Mixed Ba1−xLaxF2+x fluoride materials as catalyst for the gas phase fluorination of 2-chloropyridine by HF

• Published in: Applied catalysis. B, Environmental Vol. 204; pp. 107 - 118
• Main Authors: Astruc, A., Célérier, S., Pavon, E., Mamede, A.-S., Delevoye, L., Brunet, S.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 05.05.2017; Elsevier
• Subjects: 2-fluoropyridine; Barium fluoride; Catalysis; Chemical Sciences; Fluorination; Lanthanum fluoride; Mixed metal fluoride; Barium fluoride; Lanthanum fluoride; Fluorination; Mixed metal fluoride; 2-fluoropyridine
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2016.11.019

[Display omitted] •Ba1−xLaxF2+x mixed fluorides are prepared by precipitation method.•Ba1−xLaxF2+x is used as solid catalyst for the fluorination of 2-chloropyridine by HF.•Moisture of atmosphere acts as sintering agent for BaF2.•BaF2−xClx is formed from BaF2 during the Cl/F exchange of 2-chloropyridine.•The presence of lanthanum stabilizes barium based catalysts. The stability under different atmospheres (dry or wet nitrogen or air, HF, reaction medium) and the catalytic performances of BaF2-LaF3 based catalysts for the fluorination of 2-choropyridine by Cl/F exchange with HF as fluorinating agent were investigated. Thermal decomposition of metal trifluoroacetate and precipitation from nitrate precursor methods were used as synthesis methods. Depending on the synthesis method and the La/La+Ba molar ratio (x), an intimate mixture of BaF2 and LaF3 metal fluorides or a Ba1−xLaxF2+x mixed metal fluoride with high specific surface area were formed. In comparison with BaF2, the mixed metal fluorides led to higher specific surface areas and prevented the sintering phenomenon observed under wet atmosphere which led to a significant decrease of the specific surface area. Moreover, Ba1−xLaxF2+x catalysts had not evolved under the fluorination reaction contrary to BaF2 for which a stable BaF2−xClx material (with x close to 0.8) was formed by reaction with the by-product HCl. The turn over frequency (TOF) was similar for all barium based catalysts for the fluorination of 2-chloropyridine. Nevertheless, among the studied materials, Ba0.5La0.5F2.5 was the most promising catalyst for the transformation of 2-chloropyridine due to high activity (related to its high specific surface area and its moderate strength of Lewis acidity) and high stability.