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[二噁英在11种吸附剂上的热吸附与解吸性能评估]

[Evaluation of thermal adsorption and desorption properties of dioxins on 11 adsorbents].

作者信息

Wang Lin, Wang Longxing, Ni Yuwen, Zhang Haijun, Chen Jiping

机构信息

CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.

University of Chinese Academy of Sciences, Beijing 100049, China.

出版信息

Se Pu. 2021 Apr 8;39(4):437-443. doi: 10.3724/SP.J.1123.2020.10009.

Abstract

The key to the online thermal capture of dioxins is the appropriate choice of adsorbent for efficient capture at low temperatures and rapid desorption at high temperatures. Efficient adsorbents can allow for capture and separation during the online monitoring of dioxins or during offline dioxin tests. In this study, 1,2,3,4-tetrachlorodibenzo--dioxin (1,2,3,4-TCDD) and pentachlorodibenzofuran (1,2,3,8,9-PCDF) were used as model compounds for dioxin monomers, and an electron capture detector (ECD) was used to detect the dioxin signals. The retention volumes of 1,2,3,4-TCDD and 1,2,3,8,9-PCDF on 11 types of adsorbents were determined using a packed-column gas chromatography system. Then, the corresponding van der Hoff equation was established, and these adsorbents were evaluated for the thermal trapping of dioxin. The linear coefficients of determination () of these adsorbents were greater than 0.96, which indicated a strong correlation between the adsorption capacity and 1/ (: temperature). The gas-solid partition coefficients () of the adsorbent at 120, 150 and 180 ℃ were predicted according to the van der Hoff equation, which was obtained in an earlier study. Among the 11 adsorbents, florite had the largest adsorption capacity at 120, 150, and 180 ℃, especially at 120 ℃; the values for 1,2,3,4-TCDD and 1,2,3,8,9-PCDF on florite were as high as 1.82×10 m/g and 1.46×10 m/g, respectively. Carbon-based adsorbents of the Chinese stilbene polymer porous microspheres GDX series, GDX-101, GDX-102, GDX-103, GDX-105, and GDX-203, can facilitate thermal desorption below 270 ℃, which is the maximum tolerance temperature for series 1 and 2, thus providing evidence for the feasibility of using these adsorbents for the thermal adsorption/desorption of dioxins. When the detection temperature is less than 310 ℃, 1,2,3,4-TCDD is thermally desorbed from mordenite, but 1,2,3,8,9-PCDF is not; this indicates the selective adsorption of dioxin monomers on zeolite. However, diatomite and montmorillonite have poor adsorption capacity for dioxins in the gas phase, thus being unsuitable for the thermal trapping of dioxins. Florite, silica gel, alumina, GDX-102, GDX-103, and GDX-203, which have strong adsorption capacities, were selected as possible absorbents for the next evaluation. Comparison of the ln values of dioxin monomers on the same adsorbent at 120 ℃ and 270 ℃ revealed that the retention volume of florite was the largest at both temperatures. When the thermal trapping performance of dioxin at low temperatures is considered, florite is thought to be the best among the 11 adsorbents for capturing dioxins. However, when the desorption performance at high temperatures is considered, GDX-102 is the best adsorbent for the thermal desorption of dioxins, and its ln is the smallest among those for the aforementioned six adsorbents. The ln and ln values of silica gel, GDX-103, and GDX-203 are similar to those of GDX-102, and hence, they can also be used as rapid thermal adsorption/desorption materials. In this study, the thermal adsorption/desorption properties of 1,2,3,4-TCDD and 1,2,3,7,8-PCDF on 11 adsorbents were systematically evaluated to obtain a new solution for the sampling and preparation of dioxins and to provide technical support for the thermal capture of dioxins. It should be noted that these results were obtained under ideal conditions of nitrogen, without considering the influence of the complex conditions of flue gas (such as moisture and CO) on the thermal capture. To achieve the thermal capture of dioxins in incineration flue gas, it is necessary to carry out the relevant evaluation and test research in a flue gas atmosphere.

摘要

二噁英在线热捕集的关键在于选择合适的吸附剂,使其能够在低温下高效捕集,在高温下快速解吸。高效吸附剂可用于二噁英在线监测或离线二噁英测试过程中的捕集与分离。本研究中,选用1,2,3,4-四氯二苯并 - 对二噁英(1,2,3,4-TCDD)和五氯二苯并呋喃(1,2,3,8,9-PCDF)作为二噁英单体的模型化合物,并使用电子捕获检测器(ECD)检测二噁英信号。采用填充柱气相色谱系统测定了1,2,3,4-TCDD和1,2,3,8,9-PCDF在11种吸附剂上的保留体积。然后,建立了相应的范德霍夫方程,并对这些吸附剂的二噁英热捕集性能进行了评估。这些吸附剂的线性决定系数()大于0.96,这表明吸附容量与1/(:温度)之间存在很强的相关性。根据前期研究得到的范德霍夫方程预测了吸附剂在120、150和180℃下的气固分配系数()。在11种吸附剂中,萤石在120、150和180℃下的吸附容量最大,尤其是在120℃时;1,2,3,4-TCDD和1,2,3,8,9-PCDF在萤石上的值分别高达1.82×10 m/g和1.46×10 m/g。国产苯乙烯类聚合物多孔微球GDX系列的碳基吸附剂GDX-101、GDX-102、GDX-103、GDX-105和GDX-203,在270℃以下(1、2系列的最高耐受温度)能够促进热解吸,从而为这些吸附剂用于二噁英的热吸附/解吸的可行性提供了证据。当检测温度低于310℃时,1,2,3,4-TCDD能从丝光沸石上热解吸,但1,2,3,8,9-PCDF不能;这表明二噁英单体在沸石上的选择性吸附。然而,硅藻土和蒙脱石对气相中二噁英的吸附能力较差,因此不适用于二噁英的热捕集。萤石、硅胶、氧化铝、GDX-102、GDX-103和GDX-203具有较强的吸附能力,被选为下一轮评估的可能吸附剂。比较二噁英单体在同一吸附剂上120℃和270℃时的ln值,发现萤石在两个温度下的保留体积均最大。考虑到二噁英在低温下的热捕集性能,萤石被认为是11种吸附剂中捕集二噁英的最佳选择。然而,考虑到高温下的解吸性能,GDX-102是二噁英热解吸的最佳吸附剂,其ln在上述六种吸附剂中最小。硅胶、GDX-103和GDX-203的ln和ln值与GDX-102相似,因此它们也可作为快速热吸附/解吸材料。本研究系统评估了1,2,3,4-TCDD和1,2,3,7,8-PCDF在11种吸附剂上的热吸附/解吸性能,以获得二噁英采样与制备的新解决方案,并为二噁英的热捕集提供技术支持。需要注意的是,这些结果是在理想的氮气条件下获得的,未考虑烟气复杂条件(如水分和CO)对热捕集的影响。要实现焚烧烟气中二噁英的热捕集,有必要在烟气气氛中进行相关的评估和试验研究。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/538c/9404214/02e194f15816/cjc-39-04-437-img_1.jpg

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