Malaysian Journal of Analytical Sciences, Vol 28 No 3 (2024): 555 - 568

 

GLYCEROL ACETYLATION INTO ACETINS OVER SnO2-BASED BIMETALLIC OXIDE CATALYST

 

(Pengasetilan Gliserol kepada Asetin Menggunakan Mangkin Dwilogam Oksida

Berasaskan SnO2)

 

Ain Arisya Azami1, Irmawati Ramli1,2,3*, Shera Farisya Mohamad Rasid1,2, Muhammad Shamirul Khairul Lail1, Mohd Rafein Zakaria3, and Sarwat Iqbal4

 

1Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

2Catalysis Science and Technology Research Centre (PutraCat), Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia                                                                                                                                     

 3Laboratory of Processing and Product Development, Institute of Plantation Studies, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia                                                                                                                                        

 4Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, United Kingdom

 

*Corresponding author: irmawati@upm.edu.my

 

 

Received: 12 October 2023; Accepted: 13 March 2024; Published:  29 June 2024

 

 

Abstract

Tin oxide-based bimetallic oxide catalysts, MOx (MOx = Al2O3, TiO2, Y2O3) with a molar ratio of MOx:SnO2 of 1:1 was prepared by the solid-state method. X-ray diffraction (XRD) analysis showed that tin oxide, SnO2, was present in all samples as a cassiterite phase with a tetragonal structure. The presence of other oxides, aluminum oxide (Al2O3), titanium oxide (TiO2), yttrium oxide (Y2O3) in the respective Al2O3/SnO2, TiO2/SnO2, Y2O3/SnO2 were also identified and confirmed by X-ray fluorescence (XRF) analysis. A small exothermic peak at 480 °C and 750 °C in the differential thermal gravimetric (DTG) analysis revealed the oxidation of sub-oxide defects, took place which are very common in SnO2-based samples. Further Fourier transform infrared spectroscopy (FTIR) analysis indicated the presence of Sn-O bonds, reflecting the abundance of tin-oxygen bonds in the materials. Acidity measurements by titration showed that both TiO2/ SnO2 and Y2O3/SnO2 have the same acidity value of 0.23 mmol/g whereas Al2O3/SnO2 and monoxide SnO2 at 0.20 mmol/g. These catalysts were tested for the acetylation of glycerol to monoacetin (MA), diacetin (DA) and triacetin (TA) in a batch reactor at a molar ratio of glycerol: acetic acid of 1:6 w/v, a temperature of 100 °C, a reaction time of 2 h and a catalyst loading of 0.5 g. The tests showed complete conversion of glycerol by all catalysts, with the selective product being mainly MA, which was 64%, 62%, 57% and 43% for Al2O3/SnO2, Y2O3/SnO2, SnO2 and TiO2/SnO2, respectively. The percentage selectivity of the more valuable products, DA + TA, was produced in the following order, TiO2/SnO2 > SnO2 > Y2O3/SnO2 > Al2O3/SnO2 with 57%, 43%, 37%, and 35%, respectively. Further analysis of TiO2/SnO2 revealed that the catalyst not only had a high acidity, but also an increased BET surface area of 9.8 m2/g compared to 8.6 m2/g for SnO2 when TiO2 was incorporated into SnO2. Analysis of the surface elements by energy dispersive X-ray spectroscopy (EDX) revealed a high surface oxygen content, which is consistent with the high acidity of the sample.

 

Keywords: glycerol acetylation, tin oxide, SnO2-based bimetallic oxide, monoacetin, diacetin

Abstrak

Mangkin dwilogam oksida berasaskan timah oksida, MOx (MOx = Al2O3, TiO2, Y2O3) dengan nisbah molar MOx:SnO2 pada 1:1 telah disediakan melalui kaedah keadaan pepejal. Analisis pembelauan sinar-X (XRD) menunjukkan timah oksida, SnO2, hadir di dalam semua sampel sebagai fasa kasiterit dengan struktur tetragonal. Kehadiran oksida lain iaitu aluminum oksida (Al2O3), titanium oksida (TiO2), itrium oksida (Y2O3) dalam Al2O3/SnO2, TiO2/SnO2, Y2O3/SnO2 masing-masing juga dikenal pasti dan disahkan oleh analisis pendarflor sinar-X (XRF). Puncak eksotermik kecil pada 480 °C dan 750 °C dalam analisis pembezaan gravimetrik terma (DTG) mendedahkan pengoksidaan kecacatan sub-oksida telah berlaku, iaitu kejadian yang biasa terjadi bagi sampel berasaskan SnO2. Selanjutnya, analisis spektroskopi inframerah transformasi Fourier (FTIR) menunjukkan kehadiran ikatan Sn-O yang menterjemahkan limpahan ikatan timah-oksigen dalam bahan. Pengukuran keasidan secara penitratan menunjukkan kedua-dua TiO2/SnO2 dan Y2O3/SnO2 mempunyai nilai keasidan yang sama iaitu 0.23 mmol/g, manakala Al2O3/SnO2 dan monoksida SnO2 pada 0.20 mmol/g. Semua mangkin telah diuji untuk pengasetilan gliserol kepada monoasetin (MA), diasetin (DA) dan triasetin (TA) dalam reaktor kelompok pada nisbah molar gliserol:asid asetik 1:6 b/i, suhu 100 °C, masa tindak balas 2 j dan muatan mangkin 0.5 g. Hasil ujian menunjukkan penukaran lengkap gliserol oleh semua mangkin, dengan pemilihan produk rata-ratanya MA iaitu 64%, 62%, 57% dan 43% bagi masing-masing Al2O3/SnO2, Y2O3/SnO2, SnO2 dan TiO2/SnO2. Manakala penghasilan produk yang lebih bernilai iaitu DA + TA, adalah mengikut urutan  TiO2/SnO2 > SnO2 > Y2O3/SnO2 > Al2O3/SnO2 dengan masing-masing 57%, 43%, 37%, dan 35%. Analisis lanjutan terhadap TiO2/SnO2 mendedahkan bahawa mangkin ini bukan hanya mempunyai keasidan yang tinggi tetapi juga mempunyai peningkatan luas permukaan sebanyak 9.8 m2/g berbanding 8.6 m2/g bagi SnO2, apabila TiO2 digabungkan pada SnO2. Analisis unsur permukaan oleh spektroskopi penyebaran tenaga sinar-X (EDX) menunjukkan kandungan oksigen permukaan yang tinggi, selaras dengan keasidan tinggi sampel berkenaan.

 

Kata kunci: pengasetilan gliserol, timah oksida, dwilogam oksida berasaskan SnO2, monoasetin, diasetin

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