廉价法合成TS-1分子筛中晶种作用的研究
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摘要
钛硅分子筛TS-1作为一种新型的催化材料,是在1981年由意大利人Taramasso等首次合成的,由于其特殊的催化性能,以及反应条件温和和不污染环境等优点,TS-1具有非常重要的工业应用前景。
经典法合成的TS-1需使用价格昂贵的四丙基氢氧化铵为模板剂,而廉价法采用四丙基溴化铵代替四丙基氢氧化铵,导致晶化时间变长。本文使用微米TS-1晶种来提高廉价合成TS-1的速度,即前一代产品作为下一代合成的晶种,成功合成出性能稳定的TS-1,摆脱了廉价法对纳米晶种的依赖；通过扫描电镜等表征手段,对廉价TS-1合成中晶种的导向作用进行了研究；最后探讨了在成胶过程中添加Na2SO4和吐温20对合成的影响。结论如下：
1.微米晶种传递合成中,所得催化剂的催化性能稳定。
2.在晶化的过程中,晶种首先溶解成结构单元,凝胶再渐渐晶化成晶体,并且晶种的加入大大缩短了晶化诱导期,加快了晶体的生长速率,有利于丙烯液相环氧化反应的进行。
3.在配胶过程中添加Na2SO4和吐温20,环氧丙烷的选择性明显增加,H202的转化率先上升后下降,当Na2SO4与Si的摩尔比为0.1时,环氧丙烷的选择性和H202的有效利用率都较高。
Since titanium silicalite TS-1 was successfully prepared in 1983, it has exhibited the unique catalytic performance in many selective oxidation reactions involving H2O2 as the oxidant. TS-1 has a promising perspective of industrial for the special catalytic perfor-mance under mild conditions and little pollution to the environment.
In the classical synthesis of TS-1, high cost TPAOH is used as template. The repl-ace of TPAOH with TPABr in the low-cost method results in longer crystallization tim-e than the former. The micro-TS-1 was used as seeds to short the crystallization time in this paper, TS-1 combined well stability was successfully synthetized. The dependen-ce of nano-seeds in the low cost synthesis was extricated. Through the SEM technolo-gy, the guide function of crystal seeds was investigated in the low-cost method, the eff-ect of Na2SO4 and Tween 20 introduction on the catalytic performance of propylene e-poxidation was studied. The following results have been obtained:
1. In the processing of micro-TS-1 seed-transferring, the TS-1 with stable performa-nance was got.
2. The seeds were dissolved to crystal nucleus attached on the gel at the beginning of the synthesis of TS-1, the cumulate crystal cells were dispersed to laminal crystals aft-er the gel turned to cumulate crystal cells. Crystallization time of synthesis with seeds was shorter than that of without seeds. And TS-1 with seeds showed well catalytic perf-ormance in the propylene liquid phase epoxidation reaction.
3. The introduction of Na2SO4 and Tween 20 in the phase of gel increased the sel-ectivity of PO, the conversion of H2O2 enhanced at the beginning and then fell down. TS-1 showed well catalytic performance with the molar ratio of Na2SO4 and Si is 0.1.
经典法合成的TS-1需使用价格昂贵的四丙基氢氧化铵为模板剂,而廉价法采用四丙基溴化铵代替四丙基氢氧化铵,导致晶化时间变长。本文使用微米TS-1晶种来提高廉价合成TS-1的速度,即前一代产品作为下一代合成的晶种,成功合成出性能稳定的TS-1,摆脱了廉价法对纳米晶种的依赖；通过扫描电镜等表征手段,对廉价TS-1合成中晶种的导向作用进行了研究；最后探讨了在成胶过程中添加Na2SO4和吐温20对合成的影响。结论如下：
1.微米晶种传递合成中,所得催化剂的催化性能稳定。
2.在晶化的过程中,晶种首先溶解成结构单元,凝胶再渐渐晶化成晶体,并且晶种的加入大大缩短了晶化诱导期,加快了晶体的生长速率,有利于丙烯液相环氧化反应的进行。
3.在配胶过程中添加Na2SO4和吐温20,环氧丙烷的选择性明显增加,H202的转化率先上升后下降,当Na2SO4与Si的摩尔比为0.1时,环氧丙烷的选择性和H202的有效利用率都较高。
Since titanium silicalite TS-1 was successfully prepared in 1983, it has exhibited the unique catalytic performance in many selective oxidation reactions involving H2O2 as the oxidant. TS-1 has a promising perspective of industrial for the special catalytic perfor-mance under mild conditions and little pollution to the environment.
In the classical synthesis of TS-1, high cost TPAOH is used as template. The repl-ace of TPAOH with TPABr in the low-cost method results in longer crystallization tim-e than the former. The micro-TS-1 was used as seeds to short the crystallization time in this paper, TS-1 combined well stability was successfully synthetized. The dependen-ce of nano-seeds in the low cost synthesis was extricated. Through the SEM technolo-gy, the guide function of crystal seeds was investigated in the low-cost method, the eff-ect of Na2SO4 and Tween 20 introduction on the catalytic performance of propylene e-poxidation was studied. The following results have been obtained:
1. In the processing of micro-TS-1 seed-transferring, the TS-1 with stable performa-nance was got.
2. The seeds were dissolved to crystal nucleus attached on the gel at the beginning of the synthesis of TS-1, the cumulate crystal cells were dispersed to laminal crystals aft-er the gel turned to cumulate crystal cells. Crystallization time of synthesis with seeds was shorter than that of without seeds. And TS-1 with seeds showed well catalytic perf-ormance in the propylene liquid phase epoxidation reaction.
3. The introduction of Na2SO4 and Tween 20 in the phase of gel increased the sel-ectivity of PO, the conversion of H2O2 enhanced at the beginning and then fell down. TS-1 showed well catalytic performance with the molar ratio of Na2SO4 and Si is 0.1.
引文
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