全部 标题 作者
关键词 摘要

OALib Journal期刊
ISSN: 2333-9721
费用:99美元

查看量下载量

相关文章

更多...
化工学报  2015 

混合丁烯/异丁烷硫酸烷基化反应动力学

DOI: 10.11949/j.issn.0438-1157.20141366, PP. 584-590

Keywords: 烷基化,混合丁烯,反应动力学,碳正离子,动力学模型,参数估值

Full-Text   Cite this paper   Add to My Lib

Abstract:

以硫酸为催化剂,间歇实验研究了276.2~285.2K温度范围内混合丁烯/异丁烷烷基化反应动力学。实验结果表明,随着反应温度的降低,主产物三甲基戊烷(TMPs)生成量和烷基化油整体辛烷值增大,副产物二甲基己烷(DMHs)变化较小,高碳组分(HEs)的生成量降低明显。采用基于碳正离子反应机理建立的烷基化动力学模型对TMPs、DMHs、HEs3类组分进行了计算分析,模拟计算结果表明,动力学模型对实验数据的拟合效果良好。链引发步骤异丁烯加氢离子反应表现出反Arrhenius行为,其本身及逆反应的活化能分别为45.14kJ·mol-1和41.44kJ·mol-1,增加对链传递部分C8正碳离子形成步骤的速率常数计算,部分涉及链传递和链终止反应步骤反应速率常数与文献值保持一致。

References

[1]  Corma A, Martínez A. Chemistry, catalysts and processes for isoparaffin-olefin alkylation: actual situation and future trends [J]. Catalysis Reviews - Science and Engineering, 1993, 35 (4): 483-570
[2]  Geng Yingjie (耿英杰). Industrial Alkylation and Technology (烷基化生产工艺与技术) [M]. Beijing: China Petrochemical Press, 1993: 9-11
[3]  Bi Jianguo (毕建国). Advances in alkylate manufacture technology [J]. Chemical Industry and Engineering Process (化工进展), 2007, 26 (7): 934-939
[4]  Peng Pu (彭朴), Xi Lei (葸雷), Ma Chuanyan (马传彦), Duan Qiwei (段启伟). Research process of chloroaluminate ionic liquids used as alkylation catalyst and prospect commercial application [J]. Chemical Industry and Engineering Process (化工进展), 2007, 26 (4): 456-458
[5]  Liu Ying (刘鹰), Liu Zhichang (刘植昌), Xu Chunming (徐春明), Zhang Rui (张睿). Study on room temperature ionic liquid-catalyzed alkylation of isobutane with butene at pilot-plant scale [J]. Chemical Industry and Engineering Process (化工进展), 2005, 24 (6): 656-660
[6]  Liu Ying (刘鹰), Liu Zhichang (刘植昌), Xu Chunming (徐春明). Alkylation of isobutane and 2-butene in inhibited chloroaluminate ionic liquids [J]. Journal of Chemical Industry and Engineering (China) (化工学报), 2005, 56 (11): 2119-2123
[7]  Zheng Dongmei (郑冬梅). Advances in alkylation process of isobutane with butene technology [J]. Chemical Industry and Engineering Process (化工进展), 2004, 23 (z1): 58-61
[8]  Sun Weizhen (孙伟振), Huang Huan (黄欢), Gu Xiaowu (顾晓吴), Zhao Ling (赵玲). Modeling of liquid phase oxidation kinetics of aromatic hydrocarbon based on free radical chain reaction mechanism [J]. CIESC Journal (化工学报), 2010, 61 (7): 2119-2123
[9]  He Zhiyong (何志勇), Luo Jun (罗军), Lü Chunxu (吕春旭), Xu Rong (徐容), Li Jinshan (李金山). Nitrolysis kinetics of DADN by N2O5/HNO3 [J]. CIESC Journal (化工学报), 2013, 64 (4): 1270
[10]  Lee Lien-mow, Harriott P. The kinetics of isobutane alkylation in sulfuric acid [J]. Industrial & Engineering Chemistry Process Design and Development, 1977, 16 (3): 282-287
[11]  Langley J R, Pike R W. The kinetics of alkylation of isobutene with propylene [J]. American Institute of Chemical Engineers Journal, 1972, 18 (4): 698-705
[12]  Han Minghan (韩明汉), Li Xiaojin (李晓锦), Lin Shixiong (林世雄). Alkylation of benzene with propylene over β zeolite chemical reaction kinetics [J]. Journal of Chemical Industry and Engineering (China) (化工学报), 1999, 50 (1):65-69
[13]  Sun Weizhen, Shi Yi, Chen Jie, Xi Zhenhao, Zhao Ling. Alkylation kinetics of isobutane by C4 olefins using sulfuric acid as catalyst [J]. Industrial & Engineering Chemistry Research, 2013, 52 (44): 15262-15269
[14]  Schmerling L. The mechanism of the alkylation of paraffins [J]. Journal of the American Chemical Society, 1945, 67: 1778-1783
[15]  Schemerling L. Reaction of hydrocarbons [J]. Industrial & Engineering Chemistry Research, 1953, 45 (7): 1447-1455
[16]  Whitmore F C. The common basis of intra-molecular rearrangements [J]. Journal of the American Chemical Society, 1932, 54 (8): 3274
[17]  Albright L F, Spalding M A, James A. Alkylation of isobutane with C4 olefins (Ⅰ): First-step reactions using sulfuric acid catalyst [J]. Industrial & Engineering Chemistry Research, 1988, 27: 381-386
[18]  Albright L F. Mechanism for alkylation of isobutane with light olefins//Industrial and Laboratory Alkylations [C]. Albright L F, Goldsby A R, Eds. ACS: Washington, D C, 1977, 55: 128-146
[19]  Kramer G M. Hydride transfer reactions in concentrated sulfuric acid [J]. Journal of Organic Chemistry, 1965, 30: 2671
[20]  Hofmann J E, Schriesheim A J. Ionic reactions occurring during sulfuric acid catalyzed alkylation (Ⅱ): Alkylation of isobutane with C14-labeled butenes [J]. Journal of the American Chemical Society, 1962, 84: 957-961
[21]  Hofmann J E. Ionic reactions occurring in sulfuric acid (Ⅲ): The sulfuric acid catalyzed self-alkylation of isobutane with C3—C6 olefins [J]. Journal of Organic Chemistry, 1964, 29: 1497
[22]  Lebedeva N V, Nese A, Sun F C, Matyjaszewski K, Sheiko S S. Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate [J]. Proceedings of the National Academy of Sciences of the United States of America, 2012, 109 (24): 9276-9280

Full-Text

Contact Us

service@oalib.com

QQ:3279437679

WhatsApp +8615387084133