Abstract
Kaolinite, a natural, layered phyllosilicate, has been used as the solid catalyst for the hydrolysis of cellulose in our previous work. In the present study, kaolinite was activated by mineral acid and further evaluated for the hydrolysis of cellulose in water. The acid-activated kaolinite was characterized by XRF, XRD, FT-IR, BET and TG. The effects of reaction temperature, reaction time, mass ratio and water amount were investigated in the system. It was found that the highest total reducing sugars (TRS) yield of 50.2% was obtained on the kaolinite activated by 20% HNO3 with the mass ratio of catalyst to cellulose of 0.2 and water to cellulose of 14 at 205 ℃ for 3 h. Moreover, the catalyst was easily regenerated by calcination and the yield of TRS on the regenerated catalyst changed between 50.2% and 45.2% after four times reuse. The results showed that the acid activation could influence the crystallinity and improve the specific surface area, but the high TRS yield of the activated kaolinite should be ascribed to the increasing of the interlayer Al–OH groups and the formation of inner hydrogen bonds between the octahedral sheets and tetrahedral sheets. Finally, it was suggested that this was the effective way for improving the catalytic performance by increasing the interlayer Al–OH groups on the kaolinite catalyst.
Graphic Abstract
Similar content being viewed by others
References
Phillips D, Mitchell EJS, Lea-Langton AR, Parmar KR, Jones JM, Williams A (2016) The use of conservation biomass feedstocks as potential bioenergy resources in the United Kingdom. Bioresource Technol 212:271–279
Al-Hamamre Z, Saidan M, Hararah M, Rawajfeh K, Alkhasawneh HE, Al-Shannag M (2017) Wastes and biomass materials as sustainable-renewable energy resources for Jordan. Renew Sust Energ Rev 67:295–314
Larsson M, Yan J, Nordenskjöld C, Forsberg K, Liu L (2016) Characterisation of stormwater in biomass-fired combined heat and power plants – Impact of biomass fuel storage. Appl Energ 170:116–129
Chen W, Li Q, Cao J, Liu Y, Li J, Zhang J, Luo S, Yu H (2015) Revealing the structures of cellulose nanofiber bundles obtained by mechanical nanofibrillation via TEM observation. Carbohyd Polym 117:950–956
Qu H, Liu B, Li L, Zhou Y (2020) A bifunctional recoverable catalyst based on phosphotungstic acid for cellulose hydrolysis to fermentable sugars. Fuel Process Technol 199:106272
Saher S, Saleem H, Asim AM, Uroos M, Muhammad N (2018) Pyridinium based ionic liquid: A pretreatment solvent and reaction medium for catalytic conversion of cellulose to total reducing sugars (TRS). J Mol Liq 272:330–336
Prasertsung I, Aroonraj K, Kamwilaisak K, Saito N, Damrongsakkul S (2019) Production of reducing sugar from cassava starch waste (CSW) using solution plasma process (SPP). Carbohyd Polym 205:472–479
Hu M, Yu H, Li Y, Li A, Cai Q, Liu P, Tu Y, Wang Y, Hu R, Hao B, Peng L, Xia T (2018) Distinct polymer extraction and cellulose DP reduction for complete cellulose hydrolysis under mild chemical pretreatments in sugarcane. Carbohyd Polym 202:434–443
Chen Z, Li Q, Xiao Y, Zhang C, Fu Z, Liu Y, Yi X, Zheng A, Li C, Yin D (2018) Acid–base synergistic catalysis of biochar sulfonic acid bearing polyamide for microwave-assisted hydrolysis of cellulose in water. Cellulose 26:751–762
Gromov NV, Medvedeva TB, Taran OP, Bukhtiyarov AV, Aymonier C, Prosvirin IP, Parmon VN (2018) Hydrothermal solubilization–hydrolysis–dehydration of cellulose to glucose and 5-hydroxymethylfurfural over solid acid carbon catalysts. Top Catal 61:1912–1927
Zhou L, He Y, Ma Z, Liang R, Wu T, Wu Y (2015) One-step degradation of cellulose to 5-hydroxymethylfurfural in ionic liquid under mild conditions. Carbohyd Polym 117:694–700
Mo X, Lopez D, Suwannakarn K, Liu Y, Lotero E, Goodwinjr J, Lu C (2008) Activation and deactivation characteristics of sulfonated carbon catalysts. J Catal 254:332–338
Sumiya S, Oumi Y, Sadakane M, Sano T (2009) Facile preparation of SBA-15-supported niobic acid (Nb2O5·nH2O) catalyst and its catalytic activity. Appl Catal A-Gen 365:261–267
Trombettoni V, Lanari D, Prinsen P, Luque R, Marrocchi A, Vaccaro L (2018) Recent advances in sulfonated resin catalysts for efficient biodiesel and bio-derived additives production. Prog Energ Combust 65:136–162
Lang X, Jia W, Wang Y, Zhu Z (2015) Novel fluorination of polystyrene sulfonic acid resin by CF3SO3H for high stability and strong acidity. Catal Commun 70:58–61
Chu S, Ln Y, Guo X, Dong L, Chen X, Li Y, Mu X (2018) The influence of pore structure and Si/Al ratio of HZSM-5 zeolites on the product distributions of α-cellulose hydrolysis. Mol Catal 445:240–247
Zhang X, Zhang X, Sun N, Wang S, Wang X, Jiang Z (2019) High production of levulinic acid from cellulosic feedstocks being catalyzed by temperature-responsive transition metal substituted heteropolyacids. Renew Energ 141:802–813
He Y, Zhang Q, Zhan X, Cheng D-g, Chen F (2016) Synthesis of efficient SBA-15 immobilized ionic liquid catalyst and its performance for Friedel-Crafts reaction. Catal Today 276:112–120
Wang Y, Yang X, Xu J, Wang H, Wang Z, Zhang L, Wang S, Liang J (2019) Biodiesel production from esterification of oleic acid by a sulfonated magnetic solid acid catalyst. Renew Energ 139:688–695
Zhou CH (2011) An overview on strategies towards clay-based designer catalysts for green and sustainable catalysis. Appl Clay Sci 53:87–96
Zhang D, Zhou C, Lin C, Tong D, Yu W (2010) Synthesis of clay minerals. Appl Clay Sci 50:1–11
Moronta A, Ferrer V, Quero J, Arteaga G, Choren E (2002) Influence of preparation method on the catalytic properties of acid-activated tetramethylammonium-exchanged clays. Appl Catal A-Gen 230:127–135
Kooli F, Liu Y, Alshahateet SF, Messali M, Bergaya F (2009) Reaction of acid activated montmorillonites with hexadecyl trimethylammonium bromide solution. Appl Clay Sci 43:357–363
Tong D, Xia X, Luo X, Wu L, Lin C, Yu W, Zhou C, Zhong Z (2013) Catalytic hydrolysis of cellulose to reducing sugar over acid-activated montmorillonite catalysts. Appl Clay Sci 74:147–153
Yang H, Zhou Y, Tong D, Yang M, Fang K, Zhou C, Yu W (2020) Catalytic conversion of cellulose to reducing sugars over clay-based solid acid catalyst supported nanosized SO42−-ZrO2. Appl Clay Sci 185:105376
Jia X, Cheng H, Zhou Y, Zhang S, Liu Q (2019) Time-efficient preparation and mechanism of methoxy-grafted kaolinite via acid treatment and heating. Appl Clay Sci 174:170–177
Yang H, Tong D, Dong Y, Ren L, Fang K, Zhou C, Yu W (2020) Kaolinite: A natural and stable catalyst for depolymerization of cellulose to reducing sugars in water. Appl Clay Sci 188:105512
Panda AK, Mishra BG, Mishra DK, Singh RK (2010) Effect of sulphuric acid treatment on the physico-chemical characteristics of kaolin clay. Colloid Surface A 363:98–104
Singh S, Bothara SB, Singh S, Patel R, Ughreja R (2011) Preliminary Pharmaceutical Characterization of Some Flowers as Natural Indicator: Acid-Base Titration. Pharmacognosy Journal 3:39–43
Zhu B, Qi C, Zhang Y, Bisson T, Xu Z, Fan Y, Sun Z (2019) Synthesis, characterization and acid-base properties of kaolinite and metal (Fe, Mn, Co) doped kaolinite. Appl Clay Sci 179:105138
Li C, Huang Y, Dong X, Sun Z, Duan X, Ren B, Zheng S, Dionysiou DD (2019) Highly efficient activation of peroxymonosulfate by natural negatively-charged kaolinite with abundant hydroxyl groups for the degradation of atrazine. Appl Catal B-Environ 247:10–23
Aung LL, Tertre E, Suksabye P, Worasith N, Thiravetyan P (2014) Effect of Alumina Content and Surface Area of Acid-Activated Kaolin on Bleaching of Rice Bran Oil. J Am Oil Chem Soc 92:295–304
Győrfi K, Vágvölgyi V, Zsirka B, Horváth E, Szilágyi RK, Baán K, Balogh S, Kristóf J (2020) Kaolins of high iron-content as photocatalysts: Challenges of acidic surface modifications and mechanistic insights. Appl Clay Sci 195:105722
Tao P, Zhang Y, Wu Z, Liao X, Nie S (2019) Enzymatic pretreatment for cellulose nanofibrils isolation from bagasse pulp: Transition of cellulose crystal structure. Carbohydr Polym 214:1–7
Abukhadra MR, Allah AF (2019) Synthesis and characterization of kaolinite nanotubes (KNTs) as a novel carrier for 5-fluorouracil of high encapsulation properties and controlled release. Inorg Chem Commun 103:30–36
Li X, Wang D, Liu Q, Komarneni S (2019) A comparative study of synthetic tubular kaolinite nanoscrolls and natural halloysite nanotubes. Appl Clay Sci 168:421–427
Qu H, He S, Su H (2019) Efficient preparation of kaolinite/methanol intercalation composite by using a Soxhlet extractor. Sci Rep 9:8351
Cao Y, Tan H (2004) Structural characterization of cellulose with enzymatic treatment. J Mol Struct 705:189–193
Oh SY, Yoo DI, Shin Y, Kim HC, Kim HY, Chung YS, Park WH, Youk JH (2005) Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy. Carbohyd Res 340:2376–2391
Temuujin J, Burmaa G, Amgalan J, Okada K, Jadambaa T, Mackenzie K (2001) Preparation of porous silica from mechanically activated kaolinite. J Porous Mat 8:233–238
Zhou Y, Yang M, Tong D, Yang H, Fang K (2019) Eco-Friendly Ca-Montmorillonite Grafted by Non-Acidic Ionic Liquid Used as A Solid Acid Catalyst in Cellulose Hydrolysis to Reducing Sugars. Molecules. https://doi.org/10.3390/molecules24010183
Lai D, Deng L, Li J, Liao B, Guo Q, Fu Y (2011) Hydrolysis of cellulose into glucose by magnetic solid acid. Chemsuschem 4:55–58
Tian J, Wang J, Zhao S, Jiang C, Zhang X, Wang X (2010) Hydrolysis of cellulose by the heteropoly acid H3PW12O40. Cellulose 17:587–594
Allahdin O, Wartel M, Tricot G, Revel B, Boughriet A (2016) Hydroxylation and dealumination of a metakaolinite-rich brick under acid conditions, and their influences on metal adsorption: One- and two-dimensional (1H, 27Al, 23Na, 29Si) MAS NMR, and FTIR studies. Micropor Mesopor Mat 226:360–368
Abou-El-Sherbini KS, Elzahany EAM, Wahba MA, Drweesh SA, Youssef NS (2017) Evaluation of some intercalation methods of dimethylsulphoxide onto HCl-treated and untreated Egyptian kaolinite. Appl Clay Sci 137:33–42
Hu L, Wu Z, Xu J, Sun Y, Lin L, Liu S (2014) Zeolite-promoted transformation of glucose into 5-hydroxymethylfurfural in ionic liquid. Chem Eng J 244:137–144
Shrotri A, Kobayashi H, Fukuoka A (2018) Cellulose depolymerization over heterogeneous catalysts. Acc Chem Res 51:761–768
Acknowledgements
The authors wish to acknowledge the National Natural Scientific Foundation of China (21506188), the Natural Scientific Foundation of Zhejiang Province ZJNSF (LY16B030010), China Postdoctoral Science Foundation (2018M630688), the project from Science and Technology Department of Wenzhou (ZG2020019, G20180017) and Project of Zhejiang ″151″ talents project.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declares that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Dong, Y., Tong, D., Ren, L. et al. Enhanced Hydrolysis of Cellulose to Reducing Sugars on Kaolinte Clay Activated by Mineral Acid. Catal Lett 151, 2797–2806 (2021). https://doi.org/10.1007/s10562-020-03497-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-020-03497-1