Research articleRemoval of catalyst poisons for the production of sugar alcohols from a real biomass molasses using a heterogeneous Ni catalyst
Introduction
Molasses is a viscous liquid waste that remains after the manufacture of sucrose from crops such as sugarcane. The formation amount of molasses is about 50 million tons annually [1], and the material still contains 40 to 50 wt% of sucrose, glucose, and fructose in total [2]. Accordingly, molasses is a potential biomass resource for the production of renewable chemicals. A promising target is sugar alcohols including sorbitol and mannitol, which can be synthesized by the hydrolysis of sucrose to glucose and fructose followed by the hydrogenation (Fig. 1) [3]. Sorbitol is annually produced in 650 kt as a sweetener, moisturizer, and precursor to vitamin C, sorbitan, and isosorbide [4]. Sorbitan is a feedstock for the production of surfactants for foods and horticulture supplies, while isosorbide is a medicine for glaucoma and converted to antianginal drugs and engineering plastics [[5], [6], [7], [8], [9], [10]]. In addition, conversion of sorbitol to fuels has recently been studied in laboratories [11,12]. Mannitol is a non-hygroscopic compound used as a desiccant for tablets and chewing gums, medicines, and a precursor to explosives [7]. An isosorbide analog for mannitol, isomannide, is a potential feedstock for the production of engineering plastics [5,13]. The sugar alcohols are produced from starch and fructose syrup in the current chemical industries. As an alternative resource, molasses is advantageous over the current feedstock in terms of lower price and waste utilization. However, there has been no report on the catalytic conversion of molasses to sugar alcohols to our knowledge. Moreover, such crude biomass often contains impurities that potentially work as catalyst poisons in the chemical conversion [2,14]. Especially, hydrogenation catalysts are sensitive to impurities [[15], [16], [17]]. Thus, the study on the effect of catalyst poisons and their removal is crucial to establish biorefinery.
Herein, we report the conversion of sugarcane-derived molasses to sugar alcohols with a heterogeneous nickel catalyst. Adsorption pretreatment of molasses, effect of the pretreatment on the hydrolytic hydrogenation to produce sugar alcohols, catalyst poisoning, and physical chemistry of the catalytic reaction were studied.
Section snippets
Materials
A sugarcane molasses containing 32 wt% sucrose, 4.4 wt% glucose, and 6.6 wt% fructose was provided by Mitsubishi Gas Chemical Company, Inc. Sucrose, glucose, fructose, L-cysteine, L-aspartic acid, humic acid, H2SO4, 35% hydrochloric acid, formic acid, 30% H2O2 were purchased from Wako Pure Chemical Industries. Montmorillonite K 10 (denoted MK10; 270 m2 g−1; N2 adsorption isotherm and Barrett-Joyner-Halenda (BJH) plot Fig. S1), activated carbon Norit SX Ultra (denoted AC; 985 m2 g−1; N2
Pretreatment of molasses
We studied pretreatment of molasses to remove potential catalyst poisons such as proteins and complicated organosulfur and organonitrogen compounds similar to humins [23]. Three types of pretreatments were performed for the diluted and centrifuged molasses (M-Centrifuged): filtration (M-Filtrated) and the adsorption treatment with MK10 or AC followed by filtration (M-MK10 and M-AC) (see Experimental). MK10 and AC are often used for the adsorption of proteins in food industries [24].
Sugar
Conclusions
We studied the pretreatment and catalytic conversion of sugarcane molasses to synthesize sugar alcohols using Raney® Ni catalyst. In the adsorption pretreatment of molasses, Montmorillonite K10 selectively reduced organosulfur and organonitrogen compounds with no adsorption of sugars. Pristine molasses gives only 32 %C yield of sugar alcohols, but the adsorption pretreatment with MK10 increased the yield to 53 %C. The correlation between the content of impurities and hydrogenation activity,
Acknowledgment
The authors would like to thank Mr. T. Hirokane, Mr. T. Kirino, and Ms. S. Nakamura (Mitsubishi Gas Chemical Company, Inc.) for providing the molasses sample and fruitful discussion.
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