Synthesis of Waste Cooking Oil Based Bioadditive Through Transesterification and Its Feasibility as Lubricity Enhancer Bioadditives for Low-Sulfur Diesel Fuel: Preliminary Investigation

<div class="htmlview paragraph">While sulfur in diesel fuels helps reduce friction and prevents wear and galling in fuel pump and injector systems, it also creates environmental pollution in the form of hazardous particulates and SO<sub>2</sub> emissions. The environmental concern is the driving force behind industry's efforts to come up with new alternative approaches to this problem. One such approach is to replace sulfur in diesel fuels with other chemicals that would maintain the antifriction and antiwear properties provided by sulfur in diesel fuels while at the same time reducing particulate emissions. A second alternative might be to surface-treat fuel injection parts (i.e., nitriding, carburizing, or coating the surfaces) to reduce or eliminate failures associated with the use of low-sulfur diesel fuels.</div> <div class="htmlview paragraph">Our research explores the potential usefulness of a near-frictionless carbon (NFC) film developed at Argonne National Laboratory in alleviating the aforementioned problems. The lubricity of various diesel fuels (i.e., high-sulfur, 500 ppm; low sulfur, 140 ppm; ultra-clean, 3 ppm; and synthetic diesel or Fischer-Tropsch, zero sulfur) were tested by using both uncoated and NFC-coated 52100 steel specimens in a ball-on-three-disks and a high-frequency reciprocating wear-test rig. The test program was expanded to include some gasoline fuels as well (i.e., regular gasoline and indolene) to further substantiate the usefulness of the NFC coatings in low-sulfur gasoline environments. The results showed that the NFC coating was extremely effective in reducing wear and providing lubricity in low-sulfur or sulfur-free diesel and gasoline fuels. Specifically, depending on the wear test rig, test pair, and test media, the NFC films were able to reduce wear rates of balls and flats by factors of 8 to 83. These remarkable reductions in wear rates raise the prospect for using the ultra slick carbon coatings to alleviate problems that will be caused by the use of low sulfur diesel and gasoline fuels. Surfaces of the wear scars and tracks were characterized by optical and scanning electron microscopy, and by Raman spectroscopy.</div>

A significant amount of waste cooking oil (WCO) remains in the food preparation process worldwide on a daily basis, which can cause environmental pollution if disposed of improperly. The cheapest and effective way to dispose of WCO is by blending it with diesel fuel. In this study three various blends of WCO and diesel fuel were prepared with a WCO proportion of 10%, 20% and 30% and properties were evaluated and compared with petroleum diesel fuel. The density and dynamic viscosity of the blend increase with the increase in WCO content, while the heating value decreases. The blends were then tested in tractor direct injection diesel engine to determine the effect of blending WCO with diesel fuel on the engine performances (power, torque and fuel consumption) and exhaust gases emission (CO, CO<sub>2</sub>, HC and NO<sub>x</sub>). The results show that the engine performances using WCO blends are comparable to petroleum diesel fuel and a blend with 30% WCO (B30) achieved the best results among the fuel blends. There were no significant differences in average engine power, torque and fuel consumption per hour between petroleum diesel fuel and B30 blend, while significantly lower (P˂0.05) average specific fuel consumption were achieved using diesel fuel. The significantly lower (P˂0.05) average CO and CO<sub>2</sub> emissions and significantly higher (P˂0.05) average HC emission was achieved using diesel fuel compared to B30 blend. No significant difference in average NO<sub>x</sub> emission was observed between diesel fuel and B30 blend.

<div class="section abstract"><div class="htmlview paragraph">Bio-hydro fined diesel (BHD) oil is known as a second generation oil made from bio hydro finning process. Biodiesel in the first generation is made from transesterification process and it has several disadvantages such as high density and increased the viscosity that can cause operational problems because can make some deposits in the engine. To overcome this, the second generation process of biodiesel has been modified from the first generation oil. BHD is made from the waste cooking oil by using the hydro finning process without the trans-esterification process. The results of BHD oil has nearly the same with diesel oil. BHD oil has low viscosity and high oxidation stability. Therefore, BHD oil can be used in the diesel engine without making any modifications in the engine.</div><div class="htmlview paragraph">In this study, the comparison of performance and emissions characteristics from BHD oil, waste cooking oil, and diesel oil are investigated. The experimental conditions are varied for loads (low load and partial load) and exhaust gas circulations (EGR) are zero, 10, and 20%. The engine speed was constant at 2000 rpm. The results show that the BHD oil can be an alternative fuel to replace the diesel oil because the emissions can be reduced from diesel oil, therefore it is friendly to the environment.</div></div>

The Conversion of natural gas into synthetic liquid fuel carried out through a catalytic conversion process, known as the gas-to-liquid (GTL) technology, had a great impact since its discovery. The process utilizes the Fischer-Tropsch synthesis (FTS) chemistry that was first developed in 1925. Gas-to-liquid (GTL) fuels are synthetic fuels that are intrinsically cleaner than conventional fuels.[1] They are environmentally benign due to the absence of sulfur content and the extremely low aromatic content. Gas-to-liquid (GTL) diesel fuel, being one of the most important GTL products, is therefore classified as ultra-clean fuel with lower emissions of carbon monoxide and particulates upon combustion. Nevertheless, the lack of sulfur and aromatic in the diesel fuels negatively impacts certain important physical characteristics such as lubricity and density. This fact makes these fuels improper for use in existing diesel engines. The lubricity issue is significant for GTL diesel fuels, as it not match the standards required by regulations in the United States, Europe and elsewhere. Lubricity is defined as “a qualitative term describing the ability of a fluid to affect friction between, and wear to, surfaces in relative motion under load.” [2]The aim of this research project is to design new generation ultra clean diesel fuels, from the GTL process, that are environmentally friendly, have less emissions upon combustion but also practicable and compliant with global standards. The focus of this study is to develop a comprehensive knowledge and data to observe the possibility of stretching and tailoring the GTL diesel properties such that they meet the standards needed to be used in existing engines. The enhancement of lubricity, which serves as the major disadvantage, is to be carried out while maintaining all other physical properties within the range needed for existing engines and ASTM D975 and D7467 standards.Fatty acid methyl and ethyl esters are biodiesels that can provide significant improvements in the lubricity of diesel fuel. Previous studies on the effects of fatty acid methyl esters on diesel fuel lubricity have shown an increase in lubricity associated with the addition of these esters [3]. Addition of these esters in GTL diesel was found to be the best fit for lubricity enhancement. Our campaign, unlike other studies on diesel lubricity, does not only focus on certain physical properties of diesel but provide a comprehensive study showing all changes in other properties that accompany the change of the targeted property, being diesel in this case.For this study, four lubricity enhancement additives were selected. The selection covers a wide range of biodiesel characteristics and would thus allow deeper understanding of other factors such as saturation and chain length of esters on diesel lubricity and properties enhancement. The four esters that proved to have significant impact are Methyl Oleate (C19H36O2), Methyl Stearate (C19H38O2), Ethyl Oleate (C20H38O2) and Ethyl Stearate (C20H40O2). Both methyl and ethyl esters were found to affect the lubricity. However, other studies showed variation on which serves as a better lubricity enhancement additive. Our research will validate these findings and widen the study to experiment the effect of mixing different additives on all other diesel fuel properties. The concentrations of additives were selected to be in the range of 5%–20% by volume. For this purpose 28 blends were prepared for conducting the research.Subsequently blends were tested for fuel characteristics and physical properties. The tests nclude vapor pressure, viscosity, flash point, pour point, cloud point, distillation performance, heat content and lubricity. Current results show an increase in density, viscosity, flash point and vapor pressure with increasing additive concentrations of biodiesel. In contrast, the increase in additive concentration decreased the pour point, cloud point, recovery by distillation and calculated cetane number. All the changes lie well within American Society of Testing and Materials (ASTM) standards.The work will be further continued to validate experimental results with industry partners, testing of lubricity characteristics using advanced microscopy and conducting a thorough result analysis and representation statistical methods and visualization techniques.This work will suggest ideal mixtures of GTL diesel and biodiesel additives that will best enhance the GTL diesel fuel. Such findings can be used in blending commercial GTL diesel fuel with suggested biodiesel to produce practicable, engine compliant and ASTM standard compliant GTL diesel. Since Qatar has the largest GTL plant in the world, this research is essentially significant and relevant. It also enriches Qatar's scientific research culture and serves the world by creating cleaner fuels for a cleaner environment.

Co-hydroprocessing and hydrocracking of alternative feed mixture (vacuum gas oil/waste lubricating oil/waste cooking oil) with the aim of producing high quality fuels

<div class="htmlview paragraph">Cloud point depressants (CPD) have been successfully used for many years in low-sulfur diesel fuels. For over ten years, custom-designed, specialty polymer chemistry has enabled refiners to meet cloud point (CP) guidelines with substantially less kerosene. This translates into greater refined yields through cut-point adjustment upgrades and the potential for diverting kerosene to more lucrative market opportunities, such as jet fuel.</div> <div class="htmlview paragraph">The practice of cut-point downgrades to gas oil can be costly because diesel fuel generally has greater value. Kerosene dilutions have historically been as high as 30%-40% by volume with low-sulfur diesel fuels [<span class="xref">1</span>, <span class="xref">2</span>]. While kerosene addition enables fuels to reach CP guidelines, it may negatively impact the fuel's energy content, cetane number, lubricity, flash point and density. Properly designed CP additives are able to substantially reduce or even eliminate the need for kerosene, thus substantially reducing refinery costs.</div> <div class="htmlview paragraph">With ultra-low-sulfur diesel (ULSD) fuels being mandated throughout the mass market distribution system by June 2006, the need for CP control may be greater than ever. However, waxy crude and process limitations may make it difficult for refiners to economically make low cloud point ULSD. Fortunately, CPD can overcome these limitations without negatively impacting fuel characteristics. These additives allow refiners to meet low-temperature objectives while being neutral or beneficial to most other diesel fuel properties.</div>

Flame spectroscopy of waste tire oils and waste cooking oils blends using coaxial burner

Reusing waste cooking oil (WCO) as fuel in compression ignition (CI) engine offers a sustainable solution for energy scarcity and environmental protection. WCO and n-pentanol ternary blends deliver are attractive prospects in utilization as bio-components and recycled components to moderately substitute diesel fuel. The current study intends to investigate the performance and emission characteristics of a single cylinder CI engine, having constant load at a uniform speed of 1300 rpm, using diesel-waste cooking oil n-pentanol blends. Blends chosen and analogized with diesel oil as reference fuel and their contents were the following: (1) D95-WCO5 (95%vol. diesel, WCO5%vol. waste cooking oil, (2) D65-WCO20-Pe15 (65%vol. diesel, 20%vol. waste cooking oil, and 15%vol. n-pentanol) and (3) D60-WCO20-Pe20 (60%vol. diesel, 20%vol. waste cooking oil and 20%vol. n-pentanol). The experimental results revealed that with the DF95-WCO5 blend the BSFC improved by 0.32%. However, with the addition of n-pentanol as a ternary blend; DF65-WCO20-Pe15 and DF60-WCO20-Pe20 resulted in improvements of 0.49% and 0.68% respectively. The BTE for DF95-WCO5 increased by 38.7%, while the increase was 39.2% for DF65-WCO20-Pe15 and 39.6% for DF60-WCO20-Pe20, which was less, as compared with diesel fuel. The lowermost level of CO discharge was achieved when the engine was fueled with DF65-WCO20-Pe15 and DF60-WCO20-Pe20, due to the highest level of saturation. CO2, in the cases of DF65-WCO20-Pe15 and DF60-WCO20-Pe20, increased, as compared to diesel fuel under the same engine operating conditions. However, the binary blend DF95-WCO5 resulted in decreased CO2 as analogized to diesel, because of incomplete combustion of the fuel. During experimental work it could be observed that the DF95-WCO5 binary blend produced higher Particulate material (PM-1, PM-2.5, PM-7 and PM-10) emissions, compared to DF100. Moreover, with the addition of n-pentanol as a ternary blend in the ratio of 15 to 20%, emission was further reduced. This indicated that direct exertion of WCO in engines must be promoted, as it is an impressive choice for waste recapture.

The present work aims to study the synthesis of 2-hydroxyethyl esters from castor oil and its lubrication properties, promising as a lubrication bio-additive in low sulfur diesel fuel. This compound has been successfully synthesized from castor oil and ethylene glycol. The oil to ethylene glycol molar ratio was adjusted to 1:10, and the catalyst loading was used at 9% mole oil. Then, the mixture was refluxed for 5 h. The product components were characterized using GC-MS. The standard ASTM method was used to study the kinematic viscosity and lubrication. The product was dominated by 2-hydroxyethyl esters (94.16%), di-ester (1.12%), and cyclic ester (1.92%). The analysis of friction coefficient and wear scar diameter (WSD) using High-Frequency Reciprocating Rig (HFRR) shows the coefficient of friction and WSD of the product better than reference diesel fuel. From the results of this study, the 2-hydroxyethyl ester of castor oil, especially 2-hydroxyethyl ricinoleate, is the main responsible for the lubricating properties. Thus, 2-hydroxyethyl esters of castor oil can be proposed as an alternative bio-additive to improve the lubrication of low-sulfur fossil diesel fuels.

Utilization of waste cooking oil for highly efficient recovery of unburned carbon from coal fly ash

Combustion of fuel blends containing digestate pyrolysis oil in a multi-cylinder compression ignition engine

Contribution of Hydration to Protein Folding Thermodynamics: II. The Entropy and Gibbs Energy of Hydration

The present study aims to show the tribological properties of soybean oil's ethylene glycol ester (SOEGE) and its effect on low-sulfur diesel fuel lubrication. The SOEGE or 2-hydroxyethyl ester was synthesized by a transesterification reaction of soybean oil and ethylene glycol with a potassium carbonate catalyst. The product was characterized using Gas Chromatography-Mass Spectrometry (GC-MS). Then, the lubricity of commercial diesel fuel (Pertadex) and SOEGE were tested alone using the High-Frequency Reciprocating Rig (HFRR) machine. Its mixture form with various product doses in Pertadex (0.2, 0.4, 0.6, 0.8, and 1% v/v) was also tested with the same apparatus. This study showed that the product's coefficient of friction and Wear Scar Diameters (WSD) were 0.057 and 154.4 m, respectively. This value is lower than Pertadex and Fatty Acids Methyl Ester (FAME) of Soybean oil from the literature. Furthermore, adding products into Pertadex can reduce the coefficient of friction and WSD of Pertadex. The Pertadex coefficient of friction was reduced from 0.161 to 0.135 after the addition of 0.8% product. At a concentration of 1% product, WSD Pertadex was successfully reduced by 39.42%. These phenomena imply that ester ethylene glycol has an excellent lubricating effect on low-sulfur diesel. This work's findings open opportunities for other researchers to develop alternative lubricating bio-additives for low-sulfur diesel through the in-depth study of tribochemistry or tribosurface.

Studying biodiesel as an alternative fuel is important for finding the most suitable fuel for the future. Biodiesel from waste cooking oil is one of the alternative fuels to replace fossil oil. Waste cooking oil is the used oil from cooking and is taken from hotels or restaurants. The emulsion of waste cooking oil and water is produced by adding water to the oil, as well as some additives to bind the water and the oil. In this study, the fuel properties of 100% biodiesel waste cooking oil are compared to several blends by volume: 5% of biodiesel waste cooking oil blended with 95% diesel oil (BD5), 10% of biodiesel waste cooking oil blended with 90% of diesel oil (BD10), 5% of biodiesel waste cooking oil blended with 10% of water and 18.7% of additives (BDW18.7), and 5% of biodiesel waste cooking oil blended with 10% of water and 24.7% of additives (BDW24.7). The objectives of this study are to establish the properties and characteristics of the FTIR (Fourier-transform infrared spectroscopy) of biodiesel-water emulsions from waste cooking oil and to compare them to other fuels. The chemical properties of the fuels are analyzed by using the ASTM D Method and FTIR to determine the FAME (fatty acid methyl ester) composition of biodiesel in diesel oil. The results showed that the addition of additives in the water-biodiesel oil increases the viscosity, density, and flash point. However, it decreased the caloric value due to the oxygen content in the fuel.

Growing concern regarding energy resources and the environment has been increased interest in the study of alternative energy sources.. To meet increasing energy requirements, there have been growing interests in alternative fuels like biodiesel to provide a suitable diesel oil substitute for internal combustion engines. Biodiesels are offer a very promising alternative to diesel oil since they are renewable and have been similar properties. One of the economical sources for biodiesel production which doubles in the reduction of liquid waste and the subsequent burden of sewage treatment is waste cooking oil (WCO). However, the products formed during frying process have affected the transesterification reaction and the biodiesel properties. These experiments about the performance analysis of C.I. engine using diesel and waste cooking oil blend.