Microwave-assisted enzymatic synthesis of beef tallow biodiesel

Optimal conditions for the microwave-assisted enzymatic synthesis of biodiesel have been developed by a full 2² factorial design leading to a set of seven runs with different combinations of molar ratio and temperature. The main goal was to reduce the reaction time preliminarily established by a process of conventional heating. Reactions yielding biodiesel, in which beef tallow and ethanol used as raw materials were catalyzed by lipase from Burkholderia cepacia immobilized on silica-PVA and microwave irradiations within the range of 8–15 W were performed to reach the reaction temperature. Under optimized conditions (1:6 molar ratio of beef tallow to ethanol molar ratio at 50°C) almost total conversion of the fatty acid presented in the original beef tallow was converted into ethyl esters in a reaction that required 8 h, i.e., a productivity of about 92 mg ethyl esters g⁻¹ h⁻¹. This represents an increase of sixfold for the process carried out under conventional heating. In general, the process promises low energy demand and higher biodiesel productivity. The microwave assistance speeds up the enzyme catalyzed reactions, decreases the destructive effects on the enzyme of the operational conditions such as, higher temperature, stability, and specificity to its substrate, and allows the entire reaction medium to be heated uniformly.     

Sonication-assisted production of biodiesel using soybean oil and supercritical methanol

High temperature and pressure are generally required to produce biodiesel using supercritical methanol. We reduced the harsh reaction conditions by means of sonicating the reaction mixture prior to transesterification using supercritical methanol. Soybean oil was selected as the raw material for transesterification. As soybean oil contains more unsaturated fatty acid triglycerides, the biodiesel degraded more at high temperature. The reactants were sonicated for 60 min at 35 °C prior to transesterification to avoid degradation of the product and to enhance biodiesel yield at temperatures <300 °C. The process parameters were optimized using central composite design. The variables selected for optimization were temperature, time, and the oil to methanol molar ratio. The temperature and oil to methanol molar ratios were varied from 250 to 280 °C and 1:40–1:50, respectively. The reaction time was tested between 4 and 12 min. The biodiesel was analyzed for any possible degradation by gas chromatography–mass spectroscopy and for the wt% of fatty acid methyl esters (FAME) obtained. The maximum FAME yield (84.2 wt%) was obtained at a temperature of 265.7 °C, an oil to alcohol molar ratio of 1:44.7, and a time of 8.8 min. The optimum yield was obtained at a pressure of 1,500 psi. The pressure and optimum temperature used to obtain the maximum yield were the lowest reported so far without the use of a co-solvent. Thus, the severity of the supercritical reactions was reduced by adding sonication prior to the reaction.     

Synthesis of fatty acid ethyl esters with conventional and microwave heating systems using the free lipase B from Candida antarctica

Free Candida antarctica lipase B (Lipozyme, CALB L^®) was used to produce fatty acid ethyl esters (FAEE) from refined soybean oil in solvent-free media using the conventional (CHS) and microwave (MHS) heating systems. Statistical analyses (95% confidence level) for both reaction products, FAEE and free fatty acids (FFA), were performed. An increase in ethanol:oil molar ratio decreased the catalytic performance of CALB L (p?<?.05). The best conditions using the microwave radiation were a molar ratio of ethanol:oil of 3:1, a water content of 20.3?wt.% and an enzyme loading of 3?wt.% and this resulted in a total ester content of 64.7% in 15?min, while the same condition using the conventional heating gave only 21.4%. Moreover, the reaction equilibrium was reached 16 times faster with microwave than with conventional heating. High ethanol:oil molar ratios had a negative effect on FAEE synthesis with both CHS and MHS, probably due to the partial inactivation of the enzymes. MHS improved the reaction performance of CALB L, but other process parameters will have to be optimized to enhance the resulting FAEE yields. The recovery and reuse of CALB L using a MHS was demonstrated. Hence, the use of microwave radiation under the conditions applied in this study was not detrimental to the catalytic performance of CALB L for at least one reuse.     

Microwave assisted alkali-catalyzed transesterification of Pongamia pinnata seed oil for biodiesel production

In this study, microwave assisted transesterification of Pongamia pinnata seed oil was carried out for the production of biodiesel. The experiments were carried out using methanol and two alkali catalysts i.e., sodium hydroxide (NaOH) and potassium hydroxide (KOH). The experiments were carried out at 6:1 alcohol/oil molar ratio and 60 °C reaction temperature. The effect of catalyst concentration and reaction time on the yield and quality of biodiesel was studied. The result of the study suggested that 0.5% sodium hydroxide and 1.0% potassium hydroxide catalyst concentration were optimum for biodiesel production from P. pinnata oil under microwave heating. There was a significant reduction in reaction time for microwave induced transesterification as compared to conventional heating.     

Lipase catalyzed transesterification of soybean oil using ethyl acetate,an alternative acyl acceptor

Methanol, the acyl acceptor usually used in the commercial process of biodiesel production, is associated with some problems such as immiscibility with oils and lipase deactivation. To overcome these barriers, ethyl acetate was proposed as an alternative acyl acceptor for the production of biodiesel from soybean oil using an immobilized lipase, Novozym 435, Ethyl acetate mixed well with soybean oil, and only slightly inhibited the lipase activity by 5%. The effects of various environmental parameters, such as the composition of soybean oil and ethyl acetate, lipase content, and reaction temperature, were investigated to determine the optimal conditions for biodiesel production. As a result, the highest biodiesel production yield, 63.3 (±0.6)%, was obtained by using an ethyl acetate and soybean oil mixture with a 6∶1 molar ratio, with 8% of the immobilized lipase based on the weight of oil added at 70°C and 600 rpm.     

Biocatalytic ethanolysis of palm oil for biodiesel production using microcrystalline lipase in tert-butanol system

Biocatalytic synthesis is a promising environmentally friendly process for the production of biodiesel, a sustainable alternative fuel from renewable plant resources. In order to develop an economical heterogeneous biocatalyst, protein-coated microcrystals (PCMCs) were prepared from a commercial enzyme preparation from a recombinant Aspergillus strain expressing Thermomyces lanuginosus lipase and used for synthesis of biodiesel from palm olein by ethanolysis. Reaction parameters, including catalyst loading, temperature, and oil/alcohol molar ratio have been systematically optimized. Addition of tert-butanol was found to markedly increase the biocatalyst activity and stability resulting in improved product yield. Optimized reactions (20%, w/w PCMC-lipase to triacylglycerol and 1:4 fatty acid equivalence/ethanol molar ratio) led to the production of alkyl esters from palm olein at 89.9% yield on molar basis after incubation at 45 °C for 24 h in the presence of tert-butanol at a 1:1 molar ratio to triacylglycerol. Crude palm oil and palm fatty acid distillate were also efficiently converted to biodiesel with 82.1 and 75.5% yield, respectively, with continual dehydration by molecular sieving. Operational stability of PCMC-lipase could be improved by treatment with tert-butanol allowing recycling of the biocatalyst for at least 8 consecutive batches with only slight reduction in activity. This work thus shows a promising approach for biodiesel synthesis with microcrystalline lipase which could be further developed for cost-efficient industrial production of biodiesel.     

Ethanesulfonic acid-based esterification of industrial acidic crude palm oil for biodiesel production

An industrial grade acidic crude palm oil (ACPO) pre-treatment process was carried out using ethanesulfonic acid (ESA) as a catalyst in the esterification reaction. ESA was used in different dosages to reduce free fatty acid (FFA) to a minimum level for the second stage of biodiesel production via alkaline transesterification reaction. Different process operating conditions were optimized such as ESA dosage (0.25-3.5% wt/wt), methanol to ACPO molar ratio (1:1-20:1), reaction temperature (40-70 °C), and reaction time (3-150 min). This study revealed the potential use of abundant quantities of ACPO from oil palm mills for biodiesel production. The lab scale results showed the effectiveness of the pre-treatment process using ESA catalyst. Three consecutive catalyst recycling runs were achieved without significant degradation in its performance. Second and third reuse runs needed more reaction time to achieve the target level of FFA content. Esterification and transesterification using ESA and KOH respectively is proposed for biodiesel industrial scale production. The produced biodiesel meets the international standards specifications for biodiesel fuel (EN 14214 and ASTM D6751).     

A critical comparison of methyl and ethyl esters production from soybean and rice bran oil in the presence of microwaves

Transesterification of vegetable oils (from soybeans and rice bran) into methyl and ethyl esters using a batch microwave system was investigated in this study. A critical comparison between the two alcohols was performed in terms of yields, quality, and reaction kinetics. Parameters tested were temperature (60, 70 and 80 °C) and time (5, 10, 15 and 20 min). At all tested conditions, more than 96% conversion rates were obtained for both ethanol and methanol. Use of microwave technology to assist the transesterification process resulted in faster reaction times and reduced catalyst requirement (about ten-fold decrease). Methanol required lower alcohol:oil ratios than normally used in conventional heating, whereas ethanol required higher molar ratios. All esters produced using this method met ASTM biodiesel quality specifications. Methanol performed better in terms of performance and costs, while ethanol may have some environmental and safety benefits.     

Water demand and stress from oil palm-based biodiesel production in Thailand

Purpose

The use and production of biofuels have been strongly promoted in Thailand. In order to achieve a 25 % renewable energy target in 2021, feedstock expansion is needed to satisfy the increased demand for biofuel production putting more pressure on freshwater resources. This is an important implication of biofuel production which has not yet been taken into consideration. Thus, this study intends to address the impact from freshwater use due to the biodiesel target based on life cycle assessment approach as well as to evaluate suitable areas for expansion of oil palm.

Methods

The amount of water for growing oil palm throughout its lifespan is estimated based on theoretical crop water requirement, while water demand for producing biodiesel is referred to from literature. Then, the potential impact on freshwater resources is assessed in terms of water deprivation using the water stress index of Thailand. The Alternative Energy Development Plan for 2012–2021 and areas recommended by the Ministry of Agriculture and Cooperatives are referred in this study. Additionally, two scenarios for increasing new plantation in suitable areas are proposed as expansion in a single region or spread over the three regions.

Results and discussion

The highest water requirement for oil palm-based biodiesel production is found in the central region followed by the eastern and southern (4–9, 5–16, and 4–19 m³ L^?1 biodiesel, respectively). This is because oil palm plantations in the central region are not yet fully mature. As a result, the ratio of crop water requirement associated to crop productivity will be reduced while the water productivity will be increased yearly in yield. Also, more than 99 % of the total water is required during the cultivation period. To achieve the 2021 biodiesel target with a concern towards the impact from freshwater use by means of low water deprivation, cultivating oil palm is recommended entirely in the eastern and the southern parts without expansion to the central region.

Conclusions

The impact on freshwater resources is an important implication of biofuel production as most of the water requirement of palm oil biodiesel was for oil palm cultivation. Accounting the water deprivation as one of the criteria on impact from freshwater use will provide useful support for selecting areas having less potential for inducing water stress in a watershed leads to people in these areas being less vulnerable to water stress.

     

Use of experimental design to investigate biodiesel production by multiple-stage Ultra-Shear reactor

This work presents biodiesel production from soybean oil and bioethanol by multiple-stage Ultra-Shear reactor (USR). The experiments were carried out in the following conditions: reaction time from 6 to 12 min; catalyst concentration from 0.5% to 1.5% by weight of soybean oil; ethanol: soybean oil molar ratio from 6:1 to 10:1. The experimental design was used to investigate the influence of process variables on the conversion in biodiesel. The best ethyl ester conversion obtained was 99.26 wt.%, with ethanol:soybean oil molar ratio of 6:1, catalyst concentration of 1.35% and with 12 min of reaction time.     

Optimization Studies and Chemical Kinetics of Silica Sulfuric Acid-Catalyzed Biodiesel Synthesis from Waste Cooking Oil

In the present study conversion of waste cooking oil to biodiesel has been carried out via simultaneous esterification and transesterification reaction over silica sulfuric acid as a solid acid catalyst. The process variables that influence the fatty acid methyl ester (FAME) conversion, such as reaction temperature, reaction time, catalyst concentration and methanol to oil molar ratio were investigated and optimized using Taguchi method. Highest FAME production obtained under the optimized condition was 98.66 %. Analysis of variance revealed that temperature was the most significant factor effecting the FAME production among four factors studied. From the kinetic study, the reaction was found to follow pseudo first-order kinetics and rate constant of the reaction under optimum condition was 0.00852 min^?1.     

Production of bioethanol and biodiesel using instant noodle waste

Instant noodle manufacturing waste was used as feedstock to convert it into two products, bioethanol and biodiesel. The raw material was pretreated to separate it into two potential feedstocks, starch residues and palm oil, for conversion to bioethanol and biodiesel, respectively. For the production of bioethanol, starch residues were converted into glucose by α-amylase and glucoamylase. To investigate the saccharification process of the pretreated starch residues, the optimal pretreatment conditions were determined. The bioethanol conversion reached 98.5 % of the theoretical maximum by Saccharomyces cerevisiae K35 fermentation after saccharification under optimized pretreatment conditions. Moreover, palm oil, isolated from the instant noodle waste, was converted into valuable biodiesel by use of immobilized lipase (Novozym 435). The effects of four categories of alcohol, oil-to-methanol ratio, reaction time, lipase concentration and water content on the conversion process were investigated. The maximum biodiesel conversion was 95.4 %.     

Biocatalytic methanolysis activities of cross-linked protein-coated microcrystalline lipase toward esterification/transesterification of relevant palm products

Biocatalysis by immobilized lipase is an efficient alternative process for conversion of crude vegetable oil with high free fatty acid content to biodiesel, which is the limit of the conventional alkaline-catalyzed reaction. In this study, influences of solid-state organic and inorganic buffer core matrices with different pK_a on catalytic performance of cross-linked protein coated microcrystalline biocatalysts prepared from Thermomyces lanuginosus lipase (CL-PCMC-LIP) toward esterification of palmitic acid (PA), transesterification of refined palm oil (RPO), and co-ester/transesterification of crude palm oil (CPO) to fatty acid methyl ester (FAME) was studied. Glycine, CAPSO (3-(cyclohexylamino)-2-hydroxy-1-propanesulfonic acid), and TAPS ([(2-hydroxy-1,1-bis(hydroxymethyl)ethyl)amino]-1-propanesulfonic acid) were shown to be potent core matrices for these reactions. The optimal reaction contained 4:1 [methanol]/[fatty acid] molar equivalence ratio with 20% (w/w) CL-PCMC-LIP on glycine in the presence of tert-butanol as a co-solvent. Deactivation effect of glycerol on the biocatalyst reactive surface was shown by FTIR, which could be alleviated by increasing co-solvent content. The maximal FAME yields from PA, RPO, and CPO reached 97.6, 94.9, and 95.5%, respectively on a molar basis under the optimum conditions after incubation at 50 °C for 6 h. The biocatalyst retained >80% activity after recycling in five consecutive batches. The work demonstrates the potential of CL-PCMC-LIP on one-step conversion of inexpensive crude fatty acid-rich feedstock to biodiesel.     

Fuel Characteristics of Solid Biofuel Derived from Oil Palm Biomass and Fast Growing Timber Species in Malaysia

The fuel characteristics of solid biofuels derived from biomass that is abundantly available in Malaysia are presented. The objectives of the study were to characterize fuel properties of oil palm biomass (empty fruit bunch (EFB) and oil palm trunk (OPT)) and wood from a range of fast growing timber species (Albizia falcataria, Acacia spp., Endospermum spp. and Macaranga spp.), inclusive and exclusive of bark. Among the fast-growing timber species, the higher heating values ranged from 4288 cal g^-1 to 4383 cal g^-1 for wood inclusive of bark, and 4134 cal g^-1 to 4343 cal g^-1 for wood exclusive of bark. The inclusive of bark portion in the biomass sample generally increased the heating value except for Macaranga spp. Empty fruit bunch and oil palm trunk had heating values of 4315 cal g^-1 and 4104 cal g^-1, respectively. Ash-forming elements and trace elements were much higher in the timber species samples inclusive of bark than samples exclusive of bark. On the other hand, oil palm biomass contained higher ash-forming elements and trace elements than the wood from the fast growing timber species. The European energy crops show higher HHV, Cl and Si content but lower K, Mg, Na and P compared to the local biomass used in this study. The data obtained from this study can serve as a foundation for the selection of suitable biomass to be used as solid fuel, or as a reference on the fabrication of conversion systems for the selection of biomass solid fuel.     

Characterization of Bio-oil and Bio-char from Pyrolysis of Palm Oil Wastes

The residues from the palm oil industry are the main contributors to biomass waste in Malaysia, and these wastes require extra attention with respect to handling. The biomass waste is a renewable resource that can potentially be used to produce absorbents, fuels, and chemical feedstocks through the pyrolysis process. In this study, the wastes of palm shell, empty fruit bunches, and mesocarp fiber were characterized and then pyrolyzed in a fixed-bed reactor under the following conditions: a temperature of 500 °C, a nitrogen flow rate of 2 L/min and reaction time of 60 min. After pyrolysis, characterization of the products with an emphasis on the bio-oil and the bio-char was performed using various approaches (including Karl Fischer water-content tests, FTIR, SEM, TGA and CNH/O analyses). The results showed that the pyrolysis of palm oil wastes yielded more bio-oil than bio-char or non-condensable gases. The results also indicated that all of the bio-oils were acidic and contained high levels of oxygen. The bio-oils heating values were low and varied from 10.49 MJ/kg to 14.78 MJ/kg. The heating values of the bio-chars (20–30 MJ/kg) were higher than those of the bio-oils. Among the biomasses studied in this work, palm shell contained the highest level of lignin and showed the highest levels of bio-char yield and fixed and elemental carbon in the raw and bio-char form.     

Lipase-catalyzed methanolysis of palm oil in presence and absence of organic solvent for production of biodiesel

Enzymatic production of methyl esters (biodiesel) by methanolysis of palm oil in presence and absence of organic solvent was investigated using Candida antarctica lipase immobilized on acrylic resin as a biocatalyst. Although, at least molar equivalent of methanol (methanol-palm oil ratio 3:1) is required for the complete conversion of palm oil to methyl esters, lipase catalyzed methanolysis of palm oil in absence of organic solvent was poisoned by adding more than 1/3 molar equivalent of methanol. The use of polar organic solvents prevented the lipase to be poisoned in methanolysis with a molar equivalent of methanol, and tetrahydrofuran (THF) was found to be the most effective. The presence of water in methanolysis of palm oil both in presence and absence of THF inhibited the reaction rate but this inhibition was considerably low in THF containing system. The palm oil-lipase (w/w) ratio significantly influenced the activity of lipase and the optimal ratio in presence and absence of THF was 100 and 50, respectively.     

Life cycle greenhouse gas emissions of palm oil production by wet and dry extraction processes in Thailand

Purpose

The crude palm oil (CPO) extraction is normally done by a wet extraction process, and wastewater treatment of the wet process emits high levels of greenhouse gases (GHGs). A dry process extracts mixed palm oil (MPO) from palm fruit without using water and has no GHG emissions from wastewater treatment. This work is aimed at determining the GHG emissions of a dry process and at evaluating GHG savings on changing from wet to dry process, including land use change (LUC) effects.

Methods

Life cycle assessment from cradle to gate was used. The raw material is palm fruits. The dry process includes primary production, oil room, and utilities. MPO is the main product, while palm cake and fine palm residue are co-products sold for animal feed. Case studies were undertaken without and with carbon stocks of firewood and of nitrogen recycling at plantations from fronds. Allocations by mass, economic, and heating values were conducted. The trading of GHG emissions from co-products to GHG emissions from animal feed was assessed. The GHG emissions or savings from direct LUC (dLUC) and from indirect LUC (iLUC) effects and for the change from wet to dry process were determined.

Results and discussion

Palm fruit and firewood were the major GHG emission sources. Nitrogen recycling on plantations from fronds significantly affects the GHG emissions. With the carbon stocks, the GHG emissions allocated by energy value were 550 kg CO₂ eq/t MPO. The GHG emissions were affected by ?3 to 37% for the change from wet to dry process. When the plantation area was increased by 1 ha and the palm oil extraction was changed from wet to dry process, and the change included dLUC and iLUC, the GHG savings ranged from ?0.94 to 5.08 t CO₂ eq/ha year. The iLUC was the main GHG emission source. The GHG saving mostly originated from the change of extraction process and from the dLUC effect. Based on the potential use of biodiesel production from oil palm, during 2015–2036 in Thailand, when the extraction process was changed and dLUC and iLUC effects were included, the saving in GHG emissions was estimated to range from ?35,454 to 274,774 t CO₂ eq/year.

Conclusions

The change of palm oil extraction process and the LUC effects could minimize the GHG emissions from the palm oil industry. This advantage encourages developing policies that support the dry extraction process and contribute to sustainable developments in palm oil production.

     

Conversion of waste produced by the deodorization of palm oil as feedstock for the production of biodiesel using a catalyst prepared from waste material

The distillate produced by deodorization of palm oil (DDPO) is a waste that corresponds to 4% of the product formed in this process. DDPO is 83% free of fatty acids (FFA), making it a good material for biodiesel production. In this paper, a catalyst prepared from a waste material, Amazon flint kaolin, was used for the esterification of DDPO with methanol. Leached metakaolin treated at 950 °C and activated with 4 M sulfuric acid (labeled as MF9S4) offered maximum esterification activity (92.8%) at 160 °C with a DDPO:methanol molar ratio of 1:60 and a 4-h reaction time. The influences of reaction parameters, such as the molar ratio of the reactants, alcohol chain length, temperature, time and the presence of glycerides and unsaponifiable matter, have also been investigated. Based on the catalytic results, esterification of DDPO using MF9S4 can be a cheaper alternative for production of sustainable fuels.     

Production of Cold-Flow Quality Biodiesel from High-Acidity On-Edible Oils—Esterification and Transesterification of Macauba (<Emphasis Type="Italic">Acrocomia aculeata</Emphasis>) Oil Using Various Alcohols

Biodiesel is an alternative fuel that has been used for partial or total substitution of diesel to reduce its environmental impacts. Prior studies on this topic have focused on the quest for better synthesis process, new catalysts and low-cost non-food and raw materials to improve the economic and sustainable production as well as product quality. In this study, acidic oil from macauba, a palm tree native to South America that has no food uses, was converted into biodiesel. The esterification and transesterification reactions were performed with methanol, ethanol and isobutanol with the goal of improving the cold properties of the biodiesel. The isobutyl ester exhibited the lowest freezing point temperature but underperformed outside of international specifications for kinematic viscosity; it also exhibited a low ester content. The methyl and ethyl esters were within the specifications of the international standards for ester content, density, kinematic viscosity and sulphur content. The ethyl ester produced from macauba oil displayed better properties in cold conditions than methyl and isobutyl esters studied here, with a cold filter plugging point of 0 °C. Its onset crystallisation temperature was reduced from ?5.96 to ?13.41 °C when subjected to fractional crystallisation. The ethyl ester exhibited the best lubricity value among the other esters studied.     

Biodiesel production using Aspergillus niger as a whole‐cell biocatalyst in a packed‐bed reactor

Enzymatic lipase transesterification of palm oil to biodiesel in a packed‐bed reactor (PBR) using a novel strain of the fungus Aspergillus niger, immobilized within polyurethane biomass support particles (BSPs), was investigated. A three‐step addition of methanol was used to reduce lipase inhibition by immiscible methanol. The influence of water content and PBR flow rate was investigated. FAME yield was enhanced with an increase of PBR flow rate in the range of 0.15–30 L h^?1, where inefficient mixing of the reaction mixture at lower flow rates resulted in low conversion rates i.e. 69% after 72‐h reaction. Adding the third mole equivalent of methanol resulted in lipase inhibition due to methanol migration into the accumulated glycerol layer. Glutaraldehyde (GA) solution (0.5 vol.%) was used to stabilize lipase activity, which led to a high FAME yield (>90%) in the PBR after 72‐h of reaction time at a flow rate of 15 L h^?1, and a water content of 15%. Moreover, a high conversion rate (>85%) was maintained after four palm oil batch conversion cycles in the PBR. In contrast, lipase activity of non‐GA‐treated cells decreased with each PBR batch cycle, where only 70% FAME was produced after the forth PBR cycle. Transesterification of palm oil in a PBR system using BSPs‐immobilized A. niger as a whole‐cell biocatalyst is a viable process for enzymatic biodiesel production.