稀释蒸汽中Na<sup>+</sup>及积炭对甲醇制丙烯催化剂性能影响

引用本文: 王峰, 顔蜀雋, 雍晓静, 罗春桃, 张卿, 温鹏宇, 巩雁军, 窦涛. 稀释蒸汽中Na⁺及积炭对甲醇制丙烯催化剂性能影响[J]. 物理化学学报, 2013, 29(02): 358-364. doi: 10.3866/PKU.WHXB201211143 shu

Citation: WANG Feng, YAN Shu-Jun, YONG Xiao-Jing, LUO Chun-Tao, ZHANG Qing, WEN Peng-Yu, NG Yan-Jun, DOU Tao. Effects of Na⁺ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts[J]. Acta Physico-Chimica Sinica, 2013, 29(02): 358-364. doi: 10.3866/PKU.WHXB201211143 shu

稀释蒸汽中Na⁺及积炭对甲醇制丙烯催化剂性能影响

王峰 ^1, ,
顔蜀雋 ^1, ,
雍晓静 ^1, ,
罗春桃 ^1, ,
张卿 ^2, ,
温鹏宇 ^2, ,
巩雁军 ^2, ,
窦涛 ^2,

基金项目:
国际科技与交流专项(2010DFB40440) (2010DFB40440)

宁夏回族自治区科技攻关计划(年产50 万吨煤基聚丙烯装置工业运行及下游产业关键技术研究)资助项目 (年产50 万吨煤基聚丙烯装置工业运行及下游产业关键技术研究)

摘要:

考察了稀释蒸汽中Na⁺及积炭对甲醇制丙烯(MTP)催化剂物理化学性质和催化性能影响, 及离子交换后催化性能. 采用X射线衍射(XRD)、扫描电镜(SEM)、X射线荧光(XRF)光谱、N₂吸附-脱附、程序升温氨脱附(NH3-TPD)和热重(TG)分析等方法对失活和再生催化剂进行了表征, 并在101325 Pa、470℃ 和甲醇空速(WHSV)为1.0-3.0 h^-1的反应条件下, 采用连续流动固定床微型反应器考察其催化甲醇制丙烯性能. 结果表明: MTP反应970 h后的催化剂晶体结构和形貌没有受到明显破坏, 但稀释蒸汽中Na⁺极易扩散至催化剂表面,部分取代H质子的位置, 从而使催化剂酸性逐渐下降而中毒失活; 另外, MTP催化剂表面的积炭导致分子筛微孔堵塞是造成其失活的主要原因, 可通过烧炭再生过程消除, 而水蒸汽脱铝对催化剂性能的影响缓慢但更严重. 用再生和离子交换处理后, Na⁺中毒催化剂MTP反应性能基本完全恢复. 在470 h反应过程中, 甲醇转化率保持在99%以上, 丙烯选择性大于46%, 且随着反应时间的延长, 丙烯选择性逐渐升高、乙烯选择性逐渐下降.

关键词:

English

Effects of Na⁺ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts

1.
1 Research and Development Division, Shenhua Ningxia Coal Industry Group Co. Ltd., Yinchuan 750411, P. R. China;
2 The Key Laboratory of Catalysis of CNPC, China University of Petroleum-Beijing, Beijing 102249, P. R. China
Received Date: 12 September 2012
Available Online: 14 January 2013
Fund Project:
国际科技与交流专项(2010DFB40440)

宁夏回族自治区科技攻关计划(年产50 万吨煤基聚丙烯装置工业运行及下游产业关键技术研究)资助项目

Abstract:

The effects of Na⁺ in dilution steam and coke deposition on the physicochemical properties andcatalytic performance of ZSM-5 catalysts for the methanol-to-propylene (MTP) reaction were investigated.The deactivated and regenerated catalysts were characterized by means of X-ray diffraction (XRD),scanning electron microscopy (SEM), X-ray fluorescence (XRF) spectrum, nitrogen adsorption/desorption,temperature-programmed desorption of ammonia (NH₃-TPD), and thermogravimetry (TG). Their catalyticperformance for MTP reaction was tested in a continuous flow fixed-bed micro-reactor at 470℃, 101325Pa, and with methanol weight hourly space velocity (WHSV) in the range of 1.0-3.0 h^-1. The resultsindicated that the catalyst crystal structure and morphology was not significantly altered after 970 h onstream. In the MTP reaction, Na⁺ in the dilution steam can easily enter the pore channels of the catalyst,and partially replace H protons, thereby gradually decreasing the amount of acidity and acid strength of thecatalyst, which eventually causes deactivation. In addition, coke deposits on the catalyst surface blocking its micropores are the main reason for deactivation of the MTP catalyst. Coke deposits are mostlyeliminated through the burning charcoal regeneration process. The effect of framework dealumination fromthe catalyst by steam in the MTP process is slow but more serious. Through regeneration and ionexchange process, the catalytic activity of the deactivated catalyst can be fully restored. The conversion ofmethanol is consistently above 99%, and propylene selectivity is greater than 46% even after 470 h onstream. With increasing reaction time, the propylene selectivity gradually increases, while ethyleneselectivity gradually decreases.

Key words:

1. [1]
  
  (1) Hu, S.; Zhang, Q.; Xia, Z.; ng, Y. J.; Xu, J.; Deng, F.; Dou, T.Acta Phys. -Chim. Sin. 2012, 28, 2705. [胡思, 张卿,夏至, 巩雁军, 徐君, 邓风, 窦涛. 物理化学学报,2012, 28, 2705.] doi: 10.3866/PKU.WHXB201207171
  (1) Hu, S.; Zhang, Q.; Xia, Z.; ng, Y. J.; Xu, J.; Deng, F.; Dou, T.Acta Phys. -Chim. Sin. 2012, 28, 2705. [胡思, 张卿,夏至, 巩雁军, 徐君, 邓风, 窦涛. 物理化学学报,2012, 28, 2705.] doi: 10.3866/PKU.WHXB201207171
2. [2]
  (2) Mao, D. S.; Guo, Q. S.; Meng, T. Acta Phys. -Chim. Sin. 2010,26, 338. [毛东森, 郭强胜, 孟涛. 物理化学学报, 2010, 26,338.] doi: 10.3866/PKU.WHXB20100208(2) Mao, D. S.; Guo, Q. S.; Meng, T. Acta Phys. -Chim. Sin. 2010,26, 338. [毛东森, 郭强胜, 孟涛. 物理化学学报, 2010, 26,338.] doi: 10.3866/PKU.WHXB20100208
3. [3]
  (3) Wang, F.; Zhang, Q.; Hu, S.; ng, Y. J.; Dou, T. Industrial Catalysis 2012, 20, 17. [王峰, 张卿, 胡思, 巩雁军,窦涛. 工业催化, 2012, 20, 17.](3) Wang, F.; Zhang, Q.; Hu, S.; ng, Y. J.; Dou, T. Industrial Catalysis 2012, 20, 17. [王峰, 张卿, 胡思, 巩雁军,窦涛. 工业催化, 2012, 20, 17.]
4. [4]
  (4) Sun, C.; Du, J. M.; Liu, J.; Yang, Y. S.; Ren, N.; Shen,W.; Xu,H. L.; Tang, Y. Chem. Commun. 2010, 46, 2671. doi: 10.1039/b925850g(4) Sun, C.; Du, J. M.; Liu, J.; Yang, Y. S.; Ren, N.; Shen,W.; Xu,H. L.; Tang, Y. Chem. Commun. 2010, 46, 2671. doi: 10.1039/b925850g
5. [5]
  (5) Lee, Y. J.; Kim, Y.W.; Viswanadham, N.; Jun, K.W.; Bae, J.W.Appl. Catal. A: Gen. 2010, 374, 18. doi: 10.1016/j.apcata.2009.11.019(5) Lee, Y. J.; Kim, Y.W.; Viswanadham, N.; Jun, K.W.; Bae, J.W.Appl. Catal. A: Gen. 2010, 374, 18. doi: 10.1016/j.apcata.2009.11.019
6. [6]
  (6) Firoozi, M.; Baghalha, M.; Asadi, M. T. Catal. Commun. 2009,10, 1582. doi: 10.1016/j.catcom.2009.04.021(6) Firoozi, M.; Baghalha, M.; Asadi, M. T. Catal. Commun. 2009,10, 1582. doi: 10.1016/j.catcom.2009.04.021
7. [7]
  (7) Zhang, S. H.; Zhang, B. L.; Gao, Z. X.; Han, Z. Y. Reac. Kinet. Mech. Catal. 2010, 99, 447.(7) Zhang, S. H.; Zhang, B. L.; Gao, Z. X.; Han, Z. Y. Reac. Kinet. Mech. Catal. 2010, 99, 447.
8. [8]
  (8) Liu, J.; Zhang, C. X.; Shen, Z. H.; Hua,W. M.; Tang, Y.; Shen,W.; Yue, Y. H.; Xu, H. L. Catal. Commun. 2009, 10, 1506. doi: 10.1016/j.catcom.2009.04.004(8) Liu, J.; Zhang, C. X.; Shen, Z. H.; Hua,W. M.; Tang, Y.; Shen,W.; Yue, Y. H.; Xu, H. L. Catal. Commun. 2009, 10, 1506. doi: 10.1016/j.catcom.2009.04.004
9. [9]
  (9) Mokrani, T.; Scurrell, M. Catal. Rev. -Sci. Eng. 2009, 51, 1. doi: 10.1080/01614940802477524(9) Mokrani, T.; Scurrell, M. Catal. Rev. -Sci. Eng. 2009, 51, 1. doi: 10.1080/01614940802477524
10. [10]
  (10) Valle, B.; Alonso, A.; Atutxa, A. G.; Gayubo, J. B. Catal. Today2005, 106, 115.(10) Valle, B.; Alonso, A.; Atutxa, A. G.; Gayubo, J. B. Catal. Today2005, 106, 115.
11. [11]
  (11) Vedrine, J. C.; Auroux, A.; Dejaifve, P.; Ducarme, V.; Hoser, H.;Zhou, S. J. Catal. 1982, 73, 147. doi: 10.1016/0021-9517(82)90089-6(11) Vedrine, J. C.; Auroux, A.; Dejaifve, P.; Ducarme, V.; Hoser, H.;Zhou, S. J. Catal. 1982, 73, 147. doi: 10.1016/0021-9517(82)90089-6
12. [12]
  (12) Kaarsholm, M.; Joensen, F.; Nerlov, J.; Cennib, R.; Chaoukia,J.; Patiencea, G. S. Chem. Eng. Sci. 2007, 62, 5527. doi: 10.1016/j.ces.2006.12.076(12) Kaarsholm, M.; Joensen, F.; Nerlov, J.; Cennib, R.; Chaoukia,J.; Patiencea, G. S. Chem. Eng. Sci. 2007, 62, 5527. doi: 10.1016/j.ces.2006.12.076
13. [13]
  (13) Zhao, T. S.; Takemoto, T.; Tsubaki, N. Catal. Commun. 2006, 7,647. doi: 10.1016/j.catcom.2005.11.009(13) Zhao, T. S.; Takemoto, T.; Tsubaki, N. Catal. Commun. 2006, 7,647. doi: 10.1016/j.catcom.2005.11.009
14. [14]
  (14) Bhatia, S.; Beltramini. J.; Do, D. D. Catal. Rcv. -Sci. Eng. 1989,90, 481.(14) Bhatia, S.; Beltramini. J.; Do, D. D. Catal. Rcv. -Sci. Eng. 1989,90, 481.
15. [15]
  (15) Langner, B. E. Ind. Eng. Chem. Pro. Des. Dev. 1981, 20, 326.doi: 10.1021/i200013a023(15) Langner, B. E. Ind. Eng. Chem. Pro. Des. Dev. 1981, 20, 326.doi: 10.1021/i200013a023
16. [16]
  (16) Bibby, D. M.; Milestone, N. B.; Patterson, J. E.; Aldridge, L. P.J. Catal. 1986, 97, 493. doi: 10.1016/0021-9517(86)90020-5(16) Bibby, D. M.; Milestone, N. B.; Patterson, J. E.; Aldridge, L. P.J. Catal. 1986, 97, 493. doi: 10.1016/0021-9517(86)90020-5
17. [17]
  (17) McLellan, G. D.; Howe, R. F.; Parker, L. M.; Bibby, D. M.J. Catal. l986, 99, 486.(17) McLellan, G. D.; Howe, R. F.; Parker, L. M.; Bibby, D. M.J. Catal. l986, 99, 486.
18. [18]
  (18) Wen, P. Y.; Mei, C. S.; Liu, H. X.; Yang,W. M.; Chen, Q. L.Acta Petrolei Sinica (Petroleum Processing Section) 2008, 24,446. [温鹏宇, 梅长松, 刘红星, 杨为民, 陈庆龄. 石油学报(石油加工), 2008, 24, 446.](18) Wen, P. Y.; Mei, C. S.; Liu, H. X.; Yang,W. M.; Chen, Q. L.Acta Petrolei Sinica (Petroleum Processing Section) 2008, 24,446. [温鹏宇, 梅长松, 刘红星, 杨为民, 陈庆龄. 石油学报(石油加工), 2008, 24, 446.]
19. [19]
  (19) Sexton, B. A.; Hughes, A. E.; Bibby, D. M. J. Catal. 1988, 109,126. doi: 10.1016/0021-9517(88)90190-X(19) Sexton, B. A.; Hughes, A. E.; Bibby, D. M. J. Catal. 1988, 109,126. doi: 10.1016/0021-9517(88)90190-X
20. [20]
  (20) Lee, K. Y.; Lee, H. K.; Ihm, S. K. Top. Catal. 2010, 53, 247. doi: 10.1007/s11244-009-9412-0(20) Lee, K. Y.; Lee, H. K.; Ihm, S. K. Top. Catal. 2010, 53, 247. doi: 10.1007/s11244-009-9412-0
21. [21]
  (21) Jiang, Y.; Liang, J.; Zhao, S. Q. Chin. J. Catal. 1994, 15, 463.[蒋毅, 梁鹃, 赵素琴. 催化学报, 1994, 15, 463.](21) Jiang, Y.; Liang, J.; Zhao, S. Q. Chin. J. Catal. 1994, 15, 463.[蒋毅, 梁鹃, 赵素琴. 催化学报, 1994, 15, 463.]
22. [22]
  (22) Wang, X. Q.;Wang, X. S. Acta Petrolei Sinica (Petroleum Processing Section) 1994, 10, 38. [王学勤, 王祥生. 石油学报(石油加工), 1994, 10, 38.](22) Wang, X. Q.;Wang, X. S. Acta Petrolei Sinica (Petroleum Processing Section) 1994, 10, 38. [王学勤, 王祥生. 石油学报(石油加工), 1994, 10, 38.]
23. [23]
  (23) Lu, M.; Sun, H. M.; Yang,W. M. Acta Petrolei Sinica (Petroleum Processing Section) 2001, 17, 59. [陆铭, 孙洪敏, 杨为民. 石油学报(石油加工), 2001, 17, 59.](23) Lu, M.; Sun, H. M.; Yang,W. M. Acta Petrolei Sinica (Petroleum Processing Section) 2001, 17, 59. [陆铭, 孙洪敏, 杨为民. 石油学报(石油加工), 2001, 17, 59.]
24. [24]
  (24) Bjørgen, M.; Svelle, S.; Joensen, F.; Nerlov, J.; Kolboe, S.;Bonino, F.; Palumbo, L.; Bordiga, S.; Olsbye, U. J. Catal. 2007,249, 195. doi: 10.1016/j.jcat.2007.04.006(24) Bjørgen, M.; Svelle, S.; Joensen, F.; Nerlov, J.; Kolboe, S.;Bonino, F.; Palumbo, L.; Bordiga, S.; Olsbye, U. J. Catal. 2007,249, 195. doi: 10.1016/j.jcat.2007.04.006
25. [25]
  (25) Bjørgen, M.; Joensen, F.; Lillerud, K. P.; Olsbye, U.; Svelle, S.Catal. Today 2009, 142, 90. doi: 10.1016/j.cattod.2009.01.015(25) Bjørgen, M.; Joensen, F.; Lillerud, K. P.; Olsbye, U.; Svelle, S.Catal. Today 2009, 142, 90. doi: 10.1016/j.cattod.2009.01.015
26. [26]
  (26) Svelle, S.; Joensen, F.; Nerlov, J.; Olsbye, U.; Lillerud, K. P.;Kolboe, S.; Bjørgen, M. J. Am. Chem. Soc. 2006, 128, 14770.doi: 10.1021/ja065810a(26) Svelle, S.; Joensen, F.; Nerlov, J.; Olsbye, U.; Lillerud, K. P.;Kolboe, S.; Bjørgen, M. J. Am. Chem. Soc. 2006, 128, 14770.doi: 10.1021/ja065810a
27. [27]
  (27) Zhan, Y.W.; Zhou, Y. M.; Qiu, A. D.;Wang, Y.; Xu, Y.;Wu, P.C. Acta Phys. -Chim. Sin. 2006, 22, 672. [张一卫, 周钰明, 邱安定, 王玉, 许艺, 吴沛成. 物理化学学报, 2006, 22, 672.]doi: 10.1016/S1872-1508(06)60026-0(27) Zhan, Y.W.; Zhou, Y. M.; Qiu, A. D.;Wang, Y.; Xu, Y.;Wu, P.C. Acta Phys. -Chim. Sin. 2006, 22, 672. [张一卫, 周钰明, 邱安定, 王玉, 许艺, 吴沛成. 物理化学学报, 2006, 22, 672.]doi: 10.1016/S1872-1508(06)60026-0
28. [28]
  (28) Chu, C. T.W.; Socha, R. F. J. Catal. 1984, 86, 289. doi: 10.1016/0021-9517(84)90374-9(28) Chu, C. T.W.; Socha, R. F. J. Catal. 1984, 86, 289. doi: 10.1016/0021-9517(84)90374-9
29. [29]
  (29) Kim, J.; Choi, M.; Ryoo, R. J. Catal. 2010, 269, 219. doi: 10.1016/j.jcat.2009.11.009(29) Kim, J.; Choi, M.; Ryoo, R. J. Catal. 2010, 269, 219. doi: 10.1016/j.jcat.2009.11.009
30. [30]
  (30) Choi, M.; Na, K.; Kim, J.; Sakamoto, Y.; Terasaki, O.; Ryoo, R.Nature 2009, 461, 246. doi: 10.1038/nature08288
  (30) Choi, M.; Na, K.; Kim, J.; Sakamoto, Y.; Terasaki, O.; Ryoo, R.Nature 2009, 461, 246. doi: 10.1038/nature08288

扫一扫看文章

计量

PDF下载量: 897
文章访问数: 1799
HTML全文浏览量: 14

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

稀释蒸汽中Na⁺及积炭对甲醇制丙烯催化剂性能影响

English

Effects of Na⁺ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

稀释蒸汽中Na+及积炭对甲醇制丙烯催化剂性能影响

English

Effects of Na+ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

稀释蒸汽中Na⁺及积炭对甲醇制丙烯催化剂性能影响

Effects of Na⁺ in Dilution Steam and Coke Deposition on Catalytic Performance of Methanol-to-Propylene Catalysts

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs