Thermal Cracking Approach Investigation to Improve Biodiesel Properties

Biodiesel as an alternative diesel fuel is steadily gaining more attention and significance. However, there are some drawbacks while using biodiesel regarding its properties that requires it to be blended with petrol based diesel and/or additives to improve the fuel characteristics. This study analyses thermal cracking as an alternative technology to improve biodiesel characteristics in which, FAME based biodiesel produced by transesterification of castor oil is fed into a continuous thermal cracking reactor at temperatures range of 450-500°C and flowrate range of 20-40 g/hr. Experiments designed by response surface methodology and subsequent statistical studies show that temperature and feed flowrate significantly affect the products yield. Response surfaces were used to study the impact of temperature and flowrate on the product properties. After each experiment, the produced crude bio-oil was distilled and diesel cut was separated. As shorter chain molecules are produced through thermal cracking, the distillation curve of the diesel cut fitted more with petrol based diesel curve in comparison to the biodiesel. Moreover, the produced diesel cut properties adequately pose within property ranges defined by the related standard of petrol based diesel. Cold flow properties, high heating value as the main drawbacks of the biodiesel are improved by this technology. Thermal cracking decreases kinematic viscosity, Flash point and cetane number. 

Weight Loss Degradation of Hybrid Blends LLDPE/Starch/PVA upon Exposure to UV Light and Soil Burial

Poly bag and mulch films for agricultural field caused pose environmental problem due to the non-degradable plastics wastes upon disposal. Thus, a degradable poly bag was designed with hybrid sago starch (SS) and polyvinyl alcohol (PVA). Two Different blended compositions of SS and PVA hybrid have been compounded. Then, the hybrids blended are mixed with linear line density polyethylene (LLDPE) resin to fabricate poly bag film through conventional film blowing process. Samples of LLDPE, SS and PVA hybrid film were exposed to UV light and soil burial. The weight losses were determined during degradation process. Hybrid film by degradation of starch was found to hydrolyze and hydroxyl groups decrease on esterification upon exposure to soil burial and uv radiation. It was found out that, the hybrid film for 60% of SS composition showed greatest degradation in soil and UV radiation.

The Effects of Increasing Unsaturation in Palm Oil and Incorporation of Carbon Nanotubes on Resinous Properties

Considering palm oil as non-drying oil owing to its low iodine value, an attempt was taken to increase the unsaturation in the fatty acid chains of palm oil for the preparation of alkyds. To increase the unsaturation in the palm oil, sulphuric acid (SA) and para-toluene sulphonic acid (PTSA) was used prior to alcoholysis for the dehydration process. The iodine number of the oil samples was checked for the unsaturation measurement by Wijs method. Alkyd resin was prepared using the dehydrated palm oil by following alcoholysis and esterification reaction. To improve the film properties 0.5wt.% multi-wall carbon nano tubes (MWCNTs) were used to manufacture polymeric film. The properties of the resins were characterized by various physico-chemical properties such as density, viscosity, iodine value, saponification value, etc. Structural elucidation was confirmed by Fourier transform of infrared spectroscopy and proton nuclear magnetic resonance; surfaces of the films were examined by field-emission scanning electron microscope. In addition, pencil hardness and chemical resistivity was also measured by using standard methods. The effect of enhancement of the unsaturation in the fatty acid chain found significant and motivational. The resin prepared with dehydrated palm oil showed improved properties regarding hardness and chemical resistivity testing. The incorporation of MWCNTs enhanced the thermal stability and hardness of the films as well.

Kinetic Modeling of Transesterification of Triacetin Using Synthesized Ion Exchange Resin (SIERs)

Strong anion exchange resins with QN+OH-, have the potential to be developed and employed as heterogeneous catalyst for transesterification, as they are chemically stable to leaching of the functional group. Nine different SIERs (SIER1-9) with QN+OH-were prepared by suspension polymerization of vinylbenzyl chloridedivinylbenzene (VBC-DVB) copolymers in the presence of n-heptane (pore-forming agent). The amine group was successfully grafted into the polymeric resin beads through functionalization with trimethylamine. These SIERs are then used as a catalyst for the transesterification of triacetin with methanol. A set of differential equations that represents the Langmuir-Hinshelwood-Hougen- Watson (LHHW) and Eley-Rideal (ER) models for the transesterification reaction were developed. These kinetic models of LHHW and ER were fitted to the experimental data. Overall, the synthesized ion exchange resin-catalyzed reaction were welldescribed by the Eley-Rideal model compared to LHHW models, with sum of square error (SSE) of 0.742 and 0.996, respectively.

Synthesis and Antimicrobial Profile of Newer Schiff Bases and Thiazolidinone Derivatives

Esterification of p-bromo-m-cresol led to formation of 2-(4-bromo-3-methylphenoxy)acetate (1). 2-(4-Bromo-3-methyl phenoxy)acetohydrazide (2) is derived from Compound (1) by hydrazination. Compound (2) was reacted with different aromatic aldehydes to yield N-(substituted benzylidiene)-2-(4-bromo-3-methyl phenoxy)acetamide(3a-c). Cyclization of compound (3a-c) with thioglycolic acid yielded 2-(4-bromo-3-methylphenoxy)-N-(4-oxo-2- arylthiazolidin-3-yl) acetamide (4a-c). The newly synthesized compounds were characterized on the basis of spectral studies and evaluated for antibacterial and antifungal activities.

Conversion of Jatropha curcas Oil to Ester Biolubricant Using Solid Catalyst Derived from Saltwater Clam Shell Waste (SCSW)

The discarded clam shell waste, fossil and edible oil as biolubricant feedstocks create environmental impacts and food chain dilemma, thus this work aims to circumvent these issues by using activated saltwater clam shell waste (SCSW) as solid catalyst for conversion of Jatropha curcas oil as non-edible sources to ester biolubricant. The characterization of solid catalyst was done by Differential Thermal Analysis-Thermo Gravimetric Analysis (DTATGA), X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Brunauer-Emmett-Teller (BET), Field Emission Scanning Electron Microscopy (FESEM) and Fourier Transformed Infrared Spectroscopy (FTIR) analysis. The calcined catalyst was used in the transesterification of Jatropha oil to methyl ester as the first step, and the second stage was involved the reaction of Jatropha methyl ester (JME) with trimethylolpropane (TMP) based on the various process parameters. The formated biolubricant was analyzed using the capillary column (DB-5HT) equipped Gas Chromatography (GC). The conversion results of Jatropha oil to ester biolubricant can be found nearly 96.66%, and the maximum distribution composition mainly contains 72.3% of triester (TE).

Enzymatic Synthesis of Olive-Based Ferulate Esters: Optimization by Response Surface Methodology

Ferulic acid has widespread industrial potential by virtue of its antioxidant properties. However, it is partially soluble in aqueous media, limiting their usefulness in oil-based processes in food, cosmetic, pharmaceutical, and material industry. Therefore, modification of ferulic acid should be made by producing of more lipophilic derivatives. In this study, a preliminary investigation of lipase-catalyzed trans-esterification reaction of ethyl ferulate and olive oil was investigated. The reaction was catalyzed by immobilized lipase from Candida antarctica (Novozym 435), to produce ferulate ester, a sunscreen agent. A statistical approach of Response surface methodology (RSM) was used to evaluate the interactive effects of reaction temperature (40-80°C), reaction time (4-12 hours), and amount of enzyme (0.1-0.5 g). The optimum conditions derived via RSM were reaction temperature 60°C, reaction time 2.34 hours, and amount of enzyme 0.3 g. The actual experimental yield was 59.6% ferulate ester under optimum condition, which compared well to the maximum predicted value of 58.0%.

Tribological Investigation and the Effect of Karanja Biodiesel on Engine Wear in Compression Ignition Engine

Various biomass based resources, which can be used as an extender, or a complete substitute of diesel fuel may have very significant role in the development of agriculture, industrial and transport sectors in the energy crisis. Use of Karanja oil methyl ester biodiesel in a CI DI engine was found highly compatible with engine performance along with lower exhaust emission as compared to diesel fuel but with slightly higher NOx emission and low wear characteristics. The combustion related properties of vegetable oils are somewhat similar to diesel oil. Neat vegetable oils or their blends with diesel, however, pose various long-term problems in compression ignition engines. These undesirable features of vegetable oils are because of their inherent properties like high viscosity, low volatility, and polyunsaturated character. Pongamia methyl ester (PME) was prepared by transesterification process using methanol for long term engine operations. The physical and combustion-related properties of the fuels thus developed were found to be closer to that of the diesel. A neat biodiesel (PME) was selected as a fuel for the tribological study of biofuels. Two similar new engines were completely disassembled and subjected to dimensioning of various vital moving parts and then subjected to long-term endurance tests on neat biodiesel and diesel respectively. After completion of the test, both the engines were again disassembled for physical inspection and wear measurement of various vital parts. The lubricating oil samples drawn from both engines were subjected to atomic absorption spectroscopy (AAS) for measurement of various wear metal traces present. The additional lubricating property of biodiesel fuel due to higher viscosity as compared to diesel fuel resulted in lower wear of moving parts and thus improved the engine durability with a bio-diesel fuel. Results reported from AAS tests confirmed substantially lower wear and thus improved life for biodiesel operated engines.

Effects of Soybean Methyl Ester on the Performance Characteristics of Compression Ignition Engine

Depletion and hazardous gas emissions associated with fossil fuels have caused scientists and global attention to focus on the use of “alternative, eco-friendly substitutes for use in Compression Ignition Engines. In this work, biodiesel was produced by trans-esterification of soybean obtained from a Nigerian market using Sodium Hydroxide (NaOH) as a catalyst.” After the production, the physical properties (specific gravity to kinematic viscosity and net calorific value) of the Soybean-biodiesel produced and petrol diesel obtained from a filling station in Nigeria were determined, and these properties conform to conventional standards (ASTM). A cummins-6V-92TA DDEC diesel (Compression ignition, CI) engine was run on various biodiesel-petrol diesel blends (0/100, 10/90, 20/80, 30/70 and 40/60), the B20 (blend 20/80) was found to be the most satisfactory.

Characterization of Fish Bone Catalyst for Biodiesel Production

In this study, fish bone waste was used as a new catalyst for biodiesel production. Instead of discarding the fish bone waste, it will be utilized as a source for catalyst that can provide significant benefit to the environment. Also, it can be substitute as a calcium oxide source instead of using eggshell, crab shell and snail shell. The XRD and SEM analysis proved that calcined fish bone contains calcium oxide, calcium phosphate and hydroxyapatite. The catalyst was characterized using Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD).

Transesterification of Jojoba Oil-Wax Using Microwave Technique

Jojoba oil-wax is extracted from the seeds of the jojoba (Simmondsia chinensis Link Schneider), a perennial shrub that grows in semi desert areas in Egypt and in some parts of the world. The main uses of jojoba oil-wax are in the cosmetics and pharmaceutical industry, but new uses could arise related to the search of new energetic crops. This paper summarizes a process to convert the jojoba oil-wax to biodiesel by transesterification with ethanol and a series of aliphatic alcohols using a more economic and energy saving method in a domestic microwave. The effect of time and power of the microwave on the extent of the transesterification using ethanol and other aliphatic alcohols has been studied. The separation of the alkyl esters from the fatty alcohols rich fraction has been done in a single crystallization step at low temperature (−18°C) from low boiling point petroleum ether. Gas chromatography has been used to follow up the transesterification process. All products have been characterized by spectral analysis.

Life Cycle Assessment Comparison between Methanol and Ethanol Feedstock for the Biodiesel from Soybean Oil

As the limited availability of petroleum-based fuel has been a major concern, biodiesel is one of the most attractive alternative fuels because it is renewable and it also has advantages over the conventional petroleum-base diesel. At Present, productions of biodiesel generally perform by transesterification of vegetable oils with low molecular weight alcohol, mainly methanol, using chemical catalysts. Methanol is petrochemical product that makes biodiesel producing from methanol to be not pure renewable energy source. Therefore, ethanol as a product produced by fermentation processes. It appears as a potential feed stock that makes biodiesel to be pure renewable alternative fuel. The research is conducted based on two biodiesel production processes by reacting soybean oils with methanol and ethanol. Life cycle assessment was carried out in order to evaluate the environmental impacts and to identify the process alternative. Nine mid-point impact categories are investigated. The results indicate that better performance on abiotic depletion potential (ADP) and acidification potential (AP) are observed in biodiesel production from methanol when compared with biodiesel production from ethanol due to less energy consumption during the production processes. Except for ADP and AP, using methanol as feed stock does not show any advantages over biodiesel from ethanol. The single score method is also included in this study in order to identify the best option between two processes of biodiesel production. The global normalization and weighting factor based on ecotaxes are used and it shows that producing biodiesel form ethanol has less environmental load compare to biodiesel from methanol.

Experimental Investigation of the Effect of Compression Ratio in a Direct Injection Diesel Engine Running on Different Blends of Rice Bran Oil and Ethanol

The performance, emission and combustion characteristics of a single cylinder four stroke variable compression ratio multi fuel engine when fueled with different blends of rice bran oil methyl ester and ethanol are investigated and compared with the results of standard diesel. Bio diesel produced from Rice bran oil by transesterification process has been used in this study. Experiment has been conducted at a fixed engine speed of 1500 rpm, 50% load and at compression ratios of 16.5:1, 17:1, 17.5:1 and 18:1. The impact of compression ratio on fuel consumption, brake thermal efficiency and exhaust gas emissions has been investigated and presented. Optimum compression ratio which gives best performance has been identified. The results indicate longer ignition delay, maximum rate of pressure rise, lower heat release rate and higher mass fraction burnt at higher compression ratio for waste cooking oil methyl ester when compared to that of diesel. The brake thermal efficiency at 50% load for Rice bran oil methyl ester blends and diesel has been calculated and the blend B40 is found to give maximum thermal efficiency. The blends when used as fuel results in reduction of carbon monoxide, hydrocarbon and increase in nitrogen oxides emissions.

Production of Biodiesel from Roasted Chicken Fat and Methanol: Free Catalyst

Transesterification reactions free of catalyst between roasted chicken fat with methanol were carried out in a batch reactor in order to produce biodiesel to temperatures from 120°C to 140°C. Parameters related to the transesterification reactions, including temperature, time and the molar ratio of chicken fat to methanol also investigated. The maximum yield of the reaction was of 98% under conditions of 140°C, 4 h of reaction time and a molar ratio of chicken fat to methanol of 1:31. The biodiesel thus obtained exhibited a viscosity of 6.3 mm2/s and a density of 895.9 kg/m3. The results showed this process can be right choice to produce biodiesel since this process does not use any catalyst. Therefore, the steps of neutralization and washing are avoided, indispensables in the case of the alkaline catalysis.

Production of Biodiesel from Different Edible Oils

Different vegetable oil based biodiesel (FAMES) were prepared by alkaline transesterification using refined oils as well as waste frying oil (WFO). Methanol and sodium hydroxide are used as catalyst under similar reaction conditions. To ensure the quality of biodiesel produced, a series of different ASTM Standard tests were carried out. In this context, various testwere done including viscosity, carbon residue, specific gravity, corrosion test, flash point, cloud point and pour point. Results revealed that characteristics of biodiesel depend on the feedstock and it is far better than petroleum diesel.

Enzymatic Esterification of Carboxylic Acids and Higher Alcohols in Organic Medium

The studying of enzymatic esterification of carboxylic acids and higher alcohols was performed by esterase Saccharomyces cerevisiae in water-organic medium. Investigation of the enzyme specificity to acetic substrates showed the best result with acetic acid in esterification reactions with ethanol whereas within other carboxylic acids the esterification decreased with acids: hexanoic > pentanoic > butyric > decanoic. In relation to higher alcohols C3-C5, esterification increased with alcohols propanol < butanol < amylol. Also it was determined that esterase was more specific to alcohols with branched chain such as isobutyl alcohol and isoamyl alcohol. Data obtained may have important practical implications, for example, for application of yeast esterase in producing various volatile esters as well as in enzymatic transformation of volatile acids and toxic fusel alcohols into volatile esters by providing the production of the high quality alcoholic beverages with redused content of higher alcohols as well as with improved degustational and hygienic properties.

Esterification of Free Fatty Acids in Crude Palm Oil with Sulfated Zirconia: Effect of Calcination Temperature

The production of biodiesel from crude palm oil with a homogeneous base catalyst is unlikely owing to considerable formation of soap. Free fatty acids (FFA) in crude palm oil need to be reduced, e.g. by esterification. This study investigated the activity of sulfated zirconia calcined at various temperatures for esterification of FFA in crude palm oil to biodiesel. It was found that under a proper reaction condition, sulfated zirconia well catalyzes esterification. FFA content can be reduced to an acceptable value for typical biodiesel production with a homogeneous base catalyst. Crystallinity and sulfate attachment of sulfated zirconia depend on calcination temperature during the catalyst preparation. Too low temperature of calcination gives amorphous sulfated zirconia which has low activity for esterification of FFA. In contrast, very high temperature of calcination removes sulfate group, consequently, conversion of FFA is reduced. The appropriate temperature range of calcination is 550-650 oC.

Lipase Catalyzed Synthesis of Aromatic Esters of Sugar Alcohols

Commercially available lipases (Candida antarctica lipase B, Novozyme 435, Thermomyces lanuginosus lipase, and Lipozyme TL IM), as well as sol-gel immobilized lipases, have been screened for their ability to acylate regioselectively xylitol, sorbitol, and mannitol with a phenolic ester in a binary mixture of t-butanol and dimethylsulfoxide. HPLC and MALDI-TOF MS analysis revealed the exclusive formation of monoesters for all studied sugar alcohols. The lipases immobilized by the sol-gel entrapment method proved to be efficient catalysts, leading to high conversions (up to 60%) in the investigated acylation reactions. From a sequence of silane precursors with different nonhydrolyzable groups in their structure, the presence of octyl and i-butyl group was most beneficial for the catalytic activity of sol-gel entrapped lipases in the studied process.

Waste Oils pre-Esterification for Biodiesel Synthesis: Effect of Feed Moisture Contents

A process flowsheet was developed in ChemCad 6.4 to study the effect of feed moisture contents on the pre-esterification of waste oils. Waste oils were modelled as a mixture of triolein (90%), oleic acid (5%) and water (5%). The process mainly consisted of feed drying, pre-esterification reaction and methanol recovery. The results showed that the process energy requirements would be minimized when higher degrees of feed drying and higher preesterification reaction temperatures are used.

Mathematical Correlation for Brake Thermal Efficiency and NOx Emission of CI Engine using Ester of Vegetable Oils

The aim of this study is to develop mathematical relationships for the performance parameter brake thermal efficiency (BTE) and emission parameter nitrogen oxides (NOx) for the various esters of vegetable oils used as CI engine fuel. The BTE is an important performance parameter defining the ability of engine to utilize the energy supplied and power developed similarly it is indication of efficiency of fuels used. The esters of cottonseed oil, soybean oil, jatropha oil and hingan oil are prepared using transesterification process and characterized for their physical and main fuel properties including viscosity, density, flash point and higher heating value using standard test methods. These esters are tried as CI engine fuel to analyze the performance and emission parameters in comparison to diesel. The results of the study indicate that esters as a fuel does not differ greatly with that of diesel in properties. The CI engine performance with esters as fuel is in line with the diesel where as the emission parameters are reduced with the use of esters. The correlation developed between BTE and brake power(BP), gross calorific value(CV), air-fuel ratio(A/F), heat carried away by cooling water(HCW). Another equation is developed between the NOx emission and CO, HC, smoke density (SD), exhaust gas temperature (EGT). The equations are verified by comparing the observed and calculated values which gives the coefficient of correlation of 0.99 and 0.96 for the BTE and NOx equations respectively.