Search results for: heptane

Authors: Tony K. Joseph, Balasubramanian Vathilingam, Stephane Morin

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Currently, the refiners around the world are more focused on improving the yield of light olefins (propylene and ethylene) as both of them are very prominent raw materials to produce wide spectrum of polymeric materials such as polyethylene and polypropylene. Henceforth, it is desirable to increase the yield of light olefins via selective cracking of heavy oil fractions. In this study, zeolite grown on SiC was used as the catalyst to do model cracking reaction of n-heptane. The catalytic cracking of n-heptane was performed in a fixed bed reactor (12 mm i.d.) at three different temperatures (425, 450 and 475 °C) and at atmospheric pressure. A carrier gas (N₂) was mixed with n-heptane with ratio of 90:10 (N₂:n-heptane), and the gaseous mixture was introduced into the fixed bed reactor. Various flow rate of reactants was tested to increase the yield of ethylene and propylene. For the comparison purpose, commercial zeolite was also tested in addition to Zeolite on SiC. The products were analyzed using an Agilent gas chromatograph (GC-9860) equipped with flame ionization detector (FID). The GC is connected online with the reactor and all the cracking tests were successfully reproduced. The entire catalytic evaluation results will be presented during the conference.

Keywords: cracking, catalyst, evaluation, ethylene, heptane, propylene

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Authors: Sabrina Ladjama, Aicha Rizi, Azzedine Abbaci

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In this work, we use the crossover model to formulate a comprehensive fundamental equation of state for the thermodynamic properties for several n-alkanes in the critical region that extends to the classical region. This equation of state is constructed on the basis of comparison of selected measurements of pressure-density-temperature data, isochoric and isobaric heat capacity. The model can be applied in a wide range of temperatures and densities around the critical point for n-heptane. It is found that the developed model represents most of the reliable experimental data accurately.

Keywords: crossover model, critical region, fundamental equation, n-heptane

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Authors: Saad Mohamed Elsaid Abdelrahman

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The adsorption method is one of the best modern techniques used in removing pollutants, especially organic hydrocarbon compounds, from polluted water. Through this research, bentonite clay can be used to remove organic hydrocarbon compounds, such as heptane and octane, resulting from oil spills in seawater. Bentonite clay can be obtained from the Kholayaz area, located north of Jeddah, at a distance of 80 km. Chemical analysis shows that bentonite clay consists of a mixture of silica, alumina and oxides of some elements. Bentonite clay can be activated in order to raise its adsorption efficiency and to make it suitable for removing pollutants using an ionic organic solvent. It is necessary to study some of the factors that could be in the efficiency of bentonite clay in removing oily organic compounds, such as the time of contact of the clay with heptane and octane solutions, pH and temperature, in order to reach the highest adsorption capacity of bentonite clay. The temperature can be a few degrees Celsius higher. The adsorption capacity of the clay decreases when the temperature is raised more than 4°C to reach its lowest value at the temperature of 50°C. The results show that the friction time of 30 minutes and the pH of 6.8 is the best conditions to obtain the highest adsorption capacity of the clay, 467 mg in the case of heptane and 385 mg in the case of octane compound. Experiments conducted on bentonite clay were encouraging to select it to remove heavy molecular weight pollutants such as petroleum compounds under study.

Keywords: adsorbent, bentonite clay, oil spills, removal

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Authors: Hamed Bagheri, Seyd Javid Shariati

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The effects of type and amount of solvent on lubricant which is used in disposable medical devices are investigated in this article. Two kinds of common solvent, n-Hexane and n-Heptane, are used. The mechanical behavior of syringe has shown that n-Heptane has better mixing ratio and also more effective spray process in the barrel of syringe than n-Hexane because of similar solubility parameter to silicon oil. The results revealed that movement of plunger in the barrel increases when pure silicone is used because non-uniform film is created on the surface of barrel, and also, it seems that the form of silicon is converted from oil to gel due to sterilization process. The results showed that the convenient mixing ratio of solvent/lubricant oil is 80/20.

Keywords: disposal medical devices, lubricant oil, solvent effect, solubility parameter

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Authors: Mingjun Xu, Shouxiang Lu

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Understanding the interaction mechanism between the water droplet and pool fire has an important significance in engineering application of water sprinkle/spray/mist fire suppression. The micro impact process is unclear when the droplet impacts on the burning liquid surface at present. To deepen the understanding of the mechanisms of pool fire suppression with water spray/mist, dynamic processes of single water droplet impinging onto a hot heptane surface are visualized with the aid of a high-speed digital camera at 2000 fps. Each test is repeated 20 times. The water droplet diameter is around 1.98 mm, and the impact Weber number ranges from 30 to 695. The heptane is heated by a hot plate to mimic the burning condition, and the temperature varies from 30 to 90°C. The results show that three typical phenomena, including penetration, crater-jet and surface bubble, are observed, and the pool temperature has a significant influence on the critical condition for the appearance of each phenomenon. A global picture of different phenomena is built according to impact Weber number and pool temperature. In addition, the pool temperature and Weber number have important influences on the characteristic parameters including maximum crater depth, crown height and liquid column height. For a fixed Weber number, the liquid column height increases with pool temperature.

Keywords: droplet impact, fire suppression, hot surface, water spray

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Authors: Lenuta Kloetzer, Alexandra C. Blaga, Dan Cascaval, Alexandra Tucaliuc, Anca I. Galaction

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Rosmarinic acid, an ester of caffeic acid and 3-(3,4-dihydroxyphenyl) lactic acid, is considered a valuable compound for the pharmaceutical and cosmetic industries due to its antimicrobial, antioxidant, antiviral, anti-allergic, and anti-inflammatory effects. It can be obtained by extraction from vegetable or animal materials, by chemical synthesis and biosynthesis. Indifferent of the method used for rosmarinic acid production, the separation and purification process implies high amount of raw materials and laborious stages leading to high cost for and limitations of the separation technology. This study focused on separation of rosmarinic acid by synergic reactive extraction with a mixture of two extractants, one acidic (acid di-(2ethylhexyl) phosphoric acid, D2EHPA) and one with basic character (Amberlite LA-2). The studies were performed in experimental equipment consisting of an extraction column where the phases’ mixing was made by mean of a perforated disk with 45 mm diameter and 20% free section, maintained at the initial contact interface between the aqueous and organic phases. The vibrations had a frequency of 50 s⁻¹ and 5 mm amplitude. The extraction was carried out in two solvents with different dielectric constants (n-heptane and dichloromethane) in which the extractants mixture of varying concentration was dissolved. The pH-value of initial aqueous solution was varied between 1 and 7. The efficiency of the studied extraction systems was quantified by distribution and synergic coefficients. For calculating these parameters, the rosmarinic acid concentration in the initial aqueous solution and in the raffinate have been measured by HPLC. The influences of extractants concentrations and solvent polarity on the efficiency of rosmarinic acid separation by synergic extraction with a mixture of Amberlite LA-2 and D2EHPA have been analyzed. In the reactive extraction system with a constant concentration of Amberlite LA-2 in the organic phase, the increase of D2EHPA concentration leads to decrease of the synergic coefficient. This is because the increase of D2EHPA concentration prevents the formation of amine adducts and, consequently, affects the hydrophobicity of the interfacial complex with rosmarinic acid. For these reasons, the diminution of synergic coefficient is more important for dichloromethane. By maintaining a constant value of D2EHPA concentration and increasing the concentration of Amberlite LA-2, the synergic coefficient could become higher than 1, its highest values being reached for n-heptane. Depending on the solvent polarity and D2EHPA amount in the solvent phase, the synergic effect is observed for Amberlite LA-2 concentrations over 20 g/l dissolved in n-heptane. Thus, by increasing the concentration of D2EHPA from 5 to 40 g/l, the minimum concentration value of Amberlite LA-2 corresponding to synergism increases from 20 to 40 g/l for the solvent with lower polarity, namely, n-heptane, while there is no synergic effect recorded for dichloromethane. By analysing the influences of the main factors (organic phase polarity, extractant concentration in the mixture) on the efficiency of synergic extraction of rosmarinic acid, the most important synergic effect was found to correspond to the extractants mixture containing 5 g/l D2EHPA and 40 g/l Amberlite LA-2 dissolved in n-heptane.

Keywords: Amberlite LA-2, di(2-ethylhexyl) phosphoric acid, rosmarinic acid, synergic effect

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Authors: Camilo A. Guerrero-Martin, Erik Montes Paez, Marcia C. K. Oliveira, Jonathan Campos, Elizabete F. Lucas

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Asphaltenes precipitation is considered as a formation damage problem, which can reduce the oil recovery factor. It fouls piping and surface installations, as well as cause serious flow assurance complications and decline oil well production. Therefore, researchers have shown an interest in chemical treatments to control this phenomenon. The aim of this paper is to assess the asphaltenes precipitation onset of crude oils in the presence of cardanol, by titrating the crude with n-heptane. Moreover, based on this results obtained at atmosphere pressure, the asphaltenes precipitation onset pressure were calculated to predict asphaltenes precipitation in the reservoir, by using differential liberation and refractive index data of the oils. The influence of cardanol concentrations in the asphaltenes stabilization of three Brazilian crude oils samples (with similar API densities) was studied. Therefore, four formulations of cardanol in toluene were prepared: 0, 3, 5, 10 and 15 m/m%. The formulations were added to the crude at 2:98 ratio. The petroleum samples were characterized by API density, elemental analysis and differential liberation test. The asphaltenes precipitation onset (APO) was determined by titrating with n-heptane and monitoring with near-infrared (NIR). UV-Vis spectroscopy experiments were also done to assess the precipitate asphaltenes content. The asphaltenes precipitation envelopes (APE) were also determined by numerical simulation (Multiflash). In addition, the adequate artificial lift systems (ALS) for the oils were selected. It was based on the downhole well profile and a screening methodology. Finally, the oil flowrates were modelling by NODAL analysis production system in the PIPESIM software. The results of this study show that the asphaltenes precipitation onset of the crude oils were 2.2, 2.3 and 6.0 mL of n-heptane/g of oil. The cardanol was an effective inhibitor of asphaltenes precipitation for the crude oils used in this study, since it displaces the precipitation pressure of the oil to lower values. This indicates that cardanol can increase the oil wells productivity.

Keywords: asphaltenes, NODAL analysis production system, precipitation pressure onset, inhibitory molecule

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Authors: B. Kabane, G. G. Redhi

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An ammonium based ionic liquid (methyltrioctylammonium chloride) [N_{8 8 8 1}] [Cl] was investigated as an extraction potential solvent for volatile organic solvents (in this regard, solutes), which includes alkenes, alkanes, ketones, alkynes, aromatic hydrocarbons, tetrahydrofuran (THF), alcohols, thiophene, water and acetonitrile based on the experimental activity coefficients at infinite THF measurements were conducted by the use of gas-liquid chromatography at four different temperatures (313.15 to 343.15) K. Experimental data of activity coefficients obtained across the examined temperatures were used in order to calculate the physicochemical properties at infinite dilution such as partial molar excess enthalpy, Gibbs free energy and entropy term. Capacity and selectivity data for selected petrochemical extraction problems (heptane/thiophene, heptane/benzene, cyclohaxane/cyclohexene, hexane/toluene, hexane/hexene) were computed from activity coefficients data and compared to the literature values with other ionic liquids. Evaluation of activity coefficients at infinite dilution expands the knowledge and provides a good understanding related to the interactions between the ionic liquid and the investigated compounds.

Keywords: separation, activity coefficients, methyltrioctylammonium chloride, ionic liquid, capacity

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Authors: Gracious Tendai Matayaya

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The world is facing problems in finding alternative resources to offset the decline in global petroleum reserves. The use of fossil fuels has prompted biofuel development, particularly in the transportation sector. In these circumstances, looking for alternative renewable energy sources makes sense. Petroleum-based fuels also result in a lot of carbon dioxide being released into the environment causing global warming. Replacing petroleum and fossil fuel-based fuels with biofuels has the advantage of reducing undesirable aspects of these fuels, which are mostly the production of greenhouse gas and dependence on unstable foreign suppliers. Algae refer to a group of aquatic microorganisms that produce a lot of lipids up to 60% of their total weight. This project aims to exploit the large amounts of oil produced by these microorganisms in the Soxhlet extraction to make biodiesel. Experiments were conducted to establish the cultivability of algae, harvesting methods, the oil extraction process, and the transesterification process. Although there are various methods for producing algal oil, the Soxhlet extraction method was employed for this particular research. After extraction, the oil was characterized before being used in the transesterification process that used methanol and hydrochloric acid as the process reactants. The properties of the resulting biodiesel were then determined. Because there is a requirement to dry wet algae, the experimental findings showed that Soxhlet extraction was the optimum way to produce a higher yield of microalgal oil. Upon cultivating algae, Compound D fertilizer was added as a source of nutrients (Phosphorous and Nitrogen), and the highest growth of algae was observed at 6 days (using 2 g of fertilizer), after which it started to decrease. Butanol, hexane, heptane and acetone have been experimented with as solvents, and heptane gave the highest amount of oil (89ml of oil) when 300 ml of solvent was used. This was compared to 73.21ml produced by butanol, 81.90 produced by hexane and 69.57ml produced by acetone, and as a result, heptane was used for the rest of the experiments, which included a variation of the mass of dried algae and time of extraction. This meant that the oil composition of algae was higher than other oil sources like peanuts, soybean etc. Algal oil was heated at 150℃ for 150 minutes in the presence of methanol (reactant) and hydrochloric acid (HCl), which was used as a catalyst. A temperature of 200℃ produced 93.64%, and a temperature of 250℃ produced 92.13 of biodiesel at 150 minutes.

Keywords: microalgae, algal oil, biodiesel, soxhlet extraction

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Authors: F. Mutelet, L. Cesari

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Development of safer and environmentally friendly processes and products is needed to achieve sustainable production and consumption patterns. Ionic liquids, which are of great interest to the chemical and related industries because of their attractive properties as solvents, should be considered. Ionic liquids are comprised of an asymmetric, bulky organic cation and a weakly coordinating organic or inorganic anion. A large number of possible combinations allows for the ability to ‘fine tune’ the solvent properties for a specific purpose. Physical and chemical properties of ionic liquids are not only influenced by the nature of the cation and the nature of cation substituents but also by the polarity and the size of the anion. These features infer to ionic liquids numerous applications, in organic synthesis, separation processes, and electrochemistry. Separation processes required a good knowledge of the behavior of organic compounds with ionic liquids. Gas chromatography is a useful tool to estimate the interactions between organic compounds and ionic liquids. Indeed, retention data may be used to determine infinite dilution thermodynamic properties of volatile organic compounds in ionic liquids. Among others, the activity coefficient at infinite dilution is a direct measure of solute-ionic liquid interaction. In this work, infinite dilution thermodynamic properties of volatile organic compounds in specific bis(trifluoromethylsulfonyl)imide based ionic liquids measured by gas chromatography is presented. It was found that apolar compounds are not miscible in this family of ionic liquids. As expected, the solubility of organic compounds is related to their polarity and hydrogen-bond. Through activity coefficients data, the performance of these ionic liquids was evaluated for different separation processes (benzene/heptane, thiophene/heptane and pyridine/heptane). Results indicate that ionic liquids may be used for the extraction of polar compounds (aromatics, alcohols, pyridine, thiophene, tetrahydrofuran) from aliphatic media. For example, 1-benzylpyridinium bis(trifluoromethylsulfonyl) imide and 1-cyclohexylmethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide are more efficient for the extraction of aromatics or pyridine from aliphatics than classical solvents. Ionic liquids with long alkyl chain length present important capacity values but their selectivity values are low. In conclusion, we have demonstrated that specific bis(trifluoromethylsulfonyl)imide based ILs containing polar chain grafted on the cation (for example benzyl or cyclohexyl) increases considerably their performance in separation processes.

Keywords: interaction organic solvent-ionic liquid, gas chromatography, solvation model, COSMO-RS

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Authors: Z. Haddad, C. Abid, O. Rahli, O. Margeat, W. Dachraoui, A. Mataoui

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The present study aims to measure the volumetric mass density of NiPd-heptane nanofluids synthesized using a one-step method known as thermal decomposition of metal-surfactant complexes. The particle concentration is up to 7.55 g/l and the temperature range of the experiment is from 20°C to 50°C. The measured values were compared with the mixture theory and good agreement between the theoretical equation and measurement were obtained. Moreover, the available nanofluids volumetric mass density data in the literature is reviewed.

Keywords: NiPd nanoparticles, nanofluids, volumetric mass density, stability

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Authors: Blaga Alexandra Cristina, Kloetzer Lenuta, Bompa Amalia Stela, Galaction Anca Irina, Cascaval Dan

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Vitamin B9 is an important member of vitamins B group, being a growth factor, important for making genetic material as DNA and RNA, red blood cells, for building muscle tissues, especially during periods of infancy, adolescence and pregnancy. Its production by biosynthesis is based on the high metabolic potential of mutant Bacillus subtilis, due to a superior biodisponibility compared to that obtained by chemical pathways. Pertraction, defined as the extraction and transport through liquid membranes consists in the transfer of a solute between two aqueous phases of different pH-values, phases that are separated by a solvent layer of various sizes. The pertraction efficiency and selectivity could be significantly enhanced by adding a carrier in the liquid membrane, such as organophosphoric compounds, long chain amines or crown-ethers etc., the separation process being called facilitated pertraction. The aim of the work is to determine the impact of the presence of two extractants/carriers in the bulk liquid membrane, i.e. di(2-ethylhexyl) phosphoric acid (D2EHPA) and lauryltrialkylmetilamine (Amberlite LA2) on the transport kinetics of vitamin B9. The experiments have been carried out using two pertraction equipments for a free liquid membrane or bulk liquid membrane. One pertraction cell consists on a U-shaped glass pipe (used for the dichloromethane membrane) and the second one is an H-shaped glass pipe (used for h-heptane), having 45 mm inner diameter of the total volume of 450 mL, the volume of each compartment being of 150 mL. The aqueous solutions are independently mixed by means of double blade stirrers with 6 mm diameter and 3 mm height, having the rotation speed of 500 rpm. In order to reach high diffusional rates through the solvent layer, the organic phase has been mixed with a similar stirrer, at a similar rotation speed (500 rpm). The area of mass transfer surface, both for extraction and for reextraction, was of 1.59x10-³ m2. The study on facilitated pertraction with the mixture of two carriers, namely D2EHPA and Amberlite LA-2, dissolved in two solvents with different polarities: n-heptane and dichloromethane, indicated the possibility to obtain the synergic effect. The synergism has been analyzed by considering the vitamin initial and final mass flows, as well as the permeability factors through liquid membrane. The synergic effect has been observed at low D2EHPA concentrations and high Amberlite LA-2 concentrations, being more important for the low-polar solvent (n-heptane). The results suggest that the mechanism of synergic pertraction consists on the reaction between the organophosphoric carrier and vitamin B9 at the interface between the feed and membrane phases, while the aminic carrier enhances the hydrophobicity of this compound by solvation. However, the formation of this complex reduced the reextraction rate and, consequently, affects the synergism related to the final mass flows and permeability factor. For describing the influences of carriers concentrations on the synergistic coefficients, some equations have been proposed by taking into account the vitamin mass flows or permeability factors, with an average deviations between 4.85% and 10.73%.

Keywords: pertraction, synergism, vitamin B9, Amberlite LA-2, di(2-ethylhexyl) phosphoric acid

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Authors: Hafizuddin W. Yussof, Syamsutajri S. Bahri, Adam P. Harvey

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Strong anion exchange resins with QN+OH-, have the potential to be developed and employed as heterogeneous catalyst for transesterification, as they are chemically stable to leaching of the functional group. Nine different SIERs (SIER1-9) with QN+OH- were prepared by suspension polymerization of vinylbenzyl chloride-divinylbenzene (VBC-DVB) copolymers in the presence of n-heptane (pore-forming agent). The amine group was successfully grafted into the polymeric resin beads through functionalization with trimethylamine. These SIERs are then used as a catalyst for the transesterification of triacetin with methanol. A set of differential equations that represents the Langmuir-Hinshelwood-Hougen-Watson (LHHW) and Eley-Rideal (ER) models for the transesterification reaction were developed. These kinetic models of LHHW and ER were fitted to the experimental data. Overall, the synthesized ion exchange resin-catalyzed reaction were well-described by the Eley-Rideal model compared to LHHW models, with sum of square error (SSE) of 0.742 and 0.996, respectively.

Keywords: anion exchange resin, Eley-Rideal, Langmuir-Hinshelwood-Hougen-Watson, transesterification

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Authors: A. Thakur, P. S. Panesar, M. S. Saini

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Extraction of lactic acid by emulsion liquid membrane technology (ELM) using n-trioctyl amine (TOA) in n-heptane as carrier within the organic membrane along with sodium carbonate as acceptor phase was optimized by using response surface methodology (RSM). A three level Box-Behnken design was employed for experimental design, analysis of the results and to depict the combined effect of five independent variables, vizlactic acid concentration in aqueous phase (cl), sodium carbonate concentration in stripping phase (cs), carrier concentration in membrane phase (ψ), treat ratio (φ), and batch extraction time (τ) with equal volume of organic and external aqueous phase on lactic acid extraction efficiency. The maximum lactic acid extraction efficiency (ηext) of 98.21%from aqueous phase in a batch reactor using ELM was found at the optimized values for test variables, cl, cs,, ψ, φ and τ as 0.06 [M], 0.18 [M], 4.72 (%,v/v), 1.98 (v/v) and 13.36 min respectively.

Keywords: emulsion liquid membrane, extraction, lactic acid, n-trioctylamine, response surface methodology

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Authors: Rana Th. A. Al-Rubaye, Arthur A. Garforth

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This work details the generation of thin films of structured zeolite catalysts (ZSM–5 and Y) onto the surface of a metal substrate (FeCrAlloy) using in-situ hydrothermal synthesis. In addition, the zeolite Y is post-synthetically modified by acidified ammonium ion exchange to generate US-Y. Finally the catalytic activity of the structured ZSM-5 catalyst films (Si/Al = 11, thickness 146 µm) and structured US–Y catalyst film (Si/Al = 8, thickness 23µm) were compared with the pelleted powder form of ZSM–5 and USY catalysts of similar Si/Al ratios. The structured catalyst films have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X–ray analysis (EDX) and Thermogravimetric Analysis (TGA). The transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces was followed using SEM and XRD. In addition, the robustness of the prepared coating was confirmed by subjecting these to thermal cycling (ambient to 550°C). The cracking of n–heptane over the pellets and structured catalysts for both ZSM–5 and Y zeolite showed very similar product selectivities for similar amounts of catalyst with an apparent activation energy of around 60 kJ mol-1. This paper demonstrates that structured catalysts can be manufactured with excellent zeolite adherence and when suitably activated/modified give comparable cracking results to the pelleted powder forms. These structured catalysts will improve temperature distribution in highly exothermic and endothermic catalysed processes.

Keywords: FeCrAlloy, structured catalyst, zeolite Y, zeolite ZSM-5

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Authors: Siva Kumar Bathina, Sudheer Siddapureddy

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Fires accident becomes even worse when the hazardous equipment like reactors or radioactive waste packages are engulfed in fire. In this work, large-eddy numerical fire simulations are performed using fire dynamic simulator to predict the thermal behavior of such bodies engulfed in hydrocarbon pool fires. A radiatively dominated 0.3 m circular burner with n-heptane as the fuel is considered in this work. The fire numerical simulation results without anybody inside the fire are validated with the reported experimental data. The comparison is in good agreement for different flame properties like predicted mass burning rate, flame height, time-averaged center-line temperature, time-averaged center-line velocity, puffing frequency, the irradiance at the surroundings, and the radiative heat feedback to the pool surface. Cask of different sizes is simulated with SS304L material. The results are independent of the material of the cask simulated as the adiabatic surface temperature concept is employed in this study. It is observed that the mass burning rate increases with the blockage ratio (3% ≤ B ≤ 32%). However, the change in this increment is reduced at higher blockage ratios (B > 14%). This is because the radiative heat feedback to the fuel surface is not only from the flame but also from the cask volume. As B increases, the volume of the cask increases and thereby increases the radiative contribution to the fuel surface. The radiative heat feedback in the case of the cask engulfed in the fire is increased by 2.5% to 31% compared to the fire without cask.

Keywords: adiabatic surface temperature, fire accidents, fire dynamic simulator, radiative heat feedback

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Authors: Prabir Kumar Paul, Joyeeta Mitra

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Ergosterol, is an important fungal metabolite on phylloplane which is not synthesised by plants. However, the functional requirement of ergosterol to the plants is still an enigma. Being ubiquitously present in all plants except algae needs an insight into its physiological implication. The present study aimed at understanding if and how ergosterol influences the physiology of chloroplast particularly the activity of RuBisCo and carbonic anhydrase. The concept of the study was based on one of our earlier observation of enhanced Hills reaction in plants treated with fungal metabolites which contained ergosterol. The fungal metabolite treated plants had a significantly high concentration of photosynthetic pigments. Eight-week-old tomato plants raised under aseptic conditions at 25 + 10 C, 75 % relative humidity and 12 hour L/D photoperiod. Metabolites of Aspergillus niger and Fusarium oxysporum were sprayed on plants either singly or in a 1: 1 combination. A separate group of plants was also treated with 0.5, 1.0, 3.0, 5.0. 7.0 mg ergosterol / ml of n- heptane. Control plants were treated with sterile distilled water only. Plants were sampled at 24, 48, 72 and 96 hours of treatment. RuBisCo and carbonic anhydrase was estimated from sampled leaves. RuBisCo was separated on 1D SDS-PAGE and subjected to MALDI – TOF- TOF – MS analysis. The presence of ergosterol in fungal metabolites was confirmed. Fungal metabolites significantly enhanced the concentration and activity of RuBisCo and carbonic anhydrase. The Vmax activity of the enzymes was significantly high in metabolite treated plants. 1:1 mix of metabolite was more effective than when applied individually. Insilico analysis revealed, RuBisCo subunits had a binding site for ergosterol and in its presence affinity of Co2 to the enzyme increased by several folds. Invivo activity of RuBisCo was significantly elicited by ergosterol. Results of the present study indicate that ergosterol from phylloplane microfungi probably regulates the binding of Co2 to RuBisCo along with activity of carbonic anhydrase thereby modulating the physiology of choloroplast.

Keywords: carbonic anhydrase, ergosterol, phylloplane, RuBisCo

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Authors: Claudia Matassa, Matthias Hohne, Dominic Ormerod, Yamini Satyawali

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Chiral amines integrate the backbone of several active pharmaceutical ingredients (APIs) used in modern medicine for the treatment of a vast range of diseases. Despite the demand, their synthesis remains challenging. Besides a range of chemicals and enzymatical methods, chiral amine synthesis using transaminases (EC 2.6.1.W) represents a useful alternative to access this important class of compounds. Even though transaminases exhibit excellent stereo and regioselectivity and the potential for high yield, the reaction suffers from a number of challenges, including the thermodynamic equilibrium, product inhibition, and low substrate solubility. In this work, we demonstrate a membrane assisted strategy for addressing these challenges. It involves the use of high molecular weight (HMW) amine donors for the transaminase-catalyzed synthesis of 4-phenyl-2-butylamine in both aqueous and organic solvent media. In contrast to common amine donors such as alanine or isopropylamine, these large molecules, provided in excess for thermodynamic equilibrium shifting, are easily retained by commercial nanofiltration membranes; thus a selective permeation of the desired smaller product amine is possible. The enzymatic transamination in aqueous media, combined with selective product removal shifted the equilibrium enhancing substrate conversion by an additional 25% compared to the control reaction. Along with very efficient amine product removal, there was undesirable loss of ketone substrate and low product concentration was achieved. The system was therefore further improved by performing the reaction in organic solvent (n-heptane). Coupling the reaction system with membrane-assisted product removal resulted in a highly concentrated and relatively pure ( > 97%) product solution. Moreover, a product yield of 60% was reached, compared to 15% without product removal.

Keywords: amine donor, chiral amines, in situ product removal, transamination

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Authors: Fahd I. Alghunaimi, Hind S. Dossary, Norah W. Aljuryyed, Tawfik A. Saleh

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Produced water (PW) is one of the largest by-volume waste streams and one of the most challenging effluents in the oil and gas industry. This is due to the variation of contaminants that make up PW. Severalmaterialshavebeen developed, studied, and implemented to remove hydrocarbonsfrom PW. Adsorption is one of the most effective ways ofremoving oil fromPW. In this work, three new and cost-effective hydrophobic adsorbentmaterials based on 9-octadecenoic acid grafted graphene (POG) were synthesized for oil/water separation. Graphene derived from graphite was modified with 9-octadecenoic acid to yield 9-octadecenoic acid grafted graphene (OG). The newsynthesized materials which called POG25, POG50, and POG75 were characterized by using N₂-physisorption (BET) and Fourier transform infrared (FTIR). The BET surface area of POG75 was the highest with 288 m²/g, whereas POG50 was 225 m²/g and POG25 was lowest 79 m²/g. These three materials were also evaluated for their oil-water separation efficiency using a model mixture, whichdemonstrated that POG-75 has the highest oil removal efficiency and the faster rate of the adsorption (Figure-1). POG75 was regenerated, and its performance was verified again with a little reduced adsorption rate compared to the fresh material. The mixtures that used in the performance test were prepared by mixing nonpolar organic liquids such as heptane, dodecane, or hexadecane into the colored water. In general, the new materials showed fast uptake of the certain quantity of the oildue to the high hydrophobicity nature of the materials, which repel water as confirmed by the contact angle of approximately 150˚. Besides that, novel superhydrophobic material was also synthesized by introducing hydrophobic branches of laurate on the surface of the stainless steel mesh (SSM). This novel mesh could help to hold the novel adsorbent materials in a column to remove oil from PW. Both BOG-75 and the novel mesh have the potential to remove oil contaminants from produced water, which will help to provide an opportunity to recover useful components, in addition, to reduce the environmental impact and reuse produced water in several applications such as fracturing.

Keywords: graphite to graphene, oleophilic, produced water, separation

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Authors: Mónica P. Cala, Juan S. Carreño, Roland J.W. Meesters

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Recently, collection of biological fluids on special filter papers has become a popular micro-sampling technique. Especially, the dried blood spot (DBS) micro-sampling technique has gained much attention and is momently applied in various life sciences reserach areas. As a result of this popularity, DBS are not only intensively competing with the venous blood sampling method but are at this moment widely applied in numerous bioanalytical assays. In particular, in the screening of inherited metabolic diseases, pharmacokinetic modeling and in therapeutic drug monitoring. Recently, microsampling techniques were also introduced in “omics” areas, whereunder metabolomics. For a metabolic profiling study we applied micro-sampling of biological fluids (blood and plasma) from healthy controls and from women with breast cancer. From blood samples, dried blood and plasma samples were prepared by spotting 8uL sample onto pre-cutted 5-mm paper disks followed by drying of the disks for 100 minutes. Dried disks were then extracted by 100 uL of methanol. From liquid blood and plasma samples 40 uL were deproteinized with methanol followed by centrifugation and collection of supernatants. Supernatants and extracts were evaporated until dryness by nitrogen gas and residues derivated by O-methyxyamine and MSTFA. As internal standard C17:0-methylester in heptane (10 ppm) was used. Deconvolution and alignment of and full scan (m/z 50-500) MS data were done by AMDIS and SpectConnect (http://spectconnect.mit.edu) software, respectively. Statistical Data analysis was done by Principal Component Analysis (PCA) using R software. The results obtained from our preliminary study indicate that the use of dried blood/plasma on paper disks could be a powerful new tool in metabolic profiling. Many of the metabolites observed in plasma (liquid/dried) were also positively identified in whole blood samples (liquid/dried). Whole blood could be a potential substitute matrix for plasma in Metabolomic profiling studies as well also micro-sampling techniques for the collection of samples in clinical studies. It was concluded that the separation of the different sample methodologies (liquid vs. dried) as observed by PCA was due to different sample treatment protocols applied. More experiments need to be done to confirm obtained observations as well also a more rigorous validation .of these micro-sampling techniques is needed. The novelty of our approach can be found in the application of different biological fluid micro-sampling techniques for metabolic profiling.

Keywords: biofluids, breast cancer, metabolic profiling, micro-sampling

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Authors: Belcher Fulele, W. A. A. Ddamba

Abstract:

Study of solvent systems contributes to the understanding of intermolecular interactions that occur in binary mixtures. These interactions involves among others strong dipole-dipole interactions and weak van de Waals interactions which are of significant application in pharmaceuticals, solvent extractions, design of reactors and solvent handling and storage processes. Binary mixtures of solvents can thus be used as a model to interpret thermodynamic behavior that occur in a real solution mixture. Densities of pure DFM, n-alkanes (n-pentane, n-hexane, n-heptane and n-octane) and amides (N-methylformamide, N-ethylformamide, N,N-dimethylformamide and N,N-dimethylacetamide) as well as their [DFM + ((C5-C8) n-alkane or amide)] binary mixtures over the entire composition range, have been reported at temperature 293.15, 298.15 and 303.15 K and atmospheric pressure. These data has been used to derive the thermodynamic properties: the excess molar volume of solution, apparent molar volumes, excess partial molar volumes, limiting excess partial molar volumes, limiting partial molar volumes of each component of a binary mixture. The results are discussed in terms of possible intermolecular interactions and structural effects that occur in the binary mixtures. The variation of excess molar volume with DFM composition for the [DFM + (C5-C7) n-alkane] binary mixture exhibit a sigmoidal behavior while for the [DFM + n-octane] binary system, positive deviation of excess molar volume function was observed over the entire composition range. For each of the [DFM + (C5-C8) n-alkane] binary mixture, the excess molar volume exhibited a fall with increase in temperature. The excess molar volume for each of [DFM + (NMF or NEF or DMF or DMA)] binary system was negative over the entire DFM composition at each of the three temperatures investigated. The negative deviations in excess molar volume values follow the order: DMA > DMF > NEF > NMF. Increase in temperature has a greater effect on component self-association than it has on complex formation between molecules of components in [DFM + (NMF or NEF or DMF or DMA)] binary mixture which shifts complex formation equilibrium towards complex to give a drop in excess molar volume with increase in temperature. The Prigogine-Flory-Patterson model has been applied at 298.15 K and reveals that the free volume is the most important contributing term to the excess experimental molar volume data for [DFM + (n-pentane or n-octane)] binary system. For [DFM + (NMF or DMF or DMA)] binary mixture, the interactional term and characteristic pressure term contributions are the most important contributing terms in describing the sign of experimental excess molar volume. The mixture systems contributed to the understanding of interactions of polar solvents with proteins (amides) with non-polar solvents (alkanes) in biological systems.

Keywords: alkanes, amides, excess thermodynamic parameters, Prigogine-Flory-Patterson model

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Authors: Ece A. Irmak, Amdulla O. Mekhrabov, M. Vedat Akdeniz

Abstract:

There is a growing interest on the synthesis and characterization of nanoalloys since the unique chemical, and physical properties of nanoalloys can be tuned and, consequently, new structural motifs can be created by varying the type of constituent elements, atomic and magnetic ordering, as well as size and shape of the nanoparticles. Due to the fine size effects, magnetic nanoalloys have considerable attention with their enhanced mechanical, electrical, optical and magnetic behavior. As an important magnetic nanoalloy, the novel application area of Fe-Ni based nanoalloys is expected to be widened in the chemical, aerospace industry and magnetic biomedical applications. Noble metals have been using in biomedical applications for several years because of their surface plasmon properties. In this respect, iron-nickel nanoalloys are promising materials for magnetic biomedical applications because they show novel properties such as superparamagnetism and surface plasmon resonance property. Also, there is great attention for the usage Fe-Ni based nanoalloys as radar absorbing materials in aerospace and stealth industry due to having high Curie temperature, high permeability and high saturation magnetization with good thermal stability. In this study, FeNi₃ bimetallic nanoalloys were synthesized by mechanical alloying in a planetary high energy ball mill. In mechanical alloying, micron size powders are placed into the mill with milling media. The powders are repeatedly deformed, fractured and alloyed by high energy collision under the impact of balls until the desired composition and particle size is achieved. The experimental studies were carried out in two parts. Firstly, dry mechanical alloying with high energy dry planetary ball milling was applied to obtain FeNi₃ nanoparticles. Secondly, dry milling was followed by surfactant-assisted ball milling to observe the surfactant and solvent effect on the structure, size, and properties of the FeNi₃ nanoalloys. In the first part, the powder sample of iron-nickel was prepared according to the 1:3 iron to nickel ratio to produce FeNi₃ nanoparticles and the 1:10 powder to ball weight ratio. To avoid oxidation during milling, the vials had been filled with Ar inert gas before milling started. The powders were milled for 80 hours in total and the synthesis of the FeNi₃ intermetallic nanoparticles was succeeded by mechanical alloying in 40 hours. Also, regarding the particle size, it was found that the amount of nano-sized particles raised with increasing milling time. In the second part of the study, dry milling of the Fe and Ni powders with the same stoichiometric ratio was repeated. Then, to prevent agglomeration and to obtain smaller sized nanoparticles with superparamagnetic behavior, surfactants and solvent are added to the system, after 40-hour milling time, with the completion of the mechanical alloying. During surfactant-assisted ball milling, heptane was used as milling medium, and as surfactants, oleic acid and oleylamine were used in the high energy ball milling processes. The characterization of the alloyed particles in terms of microstructure, morphology, particle size, thermal and magnetic properties with respect to milling time was done by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, vibrating-sample magnetometer, and differential scanning calorimetry.

Keywords: iron-nickel systems, magnetic nanoalloys, mechanical alloying, nanoalloy characterization, surfactant-assisted ball milling

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Authors: Saif Al Ghafri, Thomas Hughes, Armand Karimi, Kumarini Seneviratne, Jordan Oakley, Michael Johns, Eric F. May

Abstract:

Knowledge of the thermophysical properties of complex mixtures at extreme conditions of pressure and temperature have always been essential to the Liquefied Natural Gas (LNG) industry’s evolution because of the tremendous technical challenges present at all stages in the supply chain from production to liquefaction to transport. Each stage is designed using predictions of the mixture’s properties, such as density, viscosity, surface tension, heat capacity and phase behaviour as a function of temperature, pressure, and composition. Unfortunately, currently available models lead to equipment over-designs of 15% or more. To achieve better designs that work more effectively and/or over a wider range of conditions, new fundamental property data are essential, both to resolve discrepancies in our current predictive capabilities and to extend them to the higher-pressure conditions characteristic of many new gas fields. Furthermore, innovative experimental techniques are required to measure different thermophysical properties at high pressures and over a wide range of temperatures, including near the mixture’s critical points where gas and liquid become indistinguishable and most existing predictive fluid property models used breakdown. In this work, we present a wide range of experimental measurements made for different binary and ternary mixtures relevant to LNG processing, with a particular focus on viscosity, surface tension, heat capacity, bubble-points and density. For this purpose, customized and specialized apparatus were designed and validated over the temperature range (200 to 423) K at pressures to 35 MPa. The mixtures studied were (CH4 + C3H8), (CH4 + C3H8 + CO2) and (CH4 + C3H8 + C7H16); in the last of these the heptane contents was up to 10 mol %. Viscosity was measured using a vibrating wire apparatus, while mixture densities were obtained by means of a high-pressure magnetic-suspension densimeter and an isochoric cell apparatus; the latter was also used to determine bubble-points. Surface tensions were measured using the capillary rise method in a visual cell, which also enabled the location of the mixture critical point to be determined from observations of critical opalescence. Mixture heat capacities were measured using a customised high-pressure differential scanning calorimeter (DSC). The combined standard relative uncertainties were less than 0.3% for density, 2% for viscosity, 3% for heat capacity and 3 % for surface tension. The extensive experimental data gathered in this work were compared with a variety of different advanced engineering models frequently used for predicting thermophysical properties of mixtures relevant to LNG processing. In many cases the discrepancies between the predictions of different engineering models for these mixtures was large, and the high quality data allowed erroneous but often widely-used models to be identified. The data enable the development of new or improved models, to be implemented in process simulation software, so that the fluid properties needed for equipment and process design can be predicted reliably. This in turn will enable reduced capital and operational expenditure by the LNG industry. The current work also aided the community of scientists working to advance theoretical descriptions of fluid properties by allowing to identify deficiencies in theoretical descriptions and calculations.

Keywords: LNG, thermophysical, viscosity, density, surface tension, heat capacity, bubble points, models

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