|关键词||固体酸催化剂 Zsm-5分子筛 二芳基乙烷 变压器油添加剂 绝缘油|
二芳基乙烷是一种无色、无味、无毒的高沸点溶剂。其中，1-苯基-1-二甲苯基乙烷(PXE)，在相容性、热阻、润滑性和电性能方面有优良的性能，广泛用作增塑剂、高沸点溶剂、热介质、电气绝缘油和润滑油。本论文以邻二甲苯、间二甲苯、对二甲苯、乙基苯和苯乙烯为原料，用一定硅铝比的非金属矿固体酸和改性的ZSM-5分子筛为催化剂，发生烷基化反应，生成了二芳基乙烷。并对其精产品进行红外光谱、气相色谱-质谱表征，对粗制产品和精制产品进行性能测试分析实验。具体工作如下： ⒈研究了原料配比、催化剂用料、反应时间、反应温度、催化剂颗粒大小等对产品产率的影响。结果表明，催化剂（80-100目）用量（以总投料质量计）3%、二甲苯或乙苯与苯乙烯摩尔比7、反应温度140℃、苯乙烯滴加时间2h、反应时间4h为最佳反应条件.在此条件下，以邻二甲苯、间二甲苯和乙苯为原料合成的二芳基乙烷收率较高，可达90%左右；而以对二甲苯、乙苯和苯乙烯为原料合成的二芳基乙烷产率较低，为70%左右。 ⒉以邻二甲苯、间二甲苯、对二甲苯和苯乙烯的烷基化反应为探针反应，考察了不同的固体催化剂的催化性能。结果表明，非金属矿固体超强酸催化剂具有良好的催化效果，二芳基乙烷收率分别为90.8%、90.5%、78.8%，比其它的固体酸催化剂效果高很多。 ⒊利用硫酸铵溶液对ZSM-5分子筛催化剂进行改性，制备HZSM-5分子筛催化剂。以邻二甲苯和苯乙烯为原料合成二芳基乙烷，在1中提到的最佳条件下，当催化剂焙烧温度为500℃、硅铝比为40左右时，二芳基乙烷的收率分别为89.3%。 ⒋利用红外光谱、气相色谱-质谱对合成的二芳基乙烷精制后的产品进行了结构分析。采用气相色谱对精产品的不同物质进行了定量分析。 红外光谱分析结果与二芳基乙烷的结构相符合，可能是几种二芳基乙烷异构体的混合物。气相色谱-质谱分析结果表明，以邻二甲苯、间二甲苯、乙苯为原料合成的二芳基乙烷精制后产品，主要含有C16H18和C16H16，C16H18含量为90%以上，C16H16含量为10%以下，说明上述原料烷基化率较高；而以对二甲苯为原料合成的二芳基乙烷精制后的产品，C16H18含量为70%左右，C16H16含量为30%左右，这说明邻二甲苯、间二甲苯比较适合作为合成二芳基乙烷的原料。⒌对合成的二芳基乙烷进行了粗制处理和精制处理实验。并对粗制产品和精制产品进行了倾点、开口闪点、击穿电压、粘度等性能测试。结果表明：精制产品性能较好，符合国家标准GB/T2536—2011（45#），而粗制处理产品性能较差。 ⒍对二芳基乙烷精制后产品与15＃工业白油进行了调和实验。结果表明，此精产品具有增加工业白油击穿电压、减少运动粘度、降低倾点等作用，适合做变压器油或变压器油添加剂，作为添加剂，适合添加的体积分数为10%～30%。
The characteristic of diphenylethane is a kind of solvent with no color, no taste, non- poisonous and with high boiling point. Especially, one of its kind, 1-phenyl-xyxyl-ethane(PXE), it has the excellent performance in terms of compatibility, thermal resistance, lubricating and electrical property; it is widely used as plasticizer, high boiling solvent, heat medium, electrical insulated oil and lubricating oil. In the work reported here, four kinds of diphenylethane were synthesized using o-xylene, m-xylene, p-xylene, ethylbenzene and styrene as starting materials catalyzed by non-metallic mineral solid acid with special proportion of silicon and aluminum and the modified ZSM-5 molecular sieve in alkylation reaction. The author also did the analysis of refined products by IR and GC-MS spectra, the performance of crude product and purified product. Specific experiments as follows: ⒈ The key parameters such as raw material ratio, catalyst material, reaction time, reaction temperature and particle size of catalyst have been investigated and discussed in detail. The results showed that the optimal conditions were as follows：the weight percentage of the catalyst（with particle size 80-100mesh）is 3%, molar ratio of ethylbenzene to styrene is 7, reaction temperature is at 140℃, with addition time of styrene 2h and total reaction time 4h. The yield of phenyl ethylbenzene under such conditions could reach 90% when the raw materials were o-xylene, m-xylene and ethylbenzene, however, when using p-xylene , ethylbenzene and styrene as raw materials, medium yield of 70% was achieved. ⒉ O-xylene, m-xylene, p-xylene and styrene as raw materials in alkylation reaction, catalytic properties of different solid catalysts have been investigated and discussed in detail. The results showed that no-metallic mineral solid super acid catalyst has good catalytic effect, the yield of diphenylethylane was 90.8%,90.5%,78.8%,much higher than other solid acid catalyst effect. ⒊ The use of ammonium sulfate solution on the modified ZSM-5 zeolite synthesized HZSM-5 zeolite catalysts. Diphenylethylane was synthesized by O-xylene and styrene, under optimum conditions mentioned in 1, when the calcinations temperature was 500 ℃, alumina ratio was 40to 45 , the Diphenylethylane yield was 89.3%,,. ⒋ The analysis of refined products by IR and GC-MS spectra confirmed the structure of phenyl ethylbenzene ethane, and they may be mixture of several diphenylethylane isomers. Different substances analysis of refined product by Gas chromatography was analyzed quantitatively. The analysis of refined products by gas chromatography-mass spectrometry showed that o-xylene, m-xylene, ethylbenzene was raw materials, contained mainly C16H18 and C16H16. The content of C16H18 was more than 90%, the content of C16H16 was less 10%, and this indicated the higher rate of alkylation. Xylene as the starting material in the synthesis of refined product showed that the content of C16H18 was about 70%, the content of C16H16 was about 30%. This result showed that o-xylene, m-xylene was more suitable for the synthesis of diphenylethylane as feedstock. ⒌ The author also did rough preparation and purified preparation of diphenylethylane . The performance of both rude and purified product were evaluated .The performance testing included pour point, open flash point, the breakdown voltage, the viscosity and so on. The results showed that: purified product has better performance, in line with national standards GB/T2536-2011 (45 #), while crude processing performance is poor. ⒍ Experiment was also carried out to make exquisite product of diphenylethane and 15#industrial grade white oil. The results showed that the performance of purified diphenylethane was comparable to the national standard GB/T2536-20119（45#）. Furthermore, the exquisite product has many advantages and unique properties such as: the increasing breakdown voltage, reducing kinematic viscosity, reducing pour compared to the industrial grade while oil. In summary, in the work reported here, the diphenylethane synthesized and purified hold great promise for application as the transformer oil or its additives. when they were as transformer oil additives, the appropriate volume percentage was 10%～30%.
|周凤. 二芳基乙烷的合成及其性能评价[D]. 北京. 中国科学院大学,2014.|
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