新型添加剂对硫酸法C_4烷基化反应的影响
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摘要
通过低温硫酸法烷基化间歇反应实验,针对硫酸法C_4烷基化反应过程,研究了10种常见添加剂加入硫酸催化剂对该催化过程的作用及影响,并采用气相色谱分析法分析各催化体系所产烷基化产物组成分布数据,研发与评价了一种高效的新型添加剂XH-01。实验结果表明:以纯硫酸作为催化剂所得的烷基化产物中C_5～C_7,C_8和C~+_9的质量分数依次为11.74%,81.11%,7.15%。6种典型的离子液体添加剂加入对硫酸烷基化反应的改善效果轻微,2-萘磺酸、十二烷基苯磺酸、三氟甲磺酸和环丁砜在硫酸中的适量添加均能有效促进烷基化反应,其中2-萘磺酸的改善效果最为明显,其烷基化产物C_8的质量分数提高至84.40%。1%的新型添加剂XH-01加入硫酸催化剂后,其烷基化产物中C_8的质量分数增至90.84%,催化效果得到显著增强,与上述其他添加剂相比较,其烷基化反应效果显著优于实验中其他添加剂。
Aiming at the process of C_4 alkylation by sulfuric acid method, the effects of 10 common additives on the catalytic process are studied by batch experiments of low temperature sulfuric acid alkylation. Gas chromatographic analysis is used to analyze the distribution data of alkylation products produced by various catalytic systems, and a new type of additive XH-01 with high efficiency is developed and evaluated. The experimental results show that the mass fractions of C_5～C_7, C_8, and C~+_9 in the alkylation products with pure sulfuric acid as catalyst are 11.74%, 81.11%, and 7.15%, respectively. The effect of six typical ionic liquid additives on alkylation of sulfuric acid is slight. The addition of 2-Naphthalenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and sulfolane sulfonate in sulfuric acid can effectively promote the alkylation reaction. Among them, 2-Naphthalenesulfonic acid has the most obvious improvement effect, and the mass fraction of C_8 alkylated product increased to 84.40%. When 1% new additive XH-01 is added to sulfuric acid catalyst, the mass fraction of C_8 in the alkylation product increased to 90.84%, and the catalytic effect is significantly enhanced. Compared with other additives mentioned above, the alkylation effect of XH-01 is significantly better than other additives in this experiment.
Aiming at the process of C_4 alkylation by sulfuric acid method, the effects of 10 common additives on the catalytic process are studied by batch experiments of low temperature sulfuric acid alkylation. Gas chromatographic analysis is used to analyze the distribution data of alkylation products produced by various catalytic systems, and a new type of additive XH-01 with high efficiency is developed and evaluated. The experimental results show that the mass fractions of C_5～C_7, C_8, and C~+_9 in the alkylation products with pure sulfuric acid as catalyst are 11.74%, 81.11%, and 7.15%, respectively. The effect of six typical ionic liquid additives on alkylation of sulfuric acid is slight. The addition of 2-Naphthalenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid and sulfolane sulfonate in sulfuric acid can effectively promote the alkylation reaction. Among them, 2-Naphthalenesulfonic acid has the most obvious improvement effect, and the mass fraction of C_8 alkylated product increased to 84.40%. When 1% new additive XH-01 is added to sulfuric acid catalyst, the mass fraction of C_8 in the alkylation product increased to 90.84%, and the catalytic effect is significantly enhanced. Compared with other additives mentioned above, the alkylation effect of XH-01 is significantly better than other additives in this experiment.
引文
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[2] 徐春明,杨朝合.石油炼制工程[M].4版.北京:石油工业出版社,2009:120-150.
[3] 马会霞,周峰,乔凯.液体酸烷基化技术进展[J].化工进展,2014,(S1):32-40.
[4] 耿英杰.烷基化生成工艺与技术[M].2版.北京:中国石化出版社,1993:40-100.
[5] ALBRIGHT L F.Alkylation of Isobutane with C3～C5 Olefins:Feedstock Consumption,Acid Usage,and Alkylate Quality for Different Processes[J].Industrial and Engineering Chemistry Research,2002,41(23):5627-5631.
[6] LIU Z C,MENG X H,ZHANG R,et al.Reaction Performance of Isobutane Alkylation Catalyzed by a Composite Ionic Liquid at a Short Contact time[J].AIChE Journal,2014,60(6):2244-2253.
[7] HUANG Q,ZHAO G Y,ZHANG S J,et al.Improved Catalytic Lifetime of H2SO4 for Isobutane Alkylation with Trace Amount of Ionic Liquids Buffer [J].Industrial and Engineering Chemistry Research,2015,54(5):1464-1469.
[8] DAVIS J R.AlkyTech Sulfuric Acid Alkylation Management Program[C].NPRA Annual Meeting,AM-04-26,San Antonio,TX,USA,2004:203-212.