Transesterification of jojoba oil,sunflower oil,neem oil,rocket seed oil and linseed oil by tin catalysts

The methanolysis of jojoba oil has been studied in the presence of tin powder, dibutyltin diacetate (C₄H₉)₂Sn(OOCCH₃)₂, dioctyltin diacetate (C₈H₁₇)₂Sn(OOCCH₃)₂, dibutyltin oxide (C₄H₉)₂SnO, dioctyltin oxide (C₈H₁₇)₂SnO, diphenyltin oxide (C₆H₅)₂SnO, dibutyltin chloride dihydroxide (C₄H₉)₂Sn(OH)₂Cl, butyltinhydroxide hydrate (C₄H₉)Sn(=O)OH.xH₂O, Ni nanoparticles and Pd nanoparticles act as catalysts. Among these, 1 weight % of dibutyltin diacetate shows the maximum conversion. Then, methanolysis of sunflower oil, neem oil, rocket seed oil and linseed oil into methyl esters studied in the presence of 1% dibutyltin diacetate as a catalyst and was compared their percentage conversions. The experimental yield for the conversion of jojoba oil, sunflower oil, neem oil, rocket seed oil and linseed oil into biodiesel was found to be 71%, 51%, 50.78%, 40.90% and 39.66%, respectively. The experimental yield of the conversion of jojoba oil into methyl esters was found to be increased up to 96% by increasing reaction time, without emulsion formation. The synthesis of jojoba seed oil biodiesel (JSOB), soybean oil biodiesel (SOB), neem oil biodiesel (NOB), rocket seed oil biodiesel (RSOB) and linseed oil biodiesel (LSOB) was confirmed by NMR (¹H & ¹³C) and FT-IR analyses of biodiesel.     

Biodiesel production from refined sunflower vegetable oil over KOH/ZSM5 catalysts

ZSM5 zeolite was impregnated with different KOH loadings (15 wt.%, 25 wt.% and 35 wt.%) to prepare a series of KOH/ZSM5 catalysts. The catalysts were calcined at 500 °C for 3 h and then characterized by N₂ adsorption–desorption and X-ray diffraction (XRD) techniques. The catalysts were tested in the transesterification reaction in a batch reactor at 60 °C and under atmospheric pressure. It was found that KOH/ZSM5 with 35 wt.% loading showed the best catalytic performance. The best reaction conditions in the presence of KOH/ZSM5 (35 wt.%) were determined while modifying the catalyst to oil ratio and the reaction time. The highest methyl ester yield (>95%) was obtained for a reaction time of 24 h, a catalyst to oil ratio of 18 wt.%, and a methanol to oil molar ratio of 12:1. The properties of produced biodiesel complied with the ASTM specifications. The catalytic stability test showed that 35KOH/ZSM5 was stable for 3 consecutive runs. Characterization of the spent catalyst indicated that a slight deactivation might be due to the leaching of potassium oxides active sites.     

Manufacturing of zeolite based catalyst from zeolite tuft for biodiesel production from waste sunflower oil

In the present work, zeolite based catalyst was prepared from zeolite tuft by impregnation methods. The zeolite tuft was initially treated with hydrochloric acid (16%) and then several KOH/zeolite catalysts were prepared by impregnation in KOH solutions. Various solutions of KOH with different molarities (1–6 M) were used. Further modification for the catalyst was performed by a 2nd step impregnation treatment by heating and stirring the KOH/zeolite to 80 °C for 4 h. The zeolite tuft and the prepared catalysts were characterized by several analytical techniques in order to explore their physicochemical properties. These tests include: X-Ray Fluorescence (XRF), Scanning Electron Microscopy (SEM), Zero point of Charge (PHzpc), Fourier Transform Infrared (FT-IR), Energy-dispersive X-Ray analysis (EDX) and X-Ray Diffraction (XRD). The catalysts were then used for transesterification of waste sunflower vegetable oil in order to produce biodiesel. Among the different catalysts prepared, the 1–4M KOH/TZT catalyst provided the maximum biodiesel yield of 96.7% at 50 °C reaction temperature, methanol to oil molar ratio of 11.5:1, agitation speed of 800 rpm, 335 μm catalyst particle size and 2 h reaction time. The physicochemical properties of the produced biodiesel comply with the EN and ASTM standard specifications.     

Synthesis of biodiesel from vegetable oil with methanol catalyzed by Li-doped magnesium oxide catalysts

The preparation of a Li-doped MgO for biodiesel synthesis has been investigated by optimizing the catalyst composition and calcination temperatures. The results show that the formation of strong base sites is particularly promoted by the addition of Li, thus resulting in an increase of the biodiesel synthesis. The catalyst with the Li/Mg molar ratio of 0.08 and calcination temperature of 823 K exhibits the best performance. The biodiesel conversion decreases with further increasing Li/Mg molar ratio above 0.08, which is most likely attributed to the separated lithium hydroxide formed by excess Li ions and a concomitant decrease of BET values. In addition, the effects of methanol/oil molar ratio, reaction time, catalyst amount, and catalyst stability were also investigated for the optimized Li-doped MgO. The metal leaching from the Li-doped MgO catalysts was detected, indicating more studies are needed to stabilize the catalysts for its application in the large-scale biodiesel production facilities.     

Efficient preparation of biodiesel from rapeseed oil over modified CaO

In this study, the catalytic performance of commercial CaO modified by trimethylchlorosilane (TMCS) for transesterification of rapeseed oil and methanol to biodiesel production was investigated. It was found that the fatty acid methyl esters (FAME) yield of the modified CaO was greatly enhanced from 85.4% to 94.6%. The possible reason lies on promoting the absorption of grease to CaO surface. Good results of repeated experiments showed that the modified catalyst has the capacity of water resistance and can be reused for several runs without significant deactivation, which can be confirmed by the humidity test in the vapor-saturated atmosphere. Both the characterizations of the catalyst and the effects of various factors such as mass ratio of catalyst to oil, reaction temperature and molar ratio of methanol to oil were investigated.     

Opium poppy (Papaver somniferum L.) oil for preparation of biodiesel: Optimization of conditions

Opium poppy, Papaver somniferum L., is one of the ancient herbal medicines. In addition to this medical use of latex, opium that is extracted from the immature seed capsule, it is also used illegally for pleasure. It is being produced in great quantities in Turkey especially in Afyonkarahisar city. The seeds of opium poppy plant have high ratio oil content. The opium poppy seeds and oil of these seeds are purely used as an ingredient in production of bakery products. In this study, biodiesel evaluation of the opium poppy seeds that have a high oil ratio is aimed. Alkali catalyzed (NaOH) single-phase reaction was preferred to produce biodiesel from opium poppy oil. The parameters like catalyst concentration, methanol ratio, reaction temperature were optimized and biodiesel production was obtained with high yield in reaction time of 75 min. The methyl ester content in the opium poppy oil biodiesel was determined with Gas Chromatography–Frame Ionized Detector (GC–FID). In optimum conditions, methanol ratio and catalyst concentration was determined as 20 wt% and 0.5 wt%, respectively. The reaction temperature was optimized as 60 °C. Biodiesel was obtained from the opium poppy oil under optimum conditions. Some basic features of the produced methyl esters were determined.     

Calcium-based mixed oxide catalysts for methanolysis of Jatropha curcas oil to biodiesel

Calcium-based mixed oxides catalysts (CaMgO and CaZnO) have been investigated for the transesterification of Jatropha curcas oil (JCO) with methanol, in order to evaluate their potential as heterogeneous catalysts for biodiesel production. Both CaMgO and CaZnO catalysts were prepared by coprecipitation method of the corresponding mixed metal nitrate solution in the presence of a soluble carbonate salt at ∼ pH 8-9. The catalysts were characterized by X-ray diffraction (XRD), temperature programmed desorption of CO₂ (CO₂-TPD), scanning electron microscopy (SEM) and N₂ adsorption (BET). The conversion of JCO by CaMgO and CaZnO were studied and compared with calcium oxide (CaO), magnesium oxide (MgO) and zinc oxide (ZnO) catalysts. Both CaMgO and CaZnO catalysts showed high activity as CaO and were easily separated from the product. CaMgO was found more active than CaZnO in the transesterification of JCO with methanol. Under the suitable transesterification conditions at 338 K (catalyst amount = 4 wt. %, methanol/oil molar ratio = 15, reaction time = 6 h), the JCO conversion of more than 80% can be achieved over CaMgO and CaZnO catalysts. Even though CaO gave the highest activity, the conversion of JCO decreased significantly after reused for forth run whereas the conversion was only slightly lowered for CaMgO and CaZnO after sixth run.     

Ethanolysis of waste cottonseed oil over lithium impregnated calcium oxide: Kinetics and reusability studies

A series of Li/CaO catalysts has been prepared by impregnating 0.5–5.0 wt% Li in CaO by wet chemical method. Prepared Li/CaO catalysts have been characterized by powder X-ray diffraction, scanning electron and transmission electron microscopy and Brunauer–Emmett–Teller (BET) surface area studies, in order to establish the structure and surface morphology of the catalyst. Hammett indicator test study was performed to determine the basic strength of the Li/CaO catalysts. The prepared Li/CaO catalysts have been employed as a heterogeneous catalyst for the transesterification of waste cottonseed oil (having 2.8 wt% free fatty acid contents) with ethanol. Under optimal reaction conditions viz., ethanol/oil molar ratio of 12:1, catalyst to oil weight fraction of 5% and 65 °C reaction temperature, 98% fatty acid ethyl ester yield was obtained in 2.5 h of reaction duration. Under the optimized reaction conditions, the pseudo first order constant and Arrhenius activation energy were found to be 0.03 min⁻¹ and 70.0 kJ mol⁻¹, respectively. Further Li/CaO catalyst was also found to be effective for the ethanolysis and methanolysis of vegetable oils having up to 3.4 wt% free fatty acids. The use of 3-Li/CaO catalyst is advantageous considering that it not only utilizes waste cottonseed oil as a feedstock, but also renewable and nontoxic alcohol, ethanol, for the biodiesel production.     

Preparation, characterization and application of heterogeneous solid base catalyst for biodiesel production from soybean oil

A solid base catalyst was prepared by neodymium oxide loaded with potassium hydroxide and investigated for transesterification of soybean oil with methanol to biodiesel. After loading KOH of 30 wt.% on neodymium oxide followed by calcination at 600 °C, the catalyst gave the highest basicity and the best catalytic activity for this reaction. The obtained catalyst was characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Thermogravimetric analysis (TGA), N₂ adsorption-desorption measurements and the Hammett indicator method. The catalyst has longer lifetime and maintained sustained activity after being used for five times, and were noncorrosive and environmentally benign. The separate effects of the molar ratio of methanol to oil, reaction temperature, mass ratio of catalyst to oil and reaction time were investigated. The experimental results showed that a 14:1 M ratio of methanol to oil, addition of 6.0% catalyst, 60 °C reaction temperature and 1.5 h reaction time gave the best results and the biodiesel yield of 92.41% was achieved. The properties of obtained biodiesel are close to commercial diesel fuel and is rated as a realistic fuel as an alternative to diesel.     

Mixed and ground KBr-impregnated calcined snail shell and kaolin as solid base catalysts for biodiesel production

Mixed and ground activated snail shell and kaolin catalysts impregnated with KBr were investigated. The snail shell and kaolin were calcined, mixed, and ground prior to immersion with KBr solution and subsequent activation at 500 °C for 3 h. The precursor and catalysts were characterized by thermal gravimetric analysis, Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller surface area. The catalytic performance of the prepared catalysts was evaluated by transesterification of soybean oil with methanol. The effects of various parameters on biodiesel yield were investigated. A biodiesel yield of 98.5% was achieved using the catalyst prepared by 40% KBr-immersed, mixed, and ground snail shell and kaolin, which were activated at 500 °C. The transesterification conditions were as follows: reaction temperature, 65 °C; reaction time, 2 h; methanol-to-soybean oil molar ratio, 6:1; and catalyst amount (relative to the weight of soybean oil), 2.0 wt%. The solid catalyst could be reused for four times, and biodiesel yield remained over 73.6% for the fourth time.     

NaOH impregnated sepiolite based heterogeneous catalyst and its utilization for the production of biodiesel from canola oil

NaOH/sepiolite nanocomposite heterogenous base catalyst (NaOH/sep.) was prepared via impregnation process and tested in a three-neck flask equipped with thermometer and reflux condenser for the production of biodiesel from transesterification of canola oil in an excess amount of methanol. The ratio of NaOH and sepiolite was selected as 1:4. The influence of various operational parameters was examined such as methanol to oil molar ratio, catalyst dosage, and reaction temperature. Untreated sepiolite and NaOH loaded sepiolite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy and Energy dispersive spectroscopy analysis. Overall NaOH/sep. based biodiesel production yield was examined by the help of Gas chromatography-mass spectrometry analysis. The yield was calculated from the peak areas as 80.93% which is better than that of expensive catalysis system using studies.     

Preparation and catalytic performance of N-[(2-Hydroxy-3-trimethylammonium) propyl] chitosan chloride /Na2SiO3 polymer-based catalyst for biodiesel production

A novel polymer-based alkaline catalyst was prepared with sodium silicate (Na₂SiO₃) and N-[(2-Hydroxy-3-trimethylammonium) propyl] chitosan chloride (HTCC), interlinked by epichlorohydrin (ECH), for biodiesel production. The structure and properties of the catalyst were studied by Fourier transform infrared spectroscopy, thermogravimetry-mass spectrometry and transmission electron microscopy. The effects of the variables on the transesterificaton of soybean oil to biodiesel were investigated. It is found that Na₂SiO₃ was bridged on HTCC chains through ECH and well dispersed in HTCC matrix in nano size. The transesterification conversion reached at 97.0% under the reaction conditions of methanol/oil molar ratio of 6:1, catalyst loading of 4.0 wt.% at 55 °C for 60 min. After the second run, the catalytic activity kept stable, which was contributed to the stability and dispersion of Na₂SiO₃ in the catalyst.     

Production of biodiesel from high free fatty acid Karanja (Pongamia pinnata) oil

Non-edible oil contains several unsaponifiable and toxic components, which make them unsuitable for human consumption. Karanja (Pongamia pinnata) is an underutilized plant which is grown in many parts of India. Sometimes the oil is contaminated with high free fatty acids (FFAs) depending upon the moisture content in the seed during collection as well as oil expression. The present study deals with production of biodiesel from high FFA Karanja oil because the conventional alkali-catalyzed route is not the feasible route. This paper discusses the mechanism of a dual process adopted for the production of biodiesel from Karanja oil containing FFA up to 20%. The first step is acid-catalyzed esterification by using 0.5% H₂SO₄, alcohol 6:1 molar ratio with respect to the high FFA Karanja oil to produce methyl ester by lowering the acid value, and the next step is alkali-catalyzed transesterification. The yield of biodiesel from high FFA Karanja oil by dual step process has been observed to be 96.6–97%.     

Optimization of biodiesel production from camelina oil using orthogonal experiment

Camelina oil is a low-cost feedstock for biodiesel production that has received a great deal of attention in recent years. This paper describes an optimization study on the production of biodiesel from camelina seed oil using alkaline transesterification. The optimization was based on sixteen well-planned orthogonal experiments (OA₁₆ matrix). Four main process conditions in the transesterification reaction for obtaining the maximum biodiesel production yield (i.e. methanol quantity, reaction time, reaction temperature and catalyst concentration) were investigated. It was found that the order of significant factors for biodiesel production is catalyst concentration > reaction time > reaction temperature > methanol to oil ratio. Based on the results of the range analysis and analysis of variance (ANOVA), the maximum biodiesel yield was found at a molar ratio of methanol to oil of 8:1, a reaction time of 70 min, a reaction temperature of 50 °C, and a catalyst concentration of 1 wt.%. The product and FAME yields of biodiesel under optimal conditions reached 95.8% and 98.4%, respectively. The properties of the optimized biodiesel, including density, kinematic viscosity, acid value, etc., were determined and compared with those produced from other oil feedstocks. The optimized biodiesel from camelina oil meets the relevant ASTM D6571 and EN 14214 biodiesel standards and can be used as a qualified fuel for diesel engines.     

Ethanol steam reforming on Ni/Al-SBA-15 catalysts: Effect of the aluminium content

A series of Ni catalysts supported on Al-SBA-15 mesoporous materials (Si/Al = 20, 60, 140, 240, ∞) was prepared and tested in ethanol steam reforming. The catalysts were characterized by XRD, H₂-TPR, NH₃-TPD, TEM, ICP-AES, ²⁷Al-MAS-NMR and N₂-sorption measurements. It was found that the incorporation of Al atoms into SBA-15 structure is responsible for the formation of catalyst acid sites, an increase of the size of nickel species and stronger metal-support interaction between Ni and Al-SBA-15 carrier. Regarding ethanol steam reforming, catalysts with higher Al content keep ethanol conversion along time. However, Ni/Al-SBA-15 catalysts produce larger amounts of ethylene and coke, with slightly lower hydrogen selectivity than Ni/SBA-15. This is the consequence of ethanol dehydration in Ni/Al-SBA-15 acid sites, while ethanol dehydrogenation mechanism predominates in Ni/SBA-15 catalyst.     

Comparison and effect of Cinder supported with Manganese and Lanthanum oxide for biodiesel production

In this study, comparison and effect of Cinder supported with Lanthanum and Manganese oxide as catalyst for transesterification of triglyceride to methyl ester is proposed. The reaction mechanism along with the effects of methanol to oil molar ratio, amount of catalyst to oil, reaction temperature were also discussed. Moreover reusability of catalyst, catalyst resistance toward Free Fatty Acid and water were also discussed. The results show that yield of biodiesel produced with Mn:La:Cinder catalyst was 99% at ≥150 °C in 6 h. Cinder supported with Mn shows conversion of triglycerides from soybean oil in reaction with methanol after 6 h was over 99% at 150 °C. For both catalyst 3wt% of catalyst based on oil, 24:1 methanol/oil molar ratio was reused for 7 times with regeneration. The catalysts displayed great resistance toward 2.5% water and 1% wt fatty acids.     

Okra (Hibiscus esculentus) seed oil for biodiesel production

Biodiesel was derived from okra (Hibiscus esculentus) seed oil by methanol-induced transesterification using an alkali catalyst. Transesterification of the tested okra seed oil under optimum conditions: 7:1 methanol to oil molar ratio, 1.00% (w/w) NaOCH₃ catalyst, temperature 65 °C and 600 rpm agitation intensity exhibited 96.8% of okra oil methyl esters (OOMEs) yield. The OOMEs/biodiesel produced was analyzed by GC/MS, which showed that it mainly consisted of four fatty acids: linoleic (30.31%), palmitic (30.23%), oleic (29.09%) and stearic (4.93%). A small amount of 2-octyl cyclopropaneoctanoic acid with contribution 1.92% was also established. Fuel properties of OOMEs such as density, kinematic viscosity, cetane number, oxidative stability, lubricity, flash point, cold flow properties, sulfur contents and acid value were comparable with those of ASTM D 6751 and EN 14214, where applicable. It was concluded that okra seed oil is an acceptable feedstock for biodiesel production.     

Characterization and transesterification of Iranian bitter almond oil for biodiesel production

In the present work the production of biodiesel using bitter almond oil (BAO) in a potassium hydroxide catalyzed transesterification reaction was investigated. The BAO was obtained from resources available in Iran and its physical and chemical properties including iodine value, acid value, density, kinematic viscosity, fatty acid composition and mean molecular weight were specified. The low acid value of BAO (0.24 mg KOH/g) indicated that the pretreatment of raw oil with acid was not required. The fatty acid content analysis confirmed that the contribution of unsaturated fatty acids in the BAO is high (84.7 wt.%). Effect of different parameters including methanol to oil molar ratio (3–11 mol/mol), potassium hydroxide concentration (0.1–1.7% w/w) and reaction temperature (30–70 °C) on the production of biodiesel were investigated. The results indicated that these parameters were important factors affecting the tranesterification reaction. The fuel properties of biodiesel including iodine value, acid value, density, kinematic viscosity, saponification value, cetane number, flash point, cloud point, pour point and distillation characteristics were measured. The properties were compared with those of petroleum diesel, EN 14214 and ASTM 6751 biodiesel standards and an acceptable agreement was observed.     

Review and prospects of Jatropha biodiesel industry in China

Jatropha curcas L. is chosen as an ideal biodiesel crop in China because its seed kernel has high oil content (43-61%) and it does not compete with food. Its oil is non-edible, and the trees can resist drought and grow on barren and marginal lands without using arable land. This article reviews the history of Jatropha, current development status and problems in its seeds, propagation, plantation management, oil extraction, biodiesel processing and other value-added products production techniques in China. The commercial production of seed, oil and biodiesel as well as research advancement in China is also introduced and discussed. Examples about our new bred mutant and selected high-oil-yield Jatropha varieties, high-qualified produced biodiesel, and biodiesel pilot plant are presented. Finally, future prospects of Jatropha biodiesel industry in China are discussed.     

Optimization of conversion of waste rapeseed oil with high FFA to biodiesel using response surface methodology

In the present study, waste rapeseed oil with high free fatty acids (FFA) was used as feedstock for producing biodiesel. In the pretreatment step, FFA was reduced by distillation refining method. Then, biodiesel was produced by alkaline-catalyzed transesterification process, which was designed according to the 2⁴ full-factorial central composite design. The response surface methodology (RSM) was used to optimize the conditions for the maximum conversion to biodiesel and understand the significance and interaction of the factors affecting the biodiesel production. The results showed that catalyst concentration and reaction time were the limiting conditions and little variation in their value would alter the conversion. At the same time, there was a significant mutual interaction between catalyst concentration and reaction time.The biodiesel produced in the present experiment was analyzed by gas chromatography/mass spectrometry (GC/MS), which showed that it mainly contained six fatty acid methyl esters. In addition, the diesel indexes analysis showed that most of the fuel properties were in reasonable agreement with the 0# diesel standard of China (GB252-2000) and the biodiesel standard of America (ASTM D6751).