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.     

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.     

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.     

Extrication of biodiesel feedstock from early stage of food waste liquefaction

Biodiesel is commonly produced from vegetable oils, mostly edible and more expensive than petroleum diesel. By considering the cost of the conversion processes, cheap feedstock such as triglycerides and fatty acids (FA) extracted from early stage of food waste liquefaction has become a better choice than vegetable oils, as it could provide high yield of biodiesel without any compromise to food supply and other resources. In this study, FA from early stage of food waste liquefaction was extracted and tested for use as feedstock for biodiesel synthesis. The raw material was not pretreated but extraction was done by dry and wet methods. It was found that wet method could minimized the lost of short and medium-chained FA as well as reducing the number of steps required, thus, yielding higher amount of FA as feedstock. The effects of mixing, methanol ratio, reaction time and catalyst content were investigated for the acid-catalyzed esterification. The maximum biodiesel conversion obtained was 97.4 %.     

Effect of alkali catalyst on biodiesel production in South Korea from mixtures of fresh soybean oil and waste cooking oil

Biodiesel from waste cooking oil (WCO) and soybean oil (SO) mixture was produced by changing the alkali catalyst (NaOH) content and the WCO to SO ratio in the feedstock. All the prepared biodiesel samples satisfied the standard requirement in terms of free glycerol, density, and acid value. The minimum catalyst content and the highest WCO composition to get biodiesel from the WCO/SO mixture feedstock without ruining the biodiesel properties were 1.0 and 60 wt %, respectively. This conclusion implies that the waste cooking oil mixture, which contains 40 wt % fresh soybean oil, could be treated like the fresh soybean oil to produce biodiesel, and that this behavior would be helpful to reduce the biodiesel production cost when waste cooking oil used as feedstock. The unsaturated methyl esters such as linoleic, and oleic acid were dominant (almost 80 % w/w) in the fresh soybean oil. However the saturated methyl ester was increased due to the double bond breaking during the frying process. These results may deteriorate the biodiesel quality by changing the methyl ester composition.     

Recovery of rare earth elements from waste fluorescent phosphors: Na2O2 molten salt decomposition

In this paper, an efficient recovery of rare earth elements from waste fluorescent phosphors has been reported and the novel process of alkali fusion and acid leaching has been proposed. The experimental results have shown that the key for efficient recycling is the complete dissolution of waste fluorescent phosphors. The Na₂O₂-to-waste mass ratio, calcination temperature and reactive time play considerable roles in rare earth elements extraction during the alkali fusion process. The optimal conditions in terms of temperature, time and Na₂O₂-to-waste mass ratio are 650 °C, 15 min and 2:1, respectively, under which more than 99.5 % rare earth elements are extracted. The possible reaction mechanism of alkali fusion has been proposed.     

Algae Biomass Based Media for Poly(3-hydroxybutyrate) (PHB) Production by Escherichia coli

In addition to biodiesel production from algae, the production of other valuable bioproducts facilitates the development of an algae-based biorefinery platform. The goal of this study was to utilize the aqueous fraction from a novel algal wet lipid extraction procedure as the medium for the production of a bio product, poly(3-hydroxybutyrate) (PHB), via the growth of recombinant Escherichia coli. PHB yield was measured at 34 % of the E. coli dry cell mass, and was increased to 51 % when the algae aqueous medium was supplemented with glucose. While the addition of inorganic nutrients to the aqueous phase did not increase PHB production or growth of E. coli, growth of E. coli was observed to increase with the supplementation of carbon substrate (glucose). The addition of carbon rich waste to the aqueous fraction of wastewater-derived algae may in the future provide a sustainable alternative. Future research will be directed at evaluating this concept to develop a sustainable process for the production of bioplastics through an algae-based biorefinery platform.     

Reducing acid leaching of manganiferous ore: effect of the iron removal operation on solid waste disposal

The process of reducing acid leaching of manganiferous ore is aimed at the extraction of manganese from low grade manganese ores. This work is focused on the iron removal operation. The following items have been considered in order to investigate the effect of the main operating conditions on solid waste disposal and on the process costs: (i) type and quantity of the base agent used for iron precipitation, (ii) effective need of leaching waste separation prior to the iron removal operation, (iii) presence of a second leaching stage with the roasted ore, which might also act as a preliminary iron removal step, and (iv) effect of tailings washing on the solid waste classification. Different base compounds have been tested, including CaO, CaCO3, NaOH, and Na2CO3. The latter gave the best results concerning both the precipitation process kinetics and the reagent consumption. The filtration of the liquor leach prior to iron removal was not necessary, implying significant savings in capital costs. A reduction of chemical consumption and an increase of manganese concentration in the solution were obtained by introducing secondary leaching tests with the previously roasted ore; this additional step was introduced without a significant decrease of global manganese extraction yield. Finally, toxicity characteristic leaching procedure (TCLP) tests carried out on the leaching solid waste showed: (i) a reduction of arsenic mobility in the presence of iron precipitates, and (ii) the need for a washing step in order to produce a waste that is classifiable as not dangerous, taking into consideration the existing Environmental National Laws.     

Tensile Strength, Elongation, Hardness, and Tensile and Flexural Moduli of Injection-Molded TPS Filled with Glycerol-Plasticized DDGS

Continuing growth of biofuel industries is generating large amounts of coproducts such as distillers dried grains with solubles (DDGS) from ethanol production and glycerol from biodiesel. Currently these coproducts are undervalued, but they have application in the plastics industry as property modifiers. This research effort has quantified the effects on mechanical properties of adding DDGS and glycerol to a commercial thermoplastic starch (TPS). The methodology was to physically mix DDGS, as filler, with the TPS pellets and injection mold the blends into test bars using glycerol as a processing aid. The bars were then mechanically tested with blends from 0 to 65 %, by weight, of plasticized filler. The test bars were typically relatively brittle with little yielding prior to fracture with elongation between 1 and 3 %. The addition of glycerol enabled molding of blends with high levels of DDGS but did not increase strength. Any presence of filler decreased the tensile strength of the starch, and up to 30 % filler, the tensile strength drops about 15 %. The 20 and 50 % blends (without glycerol) have slightly greater stiffness than pure starch. With some other blends, the presence of plasticized filler degrades the tensile modulus with 35 % filler yielding about 1/3 the stiffness. Changes in the flexural modulus are much more pronounced as 20–25 % filled TPS has a 30 % increase in flexural stiffness. In terms of surface hardness, blends up to 60 % filler are within 20 % of the TPS baseline.     

Enzyme-Assisted Extraction and Pb<Superscript>2+</Superscript> Biosorption of Polysaccharide from <Emphasis Type="Italic">Cordyceps militaris</Emphasis>

The enzyme assisted extraction conditions of polysaccharide from Cordyceps militaris mycelia were firstly investigated by kinetics analysis and the optimal operating was found to be: extraction temperature 40 °C; solid-solvent ratio 1:20; extraction pH 4.0; cellulase concentration 2.0%. The polysaccharide extraction yield was 5.99% under these optimized conditions. Furthermore, a fundamental investigation of the biosorption of Pb²⁺ from aqueous solution by the C. militaris polysaccharide was performed under batch conditions. The suitable pH (5.0), polysaccharide concentration (0.20 g L^?1), initial Pb²⁺ concentration (300 mg L^?1) and contact time (40 min) were outlined to enhance Pb²⁺ biosorption from aqueous medium. The Langmuir isotherm model and pseudo first order kinetic model fitted well to the data of Pb²⁺ biosorption, suggesting the biosorption of Pb²⁺ onto C. militaris polysaccharide was monolayer biosorption and physical adsorption might be the rate-limiting step that controlled the adsorption process. FTIR analysis showed that the main functional groups of C. militaris polysaccharide involved in adsorption process were carbonyl, carboxyl, and hydroxyl groups.     

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.     

Production of 2-Pyrrolidone from Biobased Glutamate by Using Escherichia coli

We have developed a simple and highly efficient process for the production of 2-pyrrolidone (2-PRN) from biobased l-glutamic acid (Glu). First, we produced γ-aminobutyric acid (GABA) from Glu obtained by fermentation of biomass using Escherichia coli, which is known to possess GABA producing activity. The reaction solution contained only the substrate Glu, bacterial cells, and water, and did not require buffers or coenzymes, pyridoxal-5′-phosphate (PLP). Every 24 h, cells were removed by centrifugation, and GABA containing supernatant was obtained. This reaction can be repeated 14 times by adding water and Glu, without any decrease in activity. Finally, 303.7 g of GABA was produced from 560 g (40 g × 14 times) of Glu with a yield of 77.4 %. The concentration of this solution was almost 40 %. The GABA was then converted to biobased 2-PRN by heating and distillation under reduced pressure without pretreatment. The yield obtained with this chemical process was 95.8 %. These results showed that biobased 2-PRN could be produced from biomass-derived Glu. Biobased 2-PRN has great potential as a raw material to change other petroleum-based materials to biobased materials.     

Thermo-Chemical Decomposition Study of Polyurethane Elastomer Through Glycerolysis Route with Using Crude and Refined Glycerine as a Transesterification Agent

Due to the increasing amount of polyurethane waste, chemical recycling of these materials is a topic of growing interest for many researchers. The primary purpose of polyurethane feedstock recycling is to recover the starting polyol. In this study glycerolysis using glycerine from two sources and two purity grades is proposed as a method of chemical recycling. The main effort of this paper focuses on the employment of commercial glycerine of analytical grade and waste glycerine without purification derived from the biodiesel production, as a decomposing agent for polyurethane recycling. In this study, the influence of polyurethane to glycerine mass ratio (PU/GL) and the type of decomposing agent on the chemical structure by FTIR, ¹H NMR and GPC was examined. FTIR analysis of the glycerolysates showed absorption peaks similar to the virgin polyol. Those results are in compliance with GPC chromatograms, which showed for all samples, well-defined peak at ca. 13 min of retention time. The molecular weight of glycerolysates was ranging from 800 to 1300 g mol^?1 depending on PU/GL mass ratio. The novel decomposition agent, namely waste glycerine derived from biodiesel production was successfully used in glycerolysis process.     

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.     

Gasification characteristics of sewage sludge combined with wood biomass

The gas products from gasification processes have been considered to have some limitations in gas composition and heating value from the previous studies. Gasification characteristics of sewage sludge and wood mixture were investigated using different mixing ratios with the purpose of better quality of gas product suitable for energy/power generation. The gasification experiment was performed by an indirectly heated fluidized bed reactor. As reaction temperature increased from 600 to 900 °C, the yield of gas product increased with higher generation of CO, H₂ and CH₄ by more activated gas conversion reactions. As the equivalence ratio increased from 0.2 to 0.4, composition ratio of CO₂ increased while CO, CH₄, H₂ decreased as expected. Several operating variables including mixing ratio of wood with dried sludge were also tested. From this initial stage of experiment, optimal operating conditions for the bubbling fluidized bed gasifier, could be considered 900 °C in temperature; 0.2 in equivalence ratio and 40 % in wood mixing ratio within test variables range. These results will be more thoroughly investigated for the application to the larger scale pilot system.     

Bio-oil production by fast pyrolysis of cellulose/polyethylene mixtures in the presence of metal chloride

Cellulose/polyethylene mixture (3:1 w/w) and Tetra Pak wastes with and without metal chloride (ZnCl₂, AlCl₃, CuCl₂, FeCl₃) addition were subjected to a fast pyrolysis process at 350–500 °C and heating rate 100 °C/s to evaluate the possibility of liquid product formation with a high yield. The addition of zinc, aluminum, iron and copper chlorides has influenced the range of samples decomposition as well as the chemical composition of resulting pyrolytic oils. It was found that formation of levoglucosan, the main product of cellulose thermal decomposition, and phenol and its derivatives decreased in a presence of metal chlorides. Non-catalytic fast pyrolysis of polyethylene leads to the formation of solid long chain hydrocarbons, whereas the addition of metal chlorides promotes the formation of more liquid hydrocarbons.     

Extraction of polybrominated diphenyl ethers contained in waste high impact polystyrene by supercritical carbon dioxide

A new recycling process for the supercritical CO₂ (sc-CO₂) extraction of polybrominated diphenyl ethers from waste high impact polystyrene (HIPS) was developed in this paper. HIPS was first dissolved in d-limonene. The remaining decabromo diphenyl ether (decaBDE) particles in solution were then removed by centrifugation, and the PBDEs in the centrifugate solution were further extracted by sc-CO₂. The influence of temperature and pressure, the volume ratio of sc-CO₂ to plastic solution, and the concentration of decaBDE in the solution on the separating efficiency were investigated. The decaBDE particles in 20 % of the HIPS solution can be removed by centrifugation at a speed of 10,000 r/min at 30 °C. The suitable sc-CO₂ fluid conditions were 65 °C and 20 MPa, and the optimum volume ratio of the sc-CO₂ to the HIPS solution was 2:1. More than 97 % of the PBDEs were successfully removed, and the concentration of PBDE residues in the recycled HIPS was reduced to lower than 0.1 % (dry) by this recycling process.     

A New and Sound Technology for Biogas from Solid Waste and Biomass

Organic waste, as a main constituent of municipal solid waste, has as well as solid biomass a high potential for biogas generation. Despite the importance of biogas generation from these materials, the availability of large-scale biogas processes lacks behind the demand. A newly developed double-stage solid–liquid biogas process, consisting of an open hydrolysis stage and a fixed-bed methane reactor, allows the biogas production from almost all biodegradable solid waste and renewable resources like maize, grass, sugar cane, etc. Furthermore, residues from industrial processes, like the glycerine waste water from biodiesel production, can also be converted into biogas successfully. Due to the strong separation of hydrolysis and methanation, the process is extremely stable. No malfunction has been detected so far. The open hydrolysis releases CO₂ and allows oxidation of sulfur. Consequently, the biogas has a high methane (>72%) and low H₂S concentration (<100 ppm). Stirrers or other agitation equipment are not necessary; only liquids are pumped. The biogas generation becomes controllable for the first time; thus, the actual generation can be easily adapted to the consumption.     

Microwave Assisted Short-Time Alkaline Extraction of Birch Xylan

Efficacy of microwave energy for the extraction of xylan from birch wood as an alternative to conventional method of extraction was investigated. Effect of irradiation time and microwave power input on the solubilization of wood and yield of extracted xylan was studied. The maximum yield of xylan obtained at the higher power level was significantly lesser compared to the lower power level indicating the molecular degradation of the polymer. The highest yield of xylan (60 % of the original xylan) was obtained at the lowest power level studied, 110 W, for an irradiation time of 10 min. Comparison with conventional extraction showed that 10 min of microwave extraction provided a similar wood dissolution to that at 90 °C for 1.5 h, but with a higher yield of xylan. Characterization of the precipitated xylan indicated that the extracted xylan contained 68–88 % of xylose with the major chemical structure consisting of a linear backbone of (1-4) β-d-xylopyransoyl residues. Molecular mass of the extracted xylan indicated that the xylan extracted using microwave contained 60–70 % of high molecular weight fraction, and about 30–40 % of low molecular weight fraction, whereas xylan extracted using conventional method showed a reverse trend. Molecular mass of non-aggregated xylan was reported to be 6,000 Da (in terms of dextran equivalents). Crystallinity of wood fibers increased irrespective of the method of extraction indicating no degradation of the strength of the fibers occurred during the extraction.     

A study on torrefaction characteristics of waste sawdust in an auger type pyrolyzer

Torrefaction is thermo-chemical process which can improve solid fuel quality as well as grindability. In previous studies, torrefaction has been studied mainly for removal of moisture and for improving grindability. In this experiment, the characteristics of torrefied waste sawdust were studied especially for its energy yield. Hence, torrefaction was performed on varying reaction temperatures (200, 220, 240, 260, 280, 300 °C) and solid residence time (10, 30, 60 min). The results indicated that the yield of torrefaction decreases with increasing temperature and residence time. It was found that above 280 °C, the yield got remarkably decreased. The lowest yield was obtained at the residence time of 60 min. It was also noticed that the HHV of torrefied samples increases with increasing temperature. The highest HHV was found to be 26.09 MJ/kg which was obtained at 60 min and 300 °C. However, the highest energy yield was obtained to be 104.17 % which was noticed at 30 min and 260 °C.