Biodiesel production from waste animal fats using pyrolysis method

It is necessary to utilize waste cooking oil as a raw material of biodiesel because the land area available for cultivation in Japan is limited. Waste cooking oil also includes long-chain saturated compounds and free fatty acids derived from animal fats. The former has a high freezing point and the latter forms a soap with the alkali catalyst typically used in biodiesel production, reducing the yield. To make waste cooking oil available for biodiesel production, pyrolysis of the waste oil was attempted. The resulting triacylglycerols were found to decompose at 360 to 390 °C, fatty acids were generated by cleavage of the ester bond, and short-chain hydrocarbons and short-chain fatty acids were generated by cleavage of the unsaturated bonds in the hydrocarbon chain. When the retention time was extended with a reaction temperature of 420 °C, light-oil hydrocarbons were generated by decarboxylation of the fatty acids. By adding palladium supported by activated carbon (Pd/C) as a catalyst, decarboxylation was promoted, and hydrocarbons comparable to light oil were selectively obtained in high yield at 85 wt.%. Compared to the biodiesel obtained by transesterification, the biodiesel obtained by pyrolysis showed improvement of about − 5 °C in the pseudo-cold filter plugging point.     

Winterisation of waste cooking oil methyl ester to improve cold temperature fuel properties

Waste cooking oil methyl ester (WCOME) was winterised at 1, 0, −1 and −2°C following a 4×2 factorial design with one replication per cell. The process was carried out by filtration and both the filtrate (solid phase) and the liquid phase were analysed by gas chromatography (GC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Cold filter plugging point (CFPP) and calorific values were measured.Temperatures of 0 and −1°C in conjunction with the quickest cooling rate (0.1°C min⁻¹) and 15-24 h of cooling gave the most successful results in terms of fuel properties.Improvements in the low temperature properties of the winterised fuel were reflected by a reduction of saturated fatty acid methyl esters (SFAME) in the composition by 1.5-6%, by a decrease in the CFPP values by 2-4°C and by a shift of the DSC high temperature melting peak (approx. 5°C) towards lower temperatures in comparison to the original fuel. Calorific values of the winterised WCOME did not significantly change and boiling temperatures increased (approx. 26%) in comparison to the non-winterised WCOME.     

Improving the cold flow properties of biodiesel from waste cooking oil by ternary blending with bio-based alcohols and diesel from direct coal liquefaction

The utilization and popularization of biodiesel are always limited by its poor cold flow properties. Both bio-based alcohol and diesel from direct coal liquefaction (DDCL) has potential to enhance the cold flow properties of biodiesel. In this study, ternary blends of waste cooking oil biodiesel (BWCO) with DDCL and bio-based ethanol (ET) or 1-butanol (BT) were conducted to improve the cold flow properties of biodiesel. The pour point (PP), cold filter plugging point (CFPP), and cloud point (CP) of BWCO-ET, BWCO-BT, and BWCO-DDCL binary blends, and BWCO-ET-DDCL and BWCO-BT-DDCL ternary blends were comparatively assessed. Ternary phase diagrams were also applied to analyze the blending effect of the three components on the cold flow properties of biodiesel. Results showed that both DDCL, ET, and BT can remarkably enhance the cold flow properties of BWCO. When the ternary blends contain 20 vol.% BWCO and less than 40 vol.% ET or BT, DDCL together with ET or BT exerted positive effects on enhancing the low-temperature flow properties of BWCO, especially on the CP and CFPP. For ternary blends in 20:10:70 blending ratio, BWCO-BT-DDCL exhibited the lowest PP, CFPP, and CP of −23, −19, and −17°C, respectively. The crystallization behavior and crystal morphology of blended fuels are also observed via a polarizing optical microscope, and find that DDCL together with BT in biodiesel can effectively retard the aggregation of large crystals and inhibit crystals growth.     

Winterization of biodiesel by micro process engineering

A new method for winterization of biodiesel based on waste cooking oil is demonstrated, using micro heat exchangers with channel diameters of 200 μm. Biodiesel is pumped from a vessel through a micro heat exchanger in such a way, that pure seed crystals of saturated fatty acid methyl esters are produced at the outlet of the micro channels and injected back into the biodiesel vessel. Thus micro process engineering allows the reduction of the sum of saturated fatty acid methyl esters within biodiesel based on waste cooking oil from 21.3% to 9.6%. This corresponds to a reduction in CFPP value of 11 K, which means that this biodiesel can be used at temperatures down to 264 K.     

Premium quality renewable diesel fuel by hydroprocessing of sunflower oil

Hydroprocessing of neat sunflower oil was carried out at 360-420 °C and 18 MPa over a commercial hydrocracking catalyst in a bench scale fixed bed reactor. In the studied experimental range, products consisted exclusively of hydrocarbons that differed significantly in composition. While the concentration of n-alkanes exceeded 67 wt.% in the reaction products collected at 360 °C, it decreased to just 20 wt.% in the product obtained at 420 °C. Consequently, the fuel properties of the latter product were very similar to those of standard (petroleum-derived) diesel fuel. Particularly, it exhibited excellent low-temperature properties (cloud point −11 °C; CFPP −14 °C). Reaction products obtained at 400 and 420 °C were blended into petroleum-derived diesel fuel in three concentration levels ranging from 10 to 50 wt.% and the fuel properties of these mixtures were evaluated. Diesel fuel mixtures containing the product of sunflower oil hydrocracking at 420 °C showed very good low-temperature properties including cloud point (−8 °C) and CFPP (−15 °C) that was further lowered to −25 °C due to addition of flow improvers.     

Biodiesel production from pomace oil and improvement of its properties with synthetic manganese additive

Renewable energy sources are attracting more attention due to lower cost and lower pollution relative to fossil fuels. The aim of this experimental work is the production of renewable and clean methyl ester from pomace oil as an alternative fuel. This oil was obtained from pomace which is the waste of olive oil plants. Optimum producing conditions were determined experimentally. The maximum yield was obtained at 30% of methanol/oil ratio, 60 °C temperature for 60 min with NaOH catalyst. The properties of the biodiesel thus obtained were compared with diesel fuel requirements. An organic based Manganese additive improved the biodiesel properties. Doping the fuel at a ratio of 12 μmol/l oil methyl ester led to a 20.37% decrease in viscosity, 7 °C fall in the flash point and reduced the pour point from 0 °C to −15 °C. This blend of pomace oil methyl ester-diesel fuel with manganese additive was tested in a direct injection diesel engine. The maximum effect of the new fuel blend and diesel fuel on engine performance was obtained at 1400 rpm.     

Hydrocracking of petroleum vacuum distillate containing rapeseed oil: Evaluation of diesel fuel

Hydrocracking of pure petroleum vacuum distillate and the same fraction containing 5 wt.% of rapeseed oil was carried out at 400 and 420 °C and under a hydrogen pressure of 18 MPa over commercial Ni-Mo catalyst. Reaction products were separated by distillation into kerosene, gas oil and the residue. Fuel properties of fractions suitable for diesel production were evaluated (gas oils and remixed blends of kerosene and gas oil). Gas oils obtained from co-processing showed very good fuel properties as the remixed distillates did. Gas oil obtained from co-processing at 420 °C showed also reasonable key low-temperature properties (cloud point: −23 °C, CFPP: −24 °C) similar to those of gas oil obtained from pure petroleum raw material processing.     

Continuous enzymatic production of biodiesel from virgin and waste sunflower oil in supercritical carbon dioxide

A continuous process for biodiesel production in supercritical carbon dioxide was implemented. In the transesterification of virgin sunflower oil with methanol, Lipozyme TL IM led to fatty acid methyl esters yields (FAME) that exceeded 98% at 20 MPa and 40 °C, for a residence time of 20 s and an oil to methanol molar ratio of 1:24. Even for moderate reaction conversions, a fractionation stage based on two separators afforded FAME with >96% purity. Lipozyme TL IM was less efficient with waste cooking sunflower oil. In this case, a combination of Lipozyme TL IM and Novozym 435 afforded FAME yields nearing 99%.     

Transesterification of vegetable oil to biodiesel fuel using acid catalysts in the presence of dimethyl ether

The immiscibility of methanol and vegetable oil leads to a mass-transfer resistance in the transesterification of vegetable oil. To overcome this problem, dimethyl ether (DME) was used as an environmentally friendly cosolvent to produce a homogeneous solution. Methylesterifications of corn oil in both the presence and the absence of DME were performed using p-toluenesulfonic acid (PTSA), benzenesulfonic acid and sulfuric acid. PTSA showed highest catalytic activity. The yield of FAME reached 97.1% when 4 wt% of PTSA based on the oil weight was used at 80 °C with a reaction time of 2 h in the presence of DME. The obtained biodiesel was composed of methyl palmitate (9.1 wt%), methyl oleate (33.9 wt%), methyl linoleate (53.5 wt%), methyl linolenate (3.0 wt%) and methyl arachidate (0.5 wt%), and it was similar to the biodiesel compositions from corn oil as reported. The effects of concentrations of FFA and water on FAME yields were also investigated. All results suggested that the reaction rate was greatly improved by the addition of DME to the reaction system.     

Roselle (Hibiscus sabdariffa L.) oil as an alternative feedstock for biodiesel production in Thailand

The production of biodiesel fuel from crude roselle oil was evaluated in this study. The process of alkali-catalyzed transesterification with methanol was carried out to examine the effects of reaction variables on the formation of methyl ester: variables which included methanol-to-oil molar ratios of 4:1-10:1, catalyst concentrations of 0.25-2.0% w/w of oil, reaction temperatures of 32-60 °C, and reaction times of 5-80 min. The methyl ester content from each reaction condition was analyzed by gas chromatography (GC), the optimum condition having been achieved at a methanol-to-oil molar ratio of 8:1, a catalyst concentration of 1.5% w/w of oil, a reaction temperature of 60 °C, and a reaction time of 60 min. The resultant methyl ester content of 99.4% w/w, plus all of the other measured properties of the roselle biodiesel, met the Thai biodiesel (B100) specifications and international standards EN 14214:2008 (E) and ASTM D 6751-07b, with the exception of a higher carbon residue and lower oxidation stability.     

Biodiesel production from Croton megalocarpus oil and its process optimization

Production of biodiesel from non-edible feedstocks is attracting more attention than in the past, for the purpose of manufacturing alternative fuels without interfering with the food chain. Biodiesel was produced using Croton megalocarpus oil as a non-edible feedstock. C. megalocarpus oil was obtained from north Tanzania. This study aimed at optimizing the biodiesel production process parameters experimentally. The parameters involved in the optimization process were the amount of the catalyst, of alcohol, temperature, agitation speed and reaction time. The optimum biodiesel conversion efficiency obtained was 88% at the optimal conditions of 1.0 wt.% amount of potassium hydroxide catalyst, 30 wt.% amount of methanol, 60 °C reaction temperature, 400 rpm agitation rate and 60 min reaction time. The properties of croton biodiesel which were determined fell within the recommended biodiesel standards. Croton oil was found with a free fatty acid content of 1.68% which is below the 2% recommended for the application of the one step alkaline transesterification method. The most remarkable feature of croton biodiesel is its cold flow properties. This biodiesel yielded a cloud and pour point of −4 °C and −9 °C, respectively, while its kinematic viscosity lay within the recommended standard value. This points to the viability of using croton biodiesel in cold regions.     

Ozonized vegetable oil as pour point depressant for neat biodiesel

The use of ozonized vegetable oils as pour point depressant for neat biodiesel was evaluated. Ozonized vegetable oils (1-1.5% by weight) were effective in reducing the pour point of biodiesel prepared from sunflower oil, soybean oil and rapeseed oil to −24, −12 and −30 °C, respectively. Cloud point however remained unaffected. In the case of palm oil biodiesel, significant reduction was observed in cloud point but not in pour point. Statistical analyses showed that neat biodiesel and biodiesel treated with ozonized vegetable oils showed no significant difference in other properties including density and viscosity. Although ozonized vegetable oils increase the flash point of biodiesel, the values are still within the limits set by the standards in the US and Europe. Lowest reduction in pour point was observed in cases where the biodiesel and the ozonized samples were prepared from the same vegetable oil. Hence, a correlation may exist between the nature of the biodiesel and ozonized oil. Microscopic analysis at low temperature revealed that ozonized vegetable oil impede agglomeration of biodiesel into network of solidified material giving crystals with sizes around 10 μm.     

On maximizing biodiesel mixing ratio based on final product specifications

A model predicting 12 properties of diesel-biodiesel mixtures was developed. This was based on existing correlations capable of providing quality characteristics for the mixtures. The model was also used to maximize the biodiesel fraction in the diesel-biodiesel mixtures, while taking into consideration all product quality specifications as they are defined by Greek Legislation. The properties examined were density, viscosity, cloud point, pour point, volatility at temperatures 250 °C, 350 °C and 360 °C, cetane index, cetane number, sulfur, water, higher heating value, flash point and cold filter plugging point (CFPP). The model was evaluated for mixtures between two diesel types (normal diesel and Shell extra diesel) and four biodiesel types (i.e. biodiesel produced from different vegetable oils). The model was developed in MATLAB and the corresponding biodiesel optimization studies were carried out with the MATLAB's optimization toolbox.     

Heterogeneous catalyzed biodiesel production from Moringa oleifera oil

In this study, biodiesel was produced from Moringa oleifera oil using sulfated tin oxide enhanced with SiO₂ (SO₄²⁻/SnO₂-SiO₂) as super acid solid catalyst. The experimental design was done using design of experiment (DoE), specifically, response surface methodology based on three-variable central composite design (CCD) with alpha (α) = 2. The reaction parameters studied were reaction temperature (60 °C to 180 °C), reaction period (1 h to 3 h) and methanol to oil ratio (1:6 to 1:24). It was observed that the yield up to 84 wt.% of Moringa oleifera methyl esters can be obtained with reaction conditions of 150 °C temperature, 150 min reaction time and 1:19.5 methanol to oil ratio, while catalyst concentration and agitation speed are kept at 3 wt.% and 350-360 rpm respectively. Therefore this study presents the possibility of converting a relatively new oil feedstock, Moringa oleifera oil to biodiesel and thus reducing the world's dependency on existing edible oil as biodiesel feedstock.     

Alkoxylation of biodiesel and its impact on low-temperature properties

A property of biodiesel that currently limits its use to blends of 20% or less is its relatively poor low-temperature properties. Alkoxylation of the unsaturated portion of biodiesel offers the potential benefit of reduced cloud point without compromising ignition quality or oxidation stability. Conventional biodiesel was synthesised from canola oil and the alcohols methanol, ethanol and butanol, epoxidised in situ, and alkoxylated by acid-catalysed oxirane ring opening in the presence of the alcohol of the ester group. Optimal conditions for epoxidation were H₂O₂/biodiesel molar ratio of 2:1, acetic acid/biodiesel molar ratio of 0.2:1, 2 wt% H₂SO₄, 6 h reaction at 60 °C. Alkoxylation resulted in alkoxy substitution rates of 37.1% (methyl), 34.3% (ethyl) and 32.9% (butyl). Selectivity for alkoxy biodiesel was 89.0%, 82.7% and 81.7% for methoxy, ethoxy and butoxy biodiesel, respectively. The cloud point for methyl and ethyl biodiesel increased slightly, while a reduction of 1 K was achieved for butyl biodiesel. The presence of by-products negated much of the expected improvement in cloud point for butoxy butyl biodiesel. Further optimisation work is required to improve both conversion and selectivity if significant improvements in cloud point are to be achieved.     

Continuous biodiesel production using a fixed-bed Lewis-based catalytic system

It was developed a fixed bed tubular continuous reactor to produce biodiesel, using pellets of aluminum oxide doped with zinc oxide. The pellets were placed into a tubular reactor as a 30 cm long column (2.65 kg). The reactor was feed with soybean oil (168 g h⁻¹) and methanol or ethanol (89 g h⁻¹) with the temperature fixed at 100 °C. Under these conditions it was possible to convert soybean oil into biodiesel in up to 75% yield in the case of methanol and 35% for ethanol. Increasing the temperature to 180 °C, it was possible to ethanolise soybean oil with yields up to 78%. It is important to note that after a steady state is achieved the conversions remained approximately constant with time. It is also worth to mention that the fixed bed remained active for more than 120 h, showing no catalyst leaching or deactivation, and so far it was not possible to determine its overall productivity.     

Potassium hydroxide catalyst supported on palm shell activated carbon for transesterification of palm oil

In this study, potassium hydroxide catalyst supported on palm shell activated carbon was developed for transesterification of palm oil. The Central Composite Design (CCD) of the Response Surface Methodology (RSM) was employed to investigate the effects of reaction temperature, catalyst loading and methanol to oil molar ratio on the production of biodiesel using activated carbon supported catalyst. The highest yield was obtained at 64.1 °C reaction temperature, 30.3 wt.% catalyst loading and 24:1 methanol to oil molar ratio. The physical and chemical properties of the produced biodiesel met the standard specifications. This study proves that activated carbon supported potassium hydroxide is an effective catalyst for transesterification of palm oil.     

Reduction of high content of free fatty acid in sludge palm oil via acid catalyst for biodiesel production

In this study, sulphuric acid (H₂SO₄) was used in the pretreatment of sludge palm oil for biodiesel production by an esterification process, followed by the basic catalyzed transesterification process. The purpose of the pretreatment process was to reduce the free fatty acids (FFA) content from high content FFA (> 23%) of sludge palm oil (SPO) to a minimum level for biodiesel production (> 2%). An acid catalyzed esterification process was carried out to evaluate the low content of FFA in the treated SPO with the effects of other parameters such as molar ratio of methanol to SPO (6:1-14:1), temperature (40-80 °C), reaction time (30-120 min) and stirrer speed (200-800 rpm). The results showed that the FFA of SPO was reduced from 23.2% to less than 2% FFA using 0.75% wt/wt of sulphuric acid with the molar ratio of methanol to oil of 8:1 for 60 min reaction time at 60 °C. The results on the transesterification with esterified SPO showed that the yield (ester) of biodiesel was 83.72% with the process conditions of molar ratio of methanol to SPO 10:1, reaction temperature 60 °C, reaction time 60 min, stirrer speed 400 rpm and KOH 1% (wt/wt). The biodiesel produced from the SPO was favorable as compared to the EN 14214 and ASTM D 6751 standard.     

The addition of alkoxy side-chains to biodiesel and the impact on flow properties

Butyl biodiesel was synthesised from canola oil and subsequently epoxidised via the in situ peroxyacetic acid method converting 45% of the unsaturated portion. Alkoxy butyl biodiesel was synthesised under acid conditions with a range of both straight-chain and branched alcohols. Alkoxylation of butyl biodiesel with methanol, ethanol and n-propanol did not improve the cloud or pour point over that for conventional methyl biodiesel. Alkoxylation with alcohols larger than butanol including n-pentanol, n-hexanol and n-octanol produced cloud points that were 5 °C lower than that for methyl biodiesel. The lowest cloud point achieved was for 2-ethylhexoxy butyl biodiesel at −6 °C, representing a 6 °C reduction in cloud point over methyl biodiesel. Alkoxylation did not have a significant effect on the pour point of biodiesel. Alkoxylation of butyl biodiesel resulted in significant increases in viscosity. The kinematic viscosity generally increased with increasing alkoxy chain length and ranged from 6.67 mm² s⁻¹ for methoxy butyl biodiesel to 9.76 mm² s⁻¹ for ethylhexoxy butyl biodiesel, more than double the value for methyl biodiesel. The improved low-temperature properties of the longer-chain alkoxy biodiesel were most likely due to the protruding alkoxy chain, which also resulted in an increase in viscosity. The use of alcohols larger than pentanol does not provide significant benefit in terms of low-temperature properties, and results in an undesirable increase in viscosity.     

Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes

The ionic conductivity and phase arrangement of solid polymeric electrolytes based on the block copolymer polyethylene-b-poly(ethylene oxide) (PE-b-PEO) and LiClO₄ have been investigated. One set of electrolytes was prepared from copolymers with 75% of PEO units and another set was based on a blend of copolymer with 50% PEO units and homopolymers. The differential scanning calorimetry (DSC) results, for electrolytes based on the copolymer with 75% of PEO units, were dominated by the PEO phase. The PEO block crystallinity dropped and the glass transition increased with salt addition due to the coordination of the cation by PEO oxygen. The conductivity for copolymers 75% PEO-based electrolyte with 15 wt% of salt was higher than 10⁻⁵ S/cm at room temperature and reached to 10⁻³ S/cm at 100 °C on a heating measurement. The blend of PE-b-PEO (50% PEO)/PEO/PE showed a complex thermal behavior with decoupled melting of the blocks and the homopolymers. Upon salt addition the endotherms associated with PEO domains disappeared and the PE crystals remained untouched. The conductivity results were limited at 100 °C to values close to 10⁻⁴ S/cm and at room temperature values close to 3 × 10⁻⁶ S/cm were obtained for the 15 wt% salt electrolyte. Raman study showed that the ionic association of the highly concentrated blend electrolytes at room temperature is not significant. Therefore, the lower values of conductivity in the case of the blend with 50% PEO can be assigned to the higher content of PE domains leading to a morphology with lower connectivity for ionic conduction both in the crystalline and melted state of the PE domains.