New Options for Conversion of Vegetable Oils to Alternative Fuels

Biodiesel from transesterification of vegetable oils is an excellent alternative fuel. There is, however, a need to develop a direct process for conversion of vegetable oils into gasoline-competitive biodiesel and other petroleum products. Methyl esters of vegetable oils have several outstanding advantages among other new-renewable and clean engine fuel alternatives. The purpose of the transesterification process is to lower the viscosity of vegetable oil. Compared to No. 2 diesel fuel, all of the vegetable oils are much more viscous, whereas methyl esters of vegetable oils are slightly more viscous. The methyl esters are more volatile than those of the vegetable oils. Conversion of vegetable oils to useful fuels involves the pyrolysis and catalytic cracking of the oils into lower molecular products. Pyrolysis produces more biogasoline than biodiesel fuel. Soap pyrolysis products of vegetable oils can be used as alternative diesel engine fuel. The soaps obtained from the vegetable oils can be pyrolyzed into hydrocarbon-rich products. Zinc chloride catalyst contributed greatly to high amounts of hydrocarbons in the liquid product. The yield of ZnCl ₂ catalytic conversion of the soybean oil reached the maximum 79.9% at 660 K.     

Influence of temperature and steam on the products from the flash pyrolysis of Jordan oil shale

Oil shale samples from the Sultani deposit in the south of Jordan, were pyrolysed in a semi‐continuous fluidized bed reactor under nitrogen and nitrogen/steam atmosphere. The pyrolysis temperature between 400 and 650°C were investigated. Increasing the pyrolysis temperature from 400 to 520°C caused a large increase in the oil yield. Further increase of the pyrolysis temperature resulted in a decrease in oil yield and a large increase in the evolved gases. This increase in the hydrocarbon gas yield was attributed to oil thermal cracking reactions. The evolved gases were composed of H₂, CO, CO₂, and hydrocarbons from C₁ to C₄. The presence of steam improved the oil yield which may be a result of reducing the degree of decomposition. The derived oils were fractionated into chemical classes using mini‐column liquid chromatography. Copyright © 2002 John Wiley & Sons, Ltd.     

Microwave pyrolysis,a novel process for recycling waste automotive engine oil

Used automotive engine oil was treated using a microwave-induced pyrolysis process, with the intention of assessing the suitability of the process in recovering valuable products from this otherwise difficult to dispose of waste. The resulting pyrolysis gases were condensed into liquid oil; the yield and composition of the recovered oil and remaining incondensable gases were determined, and these were compared with those arising from fresh oil. Process temperature was shown to have a significant effect on the overall yield and formation of the recovered oils. The recovered liquid and gaseous pyrolysis products contained various light hydrocarbons which could be used as a valuable fuel and as an industrial feedstock. Our results indicate that microwave pyrolysis shows extreme promise as a means for disposing of problematic waste oil. The recovery of commercially valuable products shows advantage over traditional, more destructive disposal methods, and suggests excellent potential for scaling the process to the commercial level.     

Optimization of process parameters and catalytic pyrolysis of Cascabela thevetia seeds over low-cost catalysts towards renewable fuel production

The present study deals with the optimization of process parameters and thermocatalytic pyrolysis of Cascabela thevetia (CT) seeds in a semi-batch cylindrical-shaped reactor. Response surface methodology (RSM) was employed for the optimization of process variables, while commercial catalysts CaO and Al₂O₃ were used for catalytic pyrolysis. From results, it was concluded that 525 °C temperature, 75 °C min⁻¹ heating rate, and 75 mL min⁻¹ flow of nitrogen yielded maximum pyrolytic liquid (45.26 wt%) while with the attendance of catalysts at 20 wt% increased the yield of pyrolytic liquid (49.12 wt% and 46.87 wt% for CaO and Al₂O₃ respectively). Optimization outcomes displayed that linear and quadratic terms of utilized factors were more noteworthy while interaction effects between the factors were not significant. Further, characterization of pyrolytic oil established that utilization of catalysts expressively enhanced its properties by reducing viscosity and boosted the calorific value. FTIR examination of pyrolytic oil showed that the attendance of phenols, ethers, alcohols, ketones, alkanes, acids, etc., while ¹H NMR results supported the FTIR results. GC-MS analysis showed a substantial reduction of phenols and oxygen-rich products and boost the development of alcohol and aldehydes in pyrolytic oil with the introduction of catalysts. These parameters indicate improved properties of pyrolytic oil, which intensified its bioenergy capabilities.     

Rice straw as a bio-oil source via pyrolysis and steam pyrolysis

The pyrolysis of rice straw was studied to estimate the effect of pyrolysis conditions on product yields and bio-oil composition when the heating rate was 5 K/min. Pyrolysis temperature, particle size, sweeping gas flow rate and steam velocity were the experimental parameters. Among the four pyrolysis temperatures; namely, 673, 773, 823 and 973 K; 823 K gave the highest bio-oil yield of 27.26%. Six different particle sizes were examined and sample having a particle size of 0.425<D_p<0.85 mm had a bio-oil yield of 27.77%. Nitrogen was used as the sweeping gas with the flow rates of either 50, 100, 200 and 400 ml/min and the highest bio-oil yield was obtained when flow rate was 200 ml/min. The bio-oil yield reached a maximum value of 35.86% with the steam velocity of 2.7 cm/s. Liquid products obtained from pyrolysis, inert atmosphere pyrolysis and steam pyrolysis were then fractionated into aspalthanes and maltanes. The aliphatic subfraction obtained by column chromatography was then analysed by GC/MS. For further structural analysis, the pyrolysis oils were conducted with ¹H-NMR, oils and aliphatic subfractions with FT-IR. The chemical characterisation has shown that the oil obtained from rice straw may be potentially valuable as fuel and chemicals feedstocks.     

Comparison of catalytic and noncatalytic pyrolysis and product yields of some waste biomass species

The products obtained by fast pyrolysis of biomass can be used as an energy source or chemical raw material. In this study, samples of hazelnut shells, tea bush, and hazelnut knot selected as waste biomass were from the cities of Trabzon and Rize in the Eastern Black Sea Region. Firstly, the waste biomass samples were granulated into four different particle sizes by milling and sieving operations. Fast pyrolysis of the samples with specific mixing rates was carried out in a fixed bed reactor. Additionally, 2 wt% vanadium (V) oxide (V₂O₅) was used as catalyst to maximize the yield of pyrolysis liquid products. The influence of temperature, heating rate, and particle size on fast pyrolysis yields under both catalytic and noncatalytic conditions were investigated and compared. While the amount of liquid product increased with the addition of catalyst, the amount of solid products decreased. It has been found that the temperature and heating rate parameters are very effective in liquid product yield. In all experiments, the maximum liquid yield was acquired at the same heating rate of 450°C min^?1 and the temperature of 450°C with particle size of 0.5 to 1.0 mm. The maximum pyrolysis liquid (bio‐oil) was obtained with catalytic pyrolysis, and this value was 60.58 wt%.     

Catalytic co‐pyrolysis of Eichhornia Crassipes biomaѕѕ and polyethylene using waste Fe and CaCO3 catalysts

A wild aquatic plant, Eichhornia Crassipes, and polyethylene have been converted into liquid product thermo‐catalytically and cost effectively through co‐pyrolysis using batch steel pyrolyzer. The Fe and CaCO₃ catalysts were obtained as wastes from various mechanical processes. The catalytic process was compared with non‐catalytic pyrolysis. The effect of various reaction conditions was investigated in order to find out the optimized process conditions. It was found that the favorable reaction conditions were 450 °C temperature and 1‐h reaction time at a heating rate of 1 °C/s and 0.4‐mm biomass particle size. The bio‐oil yield was found to be 34.4% and 26.6% using Fe and CaCO₃ respectively with catalysts particle size of 0.4 mm at the optimized reaction conditions and 5 wt% of biomass. The non‐catalytic and catalytic co‐pyrolysis using Fe as catalyst produced 23.9% and 28.7% oil respectively. Thus the efficiency of processes in terms of bio‐oil production was found in order of: Fe > CaCO₃ > non‐catalytic pyrolysis. The GC/MS analysis of n‐hexane extract of bio‐oil shows that Fe catalyst favors formation of aliphatic hydrocarbons while CaCO₃ and non‐catalytic pyrolysis favors formation of aromatic hydrocarbons. Mostly unsaturated aliphatic hydrocarbons were formed in case of co‐pyrolysis reactions. The calorific value of bio‐oil was also measured in order to find out the fuel properties of the products. Copyright © 2016 John Wiley & Sons, Ltd.     

Slow, fast and flash pyrolysis of rapeseed

Pyrolysis experiments have been conducted on a sample of rapeseed to determine particularly the effects of pyrolysis temperature, heating rate, particle size and sweep gas flow rate on the pyrolysis product yields and their chemical compositions. The maximum oil yield of 73% was obtained at the final pyrolysis temperature of 550–600 °C, particle size range of +0.6–1.25 mm, and sweep gas flow rate of 100 cm³min⁻¹ (N₂) at flash pyrolysis conditions in tubular transport reactor. Chromatographic and spectroscopic studies on the pyrolytic oil showed that the oil obtained from rapeseed can be used as a renewable fuel and chemical feedstock.     

Utilization of pyrolytic oil and hydrogen enriched syngas from single feedstock (delonix regia) through pyrolysis process and its influence on performance and emission characteristics in CI engine

The main objective of the present investigation is to conduct the performance, combustion and emission analysis of CI engine operated using hydrogen enriched syngas (pyrolytic gas) and biodiesel (pyrolytic oil) as dual fuel mode condition. Both the pyrolytic oil and syngas is obtained from single feedstock delonix regia fruit pod through pyrolysis process and then pyrolytic oil is converted into biodiesel through esterification. Initially biomass is subjected to thermal degradation at various pyrolysis temperature ranges like 350–600 °C. During the pyrolysis process syngas, pyrolytic oil and char are produced. The syngas is directly used in the CI engine and pyrolytic oil is converted into biodiesel and then used in the CI engine. The pyrolytic oil and syngas is subjected to FTIR and GC/TCD analysis respectively. The syngas analysis confirms the presence of various gases like H₂, CH₄, CO₂, CO and C₂H₄ in different proportions. The various proportions of the syngas is mainly depending upon the reactor temperature and moisture content in the biomass. The syngas composition varies with increase in the temperature and at 400 °C, higher amount of hydrogen is present and its composition are H₂ 28.2%, CO is 21.9%, CH₄ is 39.1% and other gases in smaller amounts. The biodiesel of B20 and syngas of 8lpm produced from the same feedstock are considered as test sample fuels in the CI engine under dual fuel mode operation to study the performance and emission characteristics. The study reveals that BTE has slight increase than diesel of 1.5% at maximum load. On the another hand emission like CO, HC and smoke are reduced by 15%,25% and 32% respectively at full load condition, whereas NO_x emission is increased at all loads in the range of 10–15%. Therefore B20+syngas of 8lpm can be used as an alternative fuel in CI engine without any modification and major products from pyrolysis process with waste biomass is fully used as fuel in the CI engine.     

Bio‐oil production from rapid pyrolysis of cottonseed cake: product yields and compositions

Fixed‐bed fast pyrolysis experiments have been conducted on a sample of cottonseed cake to determine the effects of pyrolysis temperature, heating rate and sweep gas flow rate on pyrolysis yields and chemical compositions of the product oil. The liquid products and the subfractions of pentane soluble part were characterized by elemental analysis, FT‐IR spectroscopy, ¹H‐NMR spectroscopy and pentane subfraction was analysed by gas chromatography. The maximum oil yield of 34.8% was obtained at final temperature of 550°C with a heating rate of 700°C min^?1 and nitrogen flow rate of 100 cm³ min^?1. Chromatographic and spectroscopic studies on bio‐oil have shown that the oils obtained from cottonseed cake can be used as a renewable fuel and chemical feedstock. Copyright © 2005 John Wiley & Sons, Ltd.     

The influence of temperature and heating rate on the slow pyrolysis of biomass

The slow pyrolysis of biomass in the form of pine wood was investigated in a static batch reactor at pyrolysis temperatures from 300 to 720°C and heating rates from 5 to 80 K min⁻¹. The compositions and properties of the derived gases, pyrolytic oils and solid char were determined in relation to pyrolysis temperatures and heating rates. In addition, the wood and the major components of the wood—cellulose, hemicellulose and lignin—were pyrolysed in a thermogravimetric analyser (TGA) under the same experimental conditions as in the static batch reactor. The static batch reactor results showed that as the pyrolysis temperature was increased, the percentage mass of solid char decreased, while gas and oil products increased. There was a small effect of heating rate on product yield. The lower temperature regime of decomposition of wood showed that mainly H₂O, CO₂ and CO were evolved and at the higher temperature regime, the main decomposition products were oil, H₂O, H₂, hydrocarbon gases and lower concentrations of CO and CO₂. Fourier transformation infra-red spectroscopy and elemental analysis of the oils showed they were highly oxygenated. The TGA results for wood showed two main regimes of weight loss, the lower temperature regime could be correlated with the decomposition of hemicellulose and the initial stages of cellulose decomposition whilst the upper temperature regime correlated mainly with the later stages of cellulose decomposition. Lignin thermal decomposition occurred throughout the temperature range of pyrolysis.     

Catalytic pyrolysis of microalgae to high-quality liquid bio-fuels

The pyrolytic conversion of chlorella algae to liquid fuel precursor in presence of a catalyst (Na₂CO₃) has been studied. Thermal decomposition studies of the algae samples were performed using TGA coupled with MS. Liquid oil samples were collected from pyrolysis experiments in a fixed-bed reactor and characterized for water content and heating value. The oil composition was analyzed by GC-MS. Pretreatment of chlorella with Na₂CO₃ influences the primary conversion of chlorella by shifting the decomposition temperature to a lower value. In the presence of Na₂CO₃, gas yield increased and liquid yield decreased when compared with non-catalytic pyrolysis at the same temperatures. However, pyrolysis oil from catalytic runs carries higher heating value and lower acidity. Lower content of acids in the bio-oil, higher aromatics, combined with higher heating value show promise for production of high-quality bio-oil from algae via catalytic pyrolysis, resulting in energy recovery in bio-oil of 40%.     

Conversion of waste tires to liquid products via sodium carbonate catalytic pyrolysis

This study deals with the pyrolysis of waste tires supplied from the transport industry. The base material of tire is latex, which is derived from natural rubber trees. Nowadays rubber (Hevea brasiliensis) is a fast-growing tropical tree crop, which is being cultivated for latex and ultimately for tire production. Waste tires can be recycled for energy and valuable materials in many ways; however tire burning is the most common practice for heat generation. In recent years, the catalytic conversion of waste tires through pyrolysis into liquid, solid, and gas products was investigated. Liquids product was produced from the catalytic pyrolysis of waste tire at high temperature (up to 600°C) using sodium carbonate (Na₂CO₃) as a catalyst. Thermo-physical characteristics of the produced liquid samples showed that up to 85% of the produced oil can be used in internal combustion engines. Gasoline and diesel fuel contents in the liquid products are 45% and 40%, respectively. The gas chromatographic (GC) analysis of the volatile fraction of pyrolysis products showed styrene (28.1%) and butadiene (10.7%) as dominant compounds. The gaseous phase includes C₁–C₄ hydrocarbons (4.8%) and the liquid phase includes C₅–C₈ hydrocarbons (6.5%) of the total products.     

Fixed-bed pyrolysis of safflower seed: influence of pyrolysis parameters on product yields and compositions

Fixed-bed slow pyrolysis experiments have been conducted on a sample of safflower seed to determine particularly the effects of pyrolysis temperature, heating rate, particle size and sweep gas flow rate on the pyrolysis product yields and their chemical compositions. The maximum oil yield of 44% was obtained at the final pyrolysis temperature of 500°C, particle size range of +0.425–1.25 mm, with heating rate of 5°C min⁻¹ and sweep gas (N₂) flow rate of 100 cm³ min⁻¹ in a fixed-bed lab-scale reactor. Chromatographic and spectroscopic studies on the pyrolytic oil showed that the oil obtained from safflower seed can be used as a renewable fuel and chemical feedstock with a calorific value of 41.0 MJ/kg and empirical formula of CH_1.92O_0.11N_0.02.     

The fuel properties of pyrolytic oils obtained from catalytic pyrolysis of non-recyclable pulper rejects using activated natural minerals

In this study, catalytic pyrolysis of pulper rejects was performed with catalysts obtained from activated clinoptilolite and meerschaum for the production of pyrolytic fuel oils. The increasing proportion of polymers in rejects led to an increase in oil yield in non-catalytic process. The highest liquid (61.4%) and char (32.19%) yields were obtained using 15% clinoptilolite and 5% meerschaum, while the highest gas yield (21.44%) was obtained via the non-catalytic process. The fuel properties of the oils were significantly enhanced with the catalytic process. The clinoptilolite catalyst showed better performance compared to the meerschaum in terms of oil yield and fuel properties.     

Energy production from the pyrolysis of waste biomasses

Pyrolysis of waste biomasses was carried out at the temperatures of 450 and 500°C by heating at 5°C min^?1. Products were collected from emitted gases in a nitrogen purge stream; condensable liquids in the gases were collected by condensation. Gaseous, condensed liquid products and residual solids were collected and analyzed. Condensates were extracted with ether to recover the bio oils (BOs). The maximum liquid yield was obtained from the pyrolysis of soybean oil cake (SBOC) at 500°C with a yield of 60% ca. The BO was higher in the case of SBOC than that of sunflower oil cake (SFOC) at the temperatures of 450 and 500°C. With increasing temperature, bio char yield from the pyrolysis of SFOC decreased, while the liquid yield increased. The increase in temperature did not significantly affect the product distribution for the pyrolysis of SBOC. The compositions of BOs were similar for both SBOC and SFOC. Phenols, phenol derivatives including guaiacols and alkyl‐benzenes were the most common and predominant in BOs from both the pyrolysis of SBOC and SFOC. Carbon dioxide was the major gas product for both SBOC and SFOC. Copyright © 2008 John Wiley & Sons, Ltd.     

Enhancing the aromatic hydrocarbon yield from the catalytic copyrolysis of xylan and LDPE with a dual-catalytic-stage combined CaO/HZSM-5 catalyst

The high concentration of oxygenated compounds in pyrolytic products prohibits the conversion of hemicellulose to important biofuels and chemicals via fast pyrolysis. Herein CaO and HZSM-5 was developed to convert xylan and LDPE to valuable hydrocarbons by thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and elucidate the reaction mechanism were also investigated in detail. The results indicated that xylan/LDPE copyrolysis was more complicated than pyrolysis of the individual components. LDPE hindered the thermal decomposition and aromatic hydrocarbon formation from xylan at temperatures under 350 °C and had a synergistic effect at high temperatures. 50% LDPE was proven to be more beneficial than other percentages for the formation of monocyclic aromatic hydrocarbons. Simultaneously, the addition of CaO/HZSM-5 significantly reduced the reaction Ea and increased the reaction rate. CaO can effectively improve the deoxygenation and aromatization reaction, enhancing the yield and selectivity of aromatics to a certain extent. The maximum yield of hydrocarbons (96.01%), mono-aromatic hydrocarbons (88.53%) and S_BTXE (85.79%) were obtained at a CaO/HZSM-5 ratio of 1:2, a pyrolysis temperature of 450 °C, a catalytic temperature of 550 °C, a catalyst dose of 1:2 and a xylan-to-LDPE ratio of 1:1 via an ex situ process. The system was dominated by toluene, xylene and alkyl benzene. Diels-Alder reactions of furans and hydrocarbon pool mechanism of nonfuranic compounds improved aromatic formation. This study provides a fundamental for recovering energy and chemicals from pyrolysis of hemicellulose.     

Pyrolysis of black cumin seed cake in a fixed-bed reactor

The black cumin seed cake (BCSC) is a by-product obtained from the black cumin seeds with cold pressing. This by-product can be utilized as a biomass feedstock for conversion to bio-oil with pyrolysis process. The BCSC samples were initially pyrolyzed on a lab-scale pyrolysis system at different values in the ranges of 300-800 °C and 0.050-0.300 L min⁻¹ to determine the effects of operation temperature and N₂ flow rate on the yields on products, respectively. Then, the bio-oil in the highest yield (wB = 44.37%) which was obtained at pyrolysis final temperature (450 °C) temperature, heating rate (35 °C min⁻¹), particle size (dp > 850 ??m), and sweeping flow rate of 0.200 L min⁻¹ was characterized by Fourier Transform infra-red (FT-IR) spectroscopy, gas chromatography/mass spectrometry (GC-MS) and column chromatography. Consequently, it was shown that the operating temperature and N₂ gas flow rate parameters were effective on the product yields. Also, the important some physico-chemical properties of the pyrolytic oil obtained in high yield were determined as the calorific value of 38.48 MJ kg⁻¹, the empirical formula of CH_1.651O_0.105N_0.042S_0.001, the rich chemical content containing many different chemical groups, and the density of 970.25 kg m⁻³, and the viscosity of 63.42 mm² s⁻¹. Based on the determined properties of the pyrolytic oil, it was decided that the use of pyrolytic oil derived from the BCSC may possible be for the production of the alternative liquid fuels and finely chemicals after the necessary improvements.     

Energy Applications of Biomass: Pyrolysis of Apricot Stone

Apricot stone (Prunus armeniaca L.) was pyrolyzed in a directly heated fixed-bed reactor under nitrogen atmosphere. Effects of sweeping gas flow rates and pyrolysis temperature on the pyrolysis of the biomass were also studied. Pyrolysis runs were performed using reactor temperatures between 400°C and 700°C with heating rate of about 300°C min^?1. As the pyrolysis temperature was increased, the percentage mass of char decreased while gas product increased. The product yields were significantly influenced by the process conditions. The bio-oil obtained at 550°C, at which the liquid product yield was maximum, was analyzed. It was characterized by Fourier transform infrared spectroscopy (FT-IR). In addition, the solid and liquid products were analyzed to determine their elemental composition and calorific value. Chemical fractionation of bio-oil showed that only low quantities of hydrocarbons were present, while oxygenated and polar fractions dominated.     

Biodiesel Production Facilities from Vegetable Oils and Animal Fats

Abstract

Biodiesel is a renewable fuel that can be produced from vegetable oils, animal fats, and used cooking oil including triglycerides. Biodiesel, an alternative biodegradable diesel fuel, is derived from triglycerides by transesterification with methanol and ethanol. Concerns about the depletion of diesel fuel reserves and the pollution caused by continuously increasing energy demands make biodiesel an attractive alternative motor fuel for compression ignition engines. There are four different ways of modifying vegetable oils and fats to use them as diesel fuel, such as pyrolysis (thermal cracking), dilution with hydrocarbons (blending), emulsification and transesterification. The most commonly used process is transesterification of vegetable oils and animal fats. The transesterification reaction is affected by molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids and water content of oils or fats. In the transesterification, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness, all of which result in a low conversion. Biodiesel has over double the price of diesel. The high price of biodiesel is in large part due to the high price of the feedstock.