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Synthesis, characterization and catalytic activity of cao-based catalysts in transesterification of non-edible and waste cooking oils into glycerol-free fatty acid methyl ester / Yanna Syamsuddin

Synthesis, characterization and catalytic activity of cao-based catalysts in transesterification of non-edible and waste cooking oils into glycerol-free fatty acid methyl ester_Yanna Syamsuddin _E3_2017_MYMY
Biodiesel juga dikenali sebagai asid lemak metil ester (ALME), telah menjadi lebih menarik sebagai bahan api alternatif disebabkan oleh keboleh perbaharui dan pengeluaran bahan cemar yang rendah. Sintesis biodiesel telah dijalankan melalui transesterifikasi menggunakan dimetil karbonat (DC) untuk pengganti metanol menggunakan pemangkin heterogen untuk mengatasi produk hasil sampingan gliserol yang berlebihan dan untuk mengelakkan penggunaan air sisa yang besar untuk proses penulenan. Penyelidikan ini bertujuan untuk membangunkan mangkin heterogen yang aktif, stabil dan boleh diguna semula untuk transesterifikasi minyak sayur tidak boleh dimakan dan sisa minyak masak (SMM) dengan DC untuk menghasilkan ALME bebas gliserol. Mangkin-mangkin campuran oksida berasas CaO (Ca‒Zn, Ca‒La dan Ca‒La‒Al) telah dibangunkan melalui kaedah permendakan diikuti oleh pengkalsinan antara suhu 300 °C hingga 900 °C dan masa 1 jam hingga 5 jam. Analisis termal gravimetri, isoterma penjerapan-nyah jerapan N2, penyerakan X-ray, Infra merah pengubahan Fourier, mikroskopi elektron imbasan-X-ray taburan tenaga dan analisis penyahjerapan program suhu telah dijalankan untuk mencirikan mangkin. Prestasi mangkin telah dinilai berdasarkan tindak balas transesterifikasi menggunakan proses kelompok pada keadaan operasi yang berbeza, termasuk suhu (110-190 °C), masa tindak balas (30-360 min), nisbah DC kepada minyak (2:1-18:1) dan jumlah mangkin (1-13 % berat, bergantung kepada berat minyak). Keputusan menunjukkan bahawa mangkin campuran oksida Ca‒Zn mempunyai aktiviti mangkin yang baik untuk transesterifikasi minyak sayur dengan kandungan asam bebas berlemak (ABB) rendah dan sederhana. Mangkin boleh diguna semula hanya untuk dua kitaran tindak balas untuk transesterifikasi minyak jatropha. Mangkin campuran oksida Ca‒La menunjukkan prestasi yang lebih baik untuk empat jenis minyak yang berbeza kecuali sisa minyak masak dan ianya boleh digunakan sehingga lima kitaran. Mangkin campuran oksida Ca‒La‒Al menunjukkan prestasi yang baik untuk semua lima minyak dengan kandungan ALME tertinggi ≥ 96.5% pada pelbagai keadaan operasi, seperti suhu daripada 150-170 °C, masa tindak balas 180 min untuk minyak yang tidak boleh dimakan dan 300 min untuk SMM, nisbah molar DC kepada minyak 9: 1 untuk minyak karanj mentah (MKM) dan minyak kernel sawit mentah (MKSM) dan 15: 1 untuk minyak jatropha mentah (MJM), minyak sawit mentah (MSM) dan SMM, jumlah pemangkin 5-7 % berat bagi MJM, MKM dan MKSM dan 10% berat bagi MSM dan SMM, dan boleh diguna semula untuk 4-5 kitaran. Kajian kinetik menunjukkan proses transesterifikasi menggunakan semua jenis minyak dengan DC boleh dihuraikan melalui kadar tertib pertama peudo dengan kadar purata pemalar tindak balas kimia (k) masing-masing adalah 0.0067/min, 0.013/min, 0.011/min, 0.0067/min dan 0.0087/min, untuk MJM, MKM, MKSM, MSM dan SMM. Tenaga pengaktifan bagi semua minyak adalah dalam lingkungan 29,2-82,2 kJ/mol. Dapat disimpulkan bahawa mangkin campuran oksida Ca‒La‒Al merupakan pemangkin pepejal yang berpotensi untuk digunakan dalam laluan baru tindak balas transesterifikasi pelbagai ABB minyak sayur tidak boleh makan untuk menghasilkan ALME bebas gliserol. __________________________________________________________________________________ Biodiesel, known as fatty acid methyl ester (FAME), has become more interesting as an alternative fuel due to its renewability and low emissions. The synthesis of biodiesel was conducted via transesterification using dimethyl carbonate (DMC) over heterogeneous catalyst to overcome over production of glycerol and to avoid the use of huge wastewater for purification process. The aim of this study is to develop an active, stable and reusable heterogeneous catalyst for transesterification of non-edible vegetable oils and waste cooking oil with DMC to produce glycerol-free FAME. The CaO-based mixed-oxide catalysts (Ca‒Zn, Ca‒La and Ca‒La‒Al) were synthesized by co-precipitation method followed by calcination at various temperature of 300 oC to 900 oC and time of 1 to 5 h. The physicochemical properties of catalysts were characterized by the Thermal Gravimetric Analyze (TGA), N2 adsorption-desorption isotherm, X-ray Diffraction (XRD), Fourier Transformed Infra Red (FTIR), Scanning Electron Microscopy-Energy Dispersive X-ray (SEM-EDX) and Temperature Program Desorption (TPD) analysis. Catalysts performances were evaluated on transesterification reaction using a batch process at various operating condition, that include temperature (110-190 oC), reaction time (30-360 min), DMC-to-oil molar ratio (2:1-18:1) and amount of catalyst loading (1-13 wt.%, based on oil weight). Results revealed that Ca‒Zn catalyst has good catalytic activity for transesterification of low and moderate FFA content vegetable oils. The catalyst can be reused only for two cycles of reaction for transesterification of jatropha oil. The Ca‒La catalyst showed better performance; it can catalyzed four different types of oil except waste cooking oil and can be reused up to five reaction cycles. The Ca‒La‒Al catalyst confessed good performance for all five oils with the highest FAME content ≥ 96.5% at various best operating conditions, such as temperature of 150-170 oC, reaction time of 180 min for non-edible oils and 300 min for Waste Cooking Oil (WCO), DMC-to-oil molar ratio of 9:1 for Crude Karanj Oil (CKO) and Crude Palm Kernel Oil (CPKO) and 15:1 for Crude Jatropha Oil (CJO), Crude Palm Oil (CPO) and WCO, amount of catalyst loading of 5-7 wt.% for CJO, CKO and CPKO and 10 wt% for CPO and WCO, and reusable for 4-5 reaction cycles. The kinetic study revealed that the transesterification of all oils with DMC were fit to pseudo-first order reaction with the average rate constant (k) of 0.0067/min, 0.013/min, 0.011/min, 0.0067/min and 0.0087/min for CJO, CKO, CPKO, CPO and WCO, respectively. The activation energy was in the range of 29.2-82.2 kJ/mol. It can be concluded that the Ca‒La‒Al catalyst was a potential solid catalyst for a new route of transesterification reaction of various Free Fatty Acid (FFA) content vegetable oils to produce glycerol-free FAME.
Contributor(s):
Yanna Syamsuddin - Author
Primary Item Type:
Thesis
Identifiers:
Accession Number : 875008420
Language:
English
Subject Keywords:
glycerol; calcination; transesterification
First presented to the public:
5/1/2017
Original Publication Date:
12/4/2019
Previously Published By:
Universiti Sains Malaysia
Place Of Publication:
School of Electrical & Electronic Engineering
Citation:
Extents:
Number of Pages - 262
License Grantor / Date Granted:
  / ( View License )
Date Deposited
2019-12-04 16:33:52.358
Date Last Updated
2020-11-13 11:40:44.693
Submitter:
Mohamed Yunus Yusof

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Synthesis, characterization and catalytic activity of cao-based catalysts in transesterification of non-edible and waste cooking oils into glycerol-free fatty acid methyl ester / Yanna Syamsuddin1 2019-12-04 16:33:52.358