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用硼酸和硫酸对含Ａｌ２Ｏ３的β和ＺＳＭ５沸石进行处理，制备了一系列沸石ＭｘＯｙ和ＳＯ２４／沸石ＭｘＯｙ）催化剂。用ＮＨ３ＴＰＤ和Ｈａｍｍｅｔｔ指示剂法测定了催化剂的表面酸性。对Ｈ２ＳＯ４处理的样品进行了Ｘ射线物相分析。用ＢＥＴ法测定了Ｈβ及ＨＺＳＭ５３８对乙酸的吸附等温线和饱和吸附量。对催化剂的活性，均通过乙酸和乙醇在液相、９０℃和不分水条件下的酯化进行表征。结果表明，ＨβＡｌ２Ｏ３经硼酸和硫酸处理后，乙酸的转化率由３９．５３％提高到５４．９２％。ＨＺＳＭ５３８Ａｌ２Ｏ３经同样处理后，乙酸的转化率由２４．４５％提高到４４．８７％。ＳＯ２４／沸石ＭｘＯｙ的最佳焙烧温度范围是５００～５５０℃。此外，在固定床反应器内于１００～１３０℃和ＬＨＳＶ为６ｈ１的条件下，对ＳＯ２４／ＨβＡｌ２Ｏ３Ｂ２Ｏ３的活性位的稳定性进行了初步实验。反应在１１０℃连续进行１２ｈ后，乙酸的转化率始终稳定在６９％左右。
A series of zeolites MxOy and SO24 / zeolite MxOy) catalysts were prepared by treating the Al2O3- and ZSM5-containing zeolites with boric acid and sulfuric acid. The surface acidity of the catalyst was measured by NH3TPD and Hammett indicator method. X-ray phase analysis was performed on H2SO4-treated samples. The adsorption isotherms and saturated adsorption capacities of Hβ and HZSM538 to acetic acid were determined by BET method. The activity of the catalyst was characterized by esterification of acetic acid and ethanol in the liquid phase at 90 ° C without division. The results showed that the conversion of acetic acid increased from 39.53% to 54.92% after HβAl2O3 was treated with boric acid and sulfuric acid. After the same treatment of HZSM538Al2O3, the conversion of acetic acid increased from 24.45% to 44.87%. The optimum calcination temperature range for SO24 / zeolite MxOy is 500-550 ° C. In addition, the stability of the active site of SO24 / HβAl2O3B2O3 was tested in a fixed bed reactor at 100 ~ 130 ℃ and LHSV of 6h1. After the reaction was continued at 110 ° C for 12h, the conversion of acetic acid remained stable at about 69%.