La2O3协同增强SAPO-34的二甲醚制烯烃催化性能

doi:10.11949/j.issn.0438-1157.20170702

化工学报 ›› 2017, Vol. 68 ›› Issue (12): 4607-4614.DOI: 10.11949/j.issn.0438-1157.20170702

• 催化、动力学与反应器 • 上一篇下一篇

La₂O₃协同增强SAPO-34的二甲醚制烯烃催化性能

曹迎倩, 高玉李, 陈胜利, 袁桂梅, 王涯, 朱茹月, 陈楠

中国石油大学(北京)重质油国家重点实验室, 北京 102249

收稿日期:2017-05-31 修回日期:2017-08-18 出版日期:2017-12-05 发布日期:2017-12-05
通讯作者: 陈胜利
基金资助:
国家自然科学基金项目（91534120）。

La₂O₃synergetic effect to improve catalytic performance of SAPO-34 molecular sieve used for dimethyl ether to olefins reaction

CAO Yingqian, GAO Yuli, CHEN Shengli, YUAN Guimei, WANG Ya, ZHU Ruyue, CHEN Nan

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China

Received:2017-05-31 Revised:2017-08-18 Online:2017-12-05 Published:2017-12-05
Supported by:
supported by the National Natural Science Foundation of China (91534120).

摘要/Abstract

摘要：

La₂O₃不需要与SAPO-34接触，便可显著延长SAPO-34的二甲醚制烯烃（DTO）反应寿命，并且La₂O₃与SAPO-34比例越大，SAPO-34的反应寿命越长。当La₂O₃和SAPO-34的质量比为1：1时，SAPO-34寿命提高了约1倍。进一步的研究表明，只有当La₂O₃层夹在SAPO-34层中间时，才能提高SAPO-34的寿命，La₂O₃无论是处于SAPO-34上游还是下游，均不能提高SAPO-34的寿命。动力学和催化剂的积炭量研究表明，La₂O₃是通过降低SAPO-34的积炭速度提高其反应寿命的。初步提出了La₂O₃提高SAPO-34寿命的机理：在DTO反应过程中，二甲醚在SAPO-34分子筛上形成一种积炭前体，这种积炭前体转移到La₂O₃的表面上，反应生成不能积炭的化合物（CO、CO₂和H₂等），从而降低了SAPO-34的积炭失活速度，提高了其寿命。

关键词: SAPO-34, 分子筛, 混合, 失活, 二甲醚制烯烃, 甲醇制烯烃, 协同作用

Abstract:

The working lifetime of SAPO-34 for dimethyl ether to olefins (DTO) reaction was increased by non-contact La₂O₃. Increasing ratio of La₂O₃ to SAPO-34 prolonged working lifetime of SAPO-34. When the mass ratio of La₂O₃ to SAPO-34 was 1:1, the working lifetime of SAPO-34 was almost twice as much as that of SAPO-34 alone. La₂O₃ sandwiched in SAPO-34 had improvement, whereas La₂O₃ in upstream and downstream of SAPO-34 did not. Reaction kinetics and coke amount on SAPO-34 indicated that La₂O₃ decreased coking rate of SAPO-34. A synergetic mechanism for SAPO-34 and La₂O₃ was proposed that a coke precursor created on SAPO-34 during DTO was converted to non-coke forming species (such as CO, CO₂ and H₂) upon traveling onto La₂O₃ surface such that SAPO-34 coking rate was decreased and its working lifetime was increased.

Key words: SAPO-34, molecular sieves, mixing, deactivation, dimethyl ether to olefins, methanol to ofefins, synergetic effects

中图分类号:

O643

曹迎倩, 高玉李, 陈胜利, 袁桂梅, 王涯, 朱茹月, 陈楠. La₂O₃协同增强SAPO-34的二甲醚制烯烃催化性能[J]. 化工学报, 2017, 68(12): 4607-4614.

CAO Yingqian, GAO Yuli, CHEN Shengli, YUAN Guimei, WANG Ya, ZHU Ruyue, CHEN Nan. La₂O₃synergetic effect to improve catalytic performance of SAPO-34 molecular sieve used for dimethyl ether to olefins reaction[J]. CIESC Journal, 2017, 68(12): 4607-4614.

参考文献 31

[1]	王汉松, 何细藕. 乙烯工艺与技术[M]. 北京:中国石化出版社, 2000:83. WANG H S, HE X O. Ethylene Process and Technology[M]. Beijing:China Petrochemical Press, 2000:83
[2]	刘中民. 甲醇制烯烃[M]. 北京:科学出版社, 2015:41. LIU Z M. Methanol to Olefins[M]. Beijing:Science Press, 2015:41
[3]	CLARENCE D C. Methanol conversion to light olefins[J]. Catalysis Reviews, 1984, 26(3/4):323-345.
[4]	CHEN J Q, BOZZANO A, GLOVER B, et al. Recent advancements in ethylene and propylene production using the UOP/Hydro MTO process[J]. Catalysis Today, 2005, 106(1/2/3/4):103-107.
[5]	DEROUANE E G. Molecular shape-selective catalysis by zeolites[M]//Zeolites:Science and Technology. Netherlands:Springer, 1984:347-371.
[6]	刘中民, 黄兴云, 何长青, 等. SAPO-34分子筛的热稳定性及水热稳定性[J]. 催化学报, 1996, 17(6):540-543. LIU Z M, HUANG X Y, HE C Q, et al. Thermal and hydrothermal stability of SAPO-34 molecular sieve[J]. Chinese Journal of Catalysis, 1996, 17(6):540-543.
[7]	HIDAKA T, YOKOSE E. Catalysts for methanol conversion reactions:US6153798[P]. 2000-11-28.
[8]	WANG Q, WANG L, WANG H. Synthesis, characterization and catalytic performance of SAPO-34 molecular sieves for methanol-to-olefin (MTO) reaction[J]. Asia-Pacific Journal of Chemical Engineering, 2011, 6(4):596-605.
[9]	HU H, CAO F, YING W. Study of coke behaviour of catalyst during methanol-to-olefins process based on a special TGA reactor[J]. Chemical Engineering Journal, 2010, 160(2):770-778.
[10]	QI G, XIE Z, YANG W, et al. Behaviors of coke deposition on SAPO-34 catalyst during methanol conversion to light olefins[J]. Fuel Processing Technology, 2007, 88(5):437-441.
[11]	JUN J W, LEE J S, SEOK H Y. A facile synthesis of SAPO-34 molecular sieves with microwave irradiation in wide reaction conditions[J]. Bulletin of the Korean Chemical Society, 2011, 32(6):1957-1964.
[12]	KANG E A, KIM T W, CHAE H J, et al. Synthesis of mesoporous SAPO-34 zeolite from mesoporous silica materials for methanol to light olefins[J]. Journal of Nanoscience and Nanotechnology, 2013, 13(11):7498-7503.
[13]	LIU Y, WANG L, ZHANG J. Preparation of floral mesoporous SAPO-34 with the aid of fluoride ion[J]. Materials Letters, 2011, 65(14):2209-2212.
[14]	蔡光宇, 刘中民, 何长青, 等. 金属改性小孔磷硅铝型分子筛催化剂及其制备方法和应用:96115362.8[P]. 1997-12-17. CAI G Y, LIU Z M, HE C Q, et al. Porous phosphosilicate aluminum molecular sieve catalyst modified by metal and its preparation and application:96115362.8[P].1997-12-17.
[15]	FENG G, CHENG P, YAN W. Accelerated crystallization of zeolites via hydroxyl free radicals[J]. Science, 2016, 351(2):1188-1191.
[16]	MAJANO G, BORCHARDT L, MITCHELL S, et al. Rediscovering zeolite mechanochemistry -a pathway beyond current synthesis and modification boundaries[J]. Microporous & Mesoporous Materials, 2014, 194(8):106-114.
[17]	NASSER A, MINGELGRIN U. Cheminform abstract:mechanochemistry:a review of surface reactions and environmental applications[J]. Applied Clay Science, 2013, 44(34):141-150.
[18]	ZHANG D, WEI Y, XU L, et al. MgAPSO-34 molecular sieves with various Mg stoichiometries:synthesis, characterization and catalytic behavior in the direct transformation of chloromethane into light olefins[J]. Microporous and Mesoporous Materials, 2008, 116(1/2/3):684-692.
[19]	XU L, LIU Z, DU A, et al. Synthesis, characterization, and MTO performance of MeAPSO-34 molecular sieves[J]. Studies in Surface Science & Catalysis, 2004, 147(4):445-450.
[20]	NAWAZ Z, TANG X, ZHANG Q. SAPO-34 supported Pt-Sn-based novel catalyst for propane dehydrogenation to propylene[J]. Catalysis Communications, 2009, 10(14):1925-1930.
[21]	吕金钊. 稀土(La,Y)改性SAPO-34分子筛催化转化甲醇制烯烃研究[D]. 大连:大连理工大学, 2009. LÜ J Z. A study on catalytic of methanol to olefins over rare earth metals (La, Y) modified SAPO-34[D]. Dalian:Dalian University of Technology, 2009.
[22]	KANG M. Methanol conversion on metal-incorporated SAPO-34s (MeAPSO-34s)[J]. Journal of Molecular Catalysis A Chemical, 2000, 160(2):437-444.
[23]	JIAO F L, LI J J, PAN X L, et al. Selective conversion of syngas to light olefins[J]. Science, 2016, 351(6277):1065-1068.
[24]	WEI J, GE Q J, YAO R W, et al. Directly converting CO2 into a gasoline fuel[J]. Nature Communications, 2017, 8:15174.
[25]	GAO P, LI S G, BU X N, et al. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst[J]. Nature Chemistry, 2017, doi:10.1038/nchem.2794.
[26]	LEVIN D, VARTUIA J C. Molecular sieve compositions, catalysts thereof, their making and use in conversion processes:US7319178[P]. 2008-9-18.
[27]	AGUAYO A T, GAYUBO A G, VIVANCO R. Role of acidity and microporous structure in alternative catalysts for the transformation of methanol into olefins[J]. Applied Catalysis A General, 2005, 283(1):197-207.
[28]	FREEMAN D, WELLS P R, HUTCHINGS G J. Methanol to hydrocarbons:enhanced aromatic formation using a composite Ga2O3-H-ZSM-5 catalyst[J]. Cheminform, 2002, 33(1):1754-1755.
[29]	GAO Y L, CHEN S L, WEI Y Q, et al. Kinetics of coke formation in the dimethyl ether-to-olefins process over SAPO-34 catalyst[J]. Chemical Engineering Journal, 2017, 326(5):528-539.
[30]	WANG Y, CHEN S L, JIANG Y J, et al. Influence of template content on selective synthesis of SAPO-18, SAPO-18/34 intergrowth and SAPO-34 molecular sieves used for methanol-to-olefins process[J]. RSC Advances, 2016, 6(107):104985-104994
[31]	JANSSENS T. A new approach to the modeling of deactivation in the conversion of methanol on zeolite catalysts[J]. Journal of Catalysis, 2009, 264(2):130-137.

La₂O₃协同增强SAPO-34的二甲醚制烯烃催化性能

La₂O₃synergetic effect to improve catalytic performance of SAPO-34 molecular sieve used for dimethyl ether to olefins reaction

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