A comparison of different zeolites in their catalytic performance in the skeletal isomerization of 1-hexene
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摘要: 以HZSM-35、HZSM-5、HM和Hβ四种分子筛为1-己烯骨架异构化催化剂，比较研究了四种催化剂的异构化性能，对其构效关系进行了关联。结果表明，相比于HZSM-5和Hβ分子筛，HZSM-35和HM具有适宜的酸量，有效孔径为0.4-0.6 nm，而且无晶穴、无交叉孔道，具有良好的择形催化效应，在转化率高达95%的同时，C5-和C7+等副产物的收率在20%左右，异己烯收率可达40%-50%。进一步对四种分子筛进行酸碱改性处理，结果显示，虽然酸性质略有改变，但是一维孔结构的HZSM-35和HM分子筛的异构化性能仍明显优于多维孔结构的HZSM-5和Hβ分子筛，说明在酸性质一定的前提下，孔结构对异构化反应起关键作用。Abstract: HZSM-35, HZSM-5, HM and Hβ zeolites were used as the catalysts for the skeletal isomerization of 1-hexene; the relationship between their catalytic performance and physicochemical properties was investigated. The results show that in comparison with HZSM-5 and Hβ, HZSM-35 and HM are provided with suitable acid amount and effective pore size between 0.4-0.6 nm, without bug hole and cross channel; as a result, the later two zeolites exhibit better shape selectivity. With a high conversion of 1-hexene (> 95%), the by-products such as C5- and C7+ in the products are about 20% and the yield of iso-hexene reaches 40%-50%. After the acid-base modification treatment, a slight change in the acidity is observed; however, the catalytic performance of one-dimensional HZSM-35 and HM zeolites in pore isomerization is still much better than that of HZSM-5 and Hβ zeolites with multidimensional pore structure, suggesting that the pore structure plays a key role in the isomerization reaction.
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Key words:
- acid-base modification /
- 1-hexene /
- skeletal isomerization /
- pore structure /
- zeolites
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图 2 不同分子筛的1-己烯骨架异构化反应性能
Figure 2 Catalytic performance of different zeolites in 1-hexene skeletal isomerization
图 4 经酸碱处理的四种分子筛的XRD谱图
Figure 4 XRD patterns of four zeolites treated by acid and alkali
图 5 经酸碱处理Hβ分子筛的NH3-TPD谱图
Figure 5 NH3-TPD profiles of Hβ zeolites treated by acid and alkaline
图 6 经酸碱处理的四种分子筛的1-己烯骨架异构化性能
Figure 6 Catalytic performance of four zeolites treated by acid and alkaline in 1-hexene skeletal isomerization
图 7 经酸碱处理的四种分子筛反应后的O2-TPO谱图
Figure 7 O2-TPO profiles of four zeolites treated by acid and alkaline after reaction
表 1 不同分子筛的XRF分析
Table 1 XRF results of different zeolites
Catalyst SiO2/% Al2O3/% SiO2/Al2O3 HZSM-35 92.29 7.14 21.93 HM 91.05 7.13 21.67 HZSM-5 94.10 5.90 27.06 Hβ 89.14 7.06 21.42 
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表 2 不同分子筛的NH3-TPD分析
Table 2 NH3-TPD results of different zeolites
Catalyst Weak acid peak Strong acid peak Total acid amount peak area peak temperature t/℃ peak area peak temperature t/℃ peak area HZSM-35 274 6.17×10-9 563 4.97×10-9 1.11×10-8 HM 242 3.77×10-9 592 4.27×10-9 8.04×10-9 HZSM-5 276 8.58×10-9 520 6.00×10-9 1.46×10-8 Hβ 253 8.55×10-9 464 2.37×10-9 1.09×10-8
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表 3 不同分子筛反应后的O2-TPO分析
Table 3 O2-TPO data of different zeolites after reaction
Catalyst CO CO2 C content w/(mg·g-1) peak area C mass peak area C mass HZSM-35 6.17×10-9 9.94×10-4 1.31×10-8 1.15×10-3 2.14 HM 1.85×10-8 2.98×10-3 2.26×10-8 1.99×10-3 5.34 HZSM-5 6.29×10-9 1.01×10-3 1.03×10-8 9.06×10-4 1.92 Hβ 2.08×10-8 3.35×10-3 3.09×10-8 2.72×10-3 5.70
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表 4 经酸碱处理的四种分子筛的NH3-TPD分析
Table 4 NH3-TPD results of four zeolites treated by acid and alkaline
Catalyst Weak acid peak Strong acid peak Total acid amount peak area peak temperature t/℃ peak area peak temperature t/℃ peak area K1ZSM-35 246 7.66×10-9 - - 7.66×10-9 K1M 224 4.07×10-9 401 4.15×10-10 4.48×10-9 K1ZSM-5 248 5.92×10-9 - - 5.92×10-9 K1β 236 4.50×10-9 - - 4.50×10-9
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表 5 经酸碱处理的HZSM-35分子筛反应后的O2-TPO分析
Table 5 O2-TPO results of HZSM-35 zeolites treated by acid and alkaline after reaction
Catalyst CO CO2 C content w/(mg·g-1) peak area C mass peak area C mass K1ZSM-35 3.15×10-9 5.08×10-4 3.61×10-9 3.18×10-4 0.83 K1M 1.69×10-8 2.72×10-3 1.18×10-8 1.04×10-3 3.76 K1ZSM-5 1.69×10-8 1.38×10-3 4.31×10-9 3.79×10-4 1.76 K1β 1.13×10-8 1.82×10-3 1.17×10-8 1.03×10-3 2.85
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