Highly crystalline ZSM-5 zeolites are important for para-selective alkylation of alkyl aromatics, because they carry few external acid sites for isomerization of p-dialkyl products. Such zeolites (Si/Al = 25, 50, and ...Highly crystalline ZSM-5 zeolites are important for para-selective alkylation of alkyl aromatics, because they carry few external acid sites for isomerization of p-dialkyl products. Such zeolites (Si/Al = 25, 50, and 75) were synthesized in a fluoride medium between pH 4 and 6. Their crystallinities, crystal sizes, and surface areas were higher than those of a commercial ZSM-5 zeolite. Their para selectivities in alkylation were tested for vapor-phase tert-butylation of ethylbenzene between 200 and 400 °C. As expected, all the catalysts showed more than 90% para selectivity. At 300 °C, ethylbenzene conversion decreased in the order ZSM-5(25, commercial) > ZSM-5(25) > ZSM-5(50) > ZSM-5(75). The catalysts had weak, medium, and strong acid sites, but all the acid sites of ZSM-5(75) were weaker than those of ZSM-5(25) and ZSM-5(50). The high activity of commercial ZSM-5 was caused by its strong acid sites being stronger than those of the synthesized zeolites. Although the activity of the commercial catalyst was higher than those of the present catalysts, the selectivity for 4-t-butylethylbenzene (4-t-BEB) was low. The optimum feed ratio (ethylbenzene:t-butyl alcohol) was 2:1 and the feed rate was 1.65 h?1 for high ethylbenzene conversion and 4-t-BEB selectivity. Time-on-stream studies showed slow catalyst deactivation. Highly crystalline ZSM-5 zeolites are therefore better than a commercial zeolite for para-selective alkylation of alkyl aromatics. They do not require much post-modification for high para selectivity. A fluoride medium is therefore better than an alkaline medium for obtaining highly crystalline para-selective ZSM-5 zeolites.展开更多
A new one-dimensional（ID） fluoroaluminophosphate chain（C4H15N3）[AlPO4F2]（denoted AIPO-CJ28） was synthesized in the concentrated fluoride synthetic medium with a gel composition of 1.0Al（OPr^1）a：1.0H3PO4： 5.4...A new one-dimensional（ID） fluoroaluminophosphate chain（C4H15N3）[AlPO4F2]（denoted AIPO-CJ28） was synthesized in the concentrated fluoride synthetic medium with a gel composition of 1.0Al（OPr^1）a：1.0H3PO4： 5.4DETA：1.3HF：2.0H2O（DETA=diethylenetriamine）. The reagents were mixed directly without introducing additional water solvent. The 1D chain is constructed by alternating AlO2F2 arid doubly bridging PO4 tetrahedra to form the simplest serrate chain. AIPO-CJ28 can be transformed to another 1D aluminophosphate chain A1PO-CSC upon further crystallization at 230 ℃.展开更多
基金supported by grants from Korea CCSR&D Centre,funded by the Ministry of Education,Science and Technology of the Korean Government
文摘Highly crystalline ZSM-5 zeolites are important for para-selective alkylation of alkyl aromatics, because they carry few external acid sites for isomerization of p-dialkyl products. Such zeolites (Si/Al = 25, 50, and 75) were synthesized in a fluoride medium between pH 4 and 6. Their crystallinities, crystal sizes, and surface areas were higher than those of a commercial ZSM-5 zeolite. Their para selectivities in alkylation were tested for vapor-phase tert-butylation of ethylbenzene between 200 and 400 °C. As expected, all the catalysts showed more than 90% para selectivity. At 300 °C, ethylbenzene conversion decreased in the order ZSM-5(25, commercial) > ZSM-5(25) > ZSM-5(50) > ZSM-5(75). The catalysts had weak, medium, and strong acid sites, but all the acid sites of ZSM-5(75) were weaker than those of ZSM-5(25) and ZSM-5(50). The high activity of commercial ZSM-5 was caused by its strong acid sites being stronger than those of the synthesized zeolites. Although the activity of the commercial catalyst was higher than those of the present catalysts, the selectivity for 4-t-butylethylbenzene (4-t-BEB) was low. The optimum feed ratio (ethylbenzene:t-butyl alcohol) was 2:1 and the feed rate was 1.65 h?1 for high ethylbenzene conversion and 4-t-BEB selectivity. Time-on-stream studies showed slow catalyst deactivation. Highly crystalline ZSM-5 zeolites are therefore better than a commercial zeolite for para-selective alkylation of alkyl aromatics. They do not require much post-modification for high para selectivity. A fluoride medium is therefore better than an alkaline medium for obtaining highly crystalline para-selective ZSM-5 zeolites.
基金Supported by the National Natural Science Foundation of China(No.20871051)the Scientific and Technological Plan-ning Project of Jilin Province, China(No.20080504)
文摘A new one-dimensional（ID） fluoroaluminophosphate chain（C4H15N3）[AlPO4F2]（denoted AIPO-CJ28） was synthesized in the concentrated fluoride synthetic medium with a gel composition of 1.0Al（OPr^1）a：1.0H3PO4： 5.4DETA：1.3HF：2.0H2O（DETA=diethylenetriamine）. The reagents were mixed directly without introducing additional water solvent. The 1D chain is constructed by alternating AlO2F2 arid doubly bridging PO4 tetrahedra to form the simplest serrate chain. AIPO-CJ28 can be transformed to another 1D aluminophosphate chain A1PO-CSC upon further crystallization at 230 ℃.
