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采用Ag-SiO选择性吸附后结合GC×GC-FID对废塑料和轮胎热解油中的烯烃进行定量测定。

Quantitative determination of olefins in pyrolysis oils from waste plastics and tires using selective adsorption by Ag-SiO followed by GC×GC-FID.

作者信息

Auersvald Miloš, Šiman Michal, Vozka Petr, Straka Petr

机构信息

Department of Sustainable Fuels and Green Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic.

Department of Sustainable Fuels and Green Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic.

出版信息

Talanta. 2025 Jan 1;281:126792. doi: 10.1016/j.talanta.2024.126792. Epub 2024 Aug 30.

Abstract

Determination of olefins in pyrolysis oils from waste plastics and tires is crucial for optimizing the pyrolysis process and especially for the further advanced valorization of these oils in terms of the circular economy. Identifying olefins, even using high-resolution techniques like GC×GC, is challenging without TOF-MS, which allows modification of the ionization step. Currently, the only method for determining olefins in plastic pyrolysis oils is GC-VUV, recently standardized as ASTM D8519. However, TOF-MS and VUV are not affordable instruments for many research teams working on plastics recycling. This paper introduces a simple method for the selective micro-scale adsorption of olefins over AgNO/SiO, followed by the GC×GC-FID analysis. Olefins are determined indirectly from the loss of chromatographic area in respective hydrocarbon groups before and after removal. Only 50 μL sample and 15 min of sample separation are needed. Our method was extensively validated and provides a reliable determination of olefin content in a wide range of pyrolysis oils from plastics and tires and their products after mild hydrotreatment. It is affordable to all researchers and industrial companies working on plastics recycling by thermochemical processes as it does not require an MS detector.

摘要

测定废塑料和轮胎热解油中的烯烃对于优化热解过程至关重要,特别是从循环经济的角度来看,对于这些油的进一步高级增值而言。即使使用气相色谱×气相色谱(GC×GC)等高分辨率技术,在没有飞行时间质谱(TOF-MS)的情况下识别烯烃也具有挑战性,因为TOF-MS可以改变电离步骤。目前,测定塑料热解油中烯烃的唯一方法是气相色谱-真空紫外光谱法(GC-VUV),最近已被标准化为ASTM D8519。然而,对于许多从事塑料回收研究的团队来说,TOF-MS和VUV仪器价格昂贵。本文介绍了一种简单的方法,用于在AgNO₃/SiO₂上选择性微尺度吸附烯烃,然后进行GC×GC-火焰离子化检测器(FID)分析。通过去除前后各烃类基团色谱面积的损失间接测定烯烃。仅需50 μL样品和15分钟的样品分离时间。我们的方法经过了广泛验证,可可靠地测定来自塑料和轮胎及其温和加氢处理后产物的各种热解油中的烯烃含量。由于它不需要质谱检测器,对于所有通过热化学过程进行塑料回收研究的研究人员和工业公司来说都是经济实惠的。

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