不同纳米结构AlF3催化水解NF3的活性测试

RAN Pub Date : 2017-04-01 DOI:10.11159/icnnfc17.112
N. Park, Yong Han Jeong, T. Lee
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引用次数: 0

摘要

氟化合物是引起全球变暖的一种变暖气体。这些氟化合物,如NF3等,通常来自半导体和LCD制造行业。本研究评估了催化水解对NF3的有效分解[1,2]。采用不同的合成方法合成不同形貌的AlF3纳米结构,作为催化NF3水解的催化剂。采用气固反应合成纳米针状AlF3,采用湿化学法合成大棒状AlF3。在固定床反应器中进行催化活性试验,NF3和GHSV的含量分别固定为5000 ppmv和15000 h。蒸汽通过注射泵以NF3 / H2O = 1 / 3的体积比注入。通过XRD (x射线衍射)、SEM(扫描电子显微镜)和BET (brunauer - emmet - teller)表面积测量,观察了AlF3作为NF3水解催化剂的表征。观察到不同形态的AlF3结构,如棒状、针状和球形。大多数结构的AlF3样品的比表面积都很低,它们的比表面积没有显著差异。另一方面,不同形态的AlF3对NF3的水解活性测试结果显示出不同的催化活性。NF3对球形AlF3的转化率保持在30%左右。相比之下,针状AlF3的催化活性使NF3的转化率达到100%。在长期测试中,活性保持了300小时以上。通过XRD分析,确定了AlF3的六方晶体结构(25.321°,42.715°,51.997°,58.118°2θ)。AlF3的正交晶型结构(14.747°,24.943°,29.746°,47.463°,52.790°2θ)仅在湿法氟化法合成的AlF3的XRD峰图上得到证实。采用干氟化法合成的AlF3和AlF3纳米结构的XRD峰图相似,但商用AlF3在六方晶体结构的XRD峰图上的峰强度要高于其他AlF3样品。六方结构的AlF3对NF3水解的催化活性高于正交结构的AlF3。虽然AlF3的六角形结构对NF3的水解具有较高的催化活性,但AlF3的针状六角形结构比其他六角形结构具有更高的催化活性。六方结构的AlF3对NF3水解的催化活性高于正交结构的AlF3。因此,可以采用干式氟化法制备具有高催化活性的针状AlF3。
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Activity Test with Various AlF3 Nano-Structure for Catalytic Hydrolysis of NF3
Extended Abstract Fluorine compounds have been highlighted as a warming gas caused the global warming. These Fluorine compounds, such as NF3, etc., are commonly emitted from semiconductor and LCD manufacturing industries. This study gave assessment of catalytic hydrolysis for the effective decomposition of NF3 [1, 2]. AlF3 nano-structures with various morphologies, which were synthesized by various synthesis methods, were used as the catalyst for the hydrolysis of NF3. AlF3 with a nano-needle type was synthesized by a gas-solid reaction, and AlF3 with a large-sized rod type was synthesized using the wet chemical method. The catalytic activity tests were carried out in a fixed-bed reactor, and the content of NF3 and GHSV were fixed to 5000 ppmv, and 15000 h, respectively. Steam was injected at a volumetric ratio of NF3 / H2O = 1 / 3 via syringe pump. The characterization of AlF3 used as the catalyst for hydrolysis of NF3 was observed by XRD (X-ray diffraction), SEM (scanning electron microscopy) and BET (Brunauer-Emmett-Teller) surface areas measurements. The AlF3 structures with various morphologies, such as rod, needle, and spherical types, were observed. The AlF3 samples of most structures had a very low surface area and their surface area showed no significant difference. On the other hand, the results of the activity tests for the hydrolysis of NF3 over AlF3 with different morphologies showed different catalytic activity. The conversion of NF3 over the spherical type AlF3 was kept at approximately 30 %. In contrast, the catalytic activity of needle-shaped AlF3 resulted in 100% NF3 conversion. The activity was maintained for more than 300 h in the long-term tests. The hexagonal crystal structure of AlF3 (25.321°, 42.715°, 51.997°, and 58.118° 2θ) was confirmed by XRD analysis of all AlF3 samples used in this study. The orthorhombic crystal structure of AlF3 (14.747°, 24.943°, 29.746°, 47.463°, and 52.790° 2θ) was confirmed only on the XRD peak pattern of AlF3 synthesized by the wet fluorination process. The commercial AlF3 and AlF3 nanostructure synthesized by the dry fluorination process exhibited a similar XRD peak pattern, but the peak intensity of the commercial AlF3 on the XRD peak pattern of the hexagonal crystal structure was higher than that of the other AlF3 samples. The hexagonal structure of AlF3 has higher catalytic activity for the hydrolysis of NF3 than the orthorhombic structure of AlF3. Although the hexagonal structure of AlF3 had a high catalytic activity for the hydrolysis of NF3, the needle-like shaped hexagonal structure of AlF3 had higher catalytic activity than the other shaped hexagonal structures. The hexagonal structure of AlF3 has higher catalytic activity for the hydrolysis of NF3 than the orthorhombic structure of AlF3. Therefore, the needlelike shaped AlF3 with high catalytic activity can be prepared by a dry fluorination process.
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