By-product Of Biodiesel Production Research Articles

Synthesis of Layered LiMn1/3Ni1/3Co1/3O2 Oxides for Lithium‐Ion Batteries using Biomass‐Derived Glycerol as Solvent

AbstractIn an attempt to exploit biomass‐derived glycerol as a solvent, a sol–gel method was used to synthesize LiMn1/3Ni1/3Co1/3O2 (LMNC) layered oxide cathode materials for Li‐ion batteries. The effects of particle size and structure of the layered oxide materials at different annealing temperatures have been studied. The chemical compositions, cation ordering, and particle morphology were obtained by various advanced techniques. Electrochemical performance of the layered oxides was analyzed by cycling testing, cyclic voltammograms, and electrochemical impedance spectroscopy. A comparison of four LMNC samples in this study shows that LMNC annealed at 900 °C exhibits the most promising electrochemical properties. In particular, an initial discharge capacity of 177.1 mAh g−1 has been achieved, with a retention of the discharge capacity of more than 83.7 % after 100 cycles. Furthermore, the sample shows good rate capability up to 5 C, making it well qualified for lithium‐ion battery applications. This study demonstrated the possibility of using glycerol, a byproduct in biodiesel production, as a solvent instead of water in the sol–gel method to synthesize layered structure cathode materials.

Sustainable Approach for the Synthesis of Biopolycarbonates from Carbon Dioxide and Soybean Oil

A sustainable approach to produce biopolycarbonates was developed via copolymerizing carbon dioxide (CO2) and soybean-oil-based terminal epoxide (SOTE) monomers in the presence of catalyst SalenCoCl and cocatalyst bis(triphenylphosphine)iminium chloride (PPNCl). The SOTE monomers were obtained through the synthesis of soybean oil with recycled epichlorohydrin which can be produced from crude glycerol, a byproduct of biodiesel production. The characteristic profiles of SOTE monomers and biopolycarbonates demonstrated a 100% conversion and a biopolycarbonate yield of 83.3%. It was also found that the original functional double bonds on the linear fatty acid chains were maintained in the biopolycarbonate products, which affords a functional basis for various promising applications. The highest biopolycarbonate yield was obtained at a CO2 pressure of 4 MPa; SOTE monomers of 0.01 mol; catalyst loading SalenCoCl and cocatalyst PPNCl of 0.04 mmol each, which was around 1.2% (w/w) based on the total weight of rea...

Improvement of superoxide dismutase activity using experimental design and radical promoters

ABSTRACTThe culture conditions of Rhodotorula glutinis were optimised to obtain high activity of superoxide dismutase (SOD) enzyme, which is an important member of the antioxidant defence system. By the use of glycerol as a carbon source, which is a by-product of biodiesel production, 2.40 U of SOD activity was achieved under the optimised conditions found by Central Composite Design (pH = 5.47, T = 33.9 °C and 16.50 g L−1 glycerol). In order to provide a further increase in SOD activity, different types of radical promoters were tested and the highest enzyme activity was achieved with methyl viologen, 21.57 U mg−1 protein with a 1.6-fold increase. The effect of dissolved oxygen (DO) on SOD activity was also investigated employing different operational strategies in bioreactors. SOD activity was found to be induced only when high DO concentration was supplied starting from the beginning of the cultivation where the activity of 75 U mg−1 protein was obtained.

An extended techno-economic analysis of the utilization of glycerol as an alternative feedstock for methanol production

Glycerol is a by-product of biodiesel production and may become an environmental problem. This paper investigates the utilization of glycerol as alternative feedstock for methanol production. A mathematical model of the methanol plant encompassing the steam reforming and methanol synthesis units is employed to generate data for an economic analysis involving two comparative cases: the conventional operation of the plant using only natural gas and the operation with partial substitution of the natural gas by glycerol. The results indicate that the glycerol injection can reduce the total natural gas consumption by about 11% for a given fixed methanol production. A breakeven analysis procedure is applied to determine the limit price of glycerol that makes this operation economically feasible. Based on a natural gas price of 10.13 US$/MMbtu, this analysis demonstrates that glycerol injection is feasible if its price is lower than 78.5 US$/t. Additionally, a sensitivity analysis indicates that a variation of 10% on the natural gas price causes a 26% variation on the glycerol breakeven point. The complete set of data indicates that it is possible to explore periods of glycerol low prices to reduce the operational costs of methanol plants that suffer from high natural gas prices.

Agricultural Feedstock Supplemented with Manganese for Biosurfactant Production by Bacillus subtilis

The greatest challenge in producing biomolecules at industrial scale is cost. In order to provide cheaper sources, the present study describes the production of biosurfactant using a low-cost medium supplemented with manganese. The feedstock used to produce biosurfactant was crude glycerol, a by-product of biodiesel production. Results showed that 5% (v/v) of glycerol and 0.05 mM of manganese was the best combination to produce biosurfactant. The produced biosurfactant was able to reduce surface tension and showed emulsification activity in diesel fuel. The main functional groups of the biosurfactant were identified by 1H NMR and FTIR spectra. We identified the molecule as surfactin based on comparison with surfactin standard spectra described in the literature. This study showed conversion of low-value glycerol into value-added products as biosurfactant. The use of a by-product as a carbon source for biosurfactant production is a possible strategy for reducing production costs. In addition, biosurfactant production by Bacillus subtilis can be considered safe and commercially viable, because it is a non-pathogenic bacterium.

Composite Membranes Containing Nanoparticles of Inorganic Ion Exchangers for Electrodialytic Desalination of Glycerol

Composite membranes were obtained by modification of heterogeneous polymer cation and anion-exchange membranes with nanoparticles of zirconium hydrophosphate and hydrated zirconium dioxide, respectively. The ion-exchange materials were investigated with the methods of electron microscopy, potentiometry, voltammetry, and impedance spectroscopy. Single nanoparticles, which were precipitated in aqueous media, form aggregates, when the composites are in a contact with polar organic solvent. Both single nanoparticles (up to 10 nm) and their aggregates (up to 200 nm) were precipitated in ion-exchange polymers in glycerol media. Non-aggregated nanoparticles improve electrical conductivity of the ion-exchange materials, the aggregates are barriers against fouling. The membranes were applied to NaCl removal from highly concentrated glycerine-water mixture containing organic additives (byproduct of biodiesel production). As opposite to pristine materials, the composites demonstrate stability against fouling.

Re-utilization of waste glycerol for continuous production of bioethanol by immobilized Enterobacter aerogenes

Waste glycerol, a by-product of biodiesel production, has been continuously increasing in abundance throughout the world since biodiesel was first commercially produced. Therefore, re-utilization of this waste substance is an important area of research at the present time. This study aims to utilize waste glycerol as a media source for bioethanol production. In addition, Enterobacter aerogenes ATCC 29007, one of the greatest ethanol producers, was immobilized using alginate and a continuous stirred tank reactor (CSTR) newly designed for continuous production with immobilized cells. For efficient bioethanol production, four major media components were statistically optimized by response surface methodology (RSM). The optimal concentrations of each factor were determined: about 6.5 g/L peptone, 3.8 g/L ammonium sulfate, 2.1 g/L citrate dehydrate and 12 g/L waste glycerol. Under the optimal conditions, the ethanol production and yield were about 5.38 g/L and 0.96 mol-ethanol/mol-glycerol with pure glycerol, whereas the ethanol production and yield were approximately 5.29 g/L and 0.91 mol-ethanol/mol-glycerol with the waste glycerol during continuous fermentation. Therefore, the suggested model for media optimization was determined to be reliable. Moreover, continuous ethanol production was successfully performed with waste glycerol using the CSTR system.

THE SYNTHESIS OF GLYCEROL CARBONATE FROM BIODIESEL BYPRODUCT GLYCEROL AND UREA OVER AMBERLYST 36

The increasing use of biodiesel as renewable fuels leads to the increasing of glycerol amount as a byproduct of biodiesel production. One of the glycerol derivative products that is environmentally friendly and renewable is glycerol carbonate. Glycerol carbonate is commonly used as a raw material for polymers, surfactants, emulsifiers, lubricants, paints, also used in the cosmetics and pharmaceutical industries. In this study, the research was carried out by using a batch reactor with a three-neck flask equipped with reverse cooling, thermometers, mercury stirrer, and heating mantle with the conditions of the reaction temperature around 373 413 K, mole ratio of reactants of urea: glycerol were 1:0,5, 1:1, 1:1,5, 1:2 and 1:4 and the concentration of catalyst were 1%, 2%, 3%, 4% and 5% respectively. Reaction was done for four hours. The results showed that the formation of glycerol carbonate from glycerol and urea using a catalyst Amberlyst 36 is affected by the catalyst concentration, reaction temperature and the ratio of reactants used. The highest glycerol conversion was obtained at 55.07% at a temperature of 393 K with mole ratio of urea and glycerol 1:0,5 and the percentage of catalyst 3% of the amount of glycerol.

Analysis of the physicochemical properties of post-manufacturing waste derived from production of methyl esters from rapeseed oil

Abstract The technology of transesterification of biodiesel obtained from many agricultural products, which are often referred to as renewable resources, yields substantial amounts of by-products. They exhibit various properties that prompt scientific research into potential application thereof. Various spectroscopic methods, e.g. Fourier transform infrared spectroscopy, are being increasingly used in the research. In this paper, we present the results of Fourier transform infrared spectroscopy spectroscopy analyses of technical glycerine, distilled glycerine, and matter organic non glycerol, i.e. by-products of biodiesel production. To facilitate the spectroscopic analysis, a number of parameters were determined for all the materials, e.g. the calorific value, water content, sulphated ash content, methanol content, acidity, as well as the contents of esters, heavy metals, aldehydes, nitrogen, and phosphorus. The results indicate that the analysed products are characterised by a comparable calorific value in the range from 11.35 to 16.05 MJ kg-1 in the case of matter organic non glycerol and technical glycerine. Observation of changes in the position of selected peaks in the range of 3700-650 cm-1 in the Fourier transform infrared spectroscopy method facilitates determination of the level of degradation of the analysed material. Changes in the wavelength ranges can be used for monitoring the formation of secondary oxidation products containing carbonyl groups.

Organosolv Pretreatment of Sugar Cane Bagasse for Bioethanol Production

A reduction in glycerol price has been observed in the last years, considering it is a byproduct of biodiesel production. This fact has motivated studies about alternative uses for this compound, as in pretreatment of lignocellulosic biomass to produce ethanol, another biofuel of interest. In this context, glycerol acid-pretreatment of sugar cane bagasse (SCB) was evaluated in terms of temperature (80–120 °C), solid loading (2.5–7.5%), glycerol (85–95%) and acid concentrations (0.5–3%), and reaction time (10–60 min), using a 25–1 factorial design. The cellulose digestibility was further optimized for the variables temperature (120–130 °C), acid/SCB mass ratio (5–15%), and time (20–60 min). The optimal conditions were obtained at 130 °C temperature, 15% acid/SCB mass ratio, and 57.5 min reaction time, yielding a 68.5% digestibility. Moreover, a considerable amount of ethanol, 0.38 g/g biomass (0.57 g/L·h of productivity), was achieved using Saccharomyces cerevisiae, which also shows the efficacy of this pr...

Photocatalytic valorization of glycerol to hydrogen: Optimization of operating parameters by artificial neural network

Glycerol is a considerable by-product of biodiesel production from biomass. Photocatalytic glycerol valorization to hydrogen is an attractive approach from the sustainable development point of view. This study investigates the individual and interaction effects of main operating parameters of the photocatalytic hydrogen production process from glycerol using Pt/TiO2 photocatalyst. Four key operating parameters (i.e. glycerol%, catalyst loading, Pt% and pH) were selected as independent variables, and the amount of produced hydrogen was considered as the dependent variable (response). Experiments were conducted based on the Box-Behnken design. Response surface methodology (RSM) and Artificial Neural Network (ANN) models were developed based on the experimental design approach to predict hydrogen production. The predictive capacity of the two models was compared based on R2, R2adj, RMS, MAE and AAD. The ANN model was found more accurate and reliable, and it was therefore employed for the optimization of H2 production and parametric investigation. Analysis of the results showed that the operating parameters can also influence each other’s optimum value. Increasing glycerol% shifts the optimum values of catalyst loading, Pt%, and pH to higher values; however, Pt% has a negligible effect on the optimum values of the other parameters. Moreover, the catalyst loading and pH have no effect on the optimum value of glycerol%, but the increase of each of these two parameters reduces the optimum value of glycerol% and Pt%. The Genetic Algorithm along with the ANN model was also utilized for the optimization and it was found that the overall optimum of the system was 50% glycerol (v/v), 3.9g/L catalyst loading, 3.1% Pt, and pH 4.5. Finally, Garson’s method was employed to obtain the relative importance of each variable in the system. This analysis revealed that the variation of glycerol% and catalyst loading had, respectively, the least and the most effect on the amount of produced hydrogen.

PEMBUATAN BIOADITIF TRIACETIN DENGAN KATALIS PADAT SILICA ALUMINA

Triasetin is a bioaditif to increase the octane number of the gasoline. Triasetin was generated from the reaction between giserol and acetic acid. Glycerol is a byproduct of biodiesel production. Triasetin production can reduce glycerol which is actually a waste by converting it into bioaditif having higher value. The reaction can be accelerated by addition of catalysts either solid or liquid catalyst. The reaction in this study used a solid catalyst types Silica Alumina. The reaction takes place in the three-neck flask reactor which is equipped with heating unit, mixers, and tools to take samples at regular intervals. Variables used in this research is the variety of reaction time and the reaction temperature (70, 80, 90, 100, and 1100C). The concentration of triasetin obtained will be known through the analysis of Gas Chromatography - Mass Spectrometry (GC-MS). The results of the analysis of GC or GC-MS treated or counted so getting glycerol conversion and selectivity of triasetin. The highest glycerol conversion 8,45% occurs at a temperature of 700C the reaction time of 90 minutes with triasetin selectivity 100%.

Non-catalytic conversion of glycerol to syngas at intermediate temperatures: Numerical methods with detailed chemistry

Glycerol is available in high volumes and at low costs as a byproduct of bio-diesel production. While combustion characteristics are poor, it is appealing to investigate potential reforming processes to recover its hydrogen and carbon in the form of synthesis gas, i.e. a combustible mixture of hydrogen, carbon monoxide, methane and other small hydrocarbon species. This study pursues a non-catalytic approach, where reactions occur in the gas-phase at elevated temperatures favored by chemical kinetics. Detailed glycerol reaction chemistry involves many species and reactions, which makes a careful selection of numerical approaches critical. In this work, Eulerian and Lagrangian viewpoints for numerical calculations of a non-catalytic reforming process at intermediate temperatures are studied. All approaches are validated by propane partial oxidation, where non-catalytic experimental results are available in literature. Testing the numerical approaches for a wide range of operating conditions, it is illustrated that the Lagrangian approach outperforms other models in terms of efficiency. Using a transient zero-D Lagrangian technique, glycerol reforming characteristics are discussed at various wall temperatures and mixture conditions. The impact of fuel stoichiometry is investigated based on the oxygen ratio, which is a metric for mixture stoichiometry that accounts for the amount of oxygen bound in the fuel molecules. Results clearly indicate that wall temperatures higher than 1173K and oxygen ratios in the range of 0.3–0.45 represent conditions that are favorable for glycerol reforming. It is further shown that excess methanol – a commonly found contaminant in crude glycerol – does not affect the reforming performance. As there is a lack of information on non-catalytic glycerol reforming in literature, qualitative comparisons between non-catalytic (from this work) and catalytic (from literature) glycerol reforming are discussed.

Sacrificial photocatalysis: removal of nitrate and hydrogen production by nano-copper-loaded P25 titania. A kinetic and ecotoxicological assessment.

The photocatalytic removal of nitrate with simultaneous hydrogen generation was demonstrated using zero-valent nano-copper-modified titania (P25) as photocatalyst in the presence of UV-A-Vis radiation. Glycerol, a by-product in biodiesel production, was chosen as a hole scavenger. Under the adopted experimental conditions, a nitrate removal efficiency up to 100% and a simultaneous hydrogen production up to 14μmol/L of H2 were achieved (catalyst load=150mg/L, initial concentration of nitrate=50mg/L, initial concentration of glycerol=0.8mol/L). The reaction rates were independent of the starting glycerol concentration. This process allows accomplishing nitrate removal, with the additional benefit of producing hydrogen under artificial UV-A radiation. A kinetic model was also developed and it may represent a benchmark for a detailed understanding of the process kinetics. A set of acute and chronic bioassays (Vibrio fischeri, Raphidocelis subcapitata, and Daphnia magna) was performed to evaluate the potential ecotoxicity of the nitrate/by-product mixture formed during the photocatalytic process. The ecotoxicological assessment indicated an ecotoxic effect of oxidation intermediates and by-products produced during the process.

Glycerol steam reforming for hydrogen and synthesis gas production

In this experimental study, glycerol conversion to hydrogen and synthesis gas was carried out by utilizing thermal plasma technology. An entrained-flow reactor equipped with a direct current arc discharge plasma torch, which was used to heat plasma-forming gas via Joule heating effect, and superheated water vapor, which was used to form the plasma, as a main reaction agent and a source of active radicals generation during steam reforming process of glycerol, set up a core of the glycerol conversion system. Glycerol, which is a by-product of biodiesel production during transesterification process, is considered to be a potential feedstock for renewable energy, biofuels, and high value-added chemicals production, such as methanol, hydrogen, etc. The reforming of glycerol was performed at various experimental conditions by changing the flow rate of water vapor and glycerol as well as the plasma torch power. The obtained results showed that the main reaction products were hydrogen and carbon monoxide with total concentration up to 75%. Moreover, the process was quantified in terms of cold gas efficiency, energy efficiency, carbon conversion, and specific energy requirement. Generally, the performed study indicates that hydrogen and synthesis gas could be effectively produced from glycerol by employing thermal plasma technology.

A switchable route to valuable commodity chemicals from glycerol via electrocatalytic oxidation with an earth abundant metal oxidation catalyst

A switchable mild electrocatalytic protocol to transform glycerol, a byproduct of biodiesel production, into either lactic or glyceric acid is reported.

Small gold clusters catalyzing the conversion of glycerol to epichlorohydrin.

The conversion of glycerol to epichlorohydrin (GTE) is of great interest because the product is widely used in plastics, rubbers and adhesives, and also contributes to the disposal of the reactant glycerol, a major by-product in biodiesel production. Here we find effective catalysis by small gold clusters for the GTE reaction in water with an enhanced selectivity towards the desired product. Along with natural bond orbital (NBO) analysis rationalizing the donor-acceptor charge-transfer interactions, we illustrate the mechanism for bond activation in the reactants and intermediates over gold cluster catalysts, and present thermodynamically and kinetically favoured reaction pathways for dehydrochlorination in GTE processes.

Synthesis of Methyl Lactate from Glycerol Using Sn-Beta Zeolite

Lactic acid can not only be used to produce multiple chemicals, but can also be the building block for biodegradable and biocompatible polylactic acid identified as a renewable resource. As a by-product in biodiesel production, the glycerol yield increases with a rapid expansion of biodiesel. However, in the chemical and environmental fields it is still a great challenge to produce lactic acid or methyl lactate from glycerol. Herein, Sn-Beta zeolite was prepared through solid-state ion exchange (Sn-Beta SSIE) and was tested for base-free one-pot catalytic selective oxidation of glycerol into methyl lactate in methanol. The results showed that a maximum selectivity of up to 56.7% was achieved with a 36.8% conversion rate at 433 K within 4 h under an initial oxygen pressure of 0.1 MPa. In addition, the methyl lactate yield is not high because of its decomposition in the presence of oxygen. This study aims to contribute to the development of the polylactic acid industry.

Histopathological and Reproductive Evaluation in Male Rats Fed Jatropha curcas Seed Cake with or without Alkaline Hydrolysis and Subjected to Heat Treatment.

Jatropha curcas cake, a by-product of biodiesel production, is rich in protein and has potential to be used in livestock feed; however, the presence of antinutritional factors and phorbol esters limits its use. Thus, this study investigated toxicological and reproductive effects in male Wistar rats after subchronic exposure to J. curcas cake subjected to detoxification procedures. Rats were divided into seven groups (n = 10) and treated for 60 days. The control group received commercial feed, while experimental groups received a diet containing 5% J. curcas cake nonhydrolyzed or hydrolyzed with 5 M NaOH. The cakes were unwashed or washed with ethanol or water and were autoclaved at 121°C for 30 minutes. Alkaline hydrolysis combined with ethanol washing decreased the phorbol ester concentration in the cake by 98%. Histopathological findings included diffuse degeneration of the liver and edema around the pulmonary vessels in the nonhydrolyzed groups. In addition, nontreated females mated with males of nonhydrolyzed unwashed group showed a decreased number of live fetuses and an increased placental weight. There were no signs of toxicity in rats given hydrolyzed cakes washed and unwashed, indicating that alkaline hydrolysis associated with heat treatment is an efficient method for detoxification of the J. curcas cake.

Comparative study: bench-scale surfactin production from bacillus subtilis using analytical grade and concentrated glycerol from the biodiesel industry

The market price of glycerol worldwide tends to decrease, since it is a by-product of biodiesel production. Thus its biotechnological use might lead to significant reduction in the cost of fermentations. The aim of this study was to compare the production of surfactin in peptone culture media supplemented with analytical grade glycerol (AGG) and concentrated glycerol from biodiesel production (CGBP). Differences were observed between the two processes including cell growth and dissolved oxygen consumption. Surfactin yield was 325.19 mg/L with AGG and 71.13 mg/L with CGBP, which proves the impact and importance of the purity of glycerol on the yield of surfactin. In addition, five surfactin homologous were identified by ESI-Q-TOFMS, which were composed by two amino acid sequences ELLMDLD and ELLLDLL. Therefore, as surfactin is a high value-added product, the use of glycerol with high purity is fundamental to achieve higher productivity.