Effect of SiO2/Al2O3 ratio on the conversion of methanol to olefins over molecular sieve catalysts

doi:10.1007/s11705-010-0550-5

Front Chem Sci Eng

2011, Vol. 5

Issue (1) : 79-88 https://doi.org/10.1007/s11705-010-0550-5

RESEARCH ARTICLE

Effect of SiO₂/Al₂O₃ ratio on the conversion of methanol to olefins over molecular sieve catalysts

Qian WANG¹, Lei WANG², Hui WANG¹, Zengxi LI¹(

), Xiangping ZHANG², Suojiang ZHANG²(

), Kebin ZHOU¹

1. Graduate University of Chinese Academy of Sciences, Beijing 100049, China; 2. State Key Laboratory of Multiphase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

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Abstract

A series of SAPO-34 molecular sieves with different SiO₂/Al₂O₃ ratios have been synthesized for the methanol-to-olefin (MTO) reaction. Their physico-chemical properties are characterized by various techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR) and N₂ adsorption-desorption. The results are compared with those of the commercial HZSM-5, which show that the crystallinity and particle diameter of SAPO-34 as well as HZSM-5 increase with SiO₂/Al₂O₃ ratio. The variation of BET surface area of SAPO-34 is different from that of HZSM-5 and the sample with SiO₂/Al₂O₃ ratio of 0.4 exhibits the highest BET surface area. FT-IR spectra indicate that HZSM-5 has both Br?nsted and Lewis acid sites and Br?nsted acid sites are stronger, whereas SAPO-34 samples are dominated only by Lewis acid sites. When the SiO₂/Al₂O₃ ratio increases, propylene and butylenes become the predominant product of the MTO reaction over HZSM-5. In contrast, the main products of this reaction catalyzed by SAPO-34 are ethylene and propylene. According to the product distribution, the reaction mechanism over HZSM-5 catalysts is proposed.

Keywords HZSM-5 SAPO-34 methanol-to-olefin (MTO) SiO₂/Al₂O₃ ratio

Corresponding Author(s): LI Zengxi,Email:zxli@home.ipe.ac.cn; ZHANG Suojiang,Email:sjzhang@home.ipe.ac.cn

Issue Date: 05 March 2011

Cite this article:

Qian WANG,Lei WANG,Hui WANG, et al. Effect of SiO₂/Al₂O₃ ratio on the conversion of methanol to olefins over molecular sieve catalysts[J]. Front Chem Sci Eng, 2011, 5(1): 79-88.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-010-0550-5
https://academic.hep.com.cn/fcse/EN/Y2011/V5/I1/79

Fig.1 XRD patterns of HZSM-5 with different SiO/AlO ratio. (a) 25; (b) 50; (c) 100; (d) 300

Fig.2 XRD patterns of SAPO-34 synthesized with different SiO/AlO ratio. (a) 0.1; (b) 0.4; (c) 0.7; (d) 1.0

Tab.1 Physicochemical properties of the HZSM-5 samples

Tab.2 Physicochemical properties of the SAPO-34 samples

Fig.3 SEM photographs of HZSM-5 with different SiO/AlO ratio
(a) 25; (b) 50; (c) 100; (d) 300

Fig.4 SEM photographs of SAPO-34 synthesized with different SiO/AlO ratio
(a) 0.1; (b) 0.4; (c) 0.7; (d) 1.0

Tab.3 BET surface area, pore volume and pore diameter of the SAPO-34 samples

Fig.5 N adsorption-desorption isotherms of SAPO-34 samples synthesized with different SiO/AlO ratio. (a) 0.1; (b) 0.4; (c) 0.7; (d) 1.0

Fig.6 Distribution of mesopore using BJH method from the desorption branch of isotherm in SAPO-34 samples synthesized with different SiO/AlO ratio. (a) 0.1; (b) 0.4; (c) 0.7; (d) 1.0

Fig.7 FT-IR spectra of pyridine adsorbed and desorbed on HZSM-5 with SiO/AlO ratio of 300 (A) and SAPO-34 (B) with SiO/AlO ratio of 0.4. (a) before adsorption; (b) 20°C; (c) 100°C; (d) 200°C; (e) 300°C

Fig.8 FT-IR spectra of pyridine adsorbed at room temperature and evacuated at 200°C on the SAPO-34 samples synthesized with different SiO/AlO ratio. (a) 0.1; (b) 0.4; (c) 0.7; (d) 1.0

Fig.9 Effects of SiO/AlO ratio on methanol conversion and olefin selectivity over HZSM-5 (a) and SAPO-34 catalysts (b)

Fig.10 Effects of reaction temperature on methanol conversion and light olefin selectivity over HZSM-5 (a) and SAPO-34 catalysts (b)

Fig.11 Scheme of the reaction mechanism

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