Sains Malaysiana 47(6)(2018): 1131–1138

http://dx.doi.org/10.17576/jsm-2018-4706-08

Esterification of Levulinic Acid to Levulinate Esters in the Presence of Sulfated Silica Catalyst

(Pengesteran Asid Levulinik kepada Ester Levulinat dengan Kehadiran Pemangkin Silika Sulfat)

NUR AAINAA SYAHIRAH RAMLI¹, NUR IRSALINA HISHAM² & NOR AISHAH SAIDINA AMIN^2*

¹Advanced Oleochemical Technology Division,, Malaysian Palm Oil Board, No 6, Persiaran Institusi, Bandar Baru Bangi, 43000 Kajang, Selangor Darul Ehsan, Malaysia

²Chemical Reaction Engineering Group (CREG), Faculty of Chemical and Energy Engineering

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

Received: 6 September 2017/Accepted: 11 December 2017

ABSTRACT

Levulinic acid (LA) is one of biomass derived building block chemicals with various applications. Catalytic esterification of LA with alkyl alcohol produces levulinate ester which can be applied as fragrance, flavouring agents, as well as fuel additives. In this study, a series of sulfated silica (SiO₂) catalyst was prepared by modification of SiO₂ with sulfuric acid (H₂SO₄) at different concentrations; 0.5 M to 5 M H₂SO₄. The catalysts were characterized, and tested for esterification of LA with ethanol to ethyl levulinate (EL). The effect of various reaction parameters including reaction time, catalyst loading and molar ratio of LA to ethanol on esterification of LA to EL were inspected. The catalyst with high concentration of acid sites seemed suitable for LA esterification to EL. Among the sulfated SiO₂ catalysts tested (0.5 M-SiO₂, 1 M-SiO₂, 3 M-SiO₂ and 5 M-SiO₂), 3 M-SiO₂ exhibited the highest performance with the optimum EL yield of 54% for reaction conducted at reflux temperature for 4 h, 30% 3 M-SiO₂ loading and LA to ethanol molar ratio of 1:20. Besides, the reusability of 3 M-SiO₂ catalyst for LA esterification with ethanol was examined for five cycles. Esterification of LA with methanol and 1-butanol were also carried out for methyl levulinate (ML) and butyl levulinate (BL) productions with 69% and 40% of ML and BL yields, respectively. This study demonstrates the potential of sulfated SiO₂ catalyst for levulinate ester production from LA at mild process condition.

Keywords: Esterification; levulinic acid; levulinate ester; sulfated silica

ABSTRAK

Asid levulinik (LA) ialah bahan kimia asas daripada biojisim dengan pelbagai aplikasi. Pengesteran bermangkin asid levulinik dengan alkil alkohol menghasilkan ester levulinat yang dapat digunakan sebagai bahan pewangi dan perasa, juga aditif bahan api. Dalam kajian ini, satu siri pemangkin silika (SiO₂) sulfat telah dihasilkan melalui pengubahsuaian SiO₂ bersama asid sulfurik (H₂SO₄) berkepekatan yang berbeza; 0.5 M hingga 5 M. Pemangkin tersebut telah dicirikan dan diuji bagi pengesteran LA dengan etanol kepada etil levulinat (EL). Kesan pelbagai parameter tindak balas termasuk masa tindak balas, suapan pemangkin dan nisbah molar antara LA dan etanol terhadap pengesteran LA kepada EL telah dikaji. Pemangkin dengan kepekatan yang tinggi bagi tapak asid tampak sesuai untuk pengesteran LA. Antara SiO₂ sulfat yang telah diuji (0.5 M-SiO₂, 1 M-SiO₂, 3 M-SiO₂, dan 5 M-SiO₂), 3 M-SiO₂ menunjukkan prestasi tertinggi dengan hasil optimum EL sebanyak 54% untuk tindak balas yang dijalankan pada suhu refluks selama 4 jam, menggunakan 30% 3 M-SiO₂ suapan dan nisbah molar 1:20 antara LA dan etanol. Selain itu, kebolehgunaan semula 3 M-SiO₂ telah dikaji untuk 5 kitaran. Pengesteran LA dengan metanol dan 1-butanol untuk penghasilan metil levulinat (ML) dan butil levulinat (BL) turut ditunjukkan dengan hasil masing-masing sebanyak 69% dan 40% bagi ML dan BL. Kajian ini menunjukkan potensi SiO₂ sulfat untuk penghasilan ester levulinat daripada LA pada keadaan proses yang sederhana.

Kata kunci: Asid levulinik; ester levulinat; pengesteran; silika sulfat

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*Corresponding author; email; noraishah@cheme.utm.my