• Vol 10, No 3 (2019)
  • Chemical Engineering

One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst

Yulia Nurul Ma’rifah, Iryanti Nata, Hesti Wijayanti, Agus Mirwan, Chairul Irawan, Meilana Dharma Putra, Kawakita Hidetaka

Corresponding email: ifnata@ulm.ac.id


Cite this article as:
Ma’rifah, Y.N., Nata, I., Wijayanti, H., Mirwan, A., Irawan, C., Putra, M.D., Hidetaka, K., 2019. One-step Synthesis to Enhance the Acidity of a Biocarbon-based Sulfonated Solid Acid Catalyst. International Journal of Technology. Volume 10(3), pp. 512-520
242
Downloads
Yulia Nurul Ma’rifah Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Iryanti Nata Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Hesti Wijayanti Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Agus Mirwan Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Chairul Irawan Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Meilana Dharma Putra Chemical Engineering Study Program, Lambung Mangkurat University, Banjarbaru 70714, Indonesia
Kawakita Hidetaka Department of Chemistry and Applied Chemistry, Saga University, Saga 840-8502, Japan
Email to Corresponding Author

Abstract
image

The main purpose of this study is to produce and generate a solid acid catalyst from biomass with high reactivity that can be used in catalytical reactions such as hydrolysis, and is environmentally friendly and reusable. A biocarbon-based sulfonated catalyst was prepared by the carbonization of palm empty fruit bunches (PEFB), followed by sulfonation. In order to enhance the acidity of the biocarbon, different concentrations of hydroxyethylsulfonic acid were added to the solution during sulfonation at 180o C for 4 h in a Teflon stainless steel autoclave. The H+ ion capacity of the biocarbon-sulfonated acid catalyst (BSC) was increased twofold (3.57 mmol/g) in the presence of 10% of hydroxyethylsulfonic acid and 10% of acrylic acid. X-Ray Fluorescence (XRF) analysis showed that the BC-SO3H contained 38% of S. The original structure of the PEFB after carbonization disintegrated from the fibrous materials onto porous carbon. The crystalline index (CrI) of the PEFB significantly decreased to about 32% and a wide broad peak of a X-Ray Diffraction (XRD) pattern of around 20-30o were observed, which shows that an amorphous biocarbon structure had been identified. Fourier Transform Infra-Red (FT-IR) analysis confirmed that the -SO3H, COOH and -OH functional groups were deposited on the carbon due to specific peaks at around 1180 cm-1, 1724 cm-1 and 3431 cm-1, respectively. Decomposition of the sulfonic groups on the biocarbon-sulfonated solid catalyst was observed from 227.9o C, as it shown by thermal gravimetric analysis (TGA). 

Acid catalyst; Biocarbon; Palm empty fruit bunch; Sulfonated; Sulfonation

Introduction

Palm is one of the most important commodities in Indonesia due to its rapid development. The major product from the palm industry is Crude Palm Oil (CPO), but with its increasing production, the waste, that takes the form of empty fruit bunches, has increased. Nowadays, biomass and industrial waste have become very interesting issues as aspects of catalyst development, both in research and from the technical point of view, due to their valuable merit of industrial waste (Guerrero-Pérez et al., 2006; Kusrini et al., 2018). Biomass energy is an ideal clean and renewable energy source, characterized by its wide range of sources, low prices, strong reproducibility and less pollution creation (Wenjing et al., 2018).

In the using of solid acid catalysts, they are easy and efficient when separated from their products, are reusable and it is possible to apply them in wide of applications, but most such catalysts developed are expensive and quite difficult to prepare (Okuhara, 2002)Recently, work on sulfonated solid acid catalysts has attracted great attention from researchers for the hydrolysis reaction of cornstarch (Nata et al., 2015; Nata et al., 2017b) and biodiesel production from waste cooking oil (Zong et al., 2007; Nata et al., 2017a). Performance in the reaction of carbon-derived catalysts is dependent on the precursor as raw materials for carbon production and treatment processes (Tao et al., 2015). From the point of view of “green chemistry”, the sulfonated carbon catalyst has emerged as a promising solid acid catalyst (Jiang et al., 2012).

Theoretically, at low carbonization (400–600oC), biomass generates a highly cross-linked, multi-ringed, aromatic structure anchored to lignin that can be easily functionalized with catalytically active acidic groups by slow pyrolysis (Kastner et al., 2012). Generally, a two-step process is involved in the production of sulfonated carbonaceous materials. Saccharide is incompletely carbonized at a temperature of > 400°C for >15 h under an inert atmosphere. A large amount of sulphuric acid use in the sulfonation process at a high temperature for the inactive surface of carbonaceous material (Zong et al., 2007). This process uses hazardous material and a large amount of harmful waste is produced; moreover, the carbon in the concentrate sulphuric also needs special attention for its separation and treatment.

Hydrothermal carbonization (HTC) is a thermochemical process capable of converting wet biomass into a carbon-enriched solid as hydrochar. The HTC process consists of several reactions conducted both in series and in parallel, including hydrolysis, dehydration, decarboxylation, condensation and aromatization (Merzari et al., 2018). HTC is process which involves the decomposition of several carbohydrates in aqueous solution at 180°C. This method is cheap, mild and environmental friendly, as no organic solvents, catalysts or surfactants are used (Titirici et al., 2007). In a previous study, Xiao et al. (2010) performed hydrothermal treatment with hydroxyethylsulfonic acid as a sulfonate agent to produce carbon from glucose and used it for an esterification process in order to examine its catalytic ability. However, this procedure only achieved 1.7 mmol/g of acidity and still owned little of functional groups. Therefore, to generate carbonaceous material loaded with carboxylic groups, known as an active group that participates in the reaction, acrylic acid was added (Bautista-Toledo et al., 2005). In order to produce a high content of functional groups on the carbon material, it is possible to modify the surface by a one-step HTC process for sulfonation and thus improve the acidity of the carbon.

This work focuses on the effect of hydroxyethylsulfonic acid concentration and the addition of acrylic acid during the hydrothermal process. Therefore, the characterization of aspects such as acidity, morphological structure, crystalline structure, functional groups and thermal gravimetric analysis was investigated.


Conclusion

The strong acid content, rich of sulfonic and carboxylic groups of materials could be easily synthesized by a one-step hydrothermal process using biocarbon from incomplete carbonization of PEFB, and in the presence of hydroxyethylsulfonic, acrylic and citric acid in mild conditions. The simplicity of operation, high activity and stability, low cost of raw materials and reusability are the main features of this original biocarbon-based sulfonated solid acid catalyst, which demonstrates that biocarbon has great potential for green processes in various catalytic applications.

Acknowledgement

The authors are grateful for the financial support from International Research Collaboration and Scientific Publication (contract No. 040/UN8.2/PL/2018), Ministry of Research, Technology and Higher Education, Republic of Indonesia.  

Supplementary Material
FilenameDescription
R1-CE-2924-20190328233519.docx ---
References

Aldana-Pérez, A., Lartundo-Rojas, L., Gómez, R., Niño-Gómez, M.E., 2012. Sulfonic Groups Anchored on Mesoporous Carbon Starbons-300 and Its Use for the Esterification of Oleic Acid. Fuel, Volume 100, pp. 128–138

Bautista-Toledo, I., Ferro-García, M.A., Rivera-Utrilla, J., Moreno-Castilla, C., Vegas Fernández, F.J., 2005. Bisphenol A Removal from Water by Activated Carbon. Effects of Carbon Characteristics and Solution Chemistry. Environmental Science & Technology, Volume 39(16), pp. 6246–6250

Demir-Cakan, R., Baccile, N., Antonietti, M., Titirici, M.-M., 2009. Carboxylate-rich Carbonaceous Materials via One-step Hydrothermal Carbonization of Glucose in the Presence of Acrylic Acid. Chemistry of Materials, Volume 21(3), pp. 484–490

Fraga, A.d.C., Quitete, C.P.B., Ximenes, V.L., Sousa-Aguiar, E.F., Fonseca, I.M., Rego, A.M.B., 2016. Biomass Derived Solid Acids as Effective Hydrolysis Catalysts. Journal of Molecular Catalysis A: Chemical, Volume 422, pp. 248–257

Fraile, J.M., García-Bordejé, E., Roldán, L., 2012. Deactivation of Sulfonated Hydrothermal Carbons in the Presence of Alcohols: Evidences for Sulfonic Esters Formation. Journal of Catalysis, Volume 289, pp. 73–79

Guerrero-Pérez, M.O., Fierro, J.L.G., Bañares, M.A., 2006. Effect of Synthesis Method on Stabilized Nano-scaled Sb–V–O Catalysts for the Ammoxidation of Propane to Acrylonitrile. Topics in Catalysis, Volume 41(1-4), pp. 43–53

Hu, B., Wang, K., Wu, L., Yu, S.-H., Antonietti, M., Titirici, M.-M., 2010. Engineering Carbon Materials from the Hydrothermal Carbonization Process of Biomass. Advanced Materials, Volume 22(7), pp. 813–828

Jiang, Y., Li, X., Wang, X., Meng, L., Wang, H., Peng, G., Wang, X., Mu, X., 2012. Effective Saccharification of Lignocellulosic Biomass Over Hydrolysis Residue Derived Solid Acid under Microwave Irradiation. Green Chemistry, Volume 14(8), pp. 2162–2167

Kastner, J.R., Miller, J., Geller, D.P., Locklin, J., Keith, L.H., Johnson, T., 2012. Catalytic Esterification of Fatty Acids using Solid Acid Catalysts Generated from Biochar and Activated Carbon. Catalysis Today, Volume 190(1), pp. 122–132

Kusrini, E., Supramono, D., Degirmenci, V., Pranata, S., Bawono, A.A., Ani, F.N., 2018. Improving the Quality of Pyrolysis Oil From Co-firing High Density Polyethylene Plastic Waste and Palm Empty Fruit Bunches. International Journal of Technology, Volume 9(7), pp. 1498–1508

Lokman, I.M., Goto, M., Rashid, U., Taufiq-Yap, Y.H., 2016. Sub- and Supercritical Esterification of Palm Fatty Acid Distillate with Carbohydrate-derived Solid Acid Catalyst. Chemical Engineering Journal, Volume 284, pp. 872–878

Merzari, F., Lucian, M., Volpe, M., Andreottola, G., Fiori, L., 2018. Hydrothermal Carbonization of Biomass: Design of a Bench-scale Reactor for Evaluating the Heat of Reaction. Chemical Engineering Transaction, Volume 65, pp. 43–48

Nata, I.F., Irawan, C., Mardina, P., Lee, C.-K., 2015. Carbon-based Strong Solid Acid for Cornstarch Hydrolysis. Journal of Solid State Chemistry, Volume 230, pp. 163–168

Nata, I.F., Putra, M.D., Irawan, C., Lee, C.-K., 2017. Catalytic Performance of Sulfonated Carbon-based Solid Acid Catalyst on Esterification of Waste Cooking Oil for Biodiesel Production. Journal of Environmental Chemical Engineering, Volume 5(3), pp. 2171–2175

Nata, I.F., Putra, M.D., Nurandini, D., Irawan, C., 2017. Facile Strategy for Surface Functionalization of Corn Cob to Biocarbon and Its Catalytic Performance on Banana Peel Starch Hydrolysis. International Journal on Advanced Science Engineering Information Technology, Volume 7(4), pp. 1302–1308

Okamura, M., Takagaki, A., Toda, M., Kondo, J.N., Domen, K., Tatsumi, T., Hara, M., Hayashi, S., 2006. Acid-catalyzed Reactions on Flexible Polycyclic Aromatic Carbon in Amorphous Carbon. Chemistry of Materials, Volume 18(13), pp. 3039–3045

Okuhara, T. 2002. Water-tolerant Solid Acid Catalysts. Chemical Reviews, Volume 102(10), pp. 3641–3666

Onda, A., Ochi, T., Yanagisawa, K., 2008. Selective Hydrolysis of Cellulose into Glucose Over Solid Acid Catalysts. Green Chemistry, Volume 10(10), pp. 1033–1037

Tao, M.-L., Guan, H.-Y., Wang, X.-H., Liu, Y.-C., Louh, R.-F., 2015. Fabrication of Sulfonated Carbon Catalyst from Biomass Waste and Its Use for Glycerol Esterification. Fuel Processing Technology, Volume 138, pp. 355–360

Titirici, M.-M., Thomas, A., Antonietti, M., 2007. Replication and Coating of Silica Templates by Hydrothermal Carbonization. Adv Funct Mater, Volume 17(6), pp. 1010–1018

Wenjing Han, Xuezhen Li, Shulan Yu, Xiujie Sang, 2018, Catalytic Action of Biomass Carbon Sulfoacid in Fine Organic Synthesis, Chemical Engineering Transaction, Volume 65, pp.547-552

Xiao, H., Guo, Y., Liang, X., Qi, C., 2010. One-step Synthesis of Novel Biacidic Carbon via Hydrothermal Carbonization. Journal of Solid State Chemistry, Volume 183(7), pp. 1721–1725

Zong, M.-H., Duan, Z.-Q., Lou, W.-Y., Smith, T.J., Wu, H., 2007. Preparation of a Sugar Catalyst and Its Use for Highly Efficient Production of Biodiesel. Green Chemistry, Volume 9(5), pp. 434–437