Search results for: crude glycerol

Authors: Haniza Ahmad, Norliza Saparin, Ahmadilfitri Md Noor, Mohd Suria Affandi Yusoff

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Enzymatic remediation is applied in low free fatty acid (FFA) (<4%) crude palm oil (CPO) to investigate if further FFA reduction is able to take place to produce premium CPO (<1% FFA). There are four different lipase Candida Antartica brands used in this study. Samples submit to enzymatic remediation using rotary evaporator under 100mbar vacuum with rotation at 260rpm. Samples were taken at 4hours, 8hours and 24hours for analyses. FFA less than 1% was achieved after 24hours reaction with 1% enzyme and 2% glycerol. The FFA reduction was intensified with the presence of glycerol who provides more sites for fatty acid attachment. At 2% glycerol, 71-88% FFA was reduced whereas at 1% glycerol, 46-75% FFA reduced. However, partial glycerides was increased with presence of glycerol with 2% add in glycerol showed greater partial glycerides increment compared to 1% glycerol.

Keywords: enzymes, crude palm oil, free fatty acid, glycerol

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Authors: Lakshmidevi Rajendran, Bharathidasan Kanniappan, Gopi Raja, Muthukumar Karuppan

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This study investigates the feasibility of fed-batch mixotrophic cultivation of microalgae Scenedesmus sp. in a 3-litre airlift photobioreactor under standard operating conditions. The results of this study suggest the algae species may serve as an excellent feed for aquatic species using organic byproducts. Microalgae Scenedesmus sp., was cultured using a synthetic wastewater by stepwise addition of crude glycerol concentration ranging from 2-10g/l under fed-batch mixotrophic mode for a period of 15 days. The attempts were made with the stepwise addition of crude glycerol as a carbon source in the initial growth phase to evade the inhibitory nature of high glycerol concentration on the growth of Scenedesmus sp. Crude glycerol was chosen since it is readily accessible as byproduct from biodiesel production sectors. Highest biomass concentration was achieved to be 2.43 g/l at the crude glycerol concentration of 6g/l after 10 days which is 3 fold times the increase in the biomass concentration compared with the control medium without the addition of glycerol. Biomass growth data obtained for the microalgae Scenedesmus sp. was fitted well with the modified Logistic equation. Substrate utilization kinetics was also employed to model the biomass productivity with respect to the various crude glycerol concentration. The results indicated that the supplement of crude glycerol to the mixotrophic culture of Scenedesmus sp., enhances the biomass concentration, chlorophyll and lutein productivity. Thus the application of fed-batch mixotrophic cultivation with stepwise addition of crude glycerol to Scenedesmus sp., provides a subtle way to reduce the production cost and improvisation in the large-scale cultivation along with biochemical compound synthesis.

Keywords: airlift photobioreactor, crude glycerol, microalgae Scenedesmus sp., mixotrophic cultivation, lutein production

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Authors: P. Massanyi, L. Kichi, T. Slanina, E. Kolesar, J. Danko, N. Lukac, E. Tvrda, R. Stawarz, A. Kolesarova

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Target of this study was the analysis of the impact of crude glycerol on canine spermatozoa motility, morphology, viability, and membrane integrity. Experiments were realized in vitro. In the study, semen from 5 large dog breeds was used. They were typical representatives of large breeds, coming from healthy rearing, regularly vaccinated and integrated to the further breeding. Semen collections were realized at the owners of animals and in the veterinary clinic. Subsequently the experiments were realized at the Department of Animal Physiology of the SUA in Nitra. The spermatozoa motility was evaluated using CASA analyzer (SpermVisionTM, Minitub, Germany) at the temperature 5 and 37°C for 5 hours. In the study, 13 motility parameters were evaluated. Generally, crude glycerol has generally negative effect on spermatozoa motility. Morphological analysis was realized using Hancock staining and the preparations were evaluated at magnification 1000x using classification tables of morphologically changed spermatozoa. Data clearly detected the highest number of morphologically changed spermatozoa in the experimental groups (know twisted tails, tail torso and tail coiling). For acrosome alterations swelled acrosomes, removed acrosomes and acrosomes with undulated membrane were detected. In this study also the effect of crude glycerol on spermatozoa membrane integrity were analyzed. The highest crude glycerol concentration significantly affects spermatozoa integrity. Results of this study show that crude glycerol has effect of spermatozoa motility, viability, and membrane integrity. Detected changes are related to crude glycerol concentration, temperature, as well as time of incubation.

Keywords: dog, semen, spermatozoa, acrosome, glycerol, CASA, viability

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Authors: Idan Chiyanzu, Maruping Mangena

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Crude glycerol, a major by-product from the transesterification of triacylglycerides with alcohol to biodiesel, is known to have a broad range of applications. For example, its bioconversion can afford a wide range of chemicals including alcohols, organic acids, hydrogen, solvents and intermediate compounds. In bacteria, the 2-oxoglutarate dioxygenase (2-OGD) enzymes are widely found among the Pseudomonas syringae species and have been recognized with an emerging importance in ethylene formation. However, the use of optimized enzyme function in recombinant systems for crude glycerol conversion to ethylene is still not been reported. The present study investigated the production of ethylene from crude glycerol using engineered E. coli MG1655 and JM109 strains. Ethylene production with an optimized expression system for 2-OGD in E. coli using a codon optimized construct of the ethylene-forming gene was studied. The codon-optimization resulted in a 20-fold increase of protein production and thus an enhanced production of the ethylene gas. For a reliable bioreactor performance, the effect of temperature, fermentation time, pH, substrate concentration, the concentration of methanol, concentration of potassium hydroxide and media supplements on ethylene yield was investigated. The results demonstrate that the recombinant enzyme can be used for future studies to exploit the conversion of low-priced crude glycerol into advanced value products like light olefins, and tools including recombineering techniques for DNA, molecular biology, and bioengineering can be used to allowing unlimited the production of ethylene directly from the fermentation of crude glycerol. It can be concluded that recombinant E.coli production systems represent significantly secure, renewable and environmentally safe alternative to thermochemical approach to ethylene production.

Keywords: crude glycerol, bioethylene, recombinant E. coli, optimization

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Authors: Hsin-Yueh Chang, Pin-Chen Liao, Jo-Shu Chang, Chun-Yen Chen

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Biofuel has drawn much attention as a potential substitute to fossil fuels. However, biodiesel from waste oil, oil crops or other oil sources can only satisfy partial existing demands for transportation. Due to the feature of being clean, green and viable for mass production, using microalgae as a feedstock for biodiesel is regarded as a possible solution for a low-carbon and sustainable society. In particular, Thraustochytrium sp. BM2, an indigenous heterotrophic microalga, possesses the potential for metabolizing glycerol to produce lipids. Hence, it is being considered as a promising microalgae-based oil source for biodiesel production and other applications. This study was to optimize the culture pH, scale up, assess the feasibility of producing microalgal lipid from crude glycerol and apply operation strategies following optimal results from shake flask system in a 5L stirred-tank fermenter for further enhancing lipid productivities. Cultivation of Thraustochytrium sp. BM2 without pH control resulted in the highest lipid production of 3944 mg/L and biomass production of 4.85 g/L. Next, when initial glycerol and corn steep liquor (CSL) concentration increased five times (50 g and 62.5 g, respectively), the overall lipid productivity could reach 124 mg/L/h. However, when using crude glycerol as a sole carbon source, direct addition of crude glycerol could inhibit culture growth. Therefore, acid and metal salt pretreatment methods were utilized to purify the crude glycerol. Crude glycerol pretreated with acid and CaCl₂ had the greatest overall lipid productivity 131 mg/L/h when used as a carbon source and proved to be a better substitute for pure glycerol as carbon source in Thraustochytrium sp. BM2 cultivation medium. Engineering operation strategies such as fed-batch and semi-batch operation were applied in the cultivation of Thraustochytrium sp. BM2 for the improvement of lipid production. In cultivation of fed-batch operation strategy, harvested biomass 132.60 g and lipid 69.15 g were obtained. Also, lipid yield 0.20 g/g glycerol was same as in batch cultivation, although with poor overall lipid productivity 107 mg/L/h. In cultivation of semi-batch operation strategy, overall lipid productivity could reach 158 mg/L/h due to the shorter cultivation time. Harvested biomass and lipid achieved 232.62 g and 126.61 g respectively. Lipid yield was improved from 0.20 to 0.24 g/g glycerol. Besides, product costs of three kinds of operation strategies were also calculated. The lowest product cost 12.42 $NTD/g lipid was obtained while employing semi-batch operation strategy and reduced 33% in comparison with batch operation strategy.

Keywords: heterotrophic microalga Thrasutochytrium sp. BM2, microalgal lipid, crude glycerol, fermentation strategy, biodiesel

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Authors: Ilze Dimanta, Zane Rutkovska, Vizma Nikolajeva, Janis Kleperis, Indrikis Muiznieks

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Majority of word’s steadily increasing energy consumption is provided by non-renewable fossil resources. Need to find an alternative energy resource is essential for further socio-economic development. Hydrogen is renewable, clean energy carrier with high energy density (142 MJ/kg, accordingly – oil has 42 MJ/kg). Biological hydrogen production is an alternative way to produce hydrogen from renewable resources, e.g. using organic waste material resource fermentation that facilitate recycling of sewage and are environmentally benign. Hydrogen gas is produced during the fermentation process of bacteria in anaerobic conditions. Bacteria are producing hydrogen in the liquid phase and when thermodynamic equilibrium is reached, hydrogen is diffusing from liquid to gaseous phase. Because of large quantities of available crude glycerol and the highly reduced nature of carbon in glycerol per se, microbial conversion of it seems to be economically and environmentally viable possibility. Such industrial organic waste product as crude glycerol is perspective for usage in feedstock for hydrogen producing bacteria. The process of biodiesel production results in 41% (w/w) of crude glycerol. The developed lab-scale test system (experimental bioreactor) with hydrogen micro-electrode (Unisense, Denmark) was used to determine hydrogen production yield and rate in the liquid phase. For hydrogen analysis in the gas phase the RGAPro-100 mass-spectrometer connected to the experimental test-system was used. Fermentative bacteria strains were tested for hydrogen gas production rates. The presence of hydrogen in gaseous phase was measured using mass spectrometer but registered concentrations were comparatively small. To decrease the hydrogen partial pressure in liquid phase reactor with a system for continuous bubbling with inert gas was developed. H2 production rate for the best producer in liquid phase reached 0,40 mmol H2/l, in gaseous phase - 1,32 mmol H2/l. Hydrogen production rate is time dependent – higher rate of hydrogen production is at the fermentation process beginning when concentration increases, but after three hours of fermentation, it decreases.

Keywords: bio-hydrogen, fermentation, experimental bioreactor, crude glycerol

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Authors: Erna Astuti, Supranto, Rochmadi, Agus Prasetya

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Biodiesel production from vegetable oil will produce glycerol as by-product about 10% of the biodiesel production. The amount of glycerol that was produced needed alternative way to handling immediately so as to not become the waste that polluted environment. One of the solutions was to process glycerol to polyglycidyl nitrate (PGN). PGN is synthesized from glycerol by three-step reactions i.e. nitration of glycerol, cyclization of 13- dinitroglycerine and polymerization of glycosyl nitrate. Optimum condition of nitration of glycerol with nitric acid has not been known. Thermodynamic feasibility should be done before run experiments in the laboratory. The aim of this study was to determine the parameters those affect nitration of glycerol and nitric acid and chose the operation condition. Many parameters were simulated to verify its possibility to experiment under conditions which would get the highest conversion of 1, 3-dinitroglycerine and which was the ideal condition to get it. The parameters that need to be studied to obtain the highest conversion of 1, 3-dinitroglycerine were mol ratio of nitric acid/glycerol, reaction temperature, mol ratio of glycerol/dichloromethane and pressure. The highest conversion was obtained in the range of mol ratio of nitric acid /glycerol between 2/1 – 5/1, reaction temperature of 5-25o C and pressure of 1 atm. The parameters that need to be studied further to obtain the highest conversion of 1.3 DNG are mol ratio of nitric acid/glycerol and reaction temperature.

Keywords: Nitration, glycerol, thermodynamic, optimum condition

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Authors: Wai Keng Teng, Gek Cheng Ngoh, Rozita Yusoff, Mohamed Kheireddine Aroua

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As a by-product of the biodiesel industries, glycerol has been vastly generated which surpasses the market demand. It is imperative to develop an efficient glycerol valorization processes in minimizing the net energy requirement and intensifying the biodiesel production. In this study, base-catalyzed transesterification of glycerol with dimethyl carbonate using microwave irradiation as heating method to produce glycerol carbonate was conducted by varing grades of glycerol i.e. 70%, 86% and 99% purity that obtained from biodiesel plant. Metal oxide catalysts were used with varying operating parameters including reaction time, DMC/glycerol molar ratio, catalyst weight %, temperature and stirring speed. From the study on the effect of different operating parameters; it was found that the type of catalyst used has the most significant effect on the transesterification reaction. Admist the metal oxide catalysts examined, CaO gave the best performance. This study indicates the feasibility of producing glycerol carbonate using different grade of glycerol in both conventional thermal activation and microwave irradiation with CaO as catalyst. Microwave assisted transesterification (MAT) of glycerol into glycerol carbonate has demostrated itself as an energy efficient route by achieving 94.3% yield of GC at 65°C, 5 minutes reaction time, 1 wt% CaO and DMC/glycerol molar ratio of 2. The advantages of MAT transesterification route has made the direct utilization of bioglycerol from biodiesel production without the need of purification. This has marked a more economical and less-energy intensive glycerol carbonate synthesis route.

Keywords: base-catalyzed transesterification, glycerol, glycerol carbonate, microwave irradiation

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Authors: Ching Shya Lee, Mohamed Kheireddine Aroua, Wan Mohd Ashri Wan Daud, Patrick Cognet, Yolande Peres, Mohammed Ajeel

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In recent years, with the decreasing supply of fossil fuel, renewable energy has received a significant demand. Biodiesel which is well known as vegetable oil based fatty acid methyl ester is an alternative fuel for diesel. It can be produced from transesterification of vegetable oils, such as palm oil, sunflower oil, rapeseed oil, etc., with methanol. During the transesterification process, crude glycerol is formed as a by-product, resulting in 10% wt of the total biodiesel production. To date, due to the fast growing of biodiesel production in worldwide, the crude glycerol supply has also increased rapidly and resulted in a significant price drop for glycerol. Therefore, extensive research has been developed to use glycerol as feedstock to produce various added-value chemicals, such as tartronic acid, mesoxalic acid, glycolic acid, glyceric acid, propanediol, acrolein etc. The industrial processes that usually involved are selective oxidation, biofermentation, esterification, and hydrolysis. However, the conversion of glycerol into added-value compounds by electrochemical approach is rarely discussed. Currently, the approach is mainly focused on the electro-oxidation study of glycerol under potentiostatic mode for cogenerating energy with other chemicals. The electro-organic synthesis study from glycerol under galvanostatic mode is seldom reviewed. In this study, the glycerol was converted into various added-value compounds by electrochemical method under galvanostatic mode. This work aimed to study the possible compounds produced from glycerol by electrochemical technique in a one-pot electrolysis cell. The electro-organic synthesis study from glycerol was carried out in a single compartment reactor for 8 hours, over the platinum cathode and anode electrodes under acidic condition. Various parameters such as electric current (1.0 A to 3.0 A) and reaction temperature (27 °C to 80 °C) were evaluated. The products obtained were characterized by using gas chromatography-mass spectroscopy equipped with an aqueous-stable polyethylene glycol stationary phase column. Under the optimized reaction condition, the glycerol conversion achieved as high as 95%. The glycerol was successfully converted into various added-value chemicals such as ethylene glycol, glycolic acid, glyceric acid, acetaldehyde, formic acid, and glyceraldehyde; given the yield of 1%, 45%, 27%, 4%, 0.7% and 5%, respectively. Based on the products obtained from this study, the reaction mechanism of this process is proposed. In conclusion, this study has successfully converted glycerol into a wide variety of added-value compounds. These chemicals are found to have high market value; they can be used in the pharmaceutical, food and cosmetic industries. This study effectively opens a new approach for the electrochemical conversion of glycerol. For further enhancement on the product selectivity, electrode material is an important parameter to be considered.

Keywords: biodiesel, glycerol, electrochemical conversion, galvanostatic mode

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Authors: Ala’a H. Al-Muhtaseb, Farrukh Jamil, Lamya Al-Haj, Mohab Al-Hinai

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Bio-glycerol is considered as high boiling polar triol and immiscible with fossil fuel fractions due to which it is transformed into its respective ketals and acetals which help to improve the quality of diesel emitting less amount of aldehydes and carbon monoxide. Solketal visual appearance is transparent and it is odorless organic liquid used as fuel additive for diesel to improve its cold flow properties. Condensation of bio-glycerol with bio-acetone in presence of beta zeolite has been done for synthesizing solketal. It was observed that glycerol conversion and selectivity of solketal was largely effected by temperature, as it increases from 40 ºC to 60 ºC the conversion of glycerol rises from 80.04 % to 94.26 % and selectivity of solketal from 80.0 % to 94.21 % but further increase in temperature to 100 ºC glycerol conversion reduced to 93.06 % and solketal selectivity to 92.08 %. At the optimum conditions, the bio-glycerol conversion and solketal yield were about 94.26% and 94.21wt% respectively. This process offers an attractive route for converting bio-glycerol, the main by-product of biodiesel to solketal with bio-acetone; a value-added green product with potential industrial applications as a valuable green fuel additive or combustion promoter for gasoline/diesel engines.

Keywords: bio-acetone, bio-glycerol, acetylation, solketal

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Authors: Farrukh Jamil, Ala'a H. Al-Muhtaseb, Lamya Al-Haj, Mohab A. Al-Hinai

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Glycerol is considered as high boiling polar triol and immiscible with fossil fuel fractions due to which it is transformed into its respective ketals and acetals which help to improve the quality of diesel emitting less amount of aldehydes and carbon monoxide. Solketal visual appearance is transparent, and it is odorless organic liquid used as a fuel additive for diesel to improve its cold flow properties. Condensation of bio-glycerol with bio-acetone in presence of beta zeolite has been done for synthesizing solketal. It was observed that glycerol conversion and selectivity of solketal was largely effected by temperature, as it increases from 40 ºC to 60 ºC the conversion of glycerol rises from 80.04 % to 94.26 % and selectivity of solketal from 80.0 % to 94.21 % but further increase in temperature to 100 ºC glycerol conversion reduced to 93.06 % and solketal selectivity to 92.08 %. At the optimum conditions, the bio-glycerol conversion and solketal yield were about 94.26% and 94.21wt% respectively. This process offers an attractive route for converting bio-glycerol, the main by-product of biodiesel to solketal with bio-acetone; a value-added green product with potential industrial applications as a valuable green fuel additive or combustion promoter for gasoline/diesel engines.

Keywords: bio-glycerol, catalyst, green additive, biomass

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Authors: Mulatu Kassie Birhanu

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Electro-oxidation of glycerol is an important process to convert the less price glycerol into other expensive (essential) and energy-rich chemicals. In this study, nickel was electro-deposited on laboratory-made carbon ceramic electrode (CCE) substrate using electrochemical techniques that is cyclic voltammetry (CV) to prepare an electro-catalyst (Ni/CCE) for electro-oxidation of glycerol. Carbon ceramic electrode was prepared from graphite and methyl tri-methoxy silane (MTMOS) through the processes called hydrolysis and condensation with methanol in acidic media (HCl) by a sol-gel technique. Physico-chemical characterization of bare CCE and modified (deposited) CCE (Ni/CCE) was measured and evaluated by Fourier Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD). Electro-oxidation of glycerol was performed in 0.1 M glycerol in alkaline media (0.5 M NaOH). High-Performance Liquid Chromatography (HPLC) technique was used to identify and determine the concentration of glycerol, reaction intermediates and oxidized products of glycerol after its electro-oxidation is performed. The conversion (%) of electro-oxidation of glycerol during 9-hour oxidation was 73% and 36% at 1.8V and 1.6V vs. RHE, respectively. Formate, oxalate, glycolate and glycerate are the main oxidation products of glycerol with selectivity (%) of 75%, 8.6%, 1.1% and 0.95 % at 1.8 V vs. RHE and 55.4%, 2.2%, 1.0% and 0.6% at 1.6 V vs. RHE respectively. The result indicates that formate is the main product in the electro-oxidation of glycerol on Ni/CCE using the indicated applied potentials.

Keywords: carbon-ceramic electrode, electrodeposition, electro-oxidation, Methyltrimethoxysilane

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Authors: A. Odoom, A. Salama, H. Ibrahim

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Hydrogen is a clean source of energy for power production and transportation. The main source of hydrogen in this research is biodiesel. Glycerol also called glycerine is a by-product of biodiesel production by transesterification of vegetable oils and methanol. This is a reliable and environmentally-friendly source of hydrogen production than fossil fuels. A typical composition of crude glycerol comprises of glycerol, water, organic and inorganic salts, soap, methanol and small amounts of glycerides. Crude glycerol has limited industrial application due to its low purity thus, the usage of crude glycerol can significantly enhance the sustainability and production of biodiesel. Reforming techniques is an approach for hydrogen production mainly Steam Reforming (SR), Autothermal Reforming (ATR) and Partial Oxidation Reforming (POR). SR produces high hydrogen conversions and yield but is highly endothermic whereas POR is exothermic. On the downside, PO yields lower hydrogen as well as large amount of side reactions. ATR which is a fusion of partial oxidation reforming and steam reforming is thermally neutral because net reactor heat duty is zero. It has relatively high hydrogen yield, selectivity as well as limits coke formation. The complex chemical processes that take place during the production phases makes it relatively difficult to construct a reliable and robust numerical model. Numerical model is a tool to mimic reality and provide insight into the influence of the parameters. In this work, we introduce a finite volume numerical study for an 'in-house' lab-scale experiment of ATR. Previous numerical studies on this process have considered either using Comsol or nodal finite difference analysis. Since Comsol is a commercial package which is not readily available everywhere and lab-scale experiment can be considered well mixed in the radial direction. One spatial dimension suffices to capture the essential feature of ATR, in this work, we consider developing our own numerical approach using MATLAB. A continuum fixed bed reactor is modelled using MATLAB with both pseudo homogeneous and heterogeneous models. The drawback of nodal finite difference formulation is that it is not locally conservative which means that materials and momenta can be generated inside the domain as an artifact of the discretization. Control volume, on the other hand, is locally conservative and suites very well problems where materials are generated and consumed inside the domain. In this work, species mass balance, Darcy’s equation and energy equations are solved using operator splitting technique. Therefore, diffusion-like terms are discretized implicitly while advection-like terms are discretized explicitly. An upwind scheme is adapted for the advection term to ensure accuracy and positivity. Comparisons with the experimental data show very good agreements which build confidence in our modeling approach. The models obtained were validated and optimized for better results.

Keywords: autothermal reforming, crude glycerol, hydrogen, numerical model

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Authors: Wanthani Paengsri, Thanyarat Chuesaard, Napapha Promsawan

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Spilanthes acmella Murr. was extracted with methanol, yielding methanol crude extract 5.86 %w/w. This study aimed to examine the chemical composition and antioxidant activity of methanolic crude extract. The chemical composition of methanolic crude extract was analyzed by gas chromatography-mass spectrometry (GC-MS). The predominant components were found to be palmitic acid (40.08%), 2-hexadecanoyl glycerol (6.96%) and octadecanoic acid (4.06%). Antioxidant activity was determined using 2,2-diphenyl-1-picryl hydrazyl (DPPH) free radical, for evaluating free radicle scavenging activity. The methanolic extract at 150 µg/mL showed an antioxidant activity with high of radical scavenging activity (75.23%).

Keywords: antioxidant activity, GC-MS analysis, Spilanthes, Phak-Kratt Hauwaen

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Authors: Y. Chabouni, F. Amireche

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Densities of glycerol + 1-butanol or 2-butanol mixtures were measured over the temperature range 293.15 to 303.15 K at atmospheric pressure, over the entire composition range, with a vibrating tube densimeter. Excess molar volumes, apparent and partial molar volumes of glycerol and butanol, thermal isobaric expansivities of the mixture and partial molar expansivities of the components were calculated. The excess molar volumes of the mixtures are negative at all temperatures, and deviations from ideality increase with increasing temperature. Excess molar volumes were fitted to the Redlich–Kister equation. Partial molar volumes of glycerol decrease with increasing butanol concentration.

Keywords: 1-Butanol, 2-Butanol, density, excess molar volume, glycerol, partial molar property, thermal isobaric expansivities

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Authors: Francisco Espinosa, Juan Chavarría

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Glycerol is a byproduct of biodiesel production that can be used for aqueous-phase reforming to obtain hydrogen. Iridium is a material that has high activity and hydrogen selectivity for steam phase reforming. Nevertheless, a drawback for the use of iridium in aqueous-phase reforming is the low activity in water-gas shift reaction. Therefore, in this work, it is proposed the use of nickel and copper as a second metal in the catalyst to reach a synergetic effect. Iridium, iridium-nickel and iridium-copper catalysts were prepared by incipient wetness impregnation and evaluated in the aqueous-phase reforming of glycerol using CeO₂ or La₂O₃ as support. The catalysts were characterized by XRD, XPS, and EDX. The reactions were carried out in a fixed bed reactor feeding a solution of glycerol 10 wt% in water at 270°C, and reaction products were analyzed by gas chromatography. It was found that IrNi/CeO₂ reached highest glycerol conversion and hydrogen production, slightly above 70% and 43 vol% respectively. In terms of conversion, iridium is a promising metal, and its activity for hydrogen production can be enhanced when adding a second metal.

Keywords: aqueous-phase reforming, glycerol, hydrogen production, iridium

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Authors: Antaram Sarve, Mahesh Varma, Shriram Sonawane

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Conventional route of producing biodiesel with alcohol produces glycerol as side product which leads to oversupply and devaluation in the world market. Supercritical methyl acetate (SCMA) has been proven to convert triglycerides into fatty acid methyl esters (FAMEs) and triacetin, which is a valuable biodiesel additive as side product rather than glycerol. However, due to the low reactivity of supercritical methyl acetate on triglycerides, high reaction conditions are required to obtained maximum yields. The present study describes the renewable approach for the production of biodiesel from low-cost, high acid value mahua oil under supercritical methyl acetate condition using carbon dioxide (CO2) as a co-solvent. CO2 was employed to decrease high reaction conditions required for supercritical methyl acetate transesterification. The influence of process parameters such as temperature, oil to methyl acetate molar ratio, reaction time, and the CO2 pressure was evaluated. The properties of biodiesel produced were found to be superior compared to conventional biodiesel method. Furthermore, SCMA has a high tolerance towards free fatty acids (FFAs) which is crucial to allow the utilization of inexpensive waste oils as a biodiesel feedstock.

Keywords: supercritical methyl acetate, CO2, biodiesel, fuel properties

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Authors: Al-Saboonchi Azhar

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The effects of Iraqi crude oil on growth of three freshwater algae (Chlorella vulgaris Beij., Scenedesmus acuminatus (Lag.) Chodat. and Oscillatoria princeps Vauch.) were investigated, basing on it's biomass expressed as Chl.a. Growth rate and doubling time of the cell were calculated. Results showed that growth rate and species survival varied with concentrations of crude oil and species type. Chlorella vulgaris and Scenedesmus acuminatus were more sensitive in culture containing crude oil as compared with Oscillatoria princeps cultures. The growth of green algae were significantly inhibited in culture containing (5 mg/l) crude oil, while the growth of Oscillatoria princeps reduced in culture containing (10 mg/l) crude oil.

Keywords: algae, crude oil, green algae, Cyanobacteria

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Authors: Dalila Hammiche, Lisa Klaai, Sonia Imzi, Amar Boukerrou

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The fight against plastic pollution implies the development of polymers as alternatives to synthetic polymers. Starch is a natural polymer that can easily be plasticized by means of additives. The objective of this work is to develop and characterize biodegradable biofilms based on starch, plasticized by glycerol (20 and 30%). The elaboration of the biofilms was carried out by the casting method under simple conditions. The samples were characterized by infrared spectroscopy analysis with Fourier transform (FTIR), thermogravimetric analysis, and biodegradability test. Infrared spectral analysis showed that the 30% and 20% glycerol films have the same chemical structure and no functional group changes occurred. Thermogravimetric analysis showed that a 30% glycerol film has higher thermal stability than a 20% glycerol film. Biodegradability test showed that the lower the percentage of glycerol, the more easily the biofilm degrades.

Keywords: starch, natural sources, FTIR, thermogravimetric analysis, biodegradability test

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Authors: Mahendra Singh, Narasimhareddy Ravuru

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For the past decade, the production of biodiesel has significantly increased along with its by-product, glycerol. Biodiesel-derived glycerol massive entry into the glycerol market has caused its value to plummet. Newer ways to utilize the glycerol by-product must be implemented or the biodiesel industry will face serious economic problems. The biodiesel industry should consider steam reforming glycerol to produce hydrogen gas. Steam reforming is the most efficient way of producing hydrogen and there is a lot of demand for it in the petroleum and chemical industries. This study investigates the feasibility of glycerol steam reforming in an industrial sized fixed bed reactor. In this paper, using computational fluid dynamic (CFD) simulations, the extent of the transport resistances that would occur in an industrial sized reactor can be visualized. An important parameter in reactor design is the size of the catalyst particle. The size of the catalyst cannot be too large where transport resistances are too high, but also not too small where an extraordinary amount of pressure drop occurs. The goal of this paper is to find the best catalyst size under various flow rates that will result in the highest conversion. Computational fluid dynamics simulated the transport resistances and a pseudo-homogenous reactor model was used to evaluate the pressure drop and conversion. CFD simulations showed that glycerol steam reforming has strong internal diffusion resistances resulting in extremely low effectiveness factors. In the pseudo-homogenous reactor model, the highest conversion obtained with a Reynolds number of 100 (29.5 kg/h) was 9.14% using a 1/6 inch catalyst diameter. Due to the low effectiveness factors and high carbon deposition rates, a fluidized bed is recommended as the appropriate reactor to carry out glycerol steam reforming.

Keywords: computational fluid dynamic, fixed bed reactor, glycerol, steam reforming, biodiesel

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Authors: Olfat A. Mohamed

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Rhamnolipids biosurfactants have distinct properties given them importance in many industrial applications, especially their great new future applications in cosmetic and pharmaceutical industries. These applications have encouraged the search for diverse and renewable resources to control the cost of production. The experimental results were then applied to find a suitable mathematical model for obtaining the design criteria of the batch bioreactor. This research aims to produce Rhamnolipids from different oily wastewater sources such as petroleum crude oil (PO) and vegetable oil (VO) by using Pseudomonas aeruginosa ATCC 9027. Different concentrations of the PO and the VO are added to the media broth separately are in arrangement (0.5 1, 1.5, 2, 2.5 % v/v) and (2, 4, 6, 8 and 10%v/v). The effect of the initial concentration of oil residues and the addition of glycerol and palmitic acid was investigated as an inducer in the production of rhamnolipid and the surface tension of the broth. It was found that 2% of the waste (PO) and 6% of the waste (VO) was the best initial substrate concentration for the production of rhamnolipids (2.71, 5.01 g rhamnolipid/l) as arrangement. Addition of glycerol (10-20% v glycerol/v PO) to the 2% PO fermentation broth led to increase the rhamnolipid production (about 1.8-2 times fold). However, the addition of palmitic acid (5 and 10 g/l) to fermentation broth contained 6% VO rarely enhanced the production rate. The experimental data for 2% initially (PO) was used to estimate the various kinetic parameters. The following results were obtained, maximum rate or velocity of reaction (Vmax) = 0.06417 g/l.hr), yield of cell weight per unit weight of substrate utilized (Yx/s = 0.324 g Cx/g Cs) maximum specific growth rate (μmax = 0.05791 hr⁻¹), yield of rhamnolipid weight per unit weight of substrate utilized (Yp/s)=0.2571gCp/g Cs), maintenance coefficient (Ms =0.002419), Michaelis-Menten constant, (Km=6.1237 gmol/l), endogenous decay coefficient (Kd=0.002375 hr⁻¹). Predictive parameters and advanced mathematical models were applied to evaluate the time of the batch bioreactor. The results were as follows: 123.37, 129 and 139.3 hours in respect of microbial biomass, substrate and product concentration, respectively compared with experimental batch time of 120 hours in all cases. The expected mathematical models are compatible with the laboratory results and can, therefore, be considered as tools for expressing the actual system.

Keywords: batch bioreactor design, glycerol, kinetic parameters, petroleum crude oil, Pseudomonas aeruginosa, rhamnolipids biosurfactants, vegetable oil

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Authors: Ratna Dewi Kusumaningtyas, Riris Pristiyani, Heny Dewajani

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Biodiesel is commonly produced via the two main routes, i.e. the transesterification of triglycerides and the esterification of free fatty acid (FFA) using short-chain alcohols. Both the two routes have drawback in term of the side product yielded during the reaction. Transesterification reaction of triglyceride results in glycerol as side product. On the other hand, FFA esterification brings in water as side product. Both glycerol and water in the biodiesel production are managed as waste. Hence, a separation process is necessary to obtain a high purity biodiesel. Meanwhile, separation processes is generally the most capital and energy intensive part in industrial process. Therefore, to reduce the separation process, it is essential to produce biodiesel via an alternative route eliminating glycerol or water side-products. In this work, biodiesel synthesis was performed using a glycerol-free process through chemical interesterification of jatropha oil with ethyl acetate in the presence on sodium acetate catalyst. By using this method, triacetine, which is known as fuel bio-additive, is yielded instead of glycerol. This research studied the effects of catalyst concentration on the jatropha oil interesterification process in the range of 0.5 – 1.25% w/w oil. The reaction temperature and molar ratio of oil to ethyl acetate were varied at 50, 60, and 70°C, and 1:6, 1:9, 1:15, 1:30, and 1:60, respectively. The reaction time was evaluated from 0 to 8 hours. It was revealed that the best yield was obtained with the catalyst concentration of 0.5%, reaction temperature of 70 °C, molar ratio of oil to ethyl acetate at 1:60, at 6 hours reaction time.

Keywords: biodiesel, interesterification, glycerol-free, triacetine, jatropha oil

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Authors: Refal Hussain, Saifuddin M. Nomanbhay

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Glycerol is a valuable raw material for the production of industrially useful metabolites. Among many promising applications for the use of glycerol is its bioconversion to high value-added compounds, such as bioethanol through microbial fermentation. Bioethanol is an important industrial chemical with emerging potential as a biofuel to replace vanishing fossil fuels. The yield of liquid fuel in this process was greatly influenced by various parameters viz, temperature, pH, glycerol concentration, organic concentration, and agitation speed were considered. The present study was undertaken to investigate optimum parameters for bioethanol production from raw glycerol by immobilized mutant Escherichia coli (E.coli) (ATCC11505) strain on chitosan cross linked glutaraldehyde optimized by Taguchi statistical method in shake flasks. The initial parameters were set each at four levels and the orthogonal array layout of L16 (45) conducted. The important controlling parameters for optimized the operational fermentation was temperature 38 °C, medium pH 6.5, initial glycerol concentration (250 g/l), and organic source concentration (5 g/l). Fermentation with optimized parameters was carried out in a custom fabricated shake flask. The predicted value of bioethanol production under optimized conditions was (118.13 g/l). Immobilized cells are mainly used for economic benefits of continuous production or repeated use in continuous as well as in batch mode.

Keywords: bioethanol, Escherichia coli, immobilization, optimization

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Authors: C. Patrascioiu, M. Jamali

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The paper deals with the simulation of the crude distillation process using the Unisim Design simulator. The necessity of simulating this process is argued both by considerations related to the design of the crude distillation column, but also by considerations related to the design of advanced control systems. In order to use the Unisim Design simulator to simulate the crude distillation process, the identification of the simulators used in Romania and an analysis of the PRO/II, HYSYS, and Aspen HYSYS simulators were carried out. Analysis of the simulators for the crude distillation process has allowed the authors to elaborate the conclusions of the success of the crude modelling. A first aspect developed by the authors is the implementation of specific problems of petroleum liquid-vapors equilibrium using Unisim Design simulator. The second major element of the article is the development of the methodology and the elaboration of the simulation program for the crude distillation process, using Unisim Design resources. The obtained results validate the proposed methodology and will allow dynamic simulation of the process.  

Keywords: crude oil, distillation, simulation, Unisim Design, simulators

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Authors: Dorith Tavor, Adi Wolfson

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In the past two decades a variety of green solvents have been proposed, including water, ionic liquids, fluorous solvents, and supercritical fluids. However, their implementation in industrial processes is still limited due to their tedious and non-sustainable synthesis, lack of experimental data and familiarity, as well as operational restrictions and high cost. Several years ago we presented, for the first time, the use of glycerol-based solvents as alternative sustainable reaction mediums in both catalytic and non-catalytic organic synthesis. Glycerol is the main by-product from the conversion of oils and fats in oleochemical production. Moreover, in the past decade, its price has substantially decreased due to an increase in supply from the production and use of fatty acid derivatives in the food, cosmetics, and drugs industries and in biofuel synthesis, i.e., biodiesel. The renewable origin, beneficial physicochemical properties and reusability of glycerol-based solvents, enabled improved product yield and selectivity as well as easy product separation and catalyst recycling. Furthermore, their high boiling point and polarity make them perfect candidates for non-conventional heating and mixing techniques such as ultrasound- and microwave-assisted reactions. Finally, in some reactions, such as catalytic transfer-hydrogenation or transesterification, they can also be used simultaneously as both solvent and reactant. In our ongoing efforts to design a viable protocol that will facilitate the acceptance of glycerol and its derivatives as sustainable solvents, pure glycerol and glycerol triacetate (triacetin) as well as various glycerol-triacetin mixtures were tested as sustainable solvents in several representative organic reactions, such as nucleophilic substitution of benzyl chloride to benzyl acetate, Suzuki-Miyaura cross-coupling of iodobenzene and phenylboronic acid, baker’s yeast reduction of ketones, and transfer hydrogenation of olefins. It was found that reaction performance was affected by the glycerol to triacetin ratio, as the solubility of the substrates in the solvent determined product yield. Thereby, employing optimal glycerol to triacetin ratio resulted in maximum product yield. In addition, using glycerol-based solvents enabled easy and successful separation of the products and recycling of the catalysts.

Keywords: glycerol, green chemistry, sustainability, catalysis

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Authors: Babak Moradi, Hassan Zare-Maivan

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A greenhouse investigation has been conducted to study the effect of crude oil on morphology and protein content of Avicennia marina plant. Avicennia marina seeds were sown in different concentrations of the crude oil mixed soil (i.e., 2.5, 5, 7.5, and 10 w/w). Controls and replicates were also set up. Morphological traits were recorded 4 months after plantation. Avicennia marina seedlings could tolerate up to 10% (w/w). Results demonstrated that there was a reduction in plant shoot and root biomass with the increase of crude oil concentration. Plant height, total leaf number and length reduced significantly with increase of crude oil contamination. Investigation revealed that there is a great impact of crude oil contamination on protein content of the roots of the experimental plant. Protein content of roots grown in different concentrations of crude oil were more than those of the control plant. Further, results also showed that protein content was increased with increased concentration of crude oil.

Keywords: Avicennia marina, morphology, oil contamination, protein content

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Authors: Aida Kalantari, Boyang Ji, Tao Chen, Ivan Mijakovic

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3-hydroxypropanoic acid (3-HP) is one of the most important biomass-derivable platform chemicals that can be converted into a number of industrially important compounds. There have been several attempts at production of 3-HP from renewable sources in cell factories, focusing mainly on Escherichia coli, Klebsiella pneumoniae, and Saccharomyces cerevisiae. Despite the significant progress made in this field, commercially exploitable large-scale production of 3-HP in microbial strains has still not been achieved. In this study, we investigated the potential of Bacillus subtilis to be used as a microbial platform for bioconversion of glycerol into 3-HP. Our recombinant B. subtilis strains overexpress the two-step heterologous pathway containing glycerol dehydratase and aldehyde dehydrogenase from various backgrounds. The recombinant strains harboring the codon-optimized synthetic pathway from K. pneumoniae produced low levels of 3-HP. Since the enzymes in the heterologous pathway are sensitive to oxygen, we had to perform our experiments in micro-aerobic conditions. Under these conditions, the cell produces lactate in order to regenerate NAD+, and we found the lactate production to be in competition with the production of 3-HP. Therefore, based on the in silico predictions, we knocked out the glycerol kinase (glpk), which in combination with growth on glucose, resulted in improving the 3-HP titer to 1 g/L and the removal of lactate. Cultivation of the same strain in an enriched medium improved the 3-HP titer up to 7.6 g/L. Our findings provide the first report of successful introduction of the biosynthetic pathway for conversion of glycerol into 3-HP in B. subtilis.

Keywords: bacillus subtilis, glycerol, 3-hydroxypropanoic acid, metabolic engineering

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Authors: E. Osazee, L. U. Bashir

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This study was conducted at the Department of Biological Sciences, Usmanu Danfodiyo University, Sokoto, Nigeria, to determine the effects of different weights of cow dung on indigenous bacterial isolates in remediation of crude oil contaminated soils. The soil (1kg) was contaminated with 20g of crude oil and this was treated with three (40g, 80g and 120g) weights of cow dung. The soils were amended after two weeks of crude oil contamination. Soil samples were collected from the plastic bags for microbiological analyses. The isolates were cultured to test their ability to grow on crude oil. The ability of the isolates to utilize the crude oil was determined using media dilution technique. Bacteria such as Proteus mirabilis, Bacillus lacterosporus, Morganella morganii, Serratia marcescens and Bacillus alvei were isolated. The variables measured were heterotrophic bacterial populations, hydrocarbon utilizing bacterial populations and the percentage of crude oil degraded in the soils. Data collected were subjected to analysis of variance (ANOVA). Results obtained indicated that all the different weights of cow dung showed appreciable effect in crude oil decontamination. Based on the findings of the experiments, it could be deduced that 120g of cow dung promoted higher degradation of hydrocarbons. Thus, it should be recommended for remediation of crude oil contaminated soil in the study area.

Keywords: crude oil, cow dung, amendment, bioremediation, decontamination

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Authors: Ala’a H. Al-Muhtaseb, Farrukh Jamil, Sandeep K. Saxena

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The fast growth rate of energy consumption along with world population expected to demand 50% more energy by 2030 than nowadays. At present, the energy demand is mostly provided by limited fossil fuel sources such as oil, natural gas, and coal that are resulting in dramatic increase in CO2 emissions from combustion of fossil fuels. The growth of the biodiesel industry over the last decade has resulted in a price drop because glycerol is obtained as a by-product during transesterification of vegetable oil or animal fats, which accounts for one tenth of every gallon of biodiesel produced. The production of oxygenates from glycerol gains much importance due to the excellent diesel-blending property of the oxygenates that not only improve the quality of the fuel but also increases the overall yield of the biodiesel in helping to meet the target for energy production from renewable sources for transport in the energy utilization directives. The reaction of bio-glycerol with bio-acetone was carried out in a magnetically stirred two necked round bottom flaskS. Condensation of bio-glycerol with acetone in the presence of various modified forms of beta zeolite has been done for synthesizing solketal (AB-2 modified with nitric acid, AB-3 modified with oxalic acid). Among all modified forms of beta zeolite, AB-2 showed the best performance for maximum glycerol conversion 94.26 % with 94.21 % solketal selectivity and minimum acetal formation 0.05 %. The physiochemical properties of parent beta zeolite and all its modified forms were analyzed by XRD, SEM, TEM, BET, FTIR and TPD. It has been revealed that AB-2 catalysts with high pore volume and surface area gave high glycerol conversion with maximum solketal selectivity. Despite this, the crystallinity of AB-3 was lower than AB-2 which helps to provide the shorter path length for reactants and product but due high pore volume AB-2 was preferred which gave maximum bio-glycerol conversion. Temperature does matter the glycerol conversion and selectivity of solketal, as it increases from 40 ºC to 60 ºC the conversion of glycerol rises from 80.04 % to 94.26 % and selectivity of solketal from 80.0 % to 94.21 % but further increase in temperature to 100 ºC glycerol conversion reduced to 93.06 % and solketal selectivity to 92.08 %. AB-2 was found to be highly stable as up to 4 repeated experimental runs there was less than 10% decrease in its activity. This process offers an attractive route for converting bio-glycerol, the main by-product of biodiesel to solketal with bio-acetone; a value-added green product with potential industrial applications as a valuable green fuel additive or combustion promoter for gasoline/diesel engines.

Keywords: beta-zeolite, bio-glycerol, catalyst, solketal

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Authors: Mosaad Attia Elkasaby

Abstract:

The crude oil contains paraffines, aromatics, and asphaltenes in addition to some organic impurities, with increasing demands to reduce the cost of crude oil production, the uses of a pour point depressant is mandatory to maintain good flow rate. The wax materials cause many problems during production, storage, and transport, especially at low temperature, as these waxes tend, at low temperatures, to precipitate on the wall lines, thus leads to the high viscosity of crude oil and impede the flow rate, which represents an additional burden for crude oil pumping system from the place of production to the refinery. There are many ways to solve this problem, including, but not limited to, heat the crude and the use of organic solvents. But one of the most important disadvantages of these methods is the high economic cost. The aim of this innovation is to manufacture some polymeric materials (polymers based on aniline) that are processed locally that can be used as a pour point depressant of crude oil. For the first time, polymer based on aniline is modified and used with a number of organic solvents and tested with solvent (Styrene). It was found that the polymer based on aniline, when modified, had full solubility in styrene, unlike other organic solvent that was used in the past, such as chloroform and toluene. We also used a new solvent (PONA) that is obtained from the process of hydrotreating and separation of straight run naphtha to dissolve polymer based on aniline as a pour point depressant of crude oil. This innovative include studies conducted on highly paraffinic crude oil (C.O.1 and C.O.2). On using concentration (2500 ppm) of polymer based on aniline, the pour point of crude oil has decreased from +33 to - 9°C in case of crude oil (C.O.1) and from + 42 to – 6°C in case crude oil (C.O.2) at the same concentration.

Keywords: PPD, aniline, paraffinic crude oils, polymers

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