Wang Dehua, Tian Peng, Fan Dong, Yang Miao, Gao Beibei, Qiao Yuyan, Wang Chan, Liu Zhongmin
National Engineering Laboratory for Methanol to Olefins, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR China; Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR China; Graduate University of Chinese Academy of Sciences, Beijing 100049, PR China.
National Engineering Laboratory for Methanol to Olefins, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR China; Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, PR China.
J Colloid Interface Sci. 2015 May 1;445:119-126. doi: 10.1016/j.jcis.2014.12.029. Epub 2014 Dec 24.
In the present study, N-methyldiethanolamine (MDEA) is demonstrated to be a multifunctional structure-directing agent for the synthesis of aluminophosphate-based molecular sieves. Four types of molecular sieves, including SAPO-34, -35, AlPO-9 and -22, are for the first time acquired with MDEA as a novel template. The phase selectivity of the present synthesis is found to be condition-dependent. SAPO-34 (CHA) crystallizes from a conventional hydrothermal system with a higher MDEA concentration. When using MDEA as both the template and solvent, pure SAPO-35 (LEV) is obtained from the synthetic gel with a high P2O5/Al2O3 ratio of (2-3), in which the concentration of MDEA could be varied in a wide range. AlPO-9 and AlPO-22 (AWW) are synthesized under the similar conditions to SAPO-35, except without the addition of Si source. The physicochemical properties of the obtained samples are investigated by XRD, XRF, SEM, N2 physisorption, TG-DSC, and various NMR spectra ((13)C, (29)Si, (27)Al and (31)P). Both SAPO-34 and SAPO-35 show good thermal stability, large surface area, and high pore volume. The catalytic performance of SAPO-34 is evaluated by the methanol-to-olefins (MTO) reaction and a good (C2H4+C3H6) selectivity of 82.7% has been achieved.
在本研究中,N-甲基二乙醇胺(MDEA)被证明是用于合成磷酸铝基分子筛的多功能结构导向剂。首次以MDEA作为新型模板获得了四种类型的分子筛,包括SAPO-34、-35、AlPO-9和-22。发现本合成的相选择性取决于条件。SAPO-34(CHA)从具有较高MDEA浓度的传统水热体系中结晶。当使用MDEA作为模板和溶剂时,从P2O5/Al2O3比为(2-3)的合成凝胶中获得纯SAPO-35(LEV),其中MDEA的浓度可以在很宽的范围内变化。AlPO-9和AlPO-22(AWW)在与SAPO-35相似的条件下合成,只是不添加硅源。通过XRD、XRF、SEM、N2物理吸附、TG-DSC和各种NMR光谱((13)C、(29)Si、(27)Al和(31)P)研究所得样品的物理化学性质。SAPO-34和SAPO-35均表现出良好的热稳定性、大表面积和高孔体积。通过甲醇制烯烃(MTO)反应评估了SAPO-34的催化性能,实现了82.7%的良好(C2H4+C3H6)选择性。