聚乙烯醇辅助合成TS-1及其催化氧化脱硫性能

摘要/Abstract

摘要： 传统钛硅分子筛（TS-1）因微孔特性导致其传质过程受限。通过引入聚乙烯醇（PVA）作为结构导向剂可以调控分子筛的晶体生长取向和形貌，结合动态水热晶化法，制备了不同晶化时间的DTS-t分子筛。在相同溶胶体系下，制备了未添加PVA的动态晶化3 h样品（N-DTS-3）和添加PVA的传统TS-1分子筛（CTS-48）。利用XRD、SEM、TEM、N₂吸附-脱附、FT-IR、UV-vis和XPS等方法分析材料特性。结果表明：添加PVA制备的DTS-3在3 h内即可形成完整晶体结构；DTS-t分子筛粒径约1 μm，总比表面积均超过430 m²/g，微孔比表面积为 400 m²/g左右，无锐钛矿TiO₂。以1000 mg/L的噻吩/正辛烷为模拟油进行催化氧化脱硫性能试验，结果发现，对在60 ℃下催化性能最佳的DTS-6分子筛而言：当反应60 min时其催化氧化模拟油的脱硫率达到91%，较传统CTS-48分子筛提高了约6百分点；在反应110 min时，脱硫率提升至95.1%，较N-DTS-3分子筛提高了约28百分点，PVA的引入显著提高了TS-1的传质效率。

关键词: 钛硅分子筛, 聚乙烯醇, 动态晶化, 氧化脱硫

Abstract: The mass transfer process of traditional titanium silicalite zeolite(TS-1) is limited due to its microporous characteristics. The crystal growth orientation and morphology of TS-1 can be controlled by introducing polyvinyl alcohol (PVA) as a structure directing agent. DTS-t zeolite with different crystallization time were prepared by dynamic hydrothermal crystallization method. Furthermore, under the same sol system, the dynamic crystallization 3 h sample without PVA (N-DTS-3) and the traditional TS-1 zeolite with PVA (CTS-48) were prepared. The material properties were characterized by XRD, SEM, TEM, N₂ adsorption desorption, FT-IR, UV-vis and XPS. The results show that DTS-3 prepared by adding PVA can form a complete crystal structure within 3 h; DTS-t zeolite has a particle size of about 1μm, a total specific surface area of more than 430 m²/g, a microporous specific surface area of about 400 m²/g, and no anatase TiO₂. The catalytic oxidative desulfurization performance of 1000 mg/L thiophene/n-octane as simulated oil was tested. The results showed that for DTS-6 zeolite with the best catalytic performance at 60 ℃, the catalytic oxidative desulfurization rate reached 90% at 60 min, and increased to 95.1% at 110 min. the desulfurization rate was 20% and 6% higher than that of N-DTS-3 zeolite and traditional CTS-48 zeolite, respectively. The introduction of PVA significantly improved the mass transfer efficiency of TS-1.

Key words: titanium silicalite zeolite, polyvinyl alcohol, dynamic crystallization, oxidative desulfurization

张玉妹孙悦任铁强党阳刘宇彤. 聚乙烯醇辅助合成TS-1及其催化氧化脱硫性能[J]. 石油炼制与化工, 2026, 57(1): 28-35.

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