Water effects on the acidic property of typical solid acid catalysts by 3,3-dimethylbut-1-ene isomerization and 2-propanol dehydration reactions

- Method for the evaluation of surface acidity on working solid catalysts is provided.
- Skeletal isomerization of 3,3-dimethylbut-1-ene and dehydration of 2-propanol are used as the probe reactions.
- Typical Brønsted (H-ZSM-5), Lewis (γ-Al2O3), and water-resistant Brønsted and Lewis acidic (Nb2O5) solid acids are investigated.
- Effects of water presence on the nature (Brønsted or Lewis), density and acidity strength of the surface acidic sites are reported.

Two model reactions, namely the Brønsted-acidity-specific skeletal isomerization of 3,3-dimethylbut-1-ene for evaluating the Brønsted acidity and dehydration of 2-propanol for the overall acidity at the catalyst surface, were employed in this work to measure the effect of water on the surface acidic property of typical solid catalysts (HZSM-5, γ-Al2O3 and Nb2O5). For the isomerization reaction, water addition in the reaction feed produced little effect on the catalysis of HZSM-5 but significantly positive effect on the catalysis of Nb2O5; the typical Lewis acidic γ-Al2O3 showed no activity for this reaction in either the presence or absence of water. For the dehydration reaction, the effect of water was generally negative on the catalysis of every catalyst, demonstrating that water presence resulted in poisoning more or less of the Lewis acidity on the catalyst surface. Water poisoning of the Lewis acidity on Nb2O5 also resulted in generation of Brønsted acidity and the higher the H2O partial pressure (or H2O-to-substrate ratio) the higher the newly generated Brønsted acidity. However, generation of Brønsted acidity did not happen on γ-Al2O3 and HZSM-5, regardless of the H2O partial pressure. Three Nb2O5 samples with varying calcination temperature were involved, and their behavior clearly indicated that the water effects on Nb2O5 also depended sensitively on the sample calcination temperature. Moreover, water presence increased the activation energy and selectivity for di-isopropyl ether of the dehydration reaction over γ-Al2O3 and Nb2O5, and thus affected the acidity distribution at the catalyst surface during the reaction.

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