Synthesis of Bio-hexane and Bio-Hexene from Sorbitol Using Formic Acid as Reducing Agent

Sorbitol (C6H14O6) is a sugar alcohol that can be synthesized from cellulose and has a similar skeletal structure as hexane (C6H14) so that it can straightforwardly be converted to hexane through deoxygenation. The bio-hydrocarbon synthesis from sorbitol in this investigation consisted of two main processes, namely synthesis of 2-iodohexane and deiodization of 2-iodohexane. The synthesis of 2-iodohexane from sorbitol and hydroiodic acid (HI) was conducted in a reflux system, to which formic acid as reducing agent was added gradually during the reaction to regenerate the iodine back to HI. The HI/sorbitol ratio (2:1 and 5:1), reaction temperature (90 °C, 105 °C, and 120 °C), and reaction time (between 2 and 6 hours) were varied throughout the experiment. Deiodization of 2-iodohexane was conducted via gas phase pyrolysis at various temperatures (265 °C to 285 °C) and reaction times (30 and 45 minutes). The sorbitol was effectively converted to a mixture of 2-iodohexane, hexane and other bio-hydrocarbons, with a 2-iodohexane yield of 23.15%. In the optimal reaction condition, pyrolysis of 2-iodohexane resulted in bio-hydrocarbon with a yield of 77.52%. The resulted hydrocarbon products were mixtures consisting of alkanes and alkenes

Low Temperature Catalytic-Transfer Hydrogenation of Candlenut Oil

Fatty acids containing more than one double bond (polyunsaturated fatty acids) indicated by high iodine value (more than 120 g I2/100 g oil) are prone either to oxidative degradation or thermal degradation leading to the appearance of undesirable compounds or to thermal oligo-/polymerization causing gum formation. Therefore, polyunsaturated bonds in the fatty acid chains should be hydrogenated into monounsaturated ones. The conventional method using hydrogen (direct hydrogenation) at relatively high temperature and pressure with the aid of nickel as catalyst, which prone to explosion due to the presence of free gaseous hydrogen at high temperature and pressure. Catalytic transfer-hydrogenation (CTH) therefore is proposed as a promising alternative method, enabling CTH at room condition without the presence of free hydrogen. This research is focused to explore effects of temperature and reaction time to iodine value reduction on CTH of candlenut oil, including kinetics of its methyl ester. The hydrogenation utilizes Ag-Ni/silica 150 Å as catalyst and potassium formate (6M) as hydrogen donor. Three reaction temperatures were selected (40oC, 60oC and 78oC), where each reactions were performed for 4, 8, 12 and 16 hours. Hydrogenation was performed in batch reactor using isopropyl alcohol as solvent. Results showed that iodine values decreased with the increase of temperature and longer reaction time. The iodine value was still decreasing at 16 hours reaction time, indicating the possibility of longer reaction time. However, at 16 hours time, the iodine value yield has been within biodiesel standard range (Indonesian National Standard). The hydrogenation was first order reaction towards methyl ester double bonds concentration. Ko and E for candlenut methyl ester were 163.15/hour and 25.26 kJ/mol

Catalytic and Thermal Decarboxylation of Mg-Zn Basic Soap to Produce Drop-in Fuel in Diesel Boiling Ranges

Fatty acid deoxygenation is a method for producing renewable hydrocarbon fuels such as green diesel, jet biofuel and biogasoline. In the present commercial method, deoxygenation is directly applied to vegetable oils through liquid phase hydrotreatment. This method is expensive because it consumes a large amount of hydrogen and requires severe operating conditions. The objective of this study was the production of a diesel-like hydrocarbon fuel that can be considered as drop-in replacement for petroleum-based diesel fuels, by catalytic thermal decarboxylation of Mg-Zn basic soap. In particular, this study investigated the decarboxylation of Mg-Zn basic soap at low temperature and pressure, without external supply of hydrogen. The Mg-Zn basic soap (9/1 mole ratio of Mg/Zn) was derived from palm stearin and decarboxylated at 350 °C and atmospheric pressure for 5 hours. The basic soap effectively decarboxylated, yielding a diesel-like hydrocarbon fuel with a liquid product yield of 62%-weight. The resulting hydrocarbon product is a complex mixture consisting of normal paraffins in the range of carbon chain length C8–C19, iso-paraffins and various olefin products

Production of Biogasoline via Pyrolysis of Oleic Acid Basic Soaps

In this study, an investigation on the effect of the Ca/Mg/Zn mixing ratio on gasoline-range hydrocarbon production by oleic basic soap pyrolysis was carried out. The ratios of calcium to magnesium used were 15%, 35%, 50%, 65%, and 85% with constant Zn. Oleic basic soap was obtained by saponification with the modified fusion method. Pyrolysis experiments were carried out at 450 °C using a semi-continuous reactor with a feed flow rate of 5 g/15 min. The process produced three fractions, i.e., gas, solid, and liquid (bio-hydrocarbon + water). The gas products were characterized by GC-TCD, and the results showed the presence of carbon dioxide, hydrogen, nitrogen, oxygen, and methane. Based on the GC-FID and FT-IR results, the bio-hydrocarbon comprised mainly homologous hydrocarbon from carbon number C7 to C19 containing n-alkanes, alkenes, various iso-alkanes, and some oxygenated compounds. All calcium ratios in the oleic basic soap produced hydrocarbon in the range of gasoline (C7-C11) as the dominant product. The maximum yield of gasoline (74.86%) was achieved at 15% calcium

Studi Hidrogenasi Minyak Biji Kapok dengan Katalis Pd/C untuk Bahan Baku Biodiesel

Bahan bakar yang saat ini sangat banyak digunakan sebagai sumber energi adalahbahan bakar minyak (BBM). BBM merupakan sumber daya tak terbaharui karena prosespembentukannya yang memakan waktu yang sangat lama. Untuk mengantisipasi terjadinyakrisis bahan bakar, perlu dikembangkan bahan bakar berbasis sumber daya yang dapatdiperbaharui, salah satunya adalah biodiesel. Bahan baku biodiesel yang potensial untukdikembangkan di Indonesia adalah minyak biji kapok (Ceiba pentandra). Namun biodieselyang berasal dari biji kapok ternyata bereaksi positif pada Uji Halphen, karena masihmengandung gugus siklopropenoid. Gugus siklopropenoid bersifat reaktif sehingga membuatbiodiesel menjadi kental (viscous) dan menimbulkan deposit yang menyebabkanpenyumbatan pada nozzle mesin/motor diesel.Penelitian ini bertujuan untuk menentukan kondisi proses hidrogenasi yang cocokuntuk mengkonversi gugus siklopropenoid dalam minyak biji kapok. Penelitian dilakukandengan proses hidrogenasi perpindahan minyak biji kapok menggunakan larutan kaliumformat sebagai pendonor hidrogen. Katalis 5% palladium dengan penyangga karbon dibuatdan digunakan untuk mempercepat dan mendukung terjadinya proses hidrogenasi.Temperatur hidrogenasi dilakukan pada temperatur rendah agar reaksi polimerisasi gugussiklopropenoid tidak terjadi. Jumlah katalis Pd/C ditentukan agar proses hidrogenasi terjadidengan efisien, mengingat harga Palladium yang tinggi. Metode titrasi menggunakan reagenDurbetaki dilakukan untuk mengetahui konsentrasi gugus siklopropenoid sebelum dansetelah proses hidrogenasi.Proses hidrogenasi perpindahan dengan menggunakan larutan kalium format(KCOOH) 10M sebagai sumber hidrogen dapat mengkonversi gugus siklopropenoid yangterkandung dalam minyak kapok. Semakin lama proses hidrogenasi dilakukan, maka semakinbanyak gugus siklopropenoid yang terkonversi. Namun, minyak kapok memiliki suatubatasan dimana minyak tersebut akan berubah strukturnya akibat terjadinya reaksipolimerisasi. Dalam rentang percobaan yang telah dilakukan, proses hidrogenasi lebih baikdilakukan pada temperatur 55oC

Comparative Study of Nyamplung (Callophylum inophyllum) Kernel Oil Obtained from Mechanical and Chemical Extraction for Biofuel Production

Nyamplung (Callophylum inophyllum) contains oil around 40-73% in its seed. It has recently gained recognition as a potential source for biofuel production. The oil recovery process from renewable sources such as nyamplung is widely carried out by using chemical extraction with solvents. Nevertheless, this method is considered costly and there are safety issues as well as environmental concerns related to the solvents used. Therefore, mechanical extraction has emerged as an alternative method. In this study, the nyamplung oil recovered by mechanical extraction via hydraulic press and chemical extraction utilizing Soxhlet extraction was compared. Soxhlet extraction was carried out by using n-hexane as a solvent with a temperature of 70 oC for 5 hours. Before the extraction process, the kernel was initially pretreated to reduce the particle sizes and the water content. The results show that the oil yield recovered using the hydraulic press is 58%, which is comparable with the value obtained from Soxhlet extraction (65%). The oil characteristics were also compared, and the profiling shows no significant difference in the properties (saponification value, acid value, and iodine value) of oils recovered using both methods. The composition of fatty acids was also analyzed for utilization as a biofuel feedstock. Higher content of oleic acid was observed in oil resulted from chemical extraction while mechanical extraction yielded oil with higher palmitic acid content.A B S T R A KNyamplung (Callophylum inophyllum) mengandung minyak sebesar 40-73% dalam bijinya dan belakangan ini diakui sebagai sumber potensial untuk pembuatan biofuel. Proses perolehan minyak nabati dari biji nyamplung pada umumnya dilakukan menggunakan ekstraksi kimia dengan pelarut. Akan tetapi, metode ini cenderung berbiaya tinggi serta memiliki isu berkaitan dengan keselamatan proses dan dampak lingkungan berkaitan dengan penggunaan pelarut. Oleh karena itu, metode ekstraksi mekanis banyak dikembangkan sebagai alternatif metode ekstraksi minyak. Dalam penelitian ini, hasil perolehan minyak nyamplung melalui penekanan hidrolik dibandingkan dengan hasil dari ekstraksi Soxhlet. Ekstraksi Soxhlet dilakukan dengan pelarut n-heksana pada suhu 70 oC selama 5 jam. Sebelum proses ekstraksi, biji nyamplung mengalami perlakuan awal terlebih dahulu dengan cara digiling untuk mengurangi ukuran biji dan dipanaskan untuk mengurangi kadar air. Hasil yang diperoleh menunjukkan bahwa yield minyak dari ektraksi mekanik sebesar 58% sementara yield dari ekstraksi Soxhlet adalah 65%. Karakteristik minyak yang dihasilkan melalui kedua metode ini tidak menunjukkan perbedaan yang signifikan dalam hal nilai saponifikasi, nilai asam, dan nilai iodine. Analisis komposisi asam lemak dari kedua minyak yang dihasilkan menunjukkan bahwa minyak yang diperoleh dari ekstraksi kimia mengandung asam oleat dengan persentase yang lebih tinggi sementara minyak dari hasil ekstraksi mekanik memiliki persentase asam palmitat yang lebih tinggi

Hidrogenasi Elektrokimia Hidrokarbon Terpen

Energi merupakan kebutuhan pokok setiap manusia dan selama ini berasal dari minyak bumi yang tak terbarukan. Penggunaan minyak bumi yang berlebihan dan terus meningkat dapat menyebabkan meningkatnya suhu bumi atau pemanasan global. Oleh karena itu, dibutuhkan sumber energi terbarukan yang berasal dari tumbuhan untuk mengurangi penggunaan minyak bumi. Indonesia merupakan negara yang kaya akan sumber daya hayati oleh karena itu diperlukan pengembangan bahan bakar yang berasal dari tumbuhan. Salah satu sumber bahan baku yang dapat dimanfaatkan sebagai bahan bakar alternatif adalah minyak terpentin. Minyak tersebut dapat diolah agar kualitasnya menyerupai kerosin ataupun avtur. Proses pengolahan ini perlu dilakukan agar minyak terpentin dapat memenuhi syarat mutu titik asap dan titik beku sesuai ketentuan (standar) bagi kerosin dan avtur.Penelitian ini memiliki tujuan meningkatkan kadar hidrogen yang terdapat dalam minyak tepentin agar dapat meningkatkan titik asapnya. Kadar hidrogen dapat ditingkatkan dengan proses hidrogenasi. Pada penelitian ini dilakukan hidrogenasi secara elektrokimia (elektrokatalitik). Proses hidrogenasi elektrokimia (secara elektrokatalitik) dipilih karena proses ini dapat dilakukan pada kondisi temperatur dan tekanan rendah. Selain itu, resiko pelepasan gas hidrogen dapat dihindari karena dalam proses tersebut tidak digunakan gas hidrogen. Sumber listrik bagi sel elektrokimia pun dapat dibangkitkan dari sumber –sumber yang terbarukan misalnya dari kincir angin, turbin air mini (microhidro) dan lain-lain.Proses hidrogenasi elektrokimia dilakukan di dalam suatu sel elektrokimia. Percobaan – percobaan yang dilakukan terdiri dari percobaan pendahuluan dan percobaan utama. Pada percobaan pendahuluan dilakukan pengujian untuk menentukan kondisi tegangan kerja optimum bagi proses hidrogenasi elektrokimia. Pada percobaan utama dilakukan proses hidrogenasi elektrokimia terhadap minyak terpentin dengan memvariasikan konsentrasi larutan elektrolit serta waktu proses hidrogenasi yang dilakukan. Setelah proses hidrogenasi selesai dilakukan analisis tingkat kejenuhan dari minyak terpentin dengan cara uji brom (titrasi bromida-bromat) dan uji nyala api menggunakan lampu cempor lalu dibandingkan dengan kerosin maupun avtu

Production of Biogasoline via Pyrolysis of Oleic Acid Basic Soaps

In this study, an investigation on the effect of the Ca/Mg/Zn mixing ratio on gasoline-range hydrocarbon production by oleic basic soap pyrolysis was carried out. The ratios of calcium to magnesium used were 15%, 35%, 50%, 65%, and 85% with constant Zn. Oleic basic soap was obtained by saponification with the modified fusion method. Pyrolysis experiments were carried out at 450 °C using a semi-continuous reactor with a feed flow rate of 5 g/15 min. The process produced three fractions, i.e., gas, solid, and liquid (bio-hydrocarbon + water). The gas products were characterized by GC-TCD, and the results showed the presence of carbon dioxide, hydrogen, nitrogen, oxygen, and methane. Based on the GC-FID and FT-IR results, the bio-hydrocarbon comprised mainly homologous hydrocarbon from carbon number C7 to C19 containing n-alkanes, alkenes, various iso-alkanes, and some oxygenated compounds. All calcium ratios in the oleic basic soap produced hydrocarbon in the range of gasoline (C7-C11) as the dominant product. The maximum yield of gasoline (74.86%) was achieved at 15% calcium

Synthesis of Biokerosene Through Electrochemical Hydrogenation of Terpene Hydrocarbons From Turpentine Oil

Indonesia possesses great potential for developing renewable resources as alternative fuels. For example, turpentine oil obtained from Pinus merkusii, which contains mostly monoterpene hydrocarbons (C10H16). The oil is highly suitable to be processed for biokerosene or even jet biofuel. It consists of hydrocarbons within the range of C10 to C15. However, it contains insufficient H and thus needs to be upgraded. In the present work, electrochemical hydrogenation was used for upgrading. In the electrochemical cell, stainless steel, silver, and carbon were used alternately for the anode, while copper and silver Raschig rings were used for the cathode. An electrolyte solution of cuprous ammonium formate was utilized not only as a source of H but also to draw the unsaturated hydrocarbons into the aqueous phase. The electrolyte : oil ratio (up to 2:1), electrolyte concentration (between 0.4 and 2 M) and reaction time were varied throughout the experiments. The bromine number (unsaturation level) of the turpentine oil, which was initially 1,86 (mole Br2/mole), was lowered significantly to 0.69-0.90. Promising increase of smoke point values were observed from 11 mm to 16-24 mm, indicating a higher H content of the processed oil, thus making it suitable as a substitute for petroleum kerosene