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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