Malaysian Journal of Analytical Sciences, Vol 28 No 4 (2024): 724 - 736

 

CATALYTIC REACTION STUDY OF LEVULINIC ACID ESTERIFICATION TO ETHYL LEVULINATE USING MODIFIED CARBON CATALYST AND ACIDIC DES

 

(Kajian Tindak Balas Mangkinan Pengesteran Asid Levulinik kepada Etil Levulinat Menggunakan Mangkin Karbon Terubah Suai dan DES Berasid)

 

Nurin Qistina Saperi1, Abdull Hafidz Hassan1, Muzakkir Mohammad Zainol1,*, Mohd Asmadi2, Ahmad Rafizan Mohamad Daud1, Mohd Yazid Yusof1, and Didi Dwi Anggoro3

 

1School of Chemical Engineering, College of Engineering,

Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

2Faculty of Chemical and Energy Engineering,

Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia

3Department of Chemical Engineering,

Diponogoro University, Semarang 50273, Indonesia St. Prof. Seodarto, SH, Tembaleng, Semarang, Indonesia

 

*Corresponding author: muzakkir@uitm.edu.my

 

Received: 2 August 2023; Accepted: 5 May 2024; Published:  27 August 2024

 

Abstract

Ethyl levulinate can be synthesized by the esterification reaction of levulinic acid with ethanol in the presence of a solid acid catalyst. In this research, the catalyst was prepared from lignin as a carbon precursor at 400 °C for 2 h and modified via sulfonation in a hydrothermal reactor to produce a modified lignin-based carbon catalyst. Acidic DES, which acted as a co-catalyst, was prepared from a choline chloride-sulfanilic acid mixture. The catalyst and acidic DES were characterized to study their chemical and physical characteristics. The catalytic activity was evaluated in the levulinic acid esterification by the effect of parameters such as ethanol to levulinic acid molar ratio (3–15), catalyst loading (5–25 wt%), and reaction time (1–5 h). The reaction performance was further investigated over the catalyst and acidic DES at optimum reaction conditions. The results demonstrated that the catalyst has good thermal stability up to 400 °C with a large surface area of 368.92 m2/g to facilitate the reaction. The optimum conditions of levulinic acid esterification obtained over a modified lignin-based carbon catalyst were a 6 molar ratio of ethanol to levulinic acid, 10 wt% catalyst loading, and 3 h at 80 °C, to give 62.51 mol% of ethyl levulinate yield. The reaction performance was further improved when acidic DES was introduced with 81.65 mol% of ethyl levulinate yield. The catalyst and acidic DES have shown their potential for levulinic acid esterification and further catalyst modifications must consider obtaining better product yield.    

 

Keywords: carbon catalyst, acidic DES, ethyl levulinate, levulinic acid, lignin

 

Abstrak

Etil levulinat boleh dihasilkan melalui tindak balas pengesteran asid levulinik dengan etanol dengan kehadiran pemangkin pepejal asid. Dalam penyelidikan ini, pemangkin disediakan daripada lignin sebagai pelopor karbon pada 400 °C selama 2 jam dan diubah suai melalui proses sulfonasi dalam reaktor hidroterma untuk menghasilkan mangkin karbon berasaskan lignin terubah suai. DES berasid yang bertindak sebagai pemangkin bersama disediakan daripada campuran asid kolina klorida-sulfanilik. Pemangkin dan DES berasid dianalisa untuk mengkaji ciri kimia dan fizikal. Aktiviti mangkinan oleh pemangkin dinilai dalam tindak balas pengesteran asid levulinic melalui kesan parameter seperti nisbah molar etanol kepada asid levulinik (3–5), pemuatan mangkin (5–25 wt%), dan masa tindak balas (1–5 jam). Prestasi tindak balas telah disiasat lebih lanjut terhadap pemangkin dan DES berasid pada keadaan tindak balas optimum. Dapatan kajian menunjukkan bahawa pemangkin mempunyai kestabilan terma yang baik sehingga 400 °C dengan luas permukaan 368.92 m2/g bagi memangkin tindak balas. Kondisi optimum pengesteran asid levulinik yang diperolehi daripada mangkin karbon berasaskan lignin terubah suai adalah 6 nisbah molar etanol kepada asid levulinik, 10 wt% pemuatan mangkin, dan 3 jam masa tindak balas pada 80 °C, untuk menghasilkan 62.51 mol% hasil etil levulinat. Tindak balas mangkinan telah ditambah baik menggunakan DES berasid yang bertindak sebagai pemangkin bersama dengan 81.65 mol% hasil etil levulinat. Pemangkin dan DES berasid telah terbukti berkesan dan berpotensi untuk pengesteran asid levulinik dan pengubahsuaian mangkin selanjutnya harus diambil kira untuk mendapatkan hasil produk yang baik.    

 

Kata kunci: mangkin karbon, DES berasid, etil levulinate, asid levulinik, lignin

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