镧改性分子筛吸附剂对汽油馏分的吸附脱硫
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摘要
燃料油中的有机硫化物燃烧后形成的S02是形成酸雨的主要原因,还会使处理汽车尾气的催化剂中毒。随着人们环境保护意识的提高,各国对燃料油中的硫含量进行了日益严格的限制。传统的加氢脱硫技术虽然可使汽油深度脱硫,但同时会导致辛烷值明显下降,增加氢耗及设备投资。吸附脱硫技术操作简单、方便、快速,且不会降低汽油的辛烷值。目前,多种分子筛都被用于吸附脱硫研究,但关于吸附质和吸附剂相互作用的机理研究还比较薄弱。本论文工作分为两部分：对微孔分子筛吸附剂,研究烯烃对噻吩吸附的影响规律及影响机理；对微介孔复合分子筛吸附剂,考察吸附剂的孔道结构对脱硫性能的影响。
用液相离子交换法将La3+引入NaY分子筛中,制备La3+改性NaY分子筛吸附剂,并对其脱硫性能进行考察。在静态吸附脱硫实验中,液相离子交换法制备的吸附剂由于阳离子数目的减少,部分晶格结构遭到破坏等原因,对模型汽油中噻吩的脱除率降低。烯烃的加入使NaY分子筛的吸附脱硫能力持续降低,却在一定程度上提高了La3+改性分子筛吸附剂的噻吩脱除能力。红外光谱结果表明,噻吩分子以π络合的方式吸附在NaY分子筛上,而Y分子筛经La3+改性后,观察到S-M直接作用的新吸附方式。烯烃以其π电子与NaY分子筛表面的羟基相互作用,但在LaNaY上,却是以其烷基与吸附剂表面的羟基发生作用,特别是在LaNaY上,可观察到烯烃的碳正离子物种,结合吸附脱硫实验和GC-FPD检测,认为烯烃对LaNaY吸附脱硫的促进作用,可能是由于La3+改性后,吸附剂具有强酸性,促使烯烃和噻吩分子发生烷基化反应,生成尺寸较大的烷基噻吩,微孔填充效应增强,有利于吸附脱硫。这可能是La3+改性的NaY分子筛吸附剂对含烯烃的模型汽油表现出较高脱硫选择性的原因之一。
在考虑吸附方式对脱硫选择性的影响时,吸附剂的孔道尺寸对脱硫性能的影响也不应忽视。本论文采用纳米组装法合成微-介孔复合分子筛NaY/MCM-41,采用液相离子交换法引入La3+。表征结果显示：合成的材料为微介孔复合结构,即介孔孔壁内含有微孔分子筛的初级和次级结构单元。La3+改性后,尽管其比表面积有所下降,但仍保持微介孔复合结构。静态脱硫实验结果表明,与微孔吸附剂]LaNaY相比,复合孔吸附剂LaNaY/MCM-41随着模型油中甲苯含量的增加,脱硫率的下降趋势明显减缓。对FCC汽油的吸附脱硫结果表明,复合孔吸附剂的脱硫性能明显高于纯微孔吸附剂LaNaY和纯介孔吸附剂!LaMCM-41,初步说明吸附剂的孔道尺寸是影响其脱硫性能的主要因素之一。
SO2 from the combustion of fuels containing organic sulfur compounds is the main reason for acid rain, and it can also poison the catalysts used in the engines'exhaust treatment. With the improvement of people's environmental protection, more stringent restrictions about the sulfur content in fuel oil have been mandated in many countries. Although traditional hydro-desulfurization (HDS) can desulfurize gasoline deeply, but it can also lead to octane reduction, more hydrogen consumption and equipment investment. Adsorption desulfurization technology is simple, easy, fast, and it can not reduce the octane number of gasoline. Now, a variety of molecular sieves have been studied for adsorption desulfurization, however, there is little research on the adsorption mechanism of organic sulfur compounds on adsorbents. This dissertation involves two parts:for microporous zeolite adsorbents, the effect of olefins on the desulfurization of model gasoline and the adsorption mechanism of thiophene and cyclohexene are studied; for micro-mesoporous zeolite adsorbents, the effect of pore structure on adsorption desulfurization are discussed.
LaNaY adsorbents are prepared by liquid ion-exchanging La(NO3)3 solution with NaY zeolite. For model gasoline without cyclohexene, the desulfurization capacity of LaNaY is lower than that of NaY, because of the decrease of the number of cations and the partly broken lattice structure. In static adsorption, NaY shows declined sulfur removal with the addition of cyclohexene, while LaNaY displays evident improvement in sulfur removal with the addition of a certain amount of cyclohexene. FT-IR results demonstrate that thiophene is adsorbed on NaY byπcomplexation, but a new adsorption mode, the direct S-La3+interaction, appears on LaNaY. Cyclohexene is adsorbed on NaY byπ-OH interation and is partly adsorbed on LaNaY by alkyl-OH. It is woth noting that carbenium is detected on LaNaY. Combined with GC-FPD analysis, it can be deduced that alkylation between thiophene and cyclohexene occurs on the acidic sites of LaNaY, the lager size of alkylated thiophene enhances the micropore-filling effect, and thus promotes adsorption desulfurization. This may be one of the reasons for LaNaY shows improved sulfur removal from model gasoline containing olefin.
Besides the effect of adsorption mode on desulfurization selectivity, we should also consider the role of the adsorbent's pore size plays in desulfurization. In this dissertation, the micro-mesoporous molecular sieve NaY/MCM-41 is synthesized by the assembly of protozeolitic nanoclusters, and La3+is introduced into NaY/MCM-41 zeolite by liquid ion-exchange. The characterization results show that the systhesized NaY/MCM-41 contains the structure units of zeolite Y in its wall, and the micro-mesoporous structure of LaNaY/MCM-41 is maintained after the introduction of La3+, even though the surface area is decreased. Comparing the sulfur capacity of microporous LaNaY and composite LaNaY/MCM-41, both of them show decreased tendency with the addition of toluene, but the drop rate of the latter is lower than that of the former. The desulfurization of FCC gasoline by microporous LaNaY, mesoporous LaMCM-41 and composite LaNaY/MCM-41 also displays that the sulfur capacity of LaNaY/MCM-41 is superior to that of the other two adsorbents. These results show that the pore structure of the adsorbents is one of the key factors of the desulfurization capacity.
用液相离子交换法将La3+引入NaY分子筛中,制备La3+改性NaY分子筛吸附剂,并对其脱硫性能进行考察。在静态吸附脱硫实验中,液相离子交换法制备的吸附剂由于阳离子数目的减少,部分晶格结构遭到破坏等原因,对模型汽油中噻吩的脱除率降低。烯烃的加入使NaY分子筛的吸附脱硫能力持续降低,却在一定程度上提高了La3+改性分子筛吸附剂的噻吩脱除能力。红外光谱结果表明,噻吩分子以π络合的方式吸附在NaY分子筛上,而Y分子筛经La3+改性后,观察到S-M直接作用的新吸附方式。烯烃以其π电子与NaY分子筛表面的羟基相互作用,但在LaNaY上,却是以其烷基与吸附剂表面的羟基发生作用,特别是在LaNaY上,可观察到烯烃的碳正离子物种,结合吸附脱硫实验和GC-FPD检测,认为烯烃对LaNaY吸附脱硫的促进作用,可能是由于La3+改性后,吸附剂具有强酸性,促使烯烃和噻吩分子发生烷基化反应,生成尺寸较大的烷基噻吩,微孔填充效应增强,有利于吸附脱硫。这可能是La3+改性的NaY分子筛吸附剂对含烯烃的模型汽油表现出较高脱硫选择性的原因之一。
在考虑吸附方式对脱硫选择性的影响时,吸附剂的孔道尺寸对脱硫性能的影响也不应忽视。本论文采用纳米组装法合成微-介孔复合分子筛NaY/MCM-41,采用液相离子交换法引入La3+。表征结果显示：合成的材料为微介孔复合结构,即介孔孔壁内含有微孔分子筛的初级和次级结构单元。La3+改性后,尽管其比表面积有所下降,但仍保持微介孔复合结构。静态脱硫实验结果表明,与微孔吸附剂]LaNaY相比,复合孔吸附剂LaNaY/MCM-41随着模型油中甲苯含量的增加,脱硫率的下降趋势明显减缓。对FCC汽油的吸附脱硫结果表明,复合孔吸附剂的脱硫性能明显高于纯微孔吸附剂LaNaY和纯介孔吸附剂!LaMCM-41,初步说明吸附剂的孔道尺寸是影响其脱硫性能的主要因素之一。
SO2 from the combustion of fuels containing organic sulfur compounds is the main reason for acid rain, and it can also poison the catalysts used in the engines'exhaust treatment. With the improvement of people's environmental protection, more stringent restrictions about the sulfur content in fuel oil have been mandated in many countries. Although traditional hydro-desulfurization (HDS) can desulfurize gasoline deeply, but it can also lead to octane reduction, more hydrogen consumption and equipment investment. Adsorption desulfurization technology is simple, easy, fast, and it can not reduce the octane number of gasoline. Now, a variety of molecular sieves have been studied for adsorption desulfurization, however, there is little research on the adsorption mechanism of organic sulfur compounds on adsorbents. This dissertation involves two parts:for microporous zeolite adsorbents, the effect of olefins on the desulfurization of model gasoline and the adsorption mechanism of thiophene and cyclohexene are studied; for micro-mesoporous zeolite adsorbents, the effect of pore structure on adsorption desulfurization are discussed.
LaNaY adsorbents are prepared by liquid ion-exchanging La(NO3)3 solution with NaY zeolite. For model gasoline without cyclohexene, the desulfurization capacity of LaNaY is lower than that of NaY, because of the decrease of the number of cations and the partly broken lattice structure. In static adsorption, NaY shows declined sulfur removal with the addition of cyclohexene, while LaNaY displays evident improvement in sulfur removal with the addition of a certain amount of cyclohexene. FT-IR results demonstrate that thiophene is adsorbed on NaY byπcomplexation, but a new adsorption mode, the direct S-La3+interaction, appears on LaNaY. Cyclohexene is adsorbed on NaY byπ-OH interation and is partly adsorbed on LaNaY by alkyl-OH. It is woth noting that carbenium is detected on LaNaY. Combined with GC-FPD analysis, it can be deduced that alkylation between thiophene and cyclohexene occurs on the acidic sites of LaNaY, the lager size of alkylated thiophene enhances the micropore-filling effect, and thus promotes adsorption desulfurization. This may be one of the reasons for LaNaY shows improved sulfur removal from model gasoline containing olefin.
Besides the effect of adsorption mode on desulfurization selectivity, we should also consider the role of the adsorbent's pore size plays in desulfurization. In this dissertation, the micro-mesoporous molecular sieve NaY/MCM-41 is synthesized by the assembly of protozeolitic nanoclusters, and La3+is introduced into NaY/MCM-41 zeolite by liquid ion-exchange. The characterization results show that the systhesized NaY/MCM-41 contains the structure units of zeolite Y in its wall, and the micro-mesoporous structure of LaNaY/MCM-41 is maintained after the introduction of La3+, even though the surface area is decreased. Comparing the sulfur capacity of microporous LaNaY and composite LaNaY/MCM-41, both of them show decreased tendency with the addition of toluene, but the drop rate of the latter is lower than that of the former. The desulfurization of FCC gasoline by microporous LaNaY, mesoporous LaMCM-41 and composite LaNaY/MCM-41 also displays that the sulfur capacity of LaNaY/MCM-41 is superior to that of the other two adsorbents. These results show that the pore structure of the adsorbents is one of the key factors of the desulfurization capacity.
引文
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