• International Journal of Technology (IJTech)
  • Vol 13, No 4 (2022)

Comparison of Xylene and Ethyl Acetate as Solvent in the Isolation of Levulinic Acid from Conversion Reaction of Cellulose Rice Husk using Hierarchical Mn3O4/ZSM-5 Catalyst

Comparison of Xylene and Ethyl Acetate as Solvent in the Isolation of Levulinic Acid from Conversion Reaction of Cellulose Rice Husk using Hierarchical Mn3O4/ZSM-5 Catalyst

Title: Comparison of Xylene and Ethyl Acetate as Solvent in the Isolation of Levulinic Acid from Conversion Reaction of Cellulose Rice Husk using Hierarchical Mn3O4/ZSM-5 Catalyst
Fiona Angellinnov, Yuni K. Krisnandi, Dyah U C Rahayu, Donanta Dhaneswara

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Cite this article as:
Angellinnov, F., Krisnandi, Y.K., Rahayu, D.U.C., Dhaneswara, D., 2022. Comparison of Xylene and Ethyl Acetate as Solvent in the Isolation of Levulinic Acid from Conversion Reaction of Cellulose Rice Husk using Hierarchical Mn3O4/ZSM-5 Catalyst . International Journal of Technology. Volume 13(4), pp. 880-889

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Fiona Angellinnov Department of Metallurgical and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia
Yuni K. Krisnandi 1. Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok, 16424, Indonesia 2. Solid Inorganic Framework Laboratory, Department of Chemistry, Faculty of Ma
Dyah U C Rahayu Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok, 16424, Indonesia
Donanta Dhaneswara Department of Metallurgical and Materials Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia
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Abstract
Comparison of Xylene and Ethyl Acetate as Solvent in the Isolation of Levulinic Acid from Conversion Reaction of Cellulose Rice Husk using Hierarchical Mn3O4/ZSM-5 Catalyst

Levulinic acid is a platform chemical. This compound can be derived from conversion cellulose in lignocellulosic biomass such as rice husk. Cellulose conversion to levulinic acid can be enhanced with the help of a catalyst. Hierarchical Mn3O4/ZSM-5 was used as a catalyst in this study, which was made by wet impregnation of ZSM-5 with Mn (II). Before the conversion reaction, rice husk was pretreated with various chemical and mechanical methods to increase the amount of cellulose. The chemical method used NaOH, while mechanical methods used variations of ball milling and ultrasonication in phosphoric acid. The pretreated rice husk was then converted to levulinic acid at 130°C for 10 h in H3PO4 40% and H2O2 30% using hierarchical Mn3O4/ZSM-5 as a catalyst. The highest levulinic acid yield of 11.70% was obtained from the delignification of rice husk. The product was then extracted to obtain pure levulinic acid via solvent extraction using xylene and ethyl acetate as the organic solvents. The GC-MS examination showed that ethyl acetate is the best solvent and esterification agent in separating the levulinic acid.

Catalyst; Cellulose; Hierarchical ZSM-5; Levulinic acid; Rice husk

Introduction

Levulinic acid is commonly used as a base material in many industries such as the food, pharmaceuticals, agriculture, cosmetics, and petroleum (Kumar et al., 2019). This compound can also be converted into biofuels, including 2methyltetrahydrofuran, ????-valerolactone, levulinate esters, and 1,4-pentanediol (Yan et al., 2015). However, precursor material used to synthesize levulinic acid is no longer available due to its high cost. As a result, lignocellulosic biomass is widely used as a low-cost alternative precursor (Rackemann & Doherty, 2011).

Rice husk is a type of lignocellulosic biomass that is abundant in Indonesia. In the conversion, the cellulose is hydrolyzed to obtain glucose, which is then can be converted to hydroxymethylfurfural (5-HMF) as an intermediate product, and finally to levulinic acid (Climent et al., 2014; Li et al., 2019). However, cellulose in rice husk is bound to lignin and hemicellulose. To obtain pure cellulose, pretreatment is required. The pretreatment can be performed using chemicals via acid and/or basic solution (Harahap et al., 2019; Hermansyah et al., 2019), mechanical, or combination methods (Qu et al., 2017).

 A catalyst can be used to enhance the production of levulinic acid. In the conversion of the delignification of rice husk to levulinic acid, hierarchical MnOx/ZSM-5 catalysts, microporous MnOx/ZSM-5 catalysts, and Mn (II) homogeneous catalysts were used (Krisnandi et al., 2019). Their results showed that hierarchical MnOx/ZSM-5 gave the highest levulinic acid (15.83%) for a reaction time of 8 hours. Temperature comparison between 100°C and 130°C in the same medium has also been carried out by Pratama et al. (2020). The catalysts were also compared in their work between hierarchical Mn3O4/ZSM-5 catalysts, Mn3O4, and homogeneous Mn (II). Hierarchical Mn3O4/ZSM-5 gave the highest levulinic acid (39.75%) for a reaction time of 8 hours. 
After the conversion reaction, the obtained product usually still contains 5-HMF. Solvents such as 1-butanol, 1-hexanol, 1-pentanol, 1-octanol, dodecane, hexanoic acid, methyl isobutyl ketone, and toluene have been used and compared in separating levulinic acid from the mixture of the conversion reaction (Brouwer et al., 2017). According to their results, toluene can remove 5-HMF from levulinic acid. As a result, the purpose of this research was to study the separation of levulinic acid with 5-HMF using xylene and ethyl acetate. To the best of the author's knowledge, no literature explicitly discusses the separation of levulinic acid and 5-HMF using these solvents. Xylene has a similar structure and dielectric constant to toluene (2.27 and 2.38, respectively) (Reichardt, 2003). Therefore, it is expected that xylene can also separate 5-HMF from levulinic acid. Ethyl acetate can act as both solvent and esterification agent that reacts with levulinic acid and dissolves it from 5-HMF. 

Conclusion

    The isolation of levulinic acid from the conversion reaction of cellulose rice husk using xylene and ethyl acetate as solvents and hierarchical Mn3O4/ZSM-5 as a catalyst has been successfully carried out. The results of the conversion reaction showed the highest yield of levulinic acid at the reaction time of 10 hours, with the yield from the highest to the lowest in delignified rice husk (11.70%), dewax process only (5.17%), ball milling followed by ultrasonication (4.43%), ball milling only (3.88%), and ultrasonication only (3.76%), respectively. Based on the chromatogram from the GC-MS examination, 5-HMF was not detected in the organic phase from the extraction with xylene. Meanwhile, ethyl levulinate was seen in the chromatogram of the organic phase from the extraction with ethyl acetate. In this case, ethyl acetate is a better solvent than xylene for separating levulinic acid from 5-HMF. Ethyl acetate does not only act as a solvent but also as an esterification agent that reacts with levulinic acid resulting in ethyl levulinate.

Acknowledgement

    This work is funded by a PITTA B grant from the Directorate of Research and Community Engagement (DRPM) Universitas Indonesia No. NKB-0636/UN2.R3.1/HKP.05.00/2019.

Supplementary Material
FilenameDescription
R2-MME-5524-20220421203908.pdf ---
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