Two-stage processes of homogenous catalysed transesterification of high free fatty acid crude oil of rubber seed

Biodiesel is a diesel replacement and renewable fuel that is manufactured from vegetable oils, animal fats or waste cooking oils. The production of biodiesel from edible oil is currently much more expensive than hydrocarbon-based fuel, due to the relatively high cost of edible oils. The cost of biodiesel can be reduced by using non-edible oils instead of edible oils. The purpose of the present study was to develop a method of esterification of non-edible oil like rubber seed oil (Hevea brasiliensis). The high free fatty acid content oil reacts quickly with alkaline catalysts to form soap, which prevents the separation of biodiesel and glycerol. A two-step process was used instead of the simple alkaline catalysed transesterification process. It consisted of an acid catalysed pre-processing followed by the usual alkaline catalysed process. The physical and chemical properties of biodiesel were analysed. The quantification of methyl esters were done by high-performance liquid chromatography.     

Multivariant approach to optimize biodiesel extraction from neem oil using two-stage esterification process and its quality assessment

Finding new biofuel resources and consolidating the preliminary findings on biodiesel extraction are important to optimize mass production. In this paper biodiesel is extracted from non-edible, abundantly available, potential, and viable neem oil. Design of Experiment is employed to optimize the process parameters of the two-stage esterification process. Methanol has the greatest influence in both stages, followed by choice of catalyst and duration. Standard test procedures were followed to ensure the adequacy of the fuel properties, and the results are encouraging in regard to using neem oil as a potentially renewable and sustainable biodiesel source.     

Performance and emission evaluation of a diesel engine fueled with methyl esters of rubber seed oil

Recent concerns over the environment, increasing fuel prices and scarcity of its supply have promoted the interest in development of the alternative sources for petroleum fuels. At present, biodiesel is commercially produced from the refined edible vegetable oils such as sunflower oil, palm oil and soybean oil, etc. by alkaline-catalyzed esterification process. This process is not suitable for production of biodiesel from many unrefined non-edible vegetable oils because of their high acid value. Hence, a two-step esterification method is developed to produce biodiesel from high FFA vegetable oils. The biodiesel production method consists of acid-catalyzed pretreatment followed by an alkaline-catalyzed transesterification. The important properties of methyl esters of rubber seed oil are compared with other esters and diesel. Pure rubber seed oil, diesel and biodiesel are used as fuels in the compression ignition engine and the performance and emission characteristics of the engine are analyzed. The lower blends of biodiesel increase the brake thermal efficiency and reduce the fuel consumption. The exhaust gas emissions are reduced with increase in biodiesel concentration. The experimental results proved that the use of biodiesel (produced from unrefined rubber seed oil) in compression ignition engines is a viable alternative to diesel.     

亲水性渗透汽化膜在废油脂生物柴油生产中的应用

在酸催化剂作用下,甲醇与废油脂中的游离脂肪酸发生酯化反应,反应过程生成的水会阻碍酯化反应进程。使用亲水性渗透汽化膜分离酯化反应副产物水,在固体酸的作用下促成废油脂中游离脂肪酸的酯化反应。文章对改性后分离甲醇和水的各种渗透汽化膜的研究成果做了分析和比较,探讨了利用膜分离技术实现废油脂生产生物柴油绿色工艺的可行性。     

High free fatty acid coconut oil as a potential feedstock for biodiesel production in Thailand

Coconut oil having 12.8% free fatty acid (FFA) was used as a feedstock to produce biodiesel by a two-step process. In the first step, FFA level of the coconut oil was reduced to 0.6% by acid-catalyzed esterification. In the second step, triglycerides in product from the first step were transesterified with methanol by using an alkaline catalyst to produce methyl esters and glycerol. Effect of parameters related to these processes was studied and optimized, including methanol-to-oil ratio, catalyst concentration, reaction temperature, and reaction time. Methyl ester content of the coconut biodiesel was determined by GC to be 98.4% under the optimum condition. The viscosity of coconut biodiesel product was very close to that of Thai petroleum diesel and other measured properties met the Thai biodiesel (B100) specification.     

Influence of nanoadditives on ignition characteristics of Kusum (Schleichera oleosa) biodiesel

Biodiesel obtained from inedible sources emerged as a productive approach in Indian energy scenario due to the scarcity of food resources come up with extensive usage of edible crops. Kusum (Schleichera oleosa) oil is abundantly available in India and can be used as feedstock to produce biodiesel. However, issues such as higher viscosity, poor stability, and lower calorific value result in poor ignition characteristics, hence limiting its use in combustion applications. An improvement in performance and emission characteristics can be achieved by doping nanoparticles in Kusum biodiesel (KBD). The present work examines the impact of a metal compound and carbon‐primarily based nanoparticles on the evaporation time and ignition probability of the KBD. During the experimental process, different fuel samples of KBD were prepared by amalgamating nanoparticles; then, a sequence of hot plate (stainless steel) ignition test was conducted on these test fuels. The comparative assessment of neat biodiesel and the biodiesel fuel doped with 30 ppm each of alumina (Al2O3), and multiwalled carbon nanotubes (MWCNTs) nanoparticles were carried out. The Kusum oil was converted to biodiesel using two‐stage transesterification process. In the initial stage, refined oil was gone through the acid catalyst esterification process followed by the transesterification reaction. The prepared methyl ester was confirmed and characterized using GC‐MS technique. The thermophysical and spray properties of the test fuels including density, viscosity, calorific value, cloud/pour point, Sauter mean diameter (SMD), and specific surface area (SSA) were also calculated. The experimental result showed a significant increase in ignition probability and heat conduction properties due to improved surface area/volume ratio. Also, lower evaporation time was noted for metal/carbon‐based nanoparticles doped biodiesel as compared with neat biodiesel.     

Conversion of bio-solids (scum) from tannery effluent treatment plant into biodiesel

The search for a suitable low cost feedstock for the production of biodiesel has resulted in biodiesel being produced from bio-solids (scum) taken from the tannery effluent treatment facility. The effectively extracted oil was subjected to combined esterification and transesterification using an acid catalyst. The process was optimized for parameters like catalyst concentration, temperature, time, oil to methanol molar ratio and stirring rate. The result was the yield of 0.55 kg of biodiesel from 1 kg wet scum. The physicochemical properties of the produced biodiesel are in the acceptable range of fuel used in diesel engines. The paper also addresses the quality issues regarding minor components like heavy metals and aromatic contents.     

Cyprinus carpio fish oil: A novel feedstock for biodiesel production

Biodiesel was developed from a novel nonedible oil source, namely Cyprinus carpio fish oil. The acid value of fish oil was very low (0.70 mg KOH/g oil, 0.35 free fatty acid content). As a result, biodiesel was produced through a one-step transesterifcation process, i.e. alkali-catalyzed transesterification with methanol. The optimal conditions for producing biodiesel from fish oil were investigated. The highest biodiesel yield (97.22% ~ 96.88% w/w ester content) was obtained under optimum conditions of 0.75% KOH w/w, 7:1 methanol to oil molar ratio, 60°C reaction temperature and 60-minute duration. Properties of the produced biodiesel as well as its blends with petro-diesel fulfilled the standard limits as prescribed by ASTM D6751 and EN 14214 indicating its suitability as a fuel for diesel engines.     

Effects of water on the esterification of free fatty acids by acid catalysts

To maximize the production of biodiesel from soybean soapstock, the effects of water on the esterification of high-FFA (free fatty acid) oils were investigated. Oleic acid and high acid acid oil (HAAO) were esterified by reaction with methanol in the presence of Amberlyst-15 as a heterogeneous catalyst or sulfuric acid as a homogeneous catalyst. The yield of fatty acid methyl ester (FAME) was studied at oil to methanol molar ratios of 1:3 and 1:6 and reaction temperatures of 60 and 80 °C. The rate of esterification of oleic acid significantly decreased as the initial water content increased to 20% of the oil. The activity of Amberlyst-15 decreased more rapidly than that of sulfuric acid, due to the direct poisoning of acid sites by water. Esterification using sulfuric acid was not affected by water until there was a 5% water addition at a 1:6 molar ratio of oil to methanol. FAME content of HAAO prepared from soapstock rapidly increased for the first 30 min of esterification. Following the 30-min mark, the rate of FAME production decreased significantly due to the accumulation of water. When methanol and Amberlyst-15 were removed from the HAAO after 30 min of esterification and fresh methanol and a catalyst were added, the time required to reach 85% FAME content was reduced from 6 h to 1.8 h.     

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%.     

Biodiesel production from crude rice bran oil and properties as fuel

This research reported on the successfully production of biodiesel by transesterification of crude rice bran oil (RBO). The process included three-steps. Firstly, the acid value of RBO was reduced to below 1 mg KOH/g by two-steps pretreatment process in the presence of sulfuric acid catalyst. Secondly, the product prepared from the first process was carried out esterification with an alkaline catalyst. The influence of four variables on conversion efficiency to methyl ester, i.e., methanol/RBO molar ratio, catalyst amount, reaction temperature and reaction time, was studied at this stage. The content of methyl ester was analyzed by chromatographic analysis. Through orthogonal analysis of parameters in a four-factor and three-level test, the optimum reaction conditions for the transesterification were obtained: methanol/RBO molar ratio 6:1, usage amount of KOH 0.9% w/w, reaction temperature 60 °C and reaction time 60 min. In the third step, methyl ester prepared from the second processing step was refined to become biodiesel. Fuel properties of RBO biodiesel were studied and compared according to ASTM D6751-02 and DIN V51606 standards for biodiesel. Most fuel properties complied with the limits prescribed in the aforementioned standards. The consequent engine test showed a similar power output compared with regular diesel but consumption rate was slightly higher. Emission tests showed a marked decrease in CO, HC and PM, however, with a slight increase in NO_X.     

Heterogeneous catalysis for biodiesel production from Jatropha curcas oil (JCO)

This work focuses on the development of heterogeneous catalysts for biodiesel production from high free fatty acid (FFA) containing Jatropha curcas oil (JCO). Solid base and acid catalysts were prepared and tested for transesterification in a batch reactor under mild reaction conditions. Mixtures of solid base and acid catalysts were also tested for single-step simultaneous esterification and transesterification. More soap formation was found to be the main problem for calcium oxide (CaO) and lithium doped calcium oxide (Li-CaO) catalysts during the reaction of jatropha oil and methanol than for the rapeseed oil (RSO). CaO with Li doping showed increased conversion to biodiesel than bare CaO as a catalyst. La₂O₃/ZnO, La₂O₃/Al₂O₃ and La_0.1Ca_0.9MnO₃ catalysts were also tested and among them La₂O₃-ZnO showed higher activity. Mixture of solid base catalysts (CaO and Li-CaO) and solid acid catalyst (Fe₂(SO₄)₃) were found to give complete conversion to biodiesel in a single-step simultaneous esterification and transesterification process.     

Biodiesel production from olive–pomace oil of steam-treated alperujo

Recently interest has been revived in the use of plant-derived waste oils as renewable replacements for fossil diesel fuel. Olive–pomace oil (OPO) extracted from alperujo (by-product of processed olives for olive oil extraction), and produced it in considerable quantities throughout the Mediterranean countries, can be used for biodiesel production. A steam treatment of alperujo is being implemented in OPO extraction industry. This steam treatment improves the solid–liquid separation by centrifugation and facilitates the drying for further extraction of OPO. It has been verified that the steam treatment of this by-product also increases the concentration of OPO in the resulting treated solid, a key factor from an economic point of view. In the present work, crude OPO from steam-treated alperujo was found to be good source for producing biodiesel. Oil enrichment, acidity, biodiesel yield and fatty acid methyl ester composition were evaluated and compared with the results of the untreated samples. Yields and some general physicochemical properties of the quality of biodiesel were also compared to those obtained with other oils commonly used in biodiesel production. As for biodiesel yield no differences were observed. A transesterification process which included two steps was used (acid esterification followed by alkali transesterification). The maximum biodiesel yield was obtained using molar ratio methanol/triglycerides 6:1 in presence of sodium hydroxide at a concentration of 1% (w/w), reaction temperature 60 °C and reaction time 80 min. Under these conditions the process gave yields of about 95%, of the same order as other feedstock using similar production conditions.     

Synthesis and characterization of monk fruit seed (Siraitia grosvenorii)-based heterogeneous acid catalyst for biodiesel production through esterification process

This research investigated for the first time the synthesis of monk fruit seed (Siraitia grosvenorii)-based solid acid catalyst for biodiesel production. The catalyst was synthesized using a two-step surface functionalization method with trimethoxy phenyl silane and chlorosulfonic acid. The as-synthesized catalyst was characterized to ascertain its catalytic characteristics through surface morphology, chemical bonding, and thermal stability. The effects of activating agent impregnation ratio, carbonization temperature, and sulfonation temperature towards fatty acid methyl ester (FAME) yield were elucidated. The esterification reaction with palmitic acid was found to produce FAME yield up to 98.5% with 4 wt.% catalyst loading, 6-h reaction duration and 120°C reaction temperature. The catalyst also demonstrated high reusability with 84.4% FAME yield being successfully maintained after four successive cycles without reactivation. These proved that the as-synthesized catalyst had high prospect to become a suitable low-cost alternative for biodiesel production through catalytic esterification process in the future.     

Alkaline-catalyzed transesterification of Silurus triostegus Heckel fish oil: Optimization of transesterification parameters

The present work reports the production of biodiesel from Silurus triostegus Heckel fish oil (STFO) through alkaline-catalyzed transesterification by using potassium hydroxide (KOH) as an alkaline catalyst with methanol. Chemical and physical properties of the extracted oil were determined. It was found that STFO has a low acid value (1.90 mg KOH/g oil); hence no pre-treatment such as acid esterification is required to produce the biodiesel. The influence of the experimental parameters such as KOH concentration (0.25–1.0% w/w of oil), methanol to oil molar ratio (3:1, 6:1, 9:1 and 12:1), reaction temperature (32, 45 and 60 °C), reaction duration (30, 60, 90 and 120 min), type of the catalyst (potassium or sodium hydroxide) and step multiplicity (single- and two-step transesterification) on the yield of the biodiesel were investigated. The maximum biodiesel yield (96%) was obtained under the optimized parameters of the transesterification (KOH 0.50% w/w, 6:1 methanol to oil, at 32 °C for 60 min). The properties of the produced biodiesel were found to conform with the ASTM standard, indicating its suitability for internal combustion engines. Blending of the produced biodiesel with petro diesel with various volume percentages was investigated as well.     

Biodiesel from different oil using fixed-bed and plug-flow reactors

In this study, a pilot scale of 100 t/year biodiesel production system, mainly consisting of a fixed-bed and a down-stream plug-flow reactors, was setup to test different feedstock oils, especially a kind of high-acidified oil, trap grease, for their feasibility as biodiesel feedstock in China. The tested oils include three kinds of typical oil from Guangdong Province, China: rapeseed oil, Chinese wood oil, and trap grease. At the same time the optimum residence time for a plug-flow reactor to perform transesterification reaction was investigated in this study. At the temperature of 65 °C, methanol/oil molar ratio of 6:1 and KOH load of 1.2 wt% of oil, the optimum residence time was found to be 19 min. A type of ion-exchange resin was used to fill in the fixed-bed reactor and used as the esterification catalyst for pretreating on the high-acidified oil. For the fresh catalyst, the acid value of trap grease could be reduced from 114 mg KOH/g to about 2 mg KOH/g after 13 h at temperature 75 °C, catalyst load of 15 wt% of oil, methanol addition of 20 wt% of oil. The lifetime test for the catalyst indicated that its life is over 30 days. The quality of biodiesel derived from three feedstock oils is compared with newly published China BD100 standard of GB/T20828-2007. A comparison of the results reveals that the biodiesel generated through this system could satisfactorily meet China BD100 standard. It indicates that the designed process in this system has a good adaptability for different kinds of oil.     

Biodiesel production from waste coconut oil by esterification with ethanol: The effect of water removal by adsorption

The production of biodiesel by esterification with ethanol using waste oil generated in the refining of coconut oil was investigated in this study. The reaction was performed with and without adsorption of water in order to verify the effect of removing water on the reaction conversion. Methanol was also evaluated as an esterification agent. For both ethanol and methanol, conversions over 99% mol were observed. Simultaneous water adsorption allowed the use of lower alcohol/oil molar ratios thus enabling better economics to a possible industrial process.     

A comparative study of vegetable oil methyl esters (biodiesels)

In the present study, rubber seed oil, coconut oil and palm kernel oil, which are locally available especially in Kerala (India), are chosen and their transesterification processes have been investigated. The various process variables like temperature, catalyst concentration, amount of methanol and reaction time were optimized. Biodiesel from rubber seed oil (with high free fatty acid) was produced by employing two-step pretreatment process (acid esterification) to reduce acid value from 48 to 1.72 mg KOH/g with 0.40 and 0.35 v/v methanol-oil ratio and 1.0% v/v H₂SO₄ as catalyst at a temperature of 63(±2) °C with 1 h reaction time followed by transesterification using methanol-oil ratio of 0.30 v/v, 0.5 w/v KOH as alkaline catalyst at 55(±2) °C with 40 min reaction time to yield 98-99% biodiesel. Coconut oil and palm oil, being edible oils, transesterification with 0.25 v/v methanol-oil ratio, 0.50% w/v KOH as at 58(±2) °C, 20 min reaction time for coconut oil and 0.25% v/v methanol-oil ratio, 0.50% w/v KOH as alkaline catalyst at 60(±2) °C for palm kernel oil will convert them to 98-99% biodiesel. The brake thermal efficiency of palm oil biodiesel was higher with lower brake specific fuel consumption, but rubber seed oil biodiesel(ROB) showed less emission (CO and NO_x) compared to other biodiesels.     

Biodiesel production from Jatropha curcas oil

In view of the fast depletion of fossil fuel, the search for alternative fuels has become inevitable, looking at huge demand of diesel for transportation sector, captive power generation and agricultural sector, the biodiesel is being viewed a substitute of diesel. The vegetable oils, fats, grease are the source of feedstocks for the production of biodiesel. Significant work has been reported on the kinetics of transesterification of edible vegetable oils but little work is reported on non-edible oils. Out of various non-edible oil resources, Jatropha curcas oil (JCO) is considered as future feedstocks for biodiesel production in India and limited work is reported on the kinetics of transesterification of high FFA containing oil. The present study reports a review of kinetics of biodiesel production. The paper also reveals the results of kinetics study of two-step acid–base catalyzed transesterification process carried out at pre-determined optimum temperature of 65 and 50 °C for esterification and transesterification process, respectively, under the optimum condition of methanol to oil ratio of 3:7 (v/v), catalyst concentration 1% (w/w) for H₂SO₄ and NaOH and 400 rpm of stirring. The yield of methyl ester (ME) has been used to study the effect of different parameters. The maximum yield of 21.2% of ME during esterification and 90.1% from transesterification of pretreated JCO has been obtained. This is the first study of its kind dealing with simplified kinetics of two-step acid–base catalyzed transesterification process carried at optimum temperature of both the steps which took about 6 h for complete conversion of TG to ME.     

The reuse of waste cooking oil and spent bleaching earth to produce biodiesel

Currently, semi-refined and refined vegetable oils are used as a feedstock in biodiesel production. However, criteria such as competition with conventional fossil fuel, economic reasons, shortage supply of food and its social impact on the global scale have somewhat slowed the development of the biodiesel industry. Spent bleaching earth is currently under-utilized by deposition in landfills with no attempt to recover the oil. In this study the waste oil adsorbed on spent bleaching earth, refined soybean oil, and waste cooking oil were evaluated as potential sources of biodiesel production in Iran. Different characteristics of the oil samples, such as fatty acid composition, peroxide, iodine, acid values, etc., were evaluated. A two-step esterification reaction using methanol was conducted to produce biofuel. Subsequently, physicochemical properties of produced biodiesel were analyzed. The oil content in spent bleaching earth was 19.3%, which was lowered to 3.7% using hexane as the solvent. Gas chromatography showed that palmitic, oleic, and linoleic acids were predominantly fatty acids, respectively, and the highest content of saturated acids belonged to waste cooking oil (24%). The acidity of 8.3% was obtained for the oil recovered from spent bleaching earth followed by waste cooking oil (3.6%) and refined soybean oil (0.1%). Totally, the specifications of all biodiesel produced were in the range defined by ASTM D6751 and EN 14214 standards. Since about 2000–3000 tones of spent bleaching earth residual oil is annually dumped and the amount of waste cooking oil produced yearly is 500,000 tones, there is a great potential for Iran to produce biodiesel from waste oils.