Efficient synthesis of rare sugars from galactose in hot compressed water using eggshells as an environmentally friendly catalyst.

Aqueous galactose solutions containing eggshell was heated at 120 °C to produce calcium supplements containing rare sugars. Galactose was isomerized to rare sugars with improving rare sugar yields compared to those without eggshell. Organic acids were also formed as byproducts during the reaction. These acids were neutralized by dissolving eggshells with increasing the calcium ion concentration in the solution. When eggshell components (calcium carbonate, magnesium carbonate, or calcium phosphate) were used for the treatment, rare sugars were also formed. Especially, addition of magnesium carbonate improved rare sugar yield, but byproduct formation became more pronounced. Eggshells used in the treatment were used for repeated treatments. When eggshells were used three times, rare sugar yield changed only slightly but the selectivity of rare sugars improved significantly. By these processes, we obtained an aqueous solution of rare sugars containing calcium ion at 295 mg/L, which has potential as ingredients for dietary supplements.

Production of tagatose and talose through isomerization of galactose in a buffer solution under subcritical water conditions.

Galactose was isomerized in pure water or in 10 mmol/L sodium phosphate buffer at 160 °C under pressurized conditions. The isomerization of galactose to tagatose and talose in phosphate buffer resulted in 14% and 1.4% yields, respectively, which were significantly higher than those obtained in subcritical pure water (0.6% and <0.1%, respectively). The effect of the temperature on isomerization was examined between 100 and 160 °C. The most remarkable isomerization was observed at 120 °C or higher. The effect of the buffer solution type was also examined. The pH drop of the treated solution was lesser in MOPS and PIPES buffers than in the phosphate buffer; however, the isomerization was less likely to occur in MOPS and PIPES buffers. The relationship between the pH drop during the reaction in phosphate buffer and the yields of tagatose and talose revealed that the isomerization proceeded only when the pH was >6.3. Our results indicate that the galactose isomerization by Lobry de Bruyn-Alberda-van Ekenstein transformation rarely occurred at low pH due to the formation of organic acids.