板式V_2O_5/TiO_2脱硝催化剂的制备及性能研究
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摘要
煤炭的大量燃烧使得SO_2、NO_x（硝）和粉尘排放量严重超标。近年来，随着各项大气污染防治政策的推出，我国SO_2排放基本得到有效控制，然而NO_x排放日益增多，造成环境恶化，致使我国环保事业面临着严峻的挑战。
目前NH3选择性催化还原脱除NO_x的方法（SCR）以效率高、技术成熟等特点，在国内外得到广泛使用，所采用的催化剂主要为V_2O_5/TiO_2基催化剂。由于燃煤烟气具有高尘量和高流量的特点，工业脱硝催化剂通常为结构化形式，包括蜂窝式、板式和波纹式。由于板式催化剂具有抗尘能力强的特点，因此更适合我国燃煤烟气多灰的状况。
国内外在板式催化剂成型方面的文献报道很少，仅有一些专利；在板式催化剂机械性能研究方面几乎没有文献。本文在实验室前期研究的基础上，研制了板式催化剂强度评价装置，并以硅溶胶为无机粘结剂，系统考察了有机粘结剂种类、泥料含水量、干燥和煅烧工艺对板式催化剂机械性能和活性的影响，初步探讨了影响原因，为推进板式V_2O_5/TiO_2基催化剂的发展提供基础工艺数据。通过实验研究得出以下主要结论：
1、以PVA为有机粘结剂的泥料，其可塑性（包括流变性和粘结性）明显优于HPMC粘结剂，所制备的催化剂的机械强度和脱硝活性也较高。
2、泥料性质对其水含量非常敏感。水含量从39%增加到46%，泥料可塑性越来越好，继续增加水含量，由于泥料粘结性变差导致可塑性变差。随着泥料中水含量的增加，所制备的催化剂的中大孔增多，强度降低；脱硝活性先提高，之后基本保持不变。最优泥料水含量为46%左右。
3、干燥过程中催化剂制备中不可缺少的工序，其决定着催化剂的强度。随着干燥升温速率从0.3℃/min提高1℃/min，板式催化剂的强度变化不大，继续提高至3℃/min，催化剂的强度降低。
4、煅烧过程对催化剂强度的影响不如干燥过程显著。随着煅烧时间的增加，催化剂的强度提高。煅烧时的升温速率从5℃/min提高至20oC/min，催化剂的强度逐渐降低。
5、随着煅烧温度从450℃提高至550℃，催化剂的中大孔减少，强度提高，BET面积略有减小，但活性差别不大；继续升温至650℃，催化剂的中大孔和强度基本不变，但BET面积明显减小，活性降低。
6、综合考虑催化剂的活性和强度，板式催化剂的最佳制备条件为：泥料水含量46%左右、干燥升温速率1℃/min、煅烧温度550℃、煅烧升温速率5℃/min、煅烧时间2h。根据该工艺制备的板式催化剂，其初始强度优于工业板式催化剂，稳态磨损率与之相当（0.5%/h）；脱硝活性差别不大（90%左右），SO_2氧化率较低。
Coal-fired boiler yields a large amount of SO_2, NO_xand dust, whichhas received much attention in the last decade due to their seriouspollution to environment and human being. SO_2emission has beenefficiently controlled while NO_xemission increases significantly in recentyears. The environmental protection in our country is facing a lot ofchallenges.
NO_xremoval by selective catalytic reduction (SCR) with NH3hasbeen widely used abroad in industry due to its efficiency and reliability.The catalyst for this process is mainly V_2O_5/TiO_2-based one, which isshaped into monolithic structure, including honeycomb and plate types, toovercome dust plugging and pressure drop. The plate SCR catalyst ismore suitable for heavy-dust flue gas such as in our country due to itslarger channel.
There is few literature about shaping of plate SCR catalyst exceptsome patents. Attrition strength, an important parameter for SCR catalyst,has also never been reported. Based on our earlier work on preparation ofplate V_2O_5/TiO_2catalyst, an apparatus to evaluate attrition strength of aplate catalyst was designed and developed. This paper presents systematicstudies on effects of organic binder, moisture content in the pug, drying and calcining conditions on attrition strength and SCR activity of plateV_2O_5/TiO_2catalyst. The results obtained will provide fundamentaltechnical parameters for preparation of plate catalyst with high strengthand SCR activity. The following conclusions can be drawn:
1. PVA as the organic binder is obviously superior to HPMC. Thepug with PVA binder has a better plasticity and the corresponding platecatalyst shows stronger abrasion strength.
2. Properties of the pug are sensitive to its moisture content. Withincreasing moisture content of the pug from43%to51%, volume ofmeso/macro pores in the catalyst increases and attrition strength becomesworse. Although BET surface area of the catalyst made from the pug with43%moisture content,97m2/g, is slightly larger than those of the othercatalysts,86-93m2/g, SCR activity is slightly lower and SO_2oxidationactivity is higher.
3. The dry process is an indispensable step during catalystpreparation and determines abrasion strength of the catalyst. Abrasionstrength change little with increasing heating rate from0.3℃/min to1℃/min during the drying process, but it decreases with furtherincreasing the heating rate.
4. Calcining process shows a slighter effect on abrasion strength ofthe catalyst, in comparison to drying process. With increasing calciningtime, the abrasion strength improves. With increasing heating rating from 5℃/min to20oC/min, the abrasion strength of the catalyst decreases.
5. With increasing calcining temperature from450oC to550oC,volume of meso/macro pores in the catalyst decreases and the abrasionstrength improves. With further increasing calcining temperature to650oC, abrasion strength change little but SCR activity significantlydecreases due to the obvious decrease in BET surface area and slightincrease in TiO_2crystalline.
6. To get a catalyst of a higher SCR activity and stronger abrasionstrength, the pug with46%moisture content (an optimal value) should bedried with a heating rate of1℃/min and calcined at550℃for2h with aheating rate of5℃/min. The resulting plate catalyst has a better originalstrength than the commercial catalysts. Its steady abrasion rate (0.5%/h)and SCR activity (about90%) are equal to those of Argillon and BHK. ItsSO_2oxidation rate (1.0%) was lower than those of Argillon and BHK(above3.0%).
目前NH3选择性催化还原脱除NO_x的方法（SCR）以效率高、技术成熟等特点，在国内外得到广泛使用，所采用的催化剂主要为V_2O_5/TiO_2基催化剂。由于燃煤烟气具有高尘量和高流量的特点，工业脱硝催化剂通常为结构化形式，包括蜂窝式、板式和波纹式。由于板式催化剂具有抗尘能力强的特点，因此更适合我国燃煤烟气多灰的状况。
国内外在板式催化剂成型方面的文献报道很少，仅有一些专利；在板式催化剂机械性能研究方面几乎没有文献。本文在实验室前期研究的基础上，研制了板式催化剂强度评价装置，并以硅溶胶为无机粘结剂，系统考察了有机粘结剂种类、泥料含水量、干燥和煅烧工艺对板式催化剂机械性能和活性的影响，初步探讨了影响原因，为推进板式V_2O_5/TiO_2基催化剂的发展提供基础工艺数据。通过实验研究得出以下主要结论：
1、以PVA为有机粘结剂的泥料，其可塑性（包括流变性和粘结性）明显优于HPMC粘结剂，所制备的催化剂的机械强度和脱硝活性也较高。
2、泥料性质对其水含量非常敏感。水含量从39%增加到46%，泥料可塑性越来越好，继续增加水含量，由于泥料粘结性变差导致可塑性变差。随着泥料中水含量的增加，所制备的催化剂的中大孔增多，强度降低；脱硝活性先提高，之后基本保持不变。最优泥料水含量为46%左右。
3、干燥过程中催化剂制备中不可缺少的工序，其决定着催化剂的强度。随着干燥升温速率从0.3℃/min提高1℃/min，板式催化剂的强度变化不大，继续提高至3℃/min，催化剂的强度降低。
4、煅烧过程对催化剂强度的影响不如干燥过程显著。随着煅烧时间的增加，催化剂的强度提高。煅烧时的升温速率从5℃/min提高至20oC/min，催化剂的强度逐渐降低。
5、随着煅烧温度从450℃提高至550℃，催化剂的中大孔减少，强度提高，BET面积略有减小，但活性差别不大；继续升温至650℃，催化剂的中大孔和强度基本不变，但BET面积明显减小，活性降低。
6、综合考虑催化剂的活性和强度，板式催化剂的最佳制备条件为：泥料水含量46%左右、干燥升温速率1℃/min、煅烧温度550℃、煅烧升温速率5℃/min、煅烧时间2h。根据该工艺制备的板式催化剂，其初始强度优于工业板式催化剂，稳态磨损率与之相当（0.5%/h）；脱硝活性差别不大（90%左右），SO_2氧化率较低。
Coal-fired boiler yields a large amount of SO_2, NO_xand dust, whichhas received much attention in the last decade due to their seriouspollution to environment and human being. SO_2emission has beenefficiently controlled while NO_xemission increases significantly in recentyears. The environmental protection in our country is facing a lot ofchallenges.
NO_xremoval by selective catalytic reduction (SCR) with NH3hasbeen widely used abroad in industry due to its efficiency and reliability.The catalyst for this process is mainly V_2O_5/TiO_2-based one, which isshaped into monolithic structure, including honeycomb and plate types, toovercome dust plugging and pressure drop. The plate SCR catalyst ismore suitable for heavy-dust flue gas such as in our country due to itslarger channel.
There is few literature about shaping of plate SCR catalyst exceptsome patents. Attrition strength, an important parameter for SCR catalyst,has also never been reported. Based on our earlier work on preparation ofplate V_2O_5/TiO_2catalyst, an apparatus to evaluate attrition strength of aplate catalyst was designed and developed. This paper presents systematicstudies on effects of organic binder, moisture content in the pug, drying and calcining conditions on attrition strength and SCR activity of plateV_2O_5/TiO_2catalyst. The results obtained will provide fundamentaltechnical parameters for preparation of plate catalyst with high strengthand SCR activity. The following conclusions can be drawn:
1. PVA as the organic binder is obviously superior to HPMC. Thepug with PVA binder has a better plasticity and the corresponding platecatalyst shows stronger abrasion strength.
2. Properties of the pug are sensitive to its moisture content. Withincreasing moisture content of the pug from43%to51%, volume ofmeso/macro pores in the catalyst increases and attrition strength becomesworse. Although BET surface area of the catalyst made from the pug with43%moisture content,97m2/g, is slightly larger than those of the othercatalysts,86-93m2/g, SCR activity is slightly lower and SO_2oxidationactivity is higher.
3. The dry process is an indispensable step during catalystpreparation and determines abrasion strength of the catalyst. Abrasionstrength change little with increasing heating rate from0.3℃/min to1℃/min during the drying process, but it decreases with furtherincreasing the heating rate.
4. Calcining process shows a slighter effect on abrasion strength ofthe catalyst, in comparison to drying process. With increasing calciningtime, the abrasion strength improves. With increasing heating rating from 5℃/min to20oC/min, the abrasion strength of the catalyst decreases.
5. With increasing calcining temperature from450oC to550oC,volume of meso/macro pores in the catalyst decreases and the abrasionstrength improves. With further increasing calcining temperature to650oC, abrasion strength change little but SCR activity significantlydecreases due to the obvious decrease in BET surface area and slightincrease in TiO_2crystalline.
6. To get a catalyst of a higher SCR activity and stronger abrasionstrength, the pug with46%moisture content (an optimal value) should bedried with a heating rate of1℃/min and calcined at550℃for2h with aheating rate of5℃/min. The resulting plate catalyst has a better originalstrength than the commercial catalysts. Its steady abrasion rate (0.5%/h)and SCR activity (about90%) are equal to those of Argillon and BHK. ItsSO_2oxidation rate (1.0%) was lower than those of Argillon and BHK(above3.0%).
引文
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[2]上海瀛正科技有限公司.一种蜂窝式SCR脱硝催化剂及其制备方法和设备[P].中国专利,101474565.2009-07-08
[3]德清县三龙催化剂有限公司.一种用于火电厂烟气SCR脱硝中的钛基催化剂及制备方法[P].中国专利,101036884.2007-09-19
[4]哈尔滨工业大学.一种烟气脱硝催化剂的制备方法及由该方法制备的烟气脱硝催化剂
[P].中国专利,101428215.2009-05-13
[5]哈尔滨工业大学.一种用于电厂燃煤烟气SCR脱硝的催化剂及其制备方法[P].中国专利,101422728.2009-05-06
[6]鲁佳易,卢啸风,刘汉周,陈继辉. SCR法烟气脱硝催化剂及其应用特性的探讨[J].电站系统工程.2008,24(1):5-8
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