Transesterification of waste vegetable oil under pulse sonication using ethanol,methanol and ethanol–methanol mixtures

This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.     

Comparative analysis for the production of fatty acid alkyl esterase using whole cell biocatalyst and purified enzyme from Rhizopus oryzae on waste cooking oil (sunflower oil)

The petroleum fuel is nearing the line of extinction. Recent research and technology have provided promising outcomes to rely on biodiesel as the alternative and conventional source of fuel. The use of renewable source - vegetable oil constitutes the main stream of research. In this preliminary study, Waste Cooking Oil (WCO) was used as the substrate for biodiesel production. Lipase enzyme producing fungi Rhizopus oryzae 262 and commercially available pure lipase enzyme were used for comparative study in the production of Fatty Acid Alkyl Esters (FAAE). The whole cell (RO 262) and pure lipase enzyme (PE) were immobilized using calcium alginate beads. Calcium alginate was prepared by optimizing with different molar ratios of calcium chloride and different per cent sodium alginate. Entrapment immobilization was done for whole cell biocatalyst (WCB). PE was also immobilized by entrapment for the transesterification reaction. Seven different solvents - methanol, ethanol, n-propanol, n-butanol, iso-propanol, iso-butanol and iso-amyl alcohol were used as the acyl acceptors. The reaction parameters like temperature (30°C), molar ratio (1:3 - oil:solvent), reaction time (24 h), and amount of enzyme (10% mass ratio to oil) were also optimized for methanol alone. The same parameters were adopted for the other acyl acceptors too. Among the different acyl acceptors - methanol, whose reaction parameters were optimized showed maximum conversion of triglycerides to FAAE-94% with PE and 84% with WCB. On the whole, PE showed better catalytic converting ability with all the acyl acceptor compared to WCB. Gas chromatography analysis (GC) was done to determine the fatty acid composition of WCO (sunflower oil) and FAAE production with different acyl acceptors.     

Optimization of two-step catalyzed biodiesel production from soybean waste cooking oil

An acid–base-catalyst-based two-step biodiesel production experiment from soybean waste cooking oil was carried out to identify which parameter is the most influential among the experimental parameters by using the Taguchi method. Heterogeneous catalysts were used to avoid a water-consuming homogeneous catalyst removal process. Ferric sulfate and calcium oxide were used as acid and base catalysts, respectively, for the heterogeneous reaction. Reaction time and methanol-to-triglyceride mole ratio were significant factors. The optimum parameters for step 1 (acid esterification) were 4 h of reaction time, 4 wt. % of ferric sulfate amount, a 16:1 methanol to triglyceride mole ratio, and 400 rpm of mixing speed, respectively. For the transesterification step, the most influential factor was reaction time, and CaO amount was significant as well. On the other hand, the mole ratio of methanol and oil was relatively less significant. Optimum parameters were 3 h of reaction time, 2 wt. % of CaO, and a 12:1 methanol to triglyceride mole ratio with mixing speed at 400 rpm in this experimental range. Under the optimum conditions, waste cooking oil with 5.27 mg KOH/g of acid value was converted into crude biodiesel by a two-step process with fatty acid methyl ester content reaching 89.8 % without any further post-purification.     

Production of biodiesel from waste frying oils

Waste frying oils transesterification was studied with the purpose of achieving the best conditions for biodiesel production. Transesterification reactions were carried out for 1 h using waste frying oils (WFOs), methanol, and sodium hydroxide as catalyst. In order to determine the best conditions for biodiesel production, a series of experiments were carried out, using methanol/WFO molar ratios between 3.6 and 5.4 and catalyst/WFO weight ratios between 0.2% and 1.0%. For oils with an acid value of 0.42 mg KOH/g, results show that a methanol/WFO ratio of 4.8 and a catalyst/WFO ratio of 0.6% gives the highest yield of methyl esters. Furthermore, an increase in the amount of methanol or catalyst quantity seems to simplify the separation/purification of the methyl esters phase, as showed by a viscosity reduction and an increasing purity to values higher than 98% for methyl esters phase.     

Recovery of different waste vegetable oils for biodiesel production: A pilot experience in Bahia State,Brazil

In Brazil, and mainly in the State of Bahia, crude vegetable oils are widely used in the preparation of food. Street stalls, restaurants and canteens make a great use of palm oil and soybean oil. There is also some use of castor oil, which is widely cultivated in the Sertão Region (within the State of Bahia), and widely applied in industry. This massive use in food preparation leads to a huge amount of waste oil of different types, which needs either to be properly disposed of, or recovered. At the Laboratorio Energia e Gas-LEN (Energy & Gas lab.) of the Universidade Federal da Bahia, a cycle of experiments were carried out to evaluate the recovery of waste oils for biodiesel production. The experiences were carried out on a laboratory scale and, in a semi-industrial pilot plant using waste oils of different qualities. In the transesterification process, applied waste vegetable oils were reacted with methanol with the support of a basic catalyst, such as NaOH or KOH. The conversion rate settled at between 81% and 85% (in weight). The most suitable molar ratio of waste oils to alcohol was 1:6, and the amount of catalyst required was 0.5% (of the weight of the incoming oil), in the case of NaOH, and 1%, in case of KOH.The quality of the biodiesel produced was tested to determine the final product quality. The parameters analyzed were the acid value, kinematic viscosity, monoglycerides, diglycerides, triglycerides, free glycerine, total glycerine, clearness; the conversion yield of the process was also evaluated.     

Application of Poly(styrene-co-divinylbenzene) Macroporous Microparticles as a Catalyst Support in the Enzymatic Synthesis of Biodiesel

Macroporous poly(styrene-co-divinylbenzene) microparticles, with three different structural characteristics, have been synthesized and used as supports in the immobilization of lipase from Burkholderia cepacia. The best immobilization yield was found upon using microparticles with 35 % of divinylbenzene and the immobilized lipase on this type of particles was used as a catalyst to obtain biodiesel from soybean oil and ethanol. From the experimental results of the transesterification reaction, an empirical model quantitatively relating the temperature, the concentration of the enzyme and the transesterification yield was obtained. Statistical analysis of this model indicated that within the range of values of the variables studied (35–47 °C and 231–788 U/mg respectively) only the enzyme concentration exerted a significant influence on the reaction yield. Additionally, the good fit of a Michaelis–Menten-type model to the experimental results suggests that the limiting step of the reaction was the formation of the enzyme-substrate complex.     

Storage stability of biocrude oils from fast pyrolysis of poultry litter

The unstable nature of biocrude oils produced from conventional pyrolysis of biomass is one of the properties that limits its application. In the disposal of poultry litter via pyrolysis technology, the biocrude oil produced as a value-added product can be used for on farm applications. In this study, we investigated the influence of bedding material (wood shavings) on the storage stability of biocrude oils produced from the fast pyrolysis of poultry litter. The biocrude oils produced from manure, wood (pine and oak), and mixtures of manure and wood in proportions (75:25 50:50, and 25:75 w/w%) were stored under ambient conditions in sealed glass vials for a period of 6 months and their stability were monitored by measuring the changes in viscosity over time. The manure oil had the lowest rate of viscosity change and thus was relatively the most stable and the oils from the 50:50 w/w% litter mixtures were the least stable. The rate of viscosity change of the manure biocrude oil was 1.33 cP/day and that of the 50/50 litter mixture was 7.6 cP/day for pine and 4.17 cP/day for oak.The spectrometric analyses of the biocrude oils showed that the presence of highly reactive oxygenated functionalities in the oil were responsible for the instability characteristic of the litter biocrude oils. The poor stability of the biocrude oil from the 50:50 w/w% litter mixtures was attributed to reactions between nitrogenous compounds (amides) from protein degradation and oxygenated compounds from the decomposition of polysaccharides and lignin. The addition of 10% methanol and 10% ethanol to the oil from 50% manure and 50% pine reduced the initial viscosity of the oil and was also beneficial in slowing down the rate of viscosity change during storage.     

Biodiesel production from vegetable oil and waste animal fats in a pilot plant

In this study, corn oil as vegetable oil, chicken fat and fleshing oil as animal fats were used to produce methyl ester in a biodiesel pilot plant. The FFA level of the corn oil was below 1% while those of animal fats were too high to produce biodiesel via base catalyst. Therefore, it was needed to perform pretreatment reaction for the animal fats. For this aim, sulfuric acid was used as catalyst and methanol was used as alcohol in the pretreatment reactions. After reducing the FFA level of the animal fats to less than 1%, the transesterification reaction was completed with alkaline catalyst. Due to low FFA content of corn oil, it was directly subjected to transesterification. Potassium hydroxide was used as catalyst and methanol was used as alcohol for transesterification reactions. The fuel properties of methyl esters produced in the biodiesel pilot plant were characterized and compared to EN 14214 and ASTM D6751 biodiesel standards. According to the results, ester yield values of animal fat methyl esters were slightly lower than that of the corn oil methyl ester (COME). The production cost of COME was higher than those of animal fat methyl esters due to being high cost biodiesel feedstock. The fuel properties of produced methyl esters were close to each other. Especially, the sulfur content and cold flow properties of the COME were lower than those of animal fat methyl esters. The measured fuel properties of all produced methyl esters met ASTM D6751 (S500) biodiesel fuel standards.     

Biodiesel production from waste frying oils and its quality control

The use of biodiesel as fuel from alternative sources has increased considerably over recent years, affording numerous environmental benefits. Biodiesel an alternative fuel for diesel engines is produced from renewable sources such as vegetable oils or animal fats. However, the high costs implicated in marketing biodiesel constitute a major obstacle. To this regard therefore, the use of waste frying oils (WFO) should produce a marked reduction in the cost of biodiesel due to the ready availability of WFO at a relatively low price.In the present study waste frying oils collected from several McDonald’s restaurants in Istanbul, were used to produce biodiesel. Biodiesel from WFO was prepared by means of three different transesterification processes: a one-step base-catalyzed, a two-step base-catalyzed and a two-step acid-catalyzed transesterification followed by base transesterification. No detailed previous studies providing information for a two-step acid-catalyzed transesterification followed by a base (CH₃ONa) transesterification are present in literature. Each reaction was allowed to take place with and without tetrahydrofuran added as a co-solvent. Following production, three different procedures; washing with distilled water, dry wash with magnesol and using ion-exchange resin were applied to purify biodiesel and the best outcome determined. The biodiesel obtained to verify compliance with the European Standard 14214 (EN 14214), which also corresponds to Turkish Biodiesel Standards.     

Transesterification reaction of the fat originated from solid waste of the leather industry

The leather industry is an industry which generates a large amount of solid and liquid wastes. Most of the solid wastes originate from the pre-tanning processes while half of it comes from the fleshing step. Raw fleshing wastes which mainly consist of protein and fat have almost no recovery option and the disposal is costly. This study outlines the possibility of using the fleshing waste as an oil source for transesterification reaction. The effect of oil/alcohol molar ratio, the amount of catalyst and temperature on ester production was individually investigated and optimum reaction conditions were determined. The fuel properties of the ester product were also studied according to the EN 14214 standard. Cold filter plugging point and oxidation stability have to be improved in order to use the ester product as an alternative fuel candidate. Besides, this product can be used as a feedstock in lubricant production or cosmetic industry.     

Production of well-matured compost from night-soil sludge by an extremely short period of thermophilic composting

The effect of various operational conditions on the decomposition of organic material during the composting of night-soil treatment sludge was quantitatively examined. The optimum composting conditions were found to be a temperature of ca. 60 °C and an initial pH value of 8. Rapid decomposition of organic matter ceased by the sixth day of composting under these optimum conditions, and the final value of the cumulative emission of carbon (E_C), which represents the degree of organic matter decomposition, was less than 40%, indicating that the sludge contained only a small amount of easily degradable organic material. A plant growth assay using Komatsuna (Brassica campestris L. var. rapiferafroug) in a 1/5000a standard cultivation pot was then conducted for the compost at various degrees of organic matter decomposition: the raw composting material, the final compost obtained on day 6, and the 2 intermediate compost products (i.e., E_C = 10% and 20%). It was found that the larger the E_C, the greater the yield of Komatsuna growth. It was also found that 6 days of composting is sufficient to promote Komatsuna growth at the standard loading level, which is equivalent to a 1.5 g N/pot, since the promotion effect was as high as that obtained using chemical fertilizer. It can therefore be concluded that well-matured compost could be obtained in a short period of time (i.e., as early as 6 days), when night-soil sludge is composted under optimum conditions.     

Methanolysis and Hydrolysis of Polycarbonate Under Moderate Conditions

Alkali-catalyzed methanolysis and hydrolysis of polycarbonate (PC) in a solvent in which PC can substantially dissolve such as N-methyl-2-pyrrolidone, 1,4-dioxane, tetrahydrofuran and so on were studied. Reaction conditions were optimized for the purpose of recycling PC in the form of bisphenol A and carbon carbonate. The results showed that both the methanolysis and hydrolysis of PC could take place under moderate conditions. Under the conditions of reaction temperature 40 °C, m(PC):m(MeOH) = 1:1, m(PC):m(NaOH) = 50:1, reaction time 35 min and using tetrahydrofuran as solvent, the methanolysis conversion of PC was almost 100% and the yield of bisphenol A was over 95%. Moreover, under the conditions of reaction temperature 100 °C, m(PC):m(H₂O) = 1:0.7, m(PC):m(NaOH) = 10:1, reaction time 8 h and using 1,4-dioxane as solvent, the hydrolysis conversion of PC was almost 100% and the yield of bisphenol A was over 94%.     

Optimizing vermistabilization of waste activated sludge using vermicompost as bulking material

An integrated composting-vermicomposting system has been developed for stabilization of waste activated sludge (WAS) using matured vermicompost as bulking material and Eisenia fetida as earthworm species. Composting was considered as the main processing unit and vermicomposting as polishing unit. The integrated system was optimized by successive recycling and mixing of bulking material with WAS during composting and examining the effects of environmental condition (i.e. temperature: 10-30 °C and relative humidity: 50 and 90%) and stocking density (0-5 kg/m²) on vermicomposting. The composting stage resulted in sufficient enrichment of bulking material with organic matter after 20 cycles of recycling and mixing with WAS and produced materials acceptable for vermicomposting. Vermicomposting of composted material caused significant reduction in pH, volatile solids (VS), specific oxygen uptake rate (SOUR), total carbon (TC), total organic carbon (TOC), C/N ratio and pathogens and a substantial increase in electrical conductivity (EC), total nitrogen (TN) and total phosphorous (TP). The environmental conditions (i.e. temperature: 10-30 °C and relative humidity: 50 and 90%) and stocking density (0-5 kg/m²) have profound effects on vermicomposting. Temperature of 20 °C with high humidity is the best suited environmental condition for vermicomposting employing E. fetida. The favorable stocking density range for vermiculture is 0.5-2.0 kg/m² (optimum: 0.5 kg/m²) and for vermicomposting is 2.0-4.0 kg/m² (optimum: 3.0 kg/m²), respectively. The integrated composting-vermicomposting system potentially stabilizes and converts the hazardous WAS into quality organic manure for agronomic applications without any adverse effects.     

Anaerobic digestion of chicken feather with swine manure or slaughterhouse sludge for biogas production

Biogas production from anaerobic digestion of chicken feathers with swine manure or slaughterhouse sludge was assessed in two separate experiments. Ground feathers without any pre-treatment were added to 42-L digesters inoculated with swine manure or slaughterhouse sludge, representing 37% and 23% of total solids, respectively and incubated at 25 °C in batch mode. Compared to the control without feather addition, total CH₄ production increased by 130% (P < 0.001) and 110% (P = 0.09) in the swine manure and the slaughterhouse sludge digesters, respectively. Mixed liquor NH₄N concentration increased (P < 0.001) from 4.8 and 3.1 g/L at the beginning of the digestion to 6.9 and 3.5 g/L at the end of digestion in the swine manure and the slaughterhouse sludge digesters, respectively. The fraction of proteolytic microorganisms increased (P < 0.001) during the digestion from 12.5% to 14.5% and 11.3% to 13.0% in the swine manure and the slaughterhouse sludge digesters with feather addition, respectively, but decreased in the controls. These results are reflective of feather digestion. Feather addition did not affect CH₄ yields of the swine manure digesters (P = 0.082) and the slaughterhouse sludge digesters (P = 0.21), indicating that feathers can be digested together with swine manure or slaughterhouse sludge without negatively affecting the digestion of swine manure and slaughterhouse sludge.     

Changes in fungal population of fly ash and vinasse mixture during vermicomposting by Eudrilus eugeniae and Eisenia fetida: documentation of cellulase isozymes in vermicompost

Fly ash (FA) and vinasse (VN), two industrial wastes, are generated in huge amounts and cause serious hazards to the environment. In this experiment, different proportions of these two wastes were used as food for two epigeic earthworms (Eisenia fetida and Eudrilus eugeniae) to standardize the recycling technique of these two wastes and to study their effect on fungal especially cellulolytic fungal population, cellulase activity and their isozyme pattern, chitin content and microbial biomass of waste mixture during vermicomposting. Increasing VN proportion from 25% to 50% or even higher, counts of both fungi and cellulolytic fungi in waste mixtures were significantly (P ? 0.05) increased during vermicomposting. Higher cellulase activity in treatments having 50% or more vinasse might be attributed to the significantly (P ? 0.05) higher concentration of group I isozyme while concentrations of other isozymes (group II and III) of cellulase were statistically at par. Higher chitin content in vinasse-enriched treatments suggested that fungal biomass and fungi-to-microbial biomass ratio in these treatments were also increased due to vermicomposting. Results revealed that Eudrilus eugeniae and Eisenia fetida had comparable effect on FA and VN mixture during vermicomposting. Periodical analysis of above-mentioned biochemical and microbial properties and nutrient content of final vermicompost samples indicated that equal proportion (1:1, w/w) of FA and VN is probably the optimum composition to obtain best quality vermicompost.     

Effect of the water–oil ratio on brine/surfactant/alcohol/oil systems optimized for soil remediation

The optimum middle-phase microemulsion used for remediation of oily contaminated soils is often obtained by mixing a certain amount of a surfactant/alcohol mixture with oil and adjusting the salinity concentrations at a constant water–oil ratio. Upon introduction to the subsurface, however, the system may not be in the optimum state throughout the remediation process owing to the change in the water–oil ratio. This research has attempted to investigate the effect of the water–oil ratio on the phase behavior of systems containing brine, anionic surfactant, alcohols, and different oils. By systematically changing the water–oil ratio, while keeping the others variables constant, the systems exhibited different phase behavior. The results revealed that the effect of the water–oil ratio on system behavior was significant, and analogous to that of salinity. Increasing the water–oil ratio led the system change from winsor I → winsor III → winsor II. The greater the water–oil ratio the lower the salinity required to produce the middle-phase microemulsion, but the narrower the salinity range of the three-phase region. An empirical correlation has been developed in order to predict the changes in phase behavior with the changes in water–oil ratio. This provides a useful tool for designing optimum formulations suitable for soil remediation. Received: October 5, 1999 / Accepted: March 27, 2000     

Marsh Sensitivity to Burning of Applied Crude Oil

This research note summarizes Spartina alterniflora and Sagittaria lancifolia sensitivity to oiling and in situ burning of applied oil. Experimental plots (2.4 m × 2.4 m × 0.6 m) were constructed in salt and freshwater marsh habitats and South Louisiana Crude (SLC) applied (2 l m⁻²) to stems and leaves of marsh plants of oil and oil/burn treatment plots. Burning was initiated mid-August when winds were calm and a 15-25 cm floodwater layer covered the marsh substrate. Vegetative responses (stem density, height, carbon assimilation and biomass production) were measured for approximately one year following the in situ burns. Application of oil and burning of SLC only had short-term detrimental effects on salt and freshwater marsh vegetation. About one year after burns, vegetative responses measured in oiled and oiled/burned plots approached or exceeded control (no oil or burn) values. Field results suggest, under our experimental conditions, in situ burning of spilled oil in S. alterniflora and S. lancifolia marshes may be a remediation operation to consider.     

Effect of fresh green waste and green waste compost on mineral nitrogen, nitrous oxide and carbon dioxide from a Vertisol

Incorporation of organic waste amendments to a horticultural soil, prior to expected risk periods, could immobilise mineral N, ultimately reducing nitrogen (N) losses as nitrous oxide (N₂O) and leaching. Two organic waste amendments were selected, a fresh green waste (FGW) and green waste compost (GWC) as they had suitable biochemical attributes to initiate N immobilisation into the microbial biomass and organic N forms. These characteristics include a high C:N ratio (FGW 44:1, GWC 35:1), low total N (<1%), and high lignin content (>14%). Both products were applied at 3 t C/ha to a high N (plus N fertiliser) or low N (no fertiliser addition) Vertisol soil in PVC columns. Cumulative N₂O production over the 28 day incubation from the control soil was 1.5 mg/N₂O/m², and 11 mg/N₂O/m² from the control + N. The N₂O emission decreased with GWC addition (P < 0.05) for the high N soil, reducing cumulative N₂O emissions by 38% by the conclusion of the incubation. Analysis of mineral N concentrations at 7, 14 and 28 days identified that both FGW and GWC induced microbial immobilisation of N in the first 7 days of incubation regardless of whether the soil environment was initially high or low in N; with the FGW immobilising up to 30% of available N. It is likely that the reduced mineral N due to N immobilisation led to a reduced substrate for N₂O production during the first week of the trial, when soil N₂O emissions peaked. An additional finding was that FGW + N did not decrease cumulative N₂O emissions compared to the control + N, potentially due to the fact that it stimulated microbial respiration resulting in anaerobic micro sites in the soil and ultimately N₂O production via denitrification. Therefore, both materials could be used as post harvest amendments in horticulture to minimise N loss through nitrate-N leaching in the risk periods between crop rotations. The mature GWC has potential to reduce N₂O, an important greenhouse gas.     

用废旧电路板热解油制备酚醛树脂

在碳酸钙存在下,采用热解技术将废旧电路板中的树脂转化为富含酚的热解油,然后直接加入甲醛溶液反应制备热解油型酚醛树脂,实现了废旧电路板中树脂的再生,酚醛树脂的性能结构类似于氨催化的酚醛树脂。实验结果表明：在n（甲醛）：n（热解油）为1．8～2．1的条件下,无需外加催化剂,在60,80,90℃下分别反应30min制备的热解油型酚醛树脂的性能最佳,且可满足GB／T14732—93《木材工业胶黏剂用脲醛、酚醛、三氧氰胺甲醛树脂》中层压材料用酚醛树脂产品的相关标准。     

Removal of Linear and Branched p-Alkylphenols from Aqueous Solution by Combined Use of melB Tyrosinase and Chitosan Beads

In this study, melB tyrosinase was applied for enzymatic removal of linear and branched p-alkylphenols from aqueous solutions. First, systematic studies were carried out to estimate the effects of the process parameters such as the temperature, pH value, and enzyme dose on quinone conversion of p-cresol as a model phenol compound. A variety of p-alkylphenols were removed from aqueous solutions through the tyrosinase-catalyzed quinone conversion and subsequent nonenzymatic adsorption of quinone derivatives on chitosan beads at pH 6.0 and 30 °C under the optimum conditions determined for p-cresol. The % removal values of 98–100 were obtained for p-n-alkylphenols. Branched p-alkylphenols with a weak estrogenic activity containing 4-tert-butylphenol and 4-tert-pentylphenol, which underwent no quinone conversion by commercially available mushroom tyrosinase in the absence of H₂O₂, were also effectively removed by further increasing either the melB tyrosinase concentration or the amount of added chitosan beads. The present technique is much effective in the fact that a series of reactions rapidly progress under mild conditions and the chitosan beads can be readily separated from the reaction medium after the enzymatic treatment.