Carbonaceous Solid Supported Acid Catalysts
Carbonaceous solid supported acid catalysts are sulfonated solid carbon forms, and this is a promising class of catalysts for the
hydrolysis of cellulose into glucose [72]. This type of materials were first derived from sulfonation of carbonized D-glucose or sucrose [86] and have been used in further studies in the trans-esterification of vegetable oils with alcohol for biofuels [86, 87]. The carbonaceous solid supported acid catalysts can be prepared by carbonizing carbohydrates at 400°C under nitrogen atmosphere and then sulfonat — ing the amorphous carbon formed using fuming sulfuric acid at 150°C as shown in Figure 7.14 [2]. Another approach to these catalysts is the direct sulfonation of lignin, where under strongly acidic conditions lignin undergoes dehydration and further aromatization to produce sulfonated carbon. The catalysts consist of amorphous, polycyclic aromatic carbon sheets containing SO3H groups, COOH and OH groups as active sites as shown in Figure 7.14.
It has been suggested that these functionalized polycyclic carbon sheets can absorb cellulose on the surface allowing the SO3H on the catalyst to access the glycosidic links in cellulose. The other functional groups like carboxylic acid (COOH) and phenolic OH
1
H2SO4
p-TsOH
on the catalyst surface are believed to be supporting the binding of the cellulose onto catalyst surface. High glucose yields of up to 75% with 80% selectivity have been reported for reaction carried out at 150°C for 24 h by Fukuhara et al. [88]. Furthermore, they suggested that the mechanism of cellulose hydrolysis with carbonaceous solid supported acid catalysts is similar to that for sulfuric acid. Namely, protons in SO3H attack the в-1,4 glycosidic bonds in the solid crystalline cellulose. The apparent activation energy (110 kJ/mol) for cellulose conversion into glucose with carbonaceous solid supported acid catalysts is lower than that for sulfuric acid (170 kJ/mol) under optimal conditions. This is attributed to an increase in acidity of the SO3H groups on the carbon material with a decrease in the amount of water, as was previously demonstrated by Suganuma and coworkers [89]. Time courses of cellulose conversion in hydrolysis of pure crystalline cellulose and eucalyptus using carbon material and sulfuric acid are shown in Figure 7.15 [89]. Results for the hydrolysis of pure crystalline
■ 1
■H2SO4 ‘ p-TsOH
|
Figure 7.14 Synthesis of sulfonated amorphous carbon from glucose and lignin by different synthesis pathways. |
|
CARBON MATERIAL ——————- I Figure 7.15 Time courses of cellulose conversion in hydrolysis (catalyst, 0.300 g; cellulosic reactant, 0.025 g; water, 0.700 g; reaction temperature, 373 K) of pure crystalline cellulose and eucalyptus using carbon material (circles) and sulfuric acid (squares). Triangles represent the results for the hydrolysis of pure crystalline cellulose using niobic acid (Nb2O5-nH2O), H-mordenite, Nafion, and Amberlyst-15. (Reprinted with permission from reference [89]; copyright 2008 American Chemical Society). |
cellulose using niobic acid (Nb2O5-nH2O), H-mordenite, Nation, and Amberlyst-15 are also shown in Figure 7.15. [89]
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