Engine performance and emission characteristics of marine fish-oil biodiesel produced from the discarded parts of marine fish

Biodiesel is recognized as a clean alternative fuel or as a fuel additive to reduce pollutant emissions from combustion equipment. Because cultivated land is too limited to grow seed-oil plants sufficient to produce both food and biodiesel, non-land-based oleaginous materials have been considered important sources for the production of the latter. In this study, the discarded parts of mixed marine fish species were used as the raw material to produce biodiesel. Marine fish oil was extracted from the discarded parts of mixed marine fish and refined through a series of pretreatment processes. The refined marine fish oil was then transesterified with methyl alcohol to produce biodiesel, which was used thereafter as engine fuel to investigate its engine performance and emission characteristics. The experimental results show that, compared with commercial biodiesel from waste cooking oil, marine fish-oil biodiesel has a larger gross heating value, elemental carbon and hydrogen content, cetane index, exhaust gas temperature, brake fuel conversion efficiency, NO_x and O₂ emissions, and black smoke opacity and a lower elemental oxygen content, fuel consumption rate, brake-specific fuel consumption rate, equivalence ratio, and CO emission. Compared with ASTM No. 2D diesel, both marine fish-oil and waste cooking-oil biodiesels appear to have a lower gross heating value, cetane index, exhaust gas temperature, equivalence ratio, black smoke opacity, elemental carbon content, and CO emission and a higher fuel consumption rate and elemental oxygen content.     

Improving the economics of biodiesel production through the use of low value lipids as feedstocks: vegetable oil soapstock

Semirefined and refined vegetable oils are the predominant feedstocks for the production of biodiesel. However, their relatively high costs render the resulting fuels unable to compete with petroleum-derived fuel. We have investigated the production of fatty acid methyl esters (FAME; biodiesel) from soapstock (SS), a byproduct of edible oil refining that is substantially less expensive than edible-grade refined oils. Multiple approaches were taken in search of a route to the production of fatty acid methyl esters from soybean soapstock. The most effective method involved the complete saponification of the soapstock followed by acidulation using methods similar to those presently employed in industry. This resulted in an acid oil with a free fatty acid (FFA) content greater than 90%. These fatty acids were efficiently converted to methyl esters by acid-catalyzed esterification. The fatty acid composition of the resulting ester product reflected that of soy soapstock and was largely similar to that of soybean oil. Following a simple washing protocol, this preparation met the established specifications for biodiesel of the American Society for Testing and Materials. Engine emissions and performance during operation on soy soapstock biodiesel were comparable to those on biodiesel from soy oil. An economic analysis suggested that the production cost of soapstock biodiesel would be approximately US$ 0.41/l, a 25% reduction relative to the estimated cost of biodiesel produced from soy oil.     

Novel biodiesel production technology from soybean soapstock

This paper describes an attractive method to make biodiesel from soybean soapstock (SS). A novel recovery technology of acid oil (AO) from SS has been developed with only sulfuric acid solution under the ambient temperature (25±2 °C). After drying, AO contained 50.0% FFA, 15.5% TAG, 6.9% DAG, 3.1% MAG, 0.8% water and other inert materials. The recovery yield of AO was about 97% (w/w) based on the total fatty acids of the SS. The acid oil could be directly converted into biodiesel at 95 °C in a pressurized reactor within 5 hours. Optimal esterification conditions were determined to be a weight ratio of 1 : 1.5 : 0.1 of AO/methanol/sulfuric acid. Higher reaction temperature helps to shorten the reaction time and requires less catalyst and methanol. Ester content of the biodiesel derived from AO through one-step acid catalyzed reaction is around 92%. After distillation, the purity of the biodiesel produced from AO is 97.6% which meets the Biodiesel Specification of Korea. The yield of purified biodiesel was 94% (w/w) based on the total fatty acids of the soapstock.     

Simple, high-efficiency synthesis of fatty acid methyl esters from soapstock

We report a simple method that efficiently esterifies the fatty acids in soapstock, an inexpensive, lipid-rich by-product of edible oil production. The process involves (i) alkaline hydrolysis of all lipid-linked fatty acid ester bonds and (ii) acid-catalyzed esterification of the resulting fatty acid sodium salts. Step (i) completely saponified all glycerides and phosphoglycerides in the soapstock. Following water removal, the resulting free fatty acid sodium salts were rapidly and quantitatively converted to fatty acid methyl esters (FAME) by incubation with methanol and sulfuric acid at 35°C and ambient pressure. Minimum molar reactant ratios for full esterification were fatty acids/methanol/sulfuric acid of 1∶30∶5. The esterification reaction was substantially complete within 10 min and was not inhibited by residual water contents up to ca. 10% in the saponified soapstock. The product FAME contained >99% fatty acid esters, 0% triglycerides, <0.05% diglycerides, <0.1% monoglycerides, and <0.8% free fatty acids. Free fatty acid levels were further reduced by washing with dilute sodium hydroxide. Free and total glycerol were <0.01 and <0.015%, respectively. The water content was <0.04%. These values meet the current specifications for biodiesel, a renewable substitute for petroleum-derived diesel fuel. The identities and proportions of fatty acid esters in the FAME reflected the fatty acid content of soybean lipids. Solids formed during the reaction contained 69.1% ash and 0.8% protein. Their sodium content indicated that sodium sulfate was the prime inorganic component. Carbohydrate was the predominant organic constituent of the solid.     

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.     

The question of differences between iodine numbers of coconut oil and of the corresponding soapstock fatty acids

Summary Experiments have been made on coconut oil from pure endosperm, pure testa, and normal mixtures of the two. These experiments have shown that the spread in iodine value between refined coconut oil and the fatty acids found on the corresponding soapstock are greater than can be accounted for by the proportion of testa oil present in extracted whole crude oils. Furthermore the iodine value of the free fatty acid fraction of pure endosperm oils was found to be higher than that of the combined fatty acids in the same oils by an amount which varied inversely as the degree of hydrolysis which had occurred in the oil. From this it appears that preferential hydrolysis plays an important part in the production of coconut oil soapstock having higher iodine values than those of the corresponding refined oils. Attention is also called to some European publications which deal with this question and to the possibility that molds may be involved through their ability to decompose short chain acids to ketones.     

Enzymatic conversion of waste edible oil to biodiesel fuel in a fixed-bed bioreactor

The conversion of waste edible oil to biodiesel fuel in a fixed-bed bioreactor was investigated. Three-step methanolysis of waste oil was conducted using three columns packed with 3 g of immobilized Candida antarctica lipase. A mixture of waste oil and 1/3 molar equivalent of methanol against total fatty acids in the oil was used as substrate for the first-step reaction, and mixtures of the first- and second-step eluates and 1/3 molar equivalent of methanol were used for the second- and third-step reactions, respectively. Ninety percent of waste oil was converted to the corresponding methyl esters (ME) by feeding substrate mixtures into the first, second, and third reactors at flow rates of 6, 6 and 4 mL/h, respectively. We also attempted one-step methanolysis of waste oil. When a mixture of waste oil and 90% ME-containing eluate (1∶3, wt/wt) and an equimolar amount of methanol against total fatty acids in the waste oil was fed into a reactor packed with 3 g of immobilized C. antarctica lipase at a flow rate of 4 mL/h, the ME content in the eluate reached 90%. The immobilized biocatalyst could be used for 100 d in the two reaction systems without significant decrease in its activity. Waste oil contained 1980 ppm water and 2.5% free fatty acids, but these contaminants had little influence on enzymatic production of biodiesel fuel.     

Production of biodiesel from soapstock using an ion-exchange resin catalyst

The feasibility of biodiesel production from soapstock containing high water content and fatty matters by a solid acid catalyst was investigated. Soapstock was converted to high-acid acid oil (HAAO) by the hydrolysis by KOH and the acidulation by sulfuric acid. The acid value of soapstock-HAAO increased to 199.1 mg KOH/g but a large amount of potassium sulfate was produced. To resolve the formation of potassium sulfate, acid oil was extracted from soapstock and was converted to HAAO by using sodium dodecyl benzene sulfonate (SDBS). The maximum acid value of acid oil-HAAO was 194.2 mg KOH/g when the mass ratio of acid oil, sulfuric acid, and water was 10: 4: 10 at 2% of SDBS. In the esterification of HAAO using Amberylst-15, fatty acid methyl ester (FAME) concentration was 91.7 and 81.3% for soapstock and acid oil, respectively. After the distillation, FAME concentration became 98.1% and 96.7% for soapstock and acid oil. The distillation process decreased the total glycerin and the acid value of FAME produced a little.     

Iodine values of acidulated coconut oil soapstock

Summary Analyses and comparisons of a number of representative samples have shown that acidulated coconut oil soapstock may have an iodine value as much as 100% greater than that of the corresponding refined oil without any contamination being involved. Exactly what the spread between any given soapstock and oil will be apparently depends on the free fatty acid content of the original crude oil and the relative efficiency of the refining process. It was found that, for coconut soapstocks produced by standard laboratory refining tests, the relation between free fatty acid content and iodine value spread can be represented by the formula I.V. Spread=9.5–759 FFA. The efficiency of the refining process affects results insofar as it reduces the entrainment of neutral oil. Removing all of the neutral oil from four laboratory-produced soapstocks prior to acidulation raised the iodine value approximately two units in all cases. The practical significance of these results is obvious. A refiner processing high grade crude coconut oil of 9.5, iodine value by a highly efficient refining procedure cannot be expected to produce an acidulated soapstock of less than about 18.0 in iodine value. With higher free fatty acid crude oil and less efficient refining procedures lower iodine values are possible, but since soapstock is of minor economic value compared to refined oil, the trend will always be toward better grade crude oils and more efficient refining processes.     

Production of mixed methyl/ethyl esters from waste fish oil through transesterification with mixed methanol/ethanol system

Biodiesel (mixed fatty acid methyl/ethyl esters) was prepared from waste fish oil through base-catalyzed transesterification with mixed methanol/ethanol system. Effect of methanol/ethanol (% v/v), type and concentration of the catalyst, mixed alcohols to oil molar ratio, the reaction temperature, and the reaction time on the biodiesel yield was optimized. Maximum biodiesel yield (97.30?wt%) was produced by implementing 1:1 methanol/ethanol (v/v), 1.0?wt% KOH, 6:1 mixed alcohols to oil molar ratio, 40°C reaction temperature, and 30?min of reaction time. Conversion of the waste fish oil to mixed methyl/ethyl esters was confirmed by ¹H NMR spectroscopy. Fuel properties of the resulting biodiesel in addition to its blends with petrodiesel were in good agreement with specifications of ASTM D6751 and ASTM D7467, respectively. Therefore, it was concluded that using mixed alcohol system for biodiesel production could reduce the production cost through reducing conditions required for maximum conversion.     

Fuel properties of biodiesel produced from Camellia oleifera Abel oil through supercritical-methanol transesterification

The fuel properties of the biodiesel produced from Camellia oleifera Abel oil through supercritical-methanol transesterification with no catalyst was investigated in this study. An emulsion of raw C. oleifera Abel oil dispersed in methanol was prepared prior to being poured into a supercritical-methanol reaction system to undergo the transesterification reaction. The fuel properties of the resulting biodiesel were analyzed and compared with those of a commercial biodiesel and with ASTM No. 2D diesel fuel. The experimental results show oleic acid (C18:1) and palmitic acid (16:0) to be the two major components of the C. oleifera Abel oil biodiesel. It also contains significantly higher mono-unsaturated fatty acids and long carbon-chain fatty acids ranging from C20 to C22 than those found in the commercial biodiesel. However, relative to the commercial biodiesel, the C. oleifera Abel oil biodiesel has significantly fewer poly-unsaturated fatty acids with more than three double bonds, which implies that it also has a much higher degree of oxidative stability. In addition, the biodiesel produced from C. oleifera Abel oil was also found to have more favorable fuel properties than the commercial biodiesel produced from waste cooking oil, including a higher heat of combustion and flash point and lower levels of kinematic viscosity, water content, and carbon residue. Moreover, the former appears to have much lower peroxide and acid values, and thus a much higher degree of oxidative stability than the latter.     

Fatty acid composition of oils from 21 species of marine fish,freshwater fish and shellfish

The fatty acid composition of body lipids was determined by GLC for 14 species of saltwater fish, three species of freshwater fish and four species of shellfish. In addition, liver lipids of two species and egg lipids of one species were analyzed for comparison with the fish body lipids. The various species ranged from lean to fatty and contained from 0.7~15.5% oil in the tissues. Certain major fatty acids were found to vary widely among the species, as follows: 1.6~8.0% myristic, 9.5~33.4% palmitic, 2.0~11.2% palmitoleic, 5.2~29.1% oleic, 0.7~10.5% eicosenoic, 5.0~21.5% eicosapentaenoic, 0.2~11.6% docosenoic and 5.9~26.2% docosahexaenoic acids. Analyses of two separate mullet-oil samples illustrated the wide differences that are possible for a single species caught during different seasons. Significant differences in the amt of particular fatty acids were found in comparing freshwater-fish analyses with analyses for marine fish. Oysters and scallops showed large amt of pentaenoic and hexaenoic acids in their oils. Presented in part at the AOCS Meeting, New York, 1960.     

Elevated levels of arachidonic acid in fish from northern Australian coastal waters

The fatty acid composition of 10 species of fish caught off the northwest coast of Australia (latitude 17°S) was examined. All species contained high levels of ω6 fatty acids (9.6–23.1% of total fatty acids) with arachidonic acid being the major ω6 fatty acid (5.9–14.8% of fatty acids). Docosatetraenoic and docosapentaenoic acids of the ω6 series accounted for 3–8% of the total fatty acids. The ratio of ω6 to ω3 fatty acids in these fish varied from 0.38 to 0.93, compared with an average ratio of 0.16 for fish from the northern hemisphere (latitude >30°N). The present data and figures from the literature indicate that the marine food chain in the southern hemisphere contains significant quantities of ω6 fatty acids.     

Synthesis of biodiesel fuel from safflower oil using various reaction parameters

Biodiesel fuel is gaining more and more importance because of the depletion and uncontrollable prices of fossil fuel resources. The use of vegetable oil and their derivatives as alternatives for diesel fuel is the best answer and as old as Diesel Engine. Chemically biodiesel fuel is the mono alkyl esters of fatty acids derived from renewable feed stocks like vegetable oils and animal fats. Safflower oil contains 75-80% of linoleic acid; the presence of this unsaturated fatty acid is useful in alleviating low temperature properties like pour point, cloud point and cold filter plugging point. In this paper we studied the effect of various parameters such as temperature, molar ratio (oil to alcohol), and concentration of catalyst on synthesis of biodiesel fuel from safflower oil. The better suitable conditions of 1:6 molar ratio (oil to alcohol), 60 degrees C temperature and catalyst concentration of 2% (by wt. of oil) were determined. The finally obtained biodiesel fuel was analyzed for fatty acid composition by GLC and some other properties such as flash point, specific gravity and acid value were also determined. From the results it was clear that the produced biodiesel fuel was with in the recommended standards of biodiesel fuel with 96.8% yield.     

Performance and emission study of waste anchovy fish biodiesel in a diesel engine

Waste anchovy fish oils transesterification was studied with the purpose of achieving the conditions for biodiesel usage in a single cylinder, direct injection compression ignition. With this purpose, the pure biodiesel produced from anchovy fish oil, biodiesel-diesel fuel blends of 25%:75% biodiesel-diesel (B25), 50%:50% biodiesel-diesel (B50), 75%:25% biodiesel-diesel (B75) and petroleum diesel fuels were used in the engine to specify how the engine performance and exhaust emission parameters changed. The fuel properties of test fuels were analyzed. Tests were performed at full load engine operation with variable speeds of 1000, 1500, 2000 and 2500 rpm engine speeds. As results of investigations on comparison of fuels with each other, there has been a decrease with 4.14% in fish oil methyl ester (FOME) and its blends' engine torque, averagely 5.16% reduction in engine power, while 4.96% increase in specific fuel consumption have been observed. On one hand there has been average reduction as 4.576%, 21.3%, 33.42% in CO₂, CO, HC, respectively; on the other hand, there has been increase as 9.63%, 29.37% and 7.54% in O₂, NO_x and exhaust gas temperature has been observed. It was also found that biodiesel from anchovy fish oil contains 37.93 wt.% saturated fatty acids which helps to improve cetane number and lower NO_x emissions. Besides, for biodiesel and its blends, average smoke opacity was reduces about 16% in comparison to D2. It can be concluded that waste anchovy fish obtained from biodiesel can be used as a substitute for petroleum diesel in diesel engines.     

The potential of soapstock-derived film: Cottonseed and safflower

Oilseed soapstock is seldom used today for the recovery of fatty acids, but it is often added to oilseed meal. The energy value of oilseed meal is marginally increased by the addition of soapstock. To find alternative uses for oilseed by-products, cottonseed and safflower soapstock samples from industrial plants were characterized using American Oil Chemists’ Society recommended and modified methods. The characterization included moisture and volatiles, phosphorus and nitrogen, neutral oil, total fatty acid amount and individual fatty acid profile, and total gossypol for cottonseed soapstock samples. The characterization indicated that cottonseed soapstock samples contained a slightly larger amount of neutral oil than safflower. These soapstock samples were frozen to −40°C at 40 mm Hg for more than 8 h, thawed, and the low-boiling compounds were removed by evaporation under reduced pressure. The freeze-dried soapstocks were mechanically pulverized in an inert atmosphere until able to pass through a 50-mesh screen. When these freeze-dried soapstock particles were rehydrated with deionized water, the formation of a gel phase was observed. Casting of this gel phase onto a substrate and subsequent drying without heating resulted in a thin film, a liposomelike material, with a uniform thickness of about 0.01”. The lamination capability of freeze-dried oilseed soapstocks by rehydration may be attributed to the formation of multiple bilayer lamellae by phospholipids from the oilseed soapstock. Due to its biodegradable nature, the use of soapstock-derived film as a composite or by itself as an encapsulating agent is highly attractive. The potential of this liposome-like material as a chemical carrier is discussed.     

Biodiesel processing and production

Biodiesel is an alternative diesel fuel that is produced from vegetable oils and animal fats. It consists of the monoalkyl esters formed by a catalyzed reaction of the triglycerides in the oil or fat with a simple monohydric alcohol. The reaction conditions generally involve a trade-off between reaction time and temperature as reaction completeness is the most critical fuel quality parameter. Much of the process complexity originates from contaminants in the feedstock, such as water and free fatty acids, or impurities in the final product, such as methanol, free glycerol, and soap. Processes have been developed to produce biodiesel from high free fatty acid feedstocks, such as recycled restaurant grease, animal fats, and soapstock.     

氧化锌催化菜籽油制生物柴油

氧化锌被用于菜籽油甲醇酯交换反应催化剂并制备生物柴油,从不同的锌盐得到的氧化锌在170～220 ℃都具有很好的活性。对氧化锌催化剂进行了活性评价和反应条件研究。结果表明,氧化锌催化剂具有很好的抗酸和抗水性能,在水质量分数高达20%和游离脂肪酸高达15%时,仍保持较高的反应转化率,可大幅度简化原料油的预处理和产品的分离纯化过程。     

Prospects of non-catalytic supercritical methyl acetate process in biodiesel production

Conventional biodiesel production methods utilize alcohol as acyl acceptor and produces glycerol as side product. Hence, with escalating production of biodiesel throughout the world, it leads to oversupply of glycerol and subsequently causes devaluation in the market. In this study, methyl acetate was employed as acyl acceptor in non-catalytic supercritical methyl acetate (SCMA) process to produce fatty acid methyl esters (FAME) and side product of triacetin, a valuable fuel additive instead of glycerol. Consequently, the properties of biodiesel produced (FAME and triacetin) are superior compared to conventional biodiesel method (FAME only). In this research, the effects of reaction temperature, reaction time and molar ratio of methyl acetate to oil on the yield of biodiesel were investigated. Apart from that, the influence of impurities commonly found in waste oils/fats such as free fatty acids and water were studied as well and compared with methanol-based reactions of supercritical and heterogeneous catalysis. Results show that biodiesel yields in SCMA process could achieve 99 wt.% when the operating conditions were fixed at 400 °C/220 bar for reaction temperature, methyl acetate/oil molar ratio of 30:1 and 60 min of reaction time. Furthermore, SCMA did not suffer from adverse effect with the presence of impurities, proving that SCMA has a high tolerance towards contamination which is crucial to allow the utilization of inexpensive waste oils/fats as biodiesel feedstock.     

Production of FAME from acid oil,a by-product of vegetable oil refining

Simple alkyl FA esters have numerous uses, including serving as biodiesel, a fuel for compression ignition (diesel) engines. The use of acid-catalyzed esterification for the synthesis of FAME from acid oil, a by-product of edible vegetable oil refining that is produced from soapstock, was investigated. Soybean acid oil contained 59.3 wt% FFA, 28.0 wt% TAG, 4.4 wt% DAG, and less than 1% MAG. Maximum esterification occurred at 65°C and 26 h reaction at a molar ratio of total FA/methanol/sulfuric acid of 1∶15∶1.5. Residual unreacted species under these conditions, as a fraction of their content in unesterified acid oil, were FFA, 6.6%; TAG, 5.8%; and DAG, 2.6%. This corresponds to estimated concentrations of FFA, 3.2%; TAG, 1.3%; and DAG, 0.2%, on a mass basis, in the ester product. In an alternative approach, the acylglycerol species in soapstock were saponified prior to acidulation. High-acid (HA) acid oil made from this saponified soapstock had an FFA content of 96.2 wt% and no detectable TAG, DAG, or MAG. Optimal esterification conditions for HA acid oil at 65°C were a mole ratio of FFA/methanol/acid of 1∶1.8∶0.17, and 14 h incubation. FAME recovery under these conditions was 89% of theoretical, and the residual unesterified FFA content was approximately 20 mg/g. This was reduced to 3.5 mg/g, below the maximum FFA level allowed for biodiesel, by washing with NaCl, NaHCO₃, and Ca(OH)₂ solutions. Alternatively, by subjecting the unwashed ester layer to a second esterification, the FFA level was reduced to less than 2 mg/g. The acid value of this material exceeded the maximum allowed for biodiesel, but was reduced to an acceptable value by a brief wash with 0.5 N NaOH.