THEORETICAL STUDY ON ISOBUTENE POLYMERIZATION OVER SULFONIC ACID RESIN IN PRESENCE OF ETHANOL

Abstract

Abstract: The polymerization of isobutene over sulfonic acid resin in the presence of ethanol was studied using DFT theory and B3LYP/6-31G (d, p) algorithm method. The activation energies of the etherification reaction of ethanol and isobutylene and the polymerization reaction of isobutylene are 62.8 kJ/mol and 167.8 kJ/mol, respectively. Compared with the polymerization reaction of isobutylene, the reaction energy barrier of the etherification reaction is lower and the reaction will take place preferentially. The physical adsorption energy of ethanol on benzenesulfonic acid is -71.3 kJ/mol, and the physical adsorption energy of isobutylene on benzenesulfonic acid is -44.8 kJ/mol. The physically adsorbed isobutylene is easily protonated by the H of the sulfonic acid group to form alkoxy intermediate with chemical adsorption energy of -80.2 kJ/mol. Finally, the mechanism of ethanol in the isobutene polymerization system was analyzed.

Key words: ethanol, sulfonic acid resin, isobutene polymerization, activation energy, adsorption energy

References

[1] 何英华, 詹海容, 朱丽娜,等. 混合C4馏分综合利用技术进展[J]. 化工技术与开发, 2013(08):40-44.
[2] Feller A, Guzman A, Zuazo I, et al. On the mechanism of catalyzed isobutane/butene alkylation by zeolites[J]. Journal of Catalysis, 2004, 224(1):80-93.
[3] Zhang H, Xu J, Tang H, et al. Isobutane/2-butene Alkylation Reaction Catalyzed by Cu Modified RE-X Zeolite[J]. Industrial & Engineering Chemistry Research, 2019, 58(22).
[4] 王进善, 栾祥山，杨宗仁. 甲基叔丁基醚(MTBE)生产技术的开发[J]. 齐鲁石油化工, 1991, 019(003):175-186.
[5] Mao Jen Tsai, Kolodziej, Richard, et al. Consider new technologies to replace MTBE. [J]. Hydrocarbon Processing, 2002, 81-87.
[6] 毕建国. 烷基化油生产技术的进展[J]. 化工进展. 2007, 26(7):934-939.
[7] 温郎友, 吴巍, 刘晓欣. 间接烷基化技术进展[J]. 当代石油化工. 2004, 12(4): 36-40.
[8] 何奕工,舒兴田,龙军.正碳离子和相关的反应机理[J].石油加工,2007, 23(4):1-7.
[9] Alcantara R, Alcantara E, Canoira L, et al. Trimerization of isobutene over Amberlyst-15 catalyst[J]. Reactive & Functional Polymers. 2000,45(1):19-27.
[10] Girolamo M D, Tagliabue L. MTBE and alkylate co-production: fundamentals and operating experience[J]. Catalysis Today, 1999, 52(2):307-319.
[11] Honkela M L, Krause A O I. Influence of Polar Components in the Dimerization of Isobutene[J]. Catalysis Letters, 2003, 87(3):113-119.
[12] Girolamo M D, Marchionna M. Acidic and basic ion exchange resins for industrial applications [J]. Journal of Molecular Catalysis A: Chemical. 2001, 177:33-40.
[13] Ouni T, Honkela M, Kolah A, et al. Isobutene dimerization in a miniplant-scale reactor [J]. Chemical Engineering and Processing. 2006, 45:329-339.
[14] Liu J, Ding N, Ge Y, et al. Dimerization of isobutene in C4 mixtures in the presence of ethanol over acid ion-exchange resin DH-2[J]. Catalysis Letters, 2019,149:1277-1285.
[15] Liu J, Ge Y, Song Y, et al. Dimerization of iso-butene on sodium exchanged Amberlyst-15 resins[J]. Catalysis Communications, 2019, 119,57-61.
[16] Sharma M M. Some novel aspects of cationic ion-exchange resins as catalysts[J]. Reactive & Functional Polymers. 1995, 26: 3-23.
[17] Ma Q, Chakraborty D, Faglioni F, et al. Alkylation of phenol: a mechanistic view [J]. Journal of Physical Chemistry A, 2006, 110(6): 2246-2252.