Catalysis of ordered nanoporous materials for fructose dehydration through difructose anhydride intermediate

• Fructose reaction network including difructose anhydride cyclic path in parallel with fructose dehydration was devised.
• In biphasic solvent, MIBK could act as an extractant of HMF and also a promoter for fructose dehydration.
• Increasing reaction severity improves HMF selectivity at boosted fructose conversion over molecular sieve.
• Narrow pore zeolites and sulfated mesoporous silica catalysed 90% HMF selectivity at high fructose conversion.
• Shape selective catalysis for HMF oligomerization over large pore 12-MR zeolites led to deteriorated HMF selectivity.

A fructose reaction network, including difructose anhydride (DFA) – fructose cycle in parallel with fructose dehydration following with 5-hydroxymethylfurfural (HMF) side reactions, was devised. By applying H2O - MIBK biphasic solvent, MIBK could act as an extractant of HMF and also a promoter for fructose dehydration. By raising reaction severity, molecular sieve catalysed improved HMF selectivity by suppression of DFA formation. While narrow pore zeolites and sulfated mesoporous silica catalysed 90% HMF selectivity at 85–94% fructose conversion, the large pore 12-MR zeolites exhibited low HMF selectivity returning with excessive humin formation due to their shape selective catalysis for HMF oligomerization.

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