氟硅酸铵改性纳米HZSM-5分子筛催化甲醇制丙烯

引用本文: 胡思, 张卿, 夏至, 巩雁军, 徐君, 邓风, 窦涛. 氟硅酸铵改性纳米HZSM-5分子筛催化甲醇制丙烯[J]. 物理化学学报, 2012, 28(11): 2705-2712. doi: 10.3866/PKU.WHXB201207171 shu

Citation: HU Si, ZHANG Qing, XIA Zhi, NG Yan-Jun, XU Jun, DENG Feng, DOU Tao. Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, 2012, 28(11): 2705-2712. doi: 10.3866/PKU.WHXB201207171 shu

氟硅酸铵改性纳米HZSM-5分子筛催化甲醇制丙烯

胡思 ^1, ,
张卿 ^1, ,
夏至 ^2, ,
巩雁军 ^1, ,
徐君 ^3, ,
邓风 ^3, ,
窦涛 ^1,2,

基金项目:
国家重点基础研究发展计划(973)项目(2012CB215002) (973)项目(2012CB215002)

国家自然科学基金(10979076, 21176255) (10979076, 21176255)

国际科技合作与交流专项项目(2010DFB40440)资助 (2010DFB40440)

摘要:

在静态条件下, 采用不同浓度的氟硅酸铵溶液对纳米ZSM-5分子筛进行了改性处理. 利用粉末X射线衍射(XRD)、²⁷Al 魔角旋转固体核磁共振(²⁷Al MAS NMR)、X射线荧光光谱(XRF)、X射线光电子能谱(XPS)、N₂ 吸附、透射电镜(TEM)、NH₃程序升温脱附(NH₃-TPD)、吡啶吸附红外光谱(Py-IR)等技术对改性前后纳米ZSM-5分子筛的骨架结构、织构性质、酸性质进行了表征. 并在常压、反应温度为450℃、甲醇质量空速(WHSV)为1 h^-1的条件下, 研究了改性前后纳米HZSM- 的甲醇制丙烯(MTP)催化性能. 结果表明, 合适浓度的氟硅酸铵处理能够选择性地脱除纳米ZSM-5 分子筛的外表面铝, 从而使得HZSM-5 的酸密度降低, 比表面积和孔容增大, MTP催化性能显著提高. 氟硅酸铵改性后纳米HZSM-5 的丙烯选择性和丙烯/乙烯(P/E)质量比分别由原来的 28.8%和2.6提高到45.1%和8.0, 催化剂寿命增加了近2倍.

关键词:

English

Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite

HU Si ^1, ,
ZHANG Qing ^1, ,
XIA Zhi ^2, ,
NG Yan-Jun ^1, ,
XU Jun ^3, ,
DENG Feng ^3, ,
DOU Tao ^1,2,

1.
1 The Key Laboratory of Catalysis of CNPC, China University of Petroleum-Beijing, Beijing 102249, P. R. China;
2 Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
3 Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P. R. China
Received Date: 25 May 2012
Available Online: 17 October 2012
Fund Project:
国家重点基础研究发展计划(973)项目(2012CB215002)

国家自然科学基金(10979076, 21176255)

国际科技合作与交流专项项目(2010DFB40440)资助

Abstract:

(NH₄)₂SiF₆-modified nanosized HZSM-5 zeolite was prepared and investigated as a catalyst formethanol to propylene conversion. The effects of this modification on the framework, textural propertiesand acidity of both the parent and the modified HZSM-5 zeolite were investigated by powder X-raydiffraction (XRD), ²⁷Al magic angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), X-rayfluorescence (XRF), X-ray photoelectron spectroscopy (XPS), N₂ adsorption, transmission electronmicroscopy (TEM), temperature-programmed desorption of ammonia (NH₃-TPD), and infraredspectroscopy of adsorbed pyridine (Py-IR). The catalytic performance of these materials on the methanolto propylene (MTP) conversion process was tested under operating conditions of T=450℃, p=0.1 MPa(p_MeOH=50 KPa) and WHSV=1 h^-1. The results showed that surface aluminum on the nanosized ZSM-5zeolite could be selectively removed by the (NH₄)₂SiF₆ solution and that the number of acidic sites on theHZSM-5 zeolite gradually decreased with increasing (NH₄)₂SiF₆ concentration. Moreover, after modification with an optimally concentrated (NH₄)₂SiF₆ solution, an obvious increase in specific surface area as well asmesopore volume was observed for the nanosized HZSM-5 with a resulting dramatic improvement in thecatalytic performance of this material for the MTP reaction. Both the propylene selectivity and propylene/ethylene (P/E) mass ratio resulting from use of the modified HZSM-5 increased significantly to 45.1% and8.0, as compared to results of 28.8% and 2.6 obtained with the original material. In addition, the catalyticlifespan of the modified zeolite was double that of the original.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

氟硅酸铵改性纳米HZSM-5分子筛催化甲醇制丙烯

English

Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite

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

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

氟硅酸铵改性纳米HZSM-5分子筛催化甲醇制丙烯

English

Catalytic Conversion of Methanol to Propylene over (NH4)2SiF6-Modified Nanosized HZSM-5 Zeolite

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

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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？

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