Kinetic study on dehydration behavior of titanium dioxide supported by denitration catalyst
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摘要: 脱硝催化剂载体二氧化钛的脱水是制备过程中的关键控制环节。通过测定不同升温速率下脱硝催化剂载体二氧化钛热分析曲线，研究了不同气氛下脱硝催化剂载体二氧化钛的脱水行为动力学和反应机理。结果表明，脱硝催化剂载体二氧化钛的脱水行为与煅烧的气氛紧密相关，在含氧气氛和无氧气氛下脱水速度不同，含氧气氛下开始脱水较快，然后缓慢脱水到反应结束；无氧气氛则缓慢完成。采用无模函数和有模函数的方法进行了动力学计算，结果表明，脱硝催化剂载体二氧化钛的脱水行为在含氧气氛下符合Avrami-Erofeev方程，无氧气氛下符合幂函数法则，脱水过程受到晶核的形成和晶核长大的影响。Abstract: The dehydration of denitration catalyst carrier titanium dioxide is a key control step in the preparation process. By measuring the thermal analysis curves of denitration catalyst carrier titanium dioxide at different heating rates, the dehydration kinetics and reaction mechanism of denitration catalyst carrier titanium dioxide under different atmospheres were studied. The results indicate that the dehydration behavior of titanium dioxide as the carrier of denitrification catalyst is closely related to the calcination atmosphere. The dehydration rate is different in oxygen-containing and oxygen-free atmosphere. Dehydration starts faster in oxygen-containing atmosphere, and then slowly dehydrates until the reaction ends, while dehydration completes slowly in oxygen-free atmosphere. Kinetic calculations were carried out by using the methods of modularless function and modularized function. The results show that the dehydration behavior of titanium dioxide, the support of denitration catalyst, conforms to the Avrami Erofeev equation in oxygen-containing atmosphere, and conforms to the power function rule in oxygen-free atmosphere. The dehydration process is affected by the formation and growth of crystal nuclei.
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Key words:
- titanium dioxide /
- denitration catalyst /
- dehydration /
- kinetics /
- atmosphere
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图 1 不同气氛下脱硝催化剂载体二氧化钛的脱水TG曲线
（a）空气气氛；（b）氮气气氛
Figure 1. Dehydration TG curves of titanium dioxide as denitration catalyst carrier under different atmospheres
图 2 不同气氛下脱硝催化剂载体二氧化钛脱水的DTG曲线
（a）空气气氛；（b）氮气气氛
Figure 2. DTG curves of titanium dioxide dehydration of denitration catalyst carrier under different atmospheres
图 3 不同气氛下脱硝催化剂二氧化钛脱水的$ E $-$ a $ 曲线
（a）空气气氛；（b）氮气气氛
Figure 3. $ E $-$ a $ diagrams of denitration catalyst carrier titanium dioxide dehydration under different atmospheres
表 1 不同气氛下脱硝催化剂载体二氧化钛脱水反应的$ \alpha -T $数据
Table 1. $ \mathit{\alpha }-\mathit{T} $ data of the dehydrating reaction of denitration catalyst carrier titanium dioxide in different atmospheres
Reaction extent Tair atmosphere/K Tnitrogen atmosphere/K 5 ℃/min 10 ℃/min 15 ℃/min 20 ℃/min 5 ℃/min 10 ℃/min 15 ℃/min 20 ℃/min 0.05 66.02 72.88 73.95 78.48 66.68 73.67 74.38 73.42 0.10 116.32 123.51 124.44 128.92 117.48 124.27 124.95 123.91 0.15 166.75 174.20 175.08 179.52 168.05 174.85 175.46 174.50 0.20 217.17 224.65 225.46 229.89 218.45 255.26 225.91 224.90 0.25 267.43 274.91 275.64 280.05 268.67 275.46 276.06 275.14 0.30 317.51 325.00 325.67 330.17 318.73 325.51 326.08 325.20 0.35 367.47 374.86 375.69 380.11 368.68 375.45 376.09 375.27 0.40 417.34 424.76 425.53 429.95 418.53 425.32 425.95 425.17 0.45 467.07 474.61 475.36 479.78 468.33 475.17 475.76 475.01 0.50 516.87 524.46 525.19 529.62 518.11 525.02 525.57 524.86 0.55 566.69 574.34 575.01 579.54 567.86 574.86 575.49 574.71 0.60 616.47 624.20 624.85 629.38 617.63 624.72 625.32 624.55 0.65 666.17 674.09 674.80 679.22 667.39 674.58 675.14 674.41 0.70 715.98 723.97 724.65 729.08 717.19 724.43 725.09 724.28 0.75 765.81 773.74 774.53 778.93 766.97 774.29 774.92 774.08 0.80 815.65 823.62 824.40 828.83 816.76 824.08 824.71 823.81 0.85 865.38 873.37 874.11 878.56 866.53 873.73 874.38 873.50 
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表 2 机理函数的积分形式和微分形式
Table 2. Integral and differential forms of mechanism functions
Function number Integral form Differential form 12# $ {[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)]}^{2/5} $ $ \dfrac{5}{2}(1-\alpha ){[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)]}^{3/5} $ 18# $ {[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)]}^{2} $ $ \dfrac{1}{2}(1-\alpha ){[-\mathrm{l}\mathrm{n}\left(1-\alpha \right)]}^{-1} $ 25# $ \alpha $ 1
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表 3 不同气氛下脱硝催化剂二氧化钛脱水反应动力学计算结果
Table 3. Kinetics of dehydration reaction under different atmospheres
Function Air atmosphere Nitrogen atmosphere E/(kJ·mol−1) lnA/s−1 R E/(kJ·mol−1) lnA/s−1 R 12# $ {\alpha }_{1} $=5 14.16 25.51 0.9764 15.57 26.44 0.9826 $ {\alpha }_{2} $=10 15.12 26.41 0.9813 14.45 26.17 0.9365 $ {\alpha }_{3} $=15 15.16 36.81 0.9804 13.91 26.66 0.9362 $ {\alpha }_{4} $=20 15.17 27.06 0.9816 14.28 26.92 0.9441 18# $ {\alpha }_{1} $=5 34.05 29.49 0.9122 32.59 28.01 0.9632 $ {\alpha }_{2} $=10 34.17 29.68 0.9269 31.47 28.88 0.9517 $ {\alpha }_{3} $=15 34.36 30.15 0.9194 30.96 29.55 0.9508 $ {\alpha }_{4} $=20 36.32 31.20 0.9327 31.29 29.84 0.9514 25# $ {\alpha }_{1} $=5 20.03 26.19 0.9362 20.09 26.23 0.9745 $ {\alpha }_{2} $=10 20.55 26.89 0.9509 19.06 26.17 0.9532 $ {\alpha }_{3} $=15 20.62 27.29 0.9454 18.45 26.41 0.9527 $ {\alpha }_{4} $=20 21.21 27.81 0.9502 19.21 27.46 0.9787
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表 4 不同升温速率下热失重曲线峰值温度
Table 4. Peak temperature of the thermogravimetric curve at different heating rates
Heating rate/( ℃·min−1) Sample mode $ {T}_{\mathrm{p}} $/K $ {\beta }_{1} $=5 BA01-01 435.61 SA90 765.58 SA100 810.63 SA200 811.22 $ {\beta }_{2} $=10 BA01-01 448.32 SA90 778.29 SA100 823.34 SA200 823.93 $ {\beta }_{3} $=15 BA01-01 456.12 SA90 786.09 SA100 831.14 SA200 831.73 $ {\beta }_{4} $=20 BA01-01 461.8 SA90 791.79 SA100 836.84 SA200 837.43 $ {\beta }_{5} $=25 BA01-01 466.29 SA90 796.26 SA100 841.31 SA200 841.90
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表 5 脱硝催化剂载体二氧化钛失重分析
Table 5. Analysis of weight loss of TiO2 as denitration catalyst carrier
Serial number Water loss rate/% Sulfate loss rate/% SA90 12.32 1.63 SA100 3.55 2.3 SA200 3.56 1.74
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