成型条件对Co/ZSM-5催化剂催化分解N_2O性能影响
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摘要
采用挤条成型法制备Co/ZSM-5催化剂,通过X射线衍射、BET比表面积、氢气程序升温还原(H_2-TPR)、氨气程序升温脱附法(NH_3-TPD)和颗粒径向抗压碎(侧压)强度测试对催化剂进行表征,在固定床微型反应器中评价催化剂催化分解N_2O活性,对Co/ZSM-5(N-50)催化剂进行稳定性测试。结果表明,钴物种以Co3O4尖晶石氧化物形式存在于Co/ZSM-5催化剂中,胶溶剂种类显著影响催化剂抗压碎强度;黏合剂用量影响催化剂抗压碎强度、酸量、氧化还原性和催化剂催化分解N_2O活性;以硝酸为胶溶剂,黏合剂(SB粉)用量为30%和50%制备的催化剂,抗压碎强度大,分别为208N/cm和230N/cm,催化分解N_2O温度T95分别为485℃和500℃。在固定床微型反应器中,模拟工业尾气组成(φN_2O=11%、φO_2=16%、N_2为平衡气),反应温度446℃、空速6000h-1条件下,Co/ZSM-5(N-50)催化剂在1000h稳定性测试中表现出良好的催化活性和稳定性,N_2O转化率高于98%。
The Co/ZSM-5 catalysts were prepared by extruding strip forming method and were characterized by XRD, BET, H_2-TPR, NH_3-TPD and particle radial crushing(side pressure) strength tests. The activity stability tests of the catalysts for catalytic decomposition of N_2 O were carried out in a fixed-bed micro reactor. It was found that the cobalt spices in the catalysts were Co3 O4 and the type of peptizers obviously influenced the mechanical strength of catalysts. The amount of adhesive also influenced the mechanical strength, the amount of acid centers, redox properties and the activities of the catalysts. Co/ZSM-5(N-50) catalyst was prepared with nitric acid as peptizer and SB powder(mass fractionof30%and50%)asadhesive.Ithasstrongmechanicalstrength(208 N/cmand230 N/cm,respectively)and the T95 for N_2 O decomposition were 485℃ and 500℃, respectively. Under the simulated industrial tail gas(φN_2 O=11%, φO_2=16% and N_2 as balance gas) condition, when the reaction temperature was 446℃ and space velocity was 6000 h-1 in the fixed-bed micro reactor, the Co/ZSM-5(N-50) catalyst showed prominent stability, and the N_2 O decomposition conversion was above 98% in a 1000 h test.
The Co/ZSM-5 catalysts were prepared by extruding strip forming method and were characterized by XRD, BET, H_2-TPR, NH_3-TPD and particle radial crushing(side pressure) strength tests. The activity stability tests of the catalysts for catalytic decomposition of N_2 O were carried out in a fixed-bed micro reactor. It was found that the cobalt spices in the catalysts were Co3 O4 and the type of peptizers obviously influenced the mechanical strength of catalysts. The amount of adhesive also influenced the mechanical strength, the amount of acid centers, redox properties and the activities of the catalysts. Co/ZSM-5(N-50) catalyst was prepared with nitric acid as peptizer and SB powder(mass fractionof30%and50%)asadhesive.Ithasstrongmechanicalstrength(208 N/cmand230 N/cm,respectively)and the T95 for N_2 O decomposition were 485℃ and 500℃, respectively. Under the simulated industrial tail gas(φN_2 O=11%, φO_2=16% and N_2 as balance gas) condition, when the reaction temperature was 446℃ and space velocity was 6000 h-1 in the fixed-bed micro reactor, the Co/ZSM-5(N-50) catalyst showed prominent stability, and the N_2 O decomposition conversion was above 98% in a 1000 h test.
引文
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[15]王维华,袁华,吴元欣,等.成型条件对CuO-Ce0.5Mn0.5O2成型载体性能的影响[J].精细化工, 2011, 28(3):247-252.WANG Weihua, YUAN Hua, WU Yuanxin, et al. Effect of forming conditionson properties of formed CuO-Ce0.5Mn0.5O2supports[J]. Fine Chemicals, 2011, 28(3):247-252.
[16]余海清,李建伟,孙晓岩,等.胶溶剂对MCM-22分子筛催化剂性能的影响[J].石油化工高等学校学报, 2009, 22(1):1-4.YU Haiqing, LI Jianwei, SUN Xiaoyan, et al. Effect of peptizator on performance of MCM-22 zeolite catalyst[J]. Journal of Petrochemical Universities, 2009, 22(1):1-4.
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[19]任冬梅,王祥生,李钢,等.不同载体成型的Mo/ZSM-5催化剂上甲烷无氧芳构化反应[J].催化学报, 2010, 31(3):348-352.REN Dongmei, WANG Xiangsheng, LI Gang, et al. Methane dehydroaromatization in the absence of oxygen over Mo/ZSM-5extruded with different oxides[J]. Chinese Journal of Catalysis, 2010,31(3):348-352.
[2] CHEN H, LU Q H, YI C H, et al. Bimetallic Rh-Fe catalysts for N2O decomposition:effects of surface structures on catalytic activity[J].Physical Chemistry Chemical Physics, 2018, 20(7):5103-5111.
[3]丁林,曹雨来,宋永吉,等. Co-Cu-M(M=Fe, Mn, Ni, Zn, Ce)催化剂催化分解N2O性能[J].化工进展, 2016, 35(11):3519-3523.DING Lin, CAO Yulai, SONG Yongji, et al. The study of catalytic decomposition of N2O over Cu-Co-M(M=Fe, Mn, Ni, Zn, Ce)[J].Chemical Industry and Engineering Progress, 2016, 35(11):3519-3523.
[4] WANG A Y, WANG Y L, WALTER ERIC D, et al. Catalytic N2O decomposition and reduction by NH3over Fe/Beta and Fe/SSZ-13catalysts[J]. Journal of Catalysis, 2018, 358:199-210.
[5] SHEN Q, WU M F, WANG H, et al. The influence of desilication on high-silica MFI and its catalytic performance for N2O decomposition[J]. Applied Surface Science, 2018, 441:474-481.
[6]李宁. N2O分解催化剂的制备[J].化工进展, 2007, 26(11):1659-1661.LI Ning. Research on catalyst of nitrous oxide decomposition[J].Chemical Industry and Engineering Progress, 2007, 26(11):1659-1661.
[7]王虹,王军利,李翠清,等. ACo2O4/HZSM-5催化剂上N2O的直接分解[J].物理化学学报, 2010, 26(10):2739-2744.WANG Hong, WANG Junli, LI Cuiqing, et al. Decomposition of N2O on ACo2O4/HZSM-5 catalysts[J]. Acta Physico-Chimica Sinica, 2010,26(10):2739-2744.
[8]李孟丽,杨晓龙,唐立平,等. N2O的催化分解研究[J].化学进展,2012, 24(9):1801-1817.LI Mengli, YANG Xiaolong, TANG Liping, et al. Catalysts for catalytic decomposition of nitrous oxide[J]. Progress in Chemistry, 2012, 24(9):1801-1817.
[9]赵晓旭,程党国,陈丰秋,等. N2O直接分解催化剂的研究进展[J].化工进展, 2009, 28(9):1562-1567.ZHAO Xiaoxu, CHENG Dangguo, CHEN Fengqiu, et al. Review of catalysts for catalytic decomposition of N2O[J]. Chemical Industry and Engineering Progress, 2009, 28(9):1562-1567.
[10]徐向阳,谷成,王虹,等. Co/Hβ催化剂上N2O的分解性能研究[J].燃料化学学报, 2014, 42(7):877-883.XU Xiangyang, GU Cheng, WANG Hong, et al. Catalytic performance of Co/Hβin N2O decomposition[J]. Journal of Fuel Chemistry and Technology, 2014, 42(7):877-883.
[11]仇媛,王长真,李海涛,等.单分散Co3O4@SiO2核壳催化剂的制备及N2O催化分解性能[J].化工学报, 2018, 69(4):1493-1499.QIU Yuan, WANG Changzhen, LI Haitao, et al. Preparation of monodispersed core-shell Co3O4@SiO2catalyst and its application in N2O catalytic decomposition[J]. CIESC Journal, 2018, 69(4):1493-1499.
[12]程火生.辽阳石化己二酸生产中N2O减排技术应用研究[D].北京:清华大学, 2010.CHENG Huosheng. Applied abatement technology of N2O in adipic acid production in Liaoyang petrochemical company[D]. Beijing:Tsinghua University, 2010.
[13]于长凤,朱小平,戴静.拟薄水铝石为粘结剂成型氧化铝陶瓷的研究[J].中国陶瓷, 2008, 44(1):35-37.YU Changfeng, ZHU Xiaoping, DAI Jing. Alumina ceramic was formed after gelling and soliding using boehmite[J]. China Ceramics, 2008, 44(1):35-37.
[14]王继元,顾越峰,陈韶辉,等.胶溶剂对TiO2成型载体性能的影响[J].石油化工高等学校学报, 2009, 22(1):26-30.WANG Jiyuan, GU Yuefeng, CHEN Shaohui, et al. Effect of peptizers on properties of formed TiO2supports[J]. Journal of Petrochemcal Universities, 2009, 22(1):26-30.
[15]王维华,袁华,吴元欣,等.成型条件对CuO-Ce0.5Mn0.5O2成型载体性能的影响[J].精细化工, 2011, 28(3):247-252.WANG Weihua, YUAN Hua, WU Yuanxin, et al. Effect of forming conditionson properties of formed CuO-Ce0.5Mn0.5O2supports[J]. Fine Chemicals, 2011, 28(3):247-252.
[16]余海清,李建伟,孙晓岩,等.胶溶剂对MCM-22分子筛催化剂性能的影响[J].石油化工高等学校学报, 2009, 22(1):1-4.YU Haiqing, LI Jianwei, SUN Xiaoyan, et al. Effect of peptizator on performance of MCM-22 zeolite catalyst[J]. Journal of Petrochemical Universities, 2009, 22(1):1-4.
[17] JIRATOVA K, JANACEK L. Effect of peptizing on the physical and chemical properties of extruded alumina[J]. International Chemical Engineering, 1983, 23(1):167-174.
[18]邱正璞. N2O氧化苯制苯酚Fe-ZSM-5催化剂成型及宏观性能研究[D].北京:北京化工大学, 2016.QIU Zhengpu. Research on extrusion conditions and macro performance of the Fe-ZSM-5 catalyst for N2O benzene to phenol[D].Beijing:Beijing University of Chemical Technology, 2016.
[19]任冬梅,王祥生,李钢,等.不同载体成型的Mo/ZSM-5催化剂上甲烷无氧芳构化反应[J].催化学报, 2010, 31(3):348-352.REN Dongmei, WANG Xiangsheng, LI Gang, et al. Methane dehydroaromatization in the absence of oxygen over Mo/ZSM-5extruded with different oxides[J]. Chinese Journal of Catalysis, 2010,31(3):348-352.