Effect of acidity on the catalytic performance of ZSM-5 zeolites in the synthesis of trioxane from formaldehyde
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摘要: ZSM-5分子筛是合成三聚甲醛的有效催化剂。本工作通过XRF、XRD、SEM、NH3-TPD、Py-FTIR和27Al MAS NMR等手段对一系列不同SiO2/Al2O3物质的量比的ZSM-5分子筛催化剂进行了表征，研究了ZSM-5分子筛中Brønsted酸中心和Lewis酸中心对其甲醛合成三聚甲醛催化性能的影响。结果表明，SiO2/Al2O3物质的量比为250的ZSM-5分子筛具有合适的Brønsted酸中心用于催化甲醛缩聚为三聚甲醛的反应，同时其Lewis酸中心量极少，可有效抑制Cannizzaro或Tishchenko等副反应，提高三聚甲醛的选择性，因而具有最佳的合成三聚甲醛催化性能。寿命实验评价结果显示，SiO2/Al2O3物质的量比为250的ZSM-5分子筛具有良好的催化稳定性，单程寿命长达114 h，并且可通过550℃焙烧再生恢复其催化活性。Abstract: ZSM-5 zeolite is considered as an effective catalyst in the synthesis of trioxane from formaldehyde. In this work, a series of ZSM-5 zeolites with different SiO2/Al2O3 molar ratios were used in the synthesis of trioxane from formaldehyde; through characterization by XRF, XRD, SEM, NH3-TPD, Py-FTIR and 27Al MAS NMR, the effect of acidity including the Brønsted and Lewis acid sites on the catalytic performance of ZSM-5 zeolites in the trioxane synthesis was investigated. The results indicate that the ZSM-5-250 zeolite with a SiO2/Al2O3 molar ratio of 250 exhibits excellent catalytic performance in the synthesis of trioxane. The ZSM-5-250 zeolite owns sufficient amount of Brønsted acid sites which are active for the synthesis of formaldehyde to trioxane; meanwhile, it has few Lewis acid sites and can then effectively inhibit various side-reactions like the Cannizzaro or Tishchenko reactions. Moreover, the ZSM-5-250 zeolite displays high stability with a single-pass lifetime of 114 h and can be regenerated easily through calcination at 550℃.
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Key words:
- trioxane /
- ZSM-5 zeolite /
- formaldehyde /
- acidity /
- Brønsted acid /
- Lewis acid
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Figure 5 27Al MAS NMR spectra of the ZSM-5 zeolites with different SiO2/Al2O3 molar ratios
Figure 6 Formaldehyde conversions and product selectivity for TOX synthesis over different catalysts the reactions were carried out under 100 ℃ for 2 h, with 100 g CH2O solution (60%) and 5 g catalyst
--○--: conversion; : DMM; : MF; : HCOOH; : MeOH; : TOX
Figure 7 Formaldehyde conversions and product selectivity for TOX synthesis over the yAl-ZSM-5-100 zeolites the reactions were carried out under 100 ℃ for 2 h, with 100 g CH2O solution (60%) and 5 g catalyst
--○--: conversion; : DMM; : MF; : HCOOH; : MeOH; : TOX
Figure 8 Conversion of HCOOH in the esterification of MeOH and HCOOH over various catalysts the reactions were carried out at 100 ℃ for 1 h, with 100 g reaction mixture solution and 5 g solid catalyst (or 2 g H2SO4)
Figure 9 Formaldehyde conversions and product selectivity for TOX synthesis over the ZSM-5-250 zeolite catalyst under continuous operation at 100 ℃, with 100 g CH2O (60%) and 5 g catalyst initially in the reactor and CH2O solution feed flow rate of 0.5-1.0 mL/min during the continuous reaction
Table 1 Al content and textural properties of various ZSM-5 zeolites and γ-Al2O3 and resin
Catalyst Al content /(mmol·g-1) ABET /(m2·g-1) vtotal /(cm3·g-1) d /nm Resin - 13 0.130 19.27 γ-Al2O3 - 206 0.540 5.23 ZSM-5-30 0.870 332 0.233 0.569 ZSM-5-100 0.295 351 0.244 0.558 ZSM-5-180 0.168 339 0.227 0.525 ZSM-5-250 0.126 339 0.230 0.559 ZSM-5-400 0.084 342 0.238 0.560 0.1Al-ZSM-5-100 0.306 347 0.241 0.553 0.3Al-ZSM-5-100 0.314 340 0.238 0.550 0.5Al-ZSM-5-100 0.323 338 0.237 0.551 note: Al content was measured by XRF, the surface area (ABET) was determined from nitrogen sorption isotherms by BET method; the total pore volume (vtotal) was obtained at a relative pressure of 0.99; the average pore diameter (D) was derived by using BJH method for resin and γ-Al2O3 and using t-plot method for the ZSM-5 zeolites 
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Table 2 Acidity and Al content of various ZSM-5 zeolites and γ-Al2O3 and resin
Catalyst Acidity by NH3-TPD
/(mmol·g-1)Acidity by Py-FTIR /(mmol·g-1) Al content /% Brønsted Lewis AlF AlEF Resin 1.320 - - - - γ-Al2O3 0.165 0.000 0.027 - ZSM-5-30 0.784 0.492 0.038 93.1 6.9 ZSM-5-100 0.296 0.178 0.034 96.2 3.8 ZSM-5-180 0.187 0.092 0.016 97.5 2.5 ZSM-5-250 0.161 0.049 0.009 97.7 2.3 ZSM-5-400 0.126 0.027 0.005 97.8 2.2 0.1Al-ZSM-5-100 0.286 0.174 0.042 93.0 7.0 0.3Al-ZSM-5-100 0.278 0.163 0.048 92.4 7.6 0.5Al-ZSM-5-100 0.251 0.150 0.057 91.9 8.2 note: the acidity of resin was determined by the acid-base titration method, the contents of framework Al (AlF) and extra-framework (AlEF) were determined by 27Al MAS NMR
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Table 3 Textural properties of the ZSM-5-250 catalyst before and after reaction test
Catalyst ABET /
(m2·g-1)vtotal /
(cm3·g-1)d /nm ZSM-5-250, fresh 339 0.230 0.559 ZSM-5-250-D, used 310 0.201 0.509 ZSM-5-250-R, regenerated 342 0.238 0.560 note: the surface area (ABET) was determined from nitrogen sorption isotherms by BET method; the total pore volume (vtotal) was obtained at a relative pressure of 0.99; the average pore diameter (d) was derived by using the t-plot method
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Table 4 Acidity of the ZSM-5-250 catalyst before and after reaction test
Catalyst Acidity by NH3-TPD /
(mmol·g-1)Acidity Py-FTIR
/(mmol·g-1)Brønsted Lewis ZSM-5-250, fresh 0.161 0.049 0.009 ZSM-5-250-D, used 0.105 0.021 0.003 ZSM-5-250-R, regenerated 0.159 0.050 0.008
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