Promoting effect of SO42- functionalization on the performance of Fe2O3 catalyst in the selective catalytic reduction of NOx with NH3
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摘要: 采用沉淀法制备了Fe（OH）3和Fe2O3。通过硫酸化处理得到SO42-/Fe（OH）3和SO42-/Fe2O3两种催化剂，并将其应用于氨选择性催化还原NOx（NH3-SCR）反应，研究了SO42-功能化处理对Fe2O3催化剂上NH3-SCR脱硝性能的促进机理。结果表明，与纯的Fe2O3相比，硫酸化处理得到的催化剂上SCR活性得到显著提升；其中，SO42-/Fe（OH）3表现出更加优异的催化性能，在250-450 ℃时NOx转化率高于80%，且具有优异的稳定性和抗H2O + SO2性能。XRD、Raman、TG、FT-IR、H2-TPR、NH3-TPD和in situ DRIFTS等表征结果显示，硫酸功能化处理能抑制Fe2O3的晶粒生长，同时SO42-与Fe3+结合形成硫酸盐复合物，提高了催化剂表面酸性位点的数量和酸强度，抑制了Fe2O3上的氨氧化反应，从而提高了其脱硝催化性能。Abstract: Fe(OH)3 and Fe2O3 were first prepared by a precipitation method and then sulfated to obtain the SO42--functionalized SO42-/Fe(OH)3 and SO42-/Fe2O3 catalysts for the selective catalytic reduction of NOx with NH3 (NH3-SCR); the promoting effect of SO42- functionalization on the performance of Fe2O3 catalyst in NH3-SCR was then investigated. The results indicate that the SCR activity of the SO42--functionalized Fe2O3 catalysts is significantly improved in comparison with that of unmodified Fe2O3. In particular, the SO42-/Fe(OH)3 catalyst exhibits excellent performance in NH3-SCR, with the NOx conversion of over 80% at 250-450 ℃; besides, it also display high catalytic stability and resistance towards H2O + SO2. A series of characterization results including XRD, Raman spectroscopy, TG analysis, FT-IR spectroscopy, H2-TPR, NH3-TPD and in situ DRIFTS reveal that the functionalization with sulfuric acid can inhibit the growth of Fe2O3 grains; moreover, SO42- combines with Fe3+ to form the sulfate complex, leading to an increase in the number of surface acid sites and the acid strength, which can inhibit the ammonia over-oxidation on Fe2O3 and enhance the deNOx performance of Fe2O3.
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图 1 不同催化剂的NH3-SCR性能
Figure 1 Catalytic performance of Fe2O3, SO42-/Fe(OH)3 and SO42-/Fe2O3 in the NH3-SCR of NOx
(a): NOx conversion; (b): NH3 conversion; (c): N2O concentration; (d): the test of stability and 0.01% SO2 + 10% H2O resistance at 300℃
图 2 不同催化剂的NH3-SCO性能
Figure 2 Catalytic performance of various catalysts in the NH3-SCO carried out in 0.06% NH3, 5% O2 and balanced N2, with a total flow rate of 400mL/min and gas hourly space velocity (GHSV) of 60000h-1
图 3 Fe2O3 ((a)、(d))、SO42-/Fe(OH)3 ((b)、(e))和SO42-/Fe2O3 ((c)、(f))催化剂的SEM照片
Figure 3 SEM images of Fe2O3 ((a) and (d)), SO42-/Fe(OH)3 ((b) and (e)) and SO42-/Fe2O3 ((c) and (f)) catalysts
图 4 不同催化剂的XRD谱图
Figure 4 XRD patterns of the Fe2O3, SO42-/Fe(OH)3 and SO42-/Fe2O3 catalysts
图 6 不同催化剂的热重(TG)分析图
Figure 6 Thermogravimetric (TG) analysis profiles of various catalysts
图 10 (a) Fe2O3、(b)SO42-/Fe(OH)3和(c)SO42-/Fe2O3催化剂上NH3吸附-脱附的原位漫反射红外光谱谱图
Figure 10 In situ DRIFTS spectra of NH3 adsorption-desorption over (a) Fe2O3, (b) SO42-/Fe(OH)3 and (c) SO42-/Fe2O3 catalysts
表 1 三种样品的比表面积、平均孔径和孔容
Table 1 Surface area, average pore size and pore volume of various catalysts
Sample Surface area A/(m 2·g -1) Pore diameter d/nm Pore volume v/(cm 3·g -1) Fe 2O 3 41.12 20.01 0.201 SO 4 2-/Fe(OH) 3 49.98 17.12 0.298 SO 4 2-/Fe 2O 3 37.25 25.88 0.189 
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表 2 三种样品的Fe2O3晶粒粒径和NH3脱附峰面积
Table 2 Crystallite size of Fe2O3 and NH3 desorption peak areas of various catalysts
Catalyst Fe2O3 crystallite size /nm Area of NH3 desorption peaks /(10-9) Fe2O3 28 3.9 SO42-/Fe(OH)3 16 80.0 SO42-/Fe2O3 20 5.6
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