Influence of barium addition on the performance of Cr2O3/Al2O3 catalysts in isobutane dehydrogenation
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摘要: 采用浸渍法制备了不同BaO负载量的Cr2O3/Al2O3催化剂，利用XRD、BET、NH3-TPD和O2-TPO等表征方法对钡改性前后的催化剂进行了分析；在反应温度560℃、反应压力0.1 MPa、催化剂用量10 mL、GHSV=400 h-1的条件下，在固定床反应器上考察了其异丁烷脱氢反应的性能。结果表明，钡的引入影响了活性组分Cr2O3的分散，导致了催化剂比表面积的降低，但影响并不显著；钡的引入降低了催化剂表面的酸性、减少了反应过程中催化剂的积炭，改善了催化剂的选择性，提高了催化剂的稳定性。当BaO负载量为3%时，催化剂的性能最佳。Abstract: Barium modified Cr2O3/Al2O3 catalysts were prepared by incipient impregnation. The catalysts were characterized by XRD, BET, NH3-TPD and O2-TPO and tested for isobutane dehydrogenation in a fixed-bed reactor at 560℃, 10 mL catalyst, pressure of 0.1 MPa, GHSV of 400 h-1 and atmospheric pressure. The results showed that the addition of Ba leads to the aggregation of Cr2O3, but no significant influence on the structure of the catalysts is observed. The surface acidity of the catalysts is weakened by the addition of Ba, which thereby inhibits the side reactions of cracking and carbon formation while the isobutene selectivity and stability of catalysts are improved. The optimal catalytic performance can be obtained when BaO content is around 3%.
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Key words:
- isobutane /
- dehydrogenation /
- Cr2O3 /
- BaO
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图 1 钡改性的Cr2O3/Al2O3催化剂的XRD谱图
Figure 1 XRD patterns of catalysts with different BaO contents
图 2 钡改性的Cr2O3/Al2O3催化剂的NH3-TPD谱图
Figure 2 NH3-TPD profiles of the catalysts with different BaO contents
图 3 钡改性的Cr2O3/Al2O3催化剂的异丁烯转化率
Figure 3 Conversion of isobutene on the catalysts with different BaO contents
图 4 钡改性的Cr2O3/Al2O3催化剂的异丁烯选择性
Figure 4 Selectivity of isobutene on the catalysts with different BaO contents
表 1 钡改性的Cr2O3/Al2O3催化剂的比表面积、孔结构和孔体积
Table 1 Specific surface area and pore structure of the catalysts with different BaO contents
BaO content
w/%ABET/
(m2·g-1)Pore volume
v/(mL·g-1)Average pore
diameter d/nm0 236.03 0.494 7 8.38 1 225.42 0.482 5 8.56 2 225.49 0.460 4 8.17 3 224.73 0.464 0 8.26 4 216.51 0.452 7 8.36 5 217.91 0.441 2 8.10 
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[1] 何英华, 王苑, 杨玉和. C4烃资源综合利用技术进展[J].化工技术与开发, 2012, 41(3): 28-34. http://www.cnki.com.cn/Article/CJFDTOTAL-GXHG201203008.htmHE Ying-hua, WANG Yuan, YANG Yu-he.Comprehensive utilization technology advancesof C4 hydrocarbon resource[J]. Technol Dev Chem Ind, 2012, 41(3): 28-34. http://www.cnki.com.cn/Article/CJFDTOTAL-GXHG201203008.htm [2] 马冰洁, 吴瑶庆, 李建忠. C4烃资源的生产、利用及发展设想[J].化工科技市场, 2005, 24(12): 8-13. http://www.wenkuxiazai.com/doc/59db336b1eb91a37f1115ca5-5.htmlMA Bing-jie, WU Yao-qing, LI Jian-zhong. Production utilization and developing asuume of C4 hydrocarbon[J]. Chem Technol, 2005, 24(12): 8-13. http://www.wenkuxiazai.com/doc/59db336b1eb91a37f1115ca5-5.html [3] 胥月兵, 岳辉, 陆江银.碳四烃综合利用研究及评述[J].新疆大学学报(自然科学版), 2007, 24(4): 430-434. http://www.cnki.com.cn/Article/CJFDTOTAL-XJDZ200704010.htmXU Yue-bing, YUE Hui, LU Jiang-yin. Reserch & comment on comprehensive utilization of C4 hydrocarbon[J]. J Xinjiang Univ (Nat Sci Ed), 2007, 24(4): 430-434. http://www.cnki.com.cn/Article/CJFDTOTAL-XJDZ200704010.htm [4] 王绍卿.由异丁烷脱氢制异丁烯的生产技术问题[J].石化技术, 1994, (1): 57-60. http://www.cnki.com.cn/Article/CJFDTOTAL-SHJS401.011.htmWANG Xu-qing. Production by the technical problems of isobutene dehydrogenation of isobutene[J]. Pet Chem Ind Technol, 1994, (1): 57-60. http://www.cnki.com.cn/Article/CJFDTOTAL-SHJS401.011.htm [5] 于庚涛.国外异丁烷催化脱氢制异丁烯概况[J].吉化科技, 1996, (4): 1-6. http://www.cnki.com.cn/Article/CJFDTOTAL-JKGH199604000.htmWANG Geng-tao. Foreign overview dehydrogenation of isobutene[J]. Jilin Sci Technol, 1994, (1): 1-6. http://www.cnki.com.cn/Article/CJFDTOTAL-JKGH199604000.htm [6] 肖锦堂.烷烃催化脱氢生产C3~C4烯烃工艺(之一)[J].天然气工业, 1994, 14(2): 64-69. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQG402.022.htmXIAO Jin-tang. Technique of alkane catalyzed degydrugenation for producing C3~C4 olefin (part Ⅰ)[J]. Nat Gas Ind, 1994, 14(2): 64-69. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQG402.022.htm [7] 肖锦堂.烷烃催化脱氢生产C3~C4烯烃工艺(之二)[J].天然气工业, 1994, 14(3): 69-73. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQG403.022.htmXIAO Jin-tang. Technique of alkane catalyzed degydrugenation for producing C3~C4 olefin (part Ⅱ)[J]. Nat Gas Ind, 1994, 14(3): 69-73. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQG403.022.htm [8] 宋艳敏, 孙守亮, 孙振乾.异丁烷催化脱氢制异丁烯技术研究[J].精细与专用化学品, 2006, (17): 10-12. http://www.cnki.com.cn/Article/CJFDTOTAL-JXHY201601061.htmSONG Yan-min, SUN Shou-liang, SUN Zhen-qian. Research on preparing of isobutylene with isobutene dehydrogenation[J]. Fine Spe Chem, 2006, (17): 10-12. http://www.cnki.com.cn/Article/CJFDTOTAL-JXHY201601061.htm [9] FRIDMAN V, LOUISVILLE K T. Catalyst for dehydrogenation of hydrocarbons. US2010/0010280 A1[P]. 2010-01-14. [10] 刘波.异丁烷脱氢铬系催化剂研究[D].烟台:烟台大学, 2013.LIU Bo. Research of Cr cataysts for isobutene dehydrogenation[D]. Yantai: Yantai University, 2013. [11] 王际东, 赵娟, 屈一新.钾对Pt-Sn/Al2O3催化剂表面酸性及异丁烷脱氢性能的影响[J].现代化工, 2011, 31(S1): 205-209. http://www.cqvip.com/QK/95539X/2011S1/1003574804.htmlWANG Ji-dong, ZHAO Juan, QU Yi-xin. Influences of Potassium on acidity and isobutane dehydrogenation performance of Pt-Sn/Al2O3 catalyst[J]. Mod Chem Ind, 2011, 31(S1): 205-209. http://www.cqvip.com/QK/95539X/2011S1/1003574804.html [12] 王心葵, 解红娟, 张亮玫.氧化钾在K2O-Cr2O3/Al2O3脱氢催化剂中的作用[J].天然气化工, 1995, 20: 22-25. http://www.cqvip.com/QK/94489X/199503/1902368.htmlWANG Xin-kui, XIE Hong-juan, ZHANG Liang-mei. Roles of K2O promotor in K2O-Cr2O3/Al2O3 dehydrogenation catalysts[J]. Nat Gas Chem Ind, 1995, 20: 22-25. http://www.cqvip.com/QK/94489X/199503/1902368.html [13] CORTRIGHT R D, DUMESIC J A. Effect of potassium on silica-supported Pt and Pt/Sn catalysts for isobutane dehydrogenation[J]. J Catal, 1995, 157: 576-583. doi: 10.1006/jcat.1995.1322 [14] 刘皓, 姚志龙, 王若愚. CaO对Cr2O3/A12O3催化剂结构及催化异丁烷脱氢性能的影响[J].石油炼制与化工, 2013, 44(7): 33-37. http://www.sylzyhg.com/CN/abstract/abstract1294.shtmlLIU Hao, YAO Zhi-long, WANG Ruo-yu. Impact of CaO on Cr2O3/Al2O3 catalyst strcture and isobutene dehydrogenation performance[J]. Pet Process Petrochem, 2013, 44(7): 33-37. http://www.sylzyhg.com/CN/abstract/abstract1294.shtml [15] BASF Corporation. US8835347 B2[P]. 2014-09-16. [16] 张涛, 臧璟龄, 胡爱华.锂对于γ-Al2O3表面酸中心的调变作用及其积炭性能的影响[J].催化学报, 1990, 11(5): 341-347. http://www.chxb.cn/CN/abstract/abstract18255.shtmlZHANG Tao, ZANG Jing-ling, HU Ai-hua. Effect of lithium on the acidic property ofγ-Al2O3 and its carbon depositiom[J]. Chin J Catal, 1990, 11(5): 341-347. http://www.chxb.cn/CN/abstract/abstract18255.shtml [17] 马红超, 刘子玉, 王振旅.镧对V2O5/γ-Al2O3催化剂在异丁烷脱氢中活性的影响[J].高等学校化学学报, 2002, 23(5): 857-860. http://www.wenkuxiazai.com/doc/5793b937eefdc8d376ee32bc-2.htmlMA Hong-chao, LIU Zi-yu, WANG Zheng-lü. The effect of La doped on V2O5/γ-Al2O3 catalyst for activity in the dehydrogenation of isobutene[J]. Chem J Chin Univ, 2002, 23(5): 857-860. http://www.wenkuxiazai.com/doc/5793b937eefdc8d376ee32bc-2.html [18] ROMBI E, CUTRUFELLO M G, SOLINAS V, DEROSSI S, FERRARIS G, PISTONE A. Effects of potassium addition on the acidity and reducibility of chromia/alumina dehydrogenation catalysts[J]. Appl Catal A: Gen, 2003, 251(2): 255-266. doi: 10.1016/S0926-860X(03)00308-9 [19] 丁彦, 潘霞.异丁烷催化脱氢制异丁烯Cr2O3/Al2O3体系催化剂[J].分子催化, 1999, 13(5): 373-377. http://www.cqvip.com/QK/90647X/199905/3740598.htmlDING Yan, PAN Xia. Performance of Cr2O3/Al2O3 catalyst for isobutane dehydrogenation to isobutene[J]. J Mol Catal, 1999, 13(5): 373-377. http://www.cqvip.com/QK/90647X/199905/3740598.html [20] ARAKSINEN S M, HARLIN M E, KRAUSE A O I. Kinectic modeling of dehydrogenation of isobutane on chromia/aluminal catalyst[J]. Ind Eng Chem Res, 2002, 41(23): 5619-5626. doi: 10.1021/ie020371j [21] RESASCO D E, MARCUS B K, HUANG C S. Isobutane dehydrogenation over sulfide nickel catalysts[J]. J Catal, 1994, 146(1): 40-55. doi: 10.1016/0021-9517(94)90006-X -
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