Commun., 2012, 17, 49-53.
30. [30] G. Poncelet, M. A. Centeno, R. Molina, Appl. Catal. A, 2005, 288, 232-242.
31. [31] Z. Boukha, C. Jimenez-Gonzalez, B. de Rivas, J. R. Gonzalez-Velasco, J. I. Gutierrez-Ortiz, R. Lopez-Fonseca, Appl. Catal. B, 2014, 158-159, 190-201.
32. [32] R. Lopez-Fonseca, C. Jimenez-Gonzalez, B. de Rivas, J.I. Gutierrez-Ortiz, Appl. Catal. A, 2012, 437-438, 53-62.
33. [33] F. Meyer, R. Hempelmann, S. Mathurband, M. Veith, J. Mater. Chem., 1999, 9, 1755-1763.
34. [34] C. Ragupathi, J. J. Vijaya, P. Surendhar, L. J. Kennedy, Polyhedron, 2014, 72,1-7.
35. [35] R. Wang, Y. H. Li, R. H. Shi, M. M. Yang, J. Mol. Catal. A, 2011, 344, 122-127.
36. [36] T. Numaguchi, H. Eida, K. Shoji, Int. J. Hydrog. Energy, 1997, 22, 1111-1115.
37. [37] M. Tao, X. Meng, Y. H. Lu, Z. C. Bian, Z. Xin, Fuel, 2016, 165, 289-297.
38. [38] Y. H. Feng, H. B. Yin, A. L. Wang, T. Xie, T. S. Jiang, Appl. Catal. A, 2012, 425, 205-212.
39. [39] J. Li, W. P. Tian, L. Shi, Catal. Lett., 2011, 141, 565-571.
40. [40] J. H. Song, S. J. Han, J. Yoo, S. Park, D. H. Kim, I. K. Song, J. Mol. Catal. A, 2016, 415, 151-159.
41. [41] J. J. Fitzgerald, G. Piedra, S. F. Dec, M. Seger, G. E. Maciel, J. Am. Chem. Soc., 1997, 119, 7832-7842.

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沈阳化工大学材料科学与工程学院沈阳 110142

尖晶石型衍生的Ni/Al₂O₃催化剂低温催化顺酐加氢合成丁二酸酐

English

Ni/Al₂O₃ catalysts derived from spinel NiAl₂O₄ for low-temperature hydrogenation of maleic anhydride to succinic anhydride

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尖晶石型衍生的Ni/Al₂O₃催化剂低温催化顺酐加氢合成丁二酸酐

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