Preparation of TS-1 by dynamic method and study on the performance of thiophene sulfur removal
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摘要: 本研究以四丙基氢氧化铵(TPAOH)为模板剂,正硅酸乙酯(TEOS)为硅源,钛酸四丁酯(TBOT)为钛源,在动态晶化釜内合成形貌规则且粒径约为600 nm的TS-1分子筛。通过改变TBOT的用量,进而改变初始合成液中的硅钛比,考察硅钛比对TS-1分子筛的影响,并采用SEM、TEM、XRD、FT-IR、UV-vis、XPS、N2吸附-脱附技术对制得的催化剂进行表征。将合成得到的TS-1分子筛应用于以噻吩正辛烷为模拟油的体系中,考察TS-1分子筛催化氧化脱硫性能。Abstract: Using TPAOH as the template, TEOS as the silicon source and TBOT as the titanium source, the as-prepared samples utilizing a dynamic crystallizating kettle possessed regular morphology and the average particle size of 600 nm. By modulating the dosage of TBOT, and then changing the molar ratio of titanium to silicon in the initial synthesis solution, the effect of silicon to titanium ratio on TS-1 molecular sieve was investigated. TS-1 zeolite properties were characterized by means of SEM, TEM, XRD, FT-IR, UV-vis, XPS, N2 adsorption and desorption technology. Finally, using a simulated system of thiophene n-octane dissolved in octane, the catalytic oxidative desulfurization performance of TS-1 zeolite was investigated.
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表 1 合成TS-1分子筛初始合成液组成
Table 1 Initial gel composition of TS-1 synthesis
Sample Initial gel composition TS-1(20) 1.0SiO2∶0.050TiO2∶0.3TPAOH∶50H2O TS-1(30) 1.0SiO2∶0.033TiO2∶0.3TPAOH∶50H2O TS-1(40) 1.0SiO2∶0.025TiO2∶0.3TPAOH∶50H2O 表 2 不同硅钛比TS-1体相的元素原子百分比
Table 2 Elements atomic percentage of overall TS-1 samples with different ratios of silicon to titanium
Sample Element atomic percentage/% TS-1(20) 62.52 36.78 0.69 TS-1(30) 60.01 39.26 0.73 TS-1(40) 60.58 38.95 0.47 表 3 不同硅钛比TS-1的孔结构性质
Table 3 Pore structure properties of TS-1 samples with different ratios of silicon to titanium
Sample St/
(m2·g−1)Sm/
(m2·g−1)dp/
nmvm/
(cm3·g−1)vt/
(cm3·g−1)TS-1(20) 512.4 483.6 2.154 0.21 0.28 TS-1(30) 513.9 483.4 2.275 0.21 0.29 TS-1(40) 464.0 418.6 2.168 0.18 0.25 表 4 不同物质光电能谱峰处结合能
Table 4 Binding energy of different samples
Sample Ti 2p3/2 E/eV α β TS-1 460.0 ± 0.2 457.9 ± 0.2 TiO2 + SiO2 − 458.0 TiO2 − 458.8 α represents the binding energy at the spectral peak of framework titanium; β represents the binding energy at the spectral peak of non-framework titanium (TiO2) 表 5 不同硅钛比TS-1表相的元素原子百分比
Table 5 Elements atomic percentage of surface TS-1 samples with different ratios of silicon to titanium
Sample Element atomic percentage/% TS-1(20) 60.17 29.91 0.68 TS-1(30) 59.42 29.90 0.68 TS-1(40) 59.51 30.46 0.29 -
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