改性VO_x/MSU-1催化CO_2氧化异丁烷脱氢
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摘要
以分子筛MSU-1为载体,La、Ce、Cu和K为改性剂,制备了一系列改性的VO_x/MSU-1催化剂,并系统地评价了催化剂的反应活性。采用XRD、H_2-TPR及NH_3-TPD对改性催化剂La1.0V10.0/MSU-1[w(VO_x)=10.0%,w(La2O_3)=1.0%]进行了表征,并考察了最佳反应条件。结果显示:稀土元素La、Ce的加入能提高催化剂的活性,La元素的加入提高了载体MSU-1上活性组分VO_x的分散度,同时也改善了催化剂表面的酸碱性,更加有利于异丁烷氧化脱氢反应的进行。在最佳反应条件下(温度853 K,体积空速4 800 h~(-1),常压,CO_2与异丁烷体积比为3∶1),催化剂La1.0V10.0/MSU-1上异丁烷的转化率为63.6%,异丁烯的产率为52.3%。稳定性实验结果表明:8 h循环后,催化剂V10.0/MSU-1[w(VO_x)=10.0%]上异丁烷转化率降为16.5%,而La1.0V10.0/MSU-1上为28.8%,说明La改性的VO_x/MSU-1催化剂具有更好的稳定性。
For further improving the catalytic performance of VO_x/MSU-1 in the reaction of oxidative dehydrogenation of isobutane to isobutene with CO_2,in this paper,a series of modified VO_x/MSU-1catalysts were prepared using MSU-1 as the supports and La、Ce、Cu and K as the performance modifier,and then their reaction activity were evaluated systematically. Meanwhile,La1. 0V10. 0/MSU-1[w(VO_x) = 10. 0%,w(La2O_3) = 1. 0% ]was characterized by XRD,H_2-TPR and NH_3-TPD methods and the reaction conditions were investigated. The results showed that La addition could improve not only the dispersion of VO_xspecies,active components,over MSU-1 support but also the acid-base properties of catalysts surface,which was favorable to the oxidative dehydrogenation of isobutane. Under the optimal reaciton conditions(temperature was 853 K; gas hourly space velocity was 4 800 h~(-1);pressures was atmospheric; volume ratio of CO_2 and isobutane was 3: 1),isobutane conversion was63. 6% and isobutene yield was 52. 3% using La1. 0V10. 0/MSU-1 as the catalyst. At last,it was demonstrated by the stability experiments of 8 h that La1. 0V10. 0/MSU-1 possessed higher catalytic stability than V10. 0/MSU-1 [w(VO_x) = 10. 0% ],isobutane conversion decreasing to 16. 5% over V10. 0/MSU-1 in contrast to 28. 8% over La1. 0V10. 0/MSU-1.
For further improving the catalytic performance of VO_x/MSU-1 in the reaction of oxidative dehydrogenation of isobutane to isobutene with CO_2,in this paper,a series of modified VO_x/MSU-1catalysts were prepared using MSU-1 as the supports and La、Ce、Cu and K as the performance modifier,and then their reaction activity were evaluated systematically. Meanwhile,La1. 0V10. 0/MSU-1[w(VO_x) = 10. 0%,w(La2O_3) = 1. 0% ]was characterized by XRD,H_2-TPR and NH_3-TPD methods and the reaction conditions were investigated. The results showed that La addition could improve not only the dispersion of VO_xspecies,active components,over MSU-1 support but also the acid-base properties of catalysts surface,which was favorable to the oxidative dehydrogenation of isobutane. Under the optimal reaciton conditions(temperature was 853 K; gas hourly space velocity was 4 800 h~(-1);pressures was atmospheric; volume ratio of CO_2 and isobutane was 3: 1),isobutane conversion was63. 6% and isobutene yield was 52. 3% using La1. 0V10. 0/MSU-1 as the catalyst. At last,it was demonstrated by the stability experiments of 8 h that La1. 0V10. 0/MSU-1 possessed higher catalytic stability than V10. 0/MSU-1 [w(VO_x) = 10. 0% ],isobutane conversion decreasing to 16. 5% over V10. 0/MSU-1 in contrast to 28. 8% over La1. 0V10. 0/MSU-1.
引文
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[14]Wang Xinkui(王心葵),Xie Hongjuan(解红娟),Zhang Liangmei(张亮玫),et al.Roles of K2O promotor in K2OCr2O3/Al2O3dehydrogenation catalyst[J].Natural Gas Chemical Industry(天然气化工),1995,20(3):22-24.
[15]Ding Yan(丁彦),Pan Xia(潘霞),Xue Jinzhen(薛锦珍),et al.Performance of Cr2O3/Al2O3catalyst for isobutane dehydrogenation to isobutene[J].Journal of Molecular Catalysis(China)(分子催化),1999,13(5):373-377.
[16]Xia Pitong(夏丕通).Determination of metal surface area on the catalysts by chemical adsorption apparatus[J].Journal of Instrumental Analysis(分析测试通报),1984,3(1):60-62.
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[18]Quah E B H,Li C.Effects of radical desorption on catalyst activity and coke formation during the catalytic pyrolysis and oxidation of light alkanes[J].Applied Catalysis A:General,2003,250(1):83-94.
[19]Voorhies Jr A.Carbon formation in catalytic cracking[J].Industrial&Engineering Chemistry,1945,37(4):318-322.
[2]Wang Dingbo(王丁博).Utilization ways of refinery C4[J].Chemical Industry and Engineering Progress(化工进展),2014,33(6):1429-1434.
[3]Geng Wang(耿旺),Tang Junhong(汤俊宏),Kong Defeng(孔德峰).Technological development in chemical utilization of isobutane[J].Petrochemical Technology(石油化工),2013,42(3):352-356.
[4]Gniot I,Kirszensztejn P,Kozlowski M.Oxidative dehydrogenation of isobutane using modified activated carbons as catalysts[J].Applied Catalysis A:General,2009,362(1):67-74.
[5]Zhang L,Deng J,Dai H,et al.Binary Cr-Mo oxide catalysts supported on Mg O-coated polyhedral three-dimensional mesoporous SBA-16 for the oxidative dehydrogenation of isobutane[J].Applied Catalysis A:General,2009,354(1/2):72-81.
[6]Ding J,Qin Z,Li X,et al.Catalytic dehydrogenation of isobutane in the presence of carbon dioxide over nickel supported on active carbon[J].Journal of Molecular Catalysis A:Chemical,2010,315(2):221-225.
[7]Ogonowski J,Skrzyn'ska K.Carbon dioxide in the dehydrogenation of isobutane over VMg Ox[J].Catalysis Communications,2009,11(2):132-136.
[8]Ma Hongchao(马红超),Wang Ziyu(刘子玉),Wang Zhenlv(王振旅),et al.Study of V2O5/γ-Al2O3catalyst for dehydrogenation of isobutane[J].Chinese Journal of Applied Chemistry(应用化学),2002,19(3):290-294.
[9]Yuan R,Li Y,Yan H,et al.Insights into the vanadia catalyzed oxidative dehydrogenation of isobutane with CO2[J].Chinese Journal of Catalysis,2014,35(8):1329-1336.
[10]Liu L,Li H,Zhang Y.Mesoporous silica-supported chromium catalyst:Characterization and excellent performance in dehydrogenation of propaneto propylene with carbon dioxide[J].Catalysis Communications,2007,8(3):565-570.
[12]Huang Qingze(黄青则),Sun Guosong(孙果宋),Wang Jinshu(王金淑),et al.Study on reaction conditions about oxidative dehydrogenation of isobutane over V-based MSU-1catalysts with CO2[J].Technology&Develoment of Chemistry Industry(化工技术与开发),2011,40(5):6-10.
[13]Sun Guosong(孙果宋),Huang qingze(黄青则),Li Huiquan(李会泉),et al.Different supports-supported Cr-based catalysts for oxidative dehydrogenation of isobutane with CO2[J].Chinese Journal of Catalysis(催化学报),2011,32(8):1424-1429.
[14]Wang Xinkui(王心葵),Xie Hongjuan(解红娟),Zhang Liangmei(张亮玫),et al.Roles of K2O promotor in K2OCr2O3/Al2O3dehydrogenation catalyst[J].Natural Gas Chemical Industry(天然气化工),1995,20(3):22-24.
[15]Ding Yan(丁彦),Pan Xia(潘霞),Xue Jinzhen(薛锦珍),et al.Performance of Cr2O3/Al2O3catalyst for isobutane dehydrogenation to isobutene[J].Journal of Molecular Catalysis(China)(分子催化),1999,13(5):373-377.
[16]Xia Pitong(夏丕通).Determination of metal surface area on the catalysts by chemical adsorption apparatus[J].Journal of Instrumental Analysis(分析测试通报),1984,3(1):60-62.
[17]Adamski A,Sojka Z,Dyrek K.Surface heterogeneity of zirconiasupported V2O5catalysts:The link between structure and catalytic properties in oxidative dehydrogenation of propane[J].Langmuir,1999,15(18):5733-5741.
[18]Quah E B H,Li C.Effects of radical desorption on catalyst activity and coke formation during the catalytic pyrolysis and oxidation of light alkanes[J].Applied Catalysis A:General,2003,250(1):83-94.
[19]Voorhies Jr A.Carbon formation in catalytic cracking[J].Industrial&Engineering Chemistry,1945,37(4):318-322.