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以SnCl4.5 H2O和聚乙二醇6000为模板剂,采用模板法合成中孔S2O82-/SnO2固体超强酸催化剂,用Hammett指示剂法、TGA-DTA、XRD、N2-吸附进行表征,以草酸与异戊醇的酯化反应为探针反应,探讨S2O82-/SnO2固体超强酸的催化活性,研究焙烧温度、酸/醇比、催化剂加入量、反应时间等对反应酯化率的影响。结果表明:介孔S2O82-/SnO2固体超强酸催化剂具有四方晶系结构,S2O82-可延迟SnO2的晶化、抑制SnO2晶粒长大,对草酸二异戊酯的合成具有良好的催化活性;在催化剂的焙烧温度为500℃、n(异戊醇)∶n(草酸)=3∶1、带水剂甲苯加入量为30 mL、m(催化剂)∶m(草酸)=7.5、反应时间为2.5 h的条件下,草酸二异戊酯收率可达到99.2%;在中国石油抚顺石化公司石油一厂催化裂化柴油中添加草酸二异戊酯后十六烷值可提高1.2~3.0个单位,而其它性质无明显变化。
The mesoporous S2O82- / SnO2 solid superacid catalyst was synthesized by the template method using SnCl4.5 H2O and polyethylene glycol 6000 as the template agents, characterized by Hammett indicator method, TGA-DTA, XRD and N2-adsorption. The esterification reaction with isopentyl alcohol was used as the probe reaction to investigate the catalytic activity of S2O82- / SnO2 solid superacid. The effects of calcination temperature, acid / alcohol ratio, catalyst loading and reaction time on the reaction esterification rate were studied. The results show that the mesoporous S2O82- / SnO2 solid superacid catalyst has a tetragonal structure. S2O82- can delay the crystallization of SnO2, inhibit the growth of SnO2 grains, and has good catalytic activity for the synthesis of diisopentyl oxalate. In the presence of The catalyst calcination temperature was 500 ℃, the molar ratio of n (isoamyl alcohol): n (oxalic acid) = 3:1, the amount of toluene added to the water-carrying agent was 30 mL, the reaction time was 2.5 h, the yield of diisopentyl oxalate can reach 99.2%. After the addition of diisopentyl oxalate to the catalytic cracking diesel oil of PetroChina Fushun Petrochemical Company, the cetane number can be increased by 1.2-3.0 units Other properties no significant change.