Low-temperature property and engine performance evaluation of ethyl and isopropyl esters of tallow and grease

Three monoalkyl fatty acid esters derived from tallow and grease were prepared by lipase-catalyzed transesterification and evaluated as prospective diesel engine fuels. The low-temperature properties of the esters, both neat and as 20% blends in No. 2 diesel fuel, were evaluated. Those properties included cloud point, pour point, cold filter plugging point, low-temperature flow test, and crystallization onset temperature. Other properties of the esters, such as kinematic viscosity, heating value, and calculated cetane number, also were determined. All three esters had acceptable physical and low-temperature properties, as well as acceptable fuel properties at the 20% level in diesel blends. Engine performance and emissions for the ester blends were determined in a direct-injection, matched two-cylinder diesel engine. Among the monoalkyl esters studied, ethyl greasate had better properties and engine performance characteristics than the two tallow esters. For the latter esters, isopropyl tallowate had better properties than ethyl tallowate. Presented in part at the 88th Annual Meeting of American Oil Chemists’ Society, Seattle, WA, May 1997.     

Low-temperature properties of alkyl esters of tallow and grease

The low-temperature properties of mono-alkyl esters derived from tallow and recycled greases were determined for neat esters and 20% ester blends in No. 2 low-sulfur diesel fuel. Properties studied included cloud point, pour point, cold filter plugging point, low-temperature flow test, crystallization onset temperature, and kinematic viscosity. Compositional properties of the alkyl esters determined included water, residual free fatty acids, and free glycerol content. In general, the secondary alkyl esters of tallow showed significantly improved cold-temperature properties over the normal tallow alkyl ester derivatives. The low-temperature flow test did not show a 1:1 correlation with cloud point as previously observed with methyl soyate and methyl tallowate. For the homologous series methyl to n-butyl tallowate, ethyl tallowate had the best broad-spectrum low-temperature properties, both neat and when blended in diesel fuel. For the greases studied, both the normal and branched alkyl ester derivatives showed improved properties over corresponding tallow esters, especially with neat esters.     

Low-temperature properties of triglyceride-based diesel fuels: Transesterified methyl esters and petroleum middle distillate/ester blends

This work examines low-temperature properties of triglyceride-based alternate fuels for direct-injection compression-ignition engines. Methyl esters from transesterified soybean oil were studied as neat fuels and in blends with petroleum middle distillates (No. 1 or No. 2 diesel fuel). Admixed methyl esters composed of 5–30 vol% tallowate methyl esters in soyate methyl esters were also examined. Pour points, cloud points, and kinematic viscosities were measured; viscosities at cooler temperatures were studied to evaluate effects of sustained exposure. Low-temperature filterability studies were conducted in accordance with two standard methodologies. The North American standard was the low-temperature flow test (LTFT), and its European equivalent was the cold-filter plugging point (CFPP). With respect to cold-flow properties, blending methyl esters with middle distillates is limited to relatively low ester contents before the properties become preclusive. Under most conditions, cold-flow properties were not greatly affected by admixing the methyl esters with up to 30 vol% tallowate (before blending). Least squares analysis showed that both LTFT and CFPP of formulations containing at least 10 vol% methyl esters are linear functions of cloud point. In addition, statistical analysis of the LTFT data showed a strong 1:1 correlation between LTFT and CP. This result may prove crucial in efforts to improve low-temperature flow properties of alternate diesel fuels that contain methyl esters derived from triglycerides.     

Fuel properties of tallow and soybean oil esters

Fuel properties of beef tallow, soybean oil, their esters, and blends with No. 2 diesel fuel and ethanol were determined. Fuel properties tested were viscosity, specific gravity, API gravity, distillation ranges, calculated cetane index, energy content, flash point, water content, sulfur content, carbon residue, particulate matter, acid value, copper-strip corrosion test, ash content, melting point, cloud point, and pour point. Gas-chromatographic analyses of tallow, soybean oil, and their esters were performed to determine their major constituents. Viscosities of soybean oil and tallow were significantly reduced by esterification. Other fuel properties of the esters and their blends with No. 2 diesel fuel and ethanol were similar to the properties of No. 2 diesel fuel.     

Fuel properties and nitrogen oxide emission levels of biodiesel produced from animal fats

FAME of lard, beef tallow, and chicken fat were prepared by base-catalyzed transesterification for use as biodiesel fuels. Selected fuel properties of the neat fat-derived methyl esters (B100) were determined and found to meet ASTM specifications. The cold-flow properties, lubricity, and oxidative stability of the B100 fat-derived fuels also were measured. In general, the cold-flow properties of the fat-based fuels were less desirable than those of soy-based biodiesel, but the lubricity and oxidative stability of the fat-based biodiesels were comparable to or better than soy-based biodiesel. Nitrogen oxide (NO_x) emission tests also were conducted with the animal fat-derived esters and compared with soybean oil biodiesel as 20 vol% blends (B20) in petroleum diesel. The data indicated that the three animal fat-based B20 fuels had lower NO_x emission levels (3.2–6.2%) than did the soy-based B20 fuel.     

Cold flow properties of fuel mixtures containing biodiesel derived from animal fatty waste

The aims of the present study were to evaluate the cold temperature behavior of methyl esters of vegetable and animal origin and of their mixtures with fossil diesel fuel, as well as to investigate the effectiveness of different depressants. Various blends of rapeseed oil methyl esters, linseed oil methyl esters, pork lard methyl esters and fossil diesel fuel were prepared, and both cloud point and cold filter plugging point (CFPP) were analyzed. It was found that mixtures with CFPP values of –5 °C and lower may contain up to 25% of pork lard methyl esters; whereas the ratio of summer fossil diesel fuel and rapeseed oil methyl esters may vary over a wide range, i.e. such mixtures can be used in a diesel engine in the summer. In the transitory periods it is possible to use up to 20% animal and vegetable ester blends (3 : 7) with winter fossil diesel, whereas only up to 5% of esters can be added to the fuel used in winter. In order to improve the cold properties of rapeseed oil, pork lard and linseed oil methyl ester mixtures, various additives were tested. Depressant Viscoplex 10–35 with an optimal dose of 5000 mg/kg was found to be the most effective.     

Improving the low-temperature properties of alternative diesel fuels: Vegetable oil-derived methyl esters

This work explores near-term approaches for improving the low-temperature properties of triglyceride oil-derived fuels for direct-injection compression-ignition (diesel) engines. Methyl esters from transesterified soybean oil were evaluated as a neat fuel and in blends with petroleum middle distillates. Winterization showed that the cloud point (CP) of methyl soyate may be reduced to −16°C. Twelve cold-flow additives marketed for distillates were tested by standard petroleum methodologies, including CP, pour point (PP), kinematic viscosity, cold filter plugging point (CFPP), and low-temperature flow test (LTFT). Results showed that additive treatment significantly improves the PP of distillate/methyl ester blends; however, additives do not greatly affect CP or viscosity. Both CFPP and LTFT were nearly linear functions of CP, a result that compares well with earlier studies with untreated distillate/methyl ester blends. In particular, additives proved capable of reducing LTFT of neart methyl esters by 5–6°C. This work supports earlier research on the low-temperature properties; that is, approaches for improving the cold flow of methyl ester-based diesel fuels should continue to focus on reducing CP.     

Crystallization characteristics of methyl tallowate and its blends with ethanol and diesel fuel

Methyl tallowate was prepared from edible beef tallow via transesterification, and was blended with ethanol and/or No.2 diesel fuel in different ratios. Crystallization characteristics of methyl tallowate and its blends were studied at temperatures ranging from 22 to −16°C. Blending ethanol with methyl tallowate reduced crystal formation at all temperatures. As the temperature of the blends was reduced from 22 to 0°C, there was no effect on crystal formation of saturated vs. unsaturated fatty acids. Below 0°C, the saturated fatty acids crystallized at a much faster rate than the unsaturated fatty acids.     

Thermal analysis of alternative diesel fuels from vegetable oils

The relatively poor cold-flow properties of monoalkyl esters of vegetable oils and animal fats (biodiesel) present a major obstacle to their development as alternative fuels and extenders for combustion in direct injection compressionignition (diesel) engines. In this work, differential scanning calorimetry (DSC) heating and cooling curves of methyl soyate (SME), methyl tallowate (TME), SME/TME admixtures, and winterized SME were analyzed. Completion of melt, crystallization onset (Onset), and other temperatures corresponding to melting and freezing peaks were correlated to predict cloud point (CP), pour point (PP), cold filter plugging point (CFPP), and low-temperature flow test (LTFT) data. Effects of treating methyl esters with cold-flow improvers were examined. Low-temperature flow properties of biodiesel may be accurately inferred from subambient DSC analyses of high-melting or freezing (β-form) peaks. The temperature of maximal heat flow for freezing peaks gave the best accuracy for predicting CP, PP, and CFPP, while freezing point gave the best accuracy for predicting LTFT. Onset also gave good correlations with respect to predicting PP, CFPP, and LTFT. Cooling scan parameters were more reliable than heating scan parameters. Presented at the 88th American Oil Chemists’ Society’s Annual Meeting & Expo, Seattle, Washington, May 11–14, 1997.     

Efficiencies of various esters of fatty acids as diesel fuels

Methyl esters of commercial grades of lauric, myristic, palmitic, stearic, linoleic and linolenic acids, as well as ethyl and butyl esters of oleic acid, were burned in a diesel engine to determine their efficiencies as fuels. Triolein and some common vegetable oils were burned as comparison fuels and No. 2 diesel fuel was used as a control. The fuels were tested in a single-cylinder direct-injection engine running at rated speed and load in short-term, performance engine tests. Specific fuel consumption and thermal efficiencies of the engine burning these fuels were then determined. Among the methyl esters of the saturated acids, thermal efficiency was inversely related to chain length of the fatty acid. Introduction of a double bond resulted in increased efficiency. Further increases in unsaturation had negligible effects on thermal efficiencies. Ethyl oleate had the highest thermal efficiency and butyl oleate had the lowest thermal efficiency of any of the ester fuels tested. Most of the ester fuels produced higher thermal efficiencies than did No. 2 diesel fuel. Triolein produced the lowest specific fuel consumption of the triglyceride fuels and peanut oil produced the lowest specific fuel consumption of the vegetable oils. The data suggest that ethyl esters of monounsaturated or short-chain fatty acids should make good alternative fuels and that they should be further evaluated in longterm engine tests.     

Performance and emissions of bus engine using blends of diesel fuel with bio-diesel of sunflower or cottonseed oils derived from Greek feedstock

An experimental investigation is conducted to evaluate the use of sunflower and cottonseed oil methyl esters (bio-diesels) of Greek origin as supplements in the diesel fuel at blend ratios of 10/90 and 20/80, in a fully instrumented, six-cylinder, turbocharged and after-cooled, direct injection (DI), Mercedes-Benz, mini-bus diesel engine installed at the authors’ laboratory. The tests are conducted using each of the above fuel blends, with the engine working at two speeds and three loads. Fuel consumption, exhaust smokiness and exhaust regulated gas emissions such as nitrogen oxides, carbon monoxide and total unburned hydrocarbons are measured. The differences in the measured performance and exhaust emissions from the baseline operation of the engine, i.e., when working with neat diesel fuel, and the two bio-diesels are determined and compared. Theoretical aspects of diesel engine combustion with the differing physical and chemical properties of these blends, aid the correct interpretation of the observed engine behavior.     

The production of fatty acid isopropyl esters and their use as a diesel engine fuel

Biodiesel is an alternative fuel for diesel engines that consists of the monoalkyl esters of vegetable oils or animal fats. Currently, most biodiesel consists of methyl esters, which have poor cold-flow properties. Methyl esters of soybean oil will crystallize and plug fuel filters and lines at about 0°C. However, isopropyl esters have better cold-flow properties than methyl esters. This paper describes the production of isopropyl esters and their evaluation in a diesel engine. The effects of the alcohol amount, the catalyst amount, and two different catalysts on producing quality biodiesel were studied. Both sodium isopropoxide and potassium isopropoxide were found to be suitable for use in the transesterification process. A 20∶1 alcohol/TG molar ratio and a catalyst amount equal to 1% by weight (based on the TG amount) of sodium metal was the most cost-effective way to produce biodiesel fuel. The emissions from a diesel engine running on isopropyl esters made from soybean oil and yellow grease were investigated by comparing them with No. 2 diesel fuel and methyl esters. For nitrogen oxide emission, the difference between the biodiesel produced from soybean oil and yellow grease was greater than the difference between the methyl and isopropyl esters of both feedstocks. The other emissions from using isopropyl esters were about 50% lower in hydrocarbons, 10–20% lower in carbon monoxide, and 40% lower in smoke number when compared with No. 2 diesel fuel.     

Use of branched-chain esters to reduce the crystallization temperature of biodiesel

To reduce the tendency of biodiesel to crystallize at low temperatures, branched-chain alcohols were used to esterify various fats and oils, and the crystallization properties of the branched esters were compared with those of methyl esters by using differential scanning calorimetry (DSC), cloud point, and pour point. Compared with the methyl esters that are commonly used in biodiesel, branched-chain esters greatly reduced the crystallization onset temperature (T_CO) of neat esters and their corresponding ester diesel fuel blends. Isopropyl and 2-butyl esters of normal (∼10 wt% palmitate) soybean oil (SBO) crystallized 7–11 and 12–14°C lower, respectively, than the corresponding methyl esters. The benefit of the branched-chain esters in lowering T_CO increased when the esters were blended with diesel fuel. Esters made from a low-palmitate (3.8%) SBO crystallized 5–6°C lower than those of normal SBO. Isopropyl esters of lard and tallow had T_CO values similar to that of methyl esters of SBO. DSC provided an accurate means of monitoring crystallization, and the DSC results correlated with cloud and pour point measurements.     

Solubility of a diesel–biodiesel–ethanol blend,its fuel properties,and its emission characteristics from diesel engine

In this work, we studied the phase diagram of diesel–biodiesel–ethanol blends at different purities of ethanol and different temperatures. Fuel properties (such as density, heat of combustion, cetane number, flash point and pour point) of the selected blends and their emissions performance in a diesel engine were examined and compared to those of base diesel. It was found that the fuel properties were close to the standard limit for diesel fuel; however, the flash point of blends containing ethanol was quite different from that of conventional diesel. The high cetane value of biodiesel could compensate for the decrease of the cetane number of the blends caused by the presence of ethanol. The heating value of the blends containing lower than 10% ethanol was not significantly different from that of diesel. As for the emissions of the blends, it was found that CO and HC reduced significantly at high engine load, whereas NO_x increased, when compared to those of diesel. Taking these facts into account, a blend of 80% diesel, 15% biodiesel and 5% ethanol was the most suitable ratio for diesohol production because of the acceptable fuel properties (except flash point) and the reduction of emissions.     

Physical and chemical properties of ethanol-diesel fuel blends

This paper discusses the physical-chemical properties of ethanol-diesel fuel blends. The attention is focused on the properties which influence the injection and engine characteristics significantly. Main properties have been investigated experimentally. The analysis of experimentally obtained fuel properties of tested fuels and their influence on engine characteristics are presented. Physical and chemical properties of diesel fuel and ethanol-diesel fuel blends were measured according to requirements and test methods for diesel fuel (EN590, 2003). The tested fuels were neat mineral diesel fuel (D100), 5% (v/v) ethanol/diesel fuel blend (E05D95), 10% (v/v) ethanol-diesel fuel blend (E10D90) and 15% (v/v) ethanol-diesel fuel blend (E15D85). It has been proved that, for ethanol-diesel fuel blends, some additives are necessary to keep stability under low temperature conditions. Also, cold weather properties test, such as cloud point and pour point tests are negatively affected by phase separation. The rest of the properties, excepting flash point, were within diesel fuel standard specifications. Based on this study, it can be concluded that using additives to avoid phase separation and to raise flash point, blends of diesel fuel with ethanol up to 15% can be used to fuel diesel engines if engine performance tests corroborate it.     

Synthesis and Physical Properties of Tallow-Oleic Estolide 2-Ethylhexyl Esters

Tallow-oleic estolide 2-ethylhexyl (2-EH) esters were synthesized in a perchloric acid catalyzed one-pot process from industrial 90% oleic and tallow fatty acids at various ratios, while varying the ratio of tallow and oleic fatty acids, with the esterification process incorporated into an in situ second step to provide a functional fluid. Their viscosities ranged 57–80 cSt at 40 °C and 10.8–14.0 cSt at 100 °C with viscosity index (VI) 169–185. The 100% tallow estolide 2-EH ester had modest low-temperature properties (pour point = −15 °C and cloud point = −14 °C), while the 50:50 mixture of oleic and tallow fatty acids produced an estolide that had better low-temperature properties (pour point = −21 °C and cloud point = −21 °C) without a large negative effect on the oxidative stability. The oxidative stability increased as the amount of saturation increased (rotating pressurized vessel oxidation test (RPVOT) × 165–274 min). The tallow-oleic estolide 2-EH esters have shown remarkably low evaporative losses of only 1% loss compared to a 15–17% loss for commercial materials of similar viscosity grade. Along with expected good biodegradability, these tallow-oleic estolide 2-EH esters had acceptable properties that should provide a specialty niche. Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Characterization of the key fuel properties of methyl ester-diesel fuel blends

Characterizing of the fuel properties of diesel fuels, alternative fuels and their blends can assist the researchers who work on alternative fuels for diesel engines. Therefore, in this study, methyl esters were produced from five edible vegetable oils (sunflower, soybean, canola, corn and cottonseed) and blended with two different diesel fuels at 2%, 5%, 10%, 20%, 50% and 75% on a volume basis to characterize the key fuel properties of the blends such as density, viscosity, pour point, distillation temperatures and flash point. The results showed that the fuel properties of the blends were very close to those of diesel fuels at low concentrations upto 20% of methyl esters.     

Methyl and ethyl soybean esters as renewable fuels for diesel engines

The primary problems associated with using straight soybean oil as a fuel in a compression ignition internal combustion engine are caused by high fuel viscosity. Transesterification of soybean oil with an alcohol provides a significant reduction in viscosity, thereby enhancing the physical properties of the renewable fuel to improve engine performance. The ethyl and methyl esters of soybean oil with commercial diesel fuel additives revealed fuel properties that compared very well with diesel fuel, with the exception of gum formation, which manifested itself in problems with the plugging of fuel filters. Engine performance using soybean ester fuels differed little from engine performance with diesel fuel. A slight power loss combined with an increase in fuel consumption were experienced with the esters, primarily because of the lower heating value of the esters than for diesel fuel. Emissions for the 2 fuels were similar, with nitrous oxide emissions higher for the esters. Measurements of engine wear and fuel-injection system tests showed no abnormal characteristics for any of the fuels after the 200-hr tests. Engine deposits were comparable in amount, but slightly different in color and texture, with the methyl ester engine experiencing greater carbon and varnish deposits on the pistons. Presented at the American Oil Chemists’ Society meeting, Chicago, May 1983.     

Oxidation and low temperature properties of biofuels obtained from pyrolysis and alcoholysis of soybean oil and their blends with petroleum diesel

Diesel-like fuels were synthesized by a pyrolysis method using soybean oil (pyrodiesel, PD) and soybean soapstock (SPD), respectively, as starting material. These pyrodiesel samples were compared with soy biodiesel (BD) samples. All these three biofuels (PD, SPD and BD) and their blends with high sulfur (HSD) and low sulfur (LSD) diesel fuels were evaluated by measuring a number of fuel properties, such as oxidative stability, low-temperature performance, acid value and corrosion properties. Compared to BD blends, PD and SPD and their blends were found to have better oxidative stability, though inferior acid values. SPD and its blends have better flow performance at low-temperature compared to BD and PD blends. All the biofuels and their blends met the copper corrosion requirement prescribed by US and European standard. Based on the results reported here, pyrodiesels from these two-different feedstocks have potential and will require some upgrading or change in pyrolysis conditions, if they are to be used as fuel blending component.     

Exhaust emissions and fuel properties of partially hydrogenated soybean oil methyl esters blended with ultra low sulfur diesel fuel

Important fuel properties and emission characteristics of blends (20 vol.%) of soybean oil methyl esters (SME) and partially hydrogenated SME (PHSME) in ultra low sulfur diesel fuel (ULSD) were determined and compared with neat ULSD. The following changes were observed for B20 blends of SME and PHSME versus neat ULSD: improved lubricity, higher kinematic viscosity and cetane number, lower sulfur content, and inferior low-temperature properties and oxidative stability. With respect to exhaust emissions, B20 blends of PHSME and SME exhibited lower PM and CO emissions in comparison to those of neat ULSD. The PHSME blend also showed a significant reduction in THC emissions. Both SME and PHSME B20 blends yielded small increases in NO_x emissions. The reduction in double bond content of PHSME did not result in a statistically significant difference in NO_x emissions versus SME at the B20 blend level. The test engine consumed a greater amount of fuel operating on the SME and PHSME blends than on neat ULSD, but the increase was smaller for the PHSME blend.