Preparation and catalytic oxidative desulfurization of sulfuric acid-acidified Ti-SBA-15

doi:10.16085/j.issn.1000-6613.2017-1391

Abstract

Abstract: SBA-15 and Ti-SBA-15 mesoporous molecular sieves were prepared by the hydrothermal method using tetraethylorthosilicate as silica source,tetrabutylorthotitanate as titanium source and poly(ethylene glycol)-block -poly(propylene glycol)-block -poly(ethylene glycol)as structure-directing agent.H₂SO₄/SBA-15 and H₂SO₄/Ti-SBA-15 were obtained from acidification of as-prepared zeolites using sulfuric acid.The structure,pore distribution,and surface morphology of SBA-15,H₂SO₄/SBA-15,and H₂SO₄/Ti-SBA-15 were characterized by fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),BET nitrogen adsorption-desorption isothermal method,electron beam scanning electron microscopy(SEM),and transmission electron microscopy(TEM).The catalytic oxidation performances of removing dibenzothiophene(DBT)from model oil were evaluated by the as-prepared zeolites as catalyst,the cyclohexanone(CYHPO)as an oxidant and acetonitrile as an extractant.The sulfur removal of SBA-15,H₂SO₄/SBA-15,and H₂SO₄/Ti-SBA-15 were 36.1%,57.8%,and 65.4%,respectively,with the reaction temperature of 343 K,the reaction time of 60 min,the acetonitrile of 7.5 mL,the molar ratio of CYHPO to DBT of 5:1, and the amount of catalysts of 0.05g.This indicates that the SBA-15 exhibits preferable catalytic oxidative desulfurization activity using acidification and Ti modification.

Key words: H₂SO₄/Ti-SBA-15, catalytic oxidation, dibenzothiophene, cyclohexanone peroxide, desulfurization

摘要： 以正硅酸乙酯为硅源、钛酸正丁酯为钛源、聚（乙二醇）-block-聚（丙二醇）-block-聚（乙二醇）为模板剂，采用水热法分别合成了介孔分子筛SBA-15和Ti-SBA-15，采用硫酸对其酸化后制得H₂SO₄/SBA-15和H₂SO₄/Ti-SBA-15。通过傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、BET氮气吸附-脱附等温方法、电子扫描电镜（SEM）及透射电镜（TEM）对SBA-15、H₂SO₄/SBA-15和H₂SO₄/Ti-SBA-15结构、孔道分布和表面形貌进行了表征。以制备的分子筛为催化剂，过氧化环己酮（CYHPO）为氧化剂和乙腈为萃取剂评价其催化氧化脱除模拟油中二苯并噻吩（DBT）性能。当反应温度为343 K，反应时间为60 min，乙腈为7.5 mL，CYHPO与DBT的摩尔比为5∶1，催化剂用量为0.05 g时，SBA-15、H₂SO₄/SBA-15和H₂SO₄/Ti-SBA-15的脱硫率分别为36.1%、57.8%和65.4%。这表明酸化和金属Ti同时改性的SBA-15具有较好的催化氧化脱硫活性。

关键词: H₂SO₄/Ti-SBA-15, 催化氧化, 二苯并噻吩, 过氧化环己酮, 脱硫

CLC Number:

TQ032
X5

LIN Zhigeng, WANG Hanlu, ZHOU Jianlong, HUANG Jiashen, LIU Yuanyuan, WANG Hongli. Preparation and catalytic oxidative desulfurization of sulfuric acid-acidified Ti-SBA-15[J]. Chemical Industry and Engineering Progress, 2017, 36(S1): 253-260.

林志耿, 王寒露, 周建龙, 黄家燊, 刘园园, 王红丽. 硫酸化Ti-SBA-15的制备及其催化氧化脱硫[J]. 化工进展, 2017, 36(S1): 253-260.

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