Removal of Hg0 from simulated coal-fired flue gas by using activated spent FCC catalysts
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摘要: 采用有机溶剂内部瞬间沸腾法活化废流体催化裂化(SFCC)催化剂，通过固定床反应器考察了吸附温度、烟气成分及活化条件等多种变量对SFCC催化剂脱汞性能的影响。结果表明，SFCC催化剂经甲醇和乙醇活化后脱汞(Hg0)效果良好，焙烧温度也会影响催化剂活性。烟气中O2的存在有利于汞的脱除。含O2气氛下，NO在FCC-E催化剂表面形成含N活性位点，促进汞的脱除。SO2因浓度差异对Hg0的脱除表现出吸附催化和竞争吸附。在6% O2、12% CO2、0.06% NO烟气组分，120 ℃吸附温度，120 ℃活化温度，乙醇活化条件下，SFCC催化剂的脱汞效率接近100%。采用X射线荧光光谱(XRF)、扫描电镜(SEM)、X射线衍射(XRD)、热重(TG)和X射线光电子能谱(XPS)表征活化和未活化SFCC催化剂，探究与其脱汞性能关联。Abstract: The spent fluid catalytic cracking (SFCC) catalysts were activated by an "internal instant vaporization (ⅡV)" method and used in the removal of Hg0 from a simulated flue gas in a fixed bed reactor; the effect of various operation parameters such as the SFCC activation conditions, adsorption temperature, and flue gas components on the Hg0 removal efficiency was investigated. The results indicate that the SFCC catalyst activated with methanol or ethanol performs adequately in terms of Hg0 removal, whilst the calcination temperature also has a great influence on the activation of the SFCC catalyst. O2 in the flue gas favors the Hg0 removal, whilst NO facilitates the oxidation of mercury and displays a positive effect on the mercury removal in the presence of O2, accompanying with the formation of N-containing active species on the activated SFCC catalyst surface. SO2 in the flue gas, depending on its concentration, may exert the effect of catalytic adsorption or competitive adsorption on the Hg0 removal. Approximately 100% Hg0 can be removed in the stream of 6% O2, 12% CO2 and 0.06% NO at 120 ℃ by using the activated SFCC catalyst with ethanol as an organic solvent and calcined at 120 ℃, suggesting that the spent FCC catalysts after activation can be a potential adsorbent for the removal of Hg0 from the coal-fired flue gas.
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Key words:
- spent FCC catalyst /
- activation /
- gaseous elemental mercury /
- coal-fired flue gas
1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813). -
Figure 2 SEM images of the activated and non-activated SFCC catalysts: ((a), (b)) SFCC; ((c), (d)) FCC-360; and ((e), (f)) FCC-M
Figure 3 TG/DTA curves of the SFCC catalyst in the air atmosphere (a) and N2 atmosphere (b)
Figure 4 XPS spectra of the FCC-120 catalyst: (a) survey of elements; (b) Fe 2p; (c) Ce 3d; and (d) O 1s
Figure 5 XRD patterns of various catalyst samples: a: SFCC; b: FCC-360; c: FCC-600; d: FCC-M; e: FCC-E; f: FCC-A; g: FCC-P
Figure 6 Effect of the calcination temperature on the Hg0 removal efficiency of activated SFCC catalysts; the operation conditions of set I specified in Table 1 are used
Figure 7 Effect of the activation organic solvent on the Hg0 removal efficiency of the activated SFCC catalysts; the operation conditions of Set II specified in Table 1 are used
Figure 8 Effect of different adsorption temperature on the Hg0 removal efficiency of FCC-E; the operation conditions of Set III specified in Table 1 are used
Figure 9 Effect of O2 concentration in the flue gas on the Hg0 removal efficiency of FCC-E; the operation conditions of Set IV specified in Table 1 are used
Figure 10 Effect of SO2 concentration in the flue gas on the Hg0 removal efficiency of FCC-E; the operation conditions of Set V specified in Table 1 are used
Figure 11 Effect of NO concentration in the flue gas on the Hg0 removal efficiency of FCC-E; the operation conditions of Set VI specified in Table 1 are used
Figure 12 TPD profile of the SFCC-E adsorbent under N2 after mercury adsorption in the presence of NO and O2 at 120 ℃
Table 1 Experimental conditions for the Hg0 adsorption tests
Set Adsorbent Activation conditions Flue gas composition Adsorption temp t/℃ calc. temp /℃ solvent I SFCC, activated SFCC 120-600 - 6% O2, 12% CO2, N2 120 II activated SFCC 120 methanol, ethanol, acetone, petroleum ether 6% O2, 12% CO2, N2 120 III activated SFCC 120 ethanol 6% O2, 12% CO2, N2 80-300 IV activated SFCC 120 ethanol 0-10%O2, 12% CO2, N2 120 V activated SFCC 120 ethanol 6% O2, 12% CO2, 0.06%-0.1% SO2, N2 120 VI activated SFCC 120 ethanol 6% O2, 12% CO2, 0.01%-0.06% NO, N2 120 
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Table 2 Textural properties of the activated and non-activated SFCC catalysts
Adsorbent Surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Pore diameter d/nm SFCC 74.9 0.09 3.181 FCC-120 78.5 0.11 3.382 FCC-360 90.4 0.11 3.795 FCC-600 101.2 0.11 4.862 FCC-M 87.3 0.10 3.804 FCC-E 83.7 0.10 3.396 FCC-A 77.9 0.09 3.400 FCC-P 76.5 0.09 3.389
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Table 3 Chemical composition of the SFCC catalysts determined by XRF
Component Percentage Component Percentage Component Percentage Al2O3 46.397 Cs2O 1.115 V2O5 0.169 SiO2 43.147 Na2O 0.782 CeO2 0.166 CaO 2.012 P2O5 0.714 Sb2O3 0.121 SO3 1.546 TiO2 0.302 ZnO 0.093 NiO 1.416 MgO 0.254 La2O3 0.089 Fe2O3 1.330 K2O 0.177 else 0.163
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