关键词: 二噁英, 吸附剂, 在线检测, 热吸附, 热脱附

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-p-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 (R²) of these adsorbents were greater than 0.96, which indicated a strong correlation between the adsorption capacity and 1/T (T: temperature). The gas-solid partition coefficients (K_SA) 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 K_SA values for 1,2,3,4-TCDD and 1,2,3,8,9-PCDF on florite were as high as 1.82×10⁸ m³/g and 1.46×10¹³ m³/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 lnK_SA 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 lnK_{SA,270 ℃} is the smallest among those for the aforementioned six adsorbents. The lnK_{SA,120 ℃} and lnK_{SA,270 ℃} 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 CO₂) 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.

Key words: dioxin, adsorbent, online monitoring, thermal adsorption, thermal desorption