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Improving Catalytic Performance and Stability of Copper-Zinc Based Catalyst on Aluminum Nitride for Formaldehyde Removal from Crude Trioxane

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Abstract

Formaldehyde-water-trioxane (HCHO–H2O–TOX) tends to form a stable azeotrope and the HCHO solution can also produce multiple by-products, making it challenging to refine and obtain high-purity TOX, resulting in increased energy consumption. Formic acid (FA) is the most easily generated and undesirable main byproduct of HCHO, which has strong corrosiveness to production equipment. However, the negative impact of HCHO mentioned above is often overlooked because of its low concentration. In this study, the CuO/ZnO–AlN catalyst was synthesized using a simple deposition precipitation method. The catalyst demonstrated a high removal rate of HCHO and inhibition of FA, along with excellent hydrothermal stability. Aluminum nitride (AlN) can form a layer of Al(OH)3 coating, acting as a physical barrier against H2O during the reaction process and releasing trace OH− to facilitate the formation of Cannizaro intermediates. It can then catalyze HCHO dehydrogenation under alkaline-free conditions to form H2 and an intermediate (HCOO−), which is further converted to H2 and CO2 under the influence of Cu0. The relevant characterization results showed that Cu0 is the active site. The strong interaction between AlN and copper refines the particle size of CuO and promotes the reduction of CuO to Cu0. In addition, an H2 atmosphere can more effectively inhibit the oxidation of Cu0 compared to an N2 atmosphere, resulting in a higher HCHO removal rate. This rate can reach 100% at 105 ℃ and 4 MPa H2 and almost no FA can be detected in the product. Cycling tests proved that the prepared catalyst could be recycled and reused three times without a noticeable reduction in catalytic activity, demonstrating its good application potential.

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Funding

This work was supported by Sichuan Science and Technology Program (2023YFG0104).

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Authors and Affiliations

  1. Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, No. 9, Section 4, Renmin South Road, Chengdu, 610041, Sichuan, People’s Republic of China

    Ruoyu Zhou, Qian Lei, Conger Deng, Linlin Liang & Honglin Chen

  2. University of Chinese Academy of Sciences, Beijing, China

    Ruoyu Zhou

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  1. Ruoyu Zhou
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  2. Qian Lei
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  3. Conger Deng
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  4. Linlin Liang
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  5. Honglin Chen
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Correspondence to Honglin Chen.

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Zhou, R., Lei, Q., Deng, C. et al. Improving Catalytic Performance and Stability of Copper-Zinc Based Catalyst on Aluminum Nitride for Formaldehyde Removal from Crude Trioxane. Catal Lett (2024). https://doi.org/10.1007/s10562-024-04592-3

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