Investigation of an Alkanethiol Modified Au Electrode as Sensor for the Antioxidant Activity of Plant Compounds
Thiol molecules are known to easily form self-assembled monolayers (SAM) on Au surfaces. Depending on the thiol’s structure, surface modifications via SAM can be used for electrode sensor development. In the presented work, 1-decanethiol coated polycrystalline Au electrodes were applied to indirectly assess the radical scavenging potential of plant compounds and extracts. Different plant compounds with reported antioxidant properties as well as an extract from the plant Gynostemma pentaphyllum were tested for their effectiveness to prevent SAM degradation on the sensor electrodes via photolytically generated radicals in aqueous media. The SAM degradation was monitored over time by differential pulse voltammetry (DPV) measurements. The results were compared to established antioxidant assays. The obtained data showed an exposure time and concentration dependent degradation process of the SAM at the electrode’s surfaces. The tested substances differed in their capacity to prevent SAM degradation. Calculated radical scavenging activities of the tested plant compounds were different for different assays. The presented method poses a simple system for radical scavenging evaluation and, considering the importance of the test system in antioxidant activity evaluation, might be taken as a bridging tool between in-vivo and in-vitro antioxidant assay in order to obtain more biologically relevant results in antioxidant research.
Solvent Extraction, Spectrophotometric Determination of Antimony (III) from Synthetic and Real Samples, Using O-Methylphenyl Thiourea as Sensitive Reagent
A simple and selective method is developed for solvent extraction spectrophotometric determination of antimony(III) using O-Methylphenyl Thiourea (OMPT) as a sensitive chromogenic chelating agent. The basis of proposed method is formation of antimony(III)-OMPT complex was extracted with 0.0025 M OMPT in chloroform from aqueous solution of antimony(III) in 1.0 M perchloric acid. The absorbance of this complex was measured at 297 nm against reagent blank. Beer’s law was obeyed up to 15µg mL-1 of antimony(III). The Molar absorptivity and Sandell’s sensitivity of the antimony(III)-OMPT complex in chloroform are 16.6730 × 103 L mol-1 cm-1 and 0.00730282 µg cm-2 respectively. The stoichiometry of antimony(III)-OMPT complex was established from slope ratio method, mole ratio method and Job’s continuous variation method was 1:2. The complex was stable for more than 48 h. The interfering effect of various foreign ions was studied and suitable masking agents are used wherever necessary to enhance selectivity of the method. The proposed method is successfully applied for determination of antimony(III) from real samples alloy and synthetic mixtures. Repetition of the method was checked by finding relative standard deviation (RSD) for 10 determinations which was 0.42%.
Manufacturing Technical Ceramics for Extreme Conditions for Catalytic Substrates by Binder Jetting Additive Manufacturing
Applying binder jetting technologies analogous to conventional inkjet printing, inks with specific rheological properties can be used in additive manufacturing printers to control the catalytic micro- and nano-scale properties of technical ceramics used as catalyst substrates, such as alumina. Using the Ohnesorge number and its inverse, Z, the printability of an ink may be determined using overall density, viscosity, surface tension and the radius of the printer nozzle. Ink mixtures are primarily composed of a solvent, binder, dispersant, plasticizer, and, less commonly, a surfactant. In this presentation, the development of novel inks is described, including the use of new mixtures of high molecular weight polymers with rheological modifiers that provide electrosteric, electrostatic, and depletion stabilization within the ink mixtures to maintain a stable green body prior to post-print processing. The use of binder-jet additive manufacturing to create catalyst substrates allows us to produce unique geometries that otherwise could not be constructed because of the limitations of current ceramic manufacturing techniques. Highly endo- and exothermic reactions, such as steam methane reforming and ammonia production, could greatly benefit from these extremely customizable catalyst geometries through improved heat and mass transfer performance.
H2/He and H2O/He Separation Experiments with Zeolite Membranes for Nuclear Fusion Applications
In future nuclear fusion reactors, tritium self-sufficiency will be ensured by tritium (3H) production via reactions between the fusion neutrons and lithium. To favor tritium breeding, a neutron multiplier must also be used. Both tritium breeder and neutron multiplier will be placed in the so-called Breeding Blanket (BB). For the European Helium-Cooled Pebble Bed (HCPB) BB concept, the tritium production and neutron multiplication will be ensured by neutron bombardment of Li4SiO4 and Be pebbles, respectively. The produced tritium is extracted from the pebbles by purging them with large flows of He (~ 104 Nm3h-1), doped with small amounts of H2 (~ 0.1 vol%) to promote tritium extraction via isotopic exchange (producing HT). Due to the presence of oxygen in the pebbles, production of tritiated water is unavoidable. Therefore, the purging gas downstream of the BB will be composed by Q2/Q2O/He (Q = 1H, 2H, 3H), with Q2/Q2O down to ppm levels, which must be further processed for tritium recovery. A two-stage continuous approach, where zeolite membranes (ZMs) are followed by a catalytic membrane reactor (CMR), has been recently proposed to fulfil this task. The tritium recovery from Q2/Q2O/He is ensured by the CMR, that requires a reduction of the gas flow coming from the BB and a pre-concentration of Q2 and Q2O to be efficient. For this reason, and to keep this stage with reasonable dimensions, ZMs are required upfront to reduce as much as possible the He flows and concentrate the Q2/Q2O species. Therefore, experimental activities have been carried out at the Tritium Laboratory Karlsruhe (TLK) to test the separation performances of different zeolite membranes for H2/H2O/He. First experiments have been performed with binary mixtures of H2/He and H2O/He with commercial MFI-ZSM5 and NaA zeolite-type membranes. Only the MFI-ZSM5 demonstrated selectivity towards H2, with a separation factor around 1.5, and H2 permeances around 0.72 µmolm-2s-1Pa-1, rather independent for feed concentrations in the range 0.1 vol%-10 vol% H2/He. The experiments with H2O/He have demonstrated that the separation factor towards H2O is highly dependent on the feed concentration and temperature. For instance, at 0.2 vol% H2O/He the separation factor with NaA is below 2 and around 1000 at 5 vol% H2O/He, at 30°C. Overall, both membranes demonstrated complementary results at equivalent temperatures. In fact, at low feed concentrations ( ≤ 1 vol% H2O/He) MFI-ZSM5 separates better than NaA, whereas the latter has higher separation factors for higher inlet water content ( ≥ 5 vol% H2O/He). In this contribution, the results obtained with both MFI-ZSM5 and NaA membranes for H2/He and H2O/H2 mixtures at different concentrations and temperatures are compared and discussed.
Bio-Furan Based Poly (β-Thioether Ester) Synthesized via Thiol-Michael Addition Polymerization with Tunable Structure and Properties
A derivative of 5-hydroxymethylfurfural (HMF) was synthesized for the thiol-Michael addition reaction. The efficiency of the catalysts (base and nucleophiles) and side reactions during the thiol-Michael addition were investigated. Dimethylphenylphosphine efficiently initiated the thiol-Michael addition polymerization for synthesizing a series of bio-based furan polymers with different structure and properties. The benzene rings or hydroxyl groups present in the polymer chains increased the glass transition temperature (Tg) of poly (β-thioether ester). Additionally, copolymers with various compositions were obtained via adding different ratio of 1,6-hexanedithiols to 1,4-benzenedithiols. 1H NMR analysis revealed that experimental ratios of two dithiols monomers matched well with theoretical ratios. The occurrence of a reversible Diels-Alder reaction between furan rings and maleimide groups allowed poly (β-thioether ester) to be dynamically crosslinked. These polymers offer the potentials to produce materials from biomass that have both practical mechanical properties and reprocessing ability.
Experimental Device for Fluorescence Measurement by Optical Fiber Combined with Dielectrophoretic Sorting in Microfluidic Chips
We present a device that combines fluorescence spectroscopy with fiber optics and dielectrophoretic micromanipulation in PDMS (poly-(dimethylsiloxane)) microfluidic chips. The device allows high speed detection (in the order of kHz) of the fluorescence signal, which is coming from the sample by an inserted optical fiber, e.g. from a micro-droplet flow in a microfluidic chip, or even from the liquid flowing in the transparent capillary, etc. The device uses a laser diode at a wavelength suitable for excitation of fluorescence, excitation and emission filters, optics for focusing the laser radiation into the optical fiber, and a highly sensitive fast photodiode for detection of fluorescence. The device is combined with dielectrophoretic sorting on a chip for sorting of micro-droplets according to their fluorescence intensity. The electrodes are created by lift-off technology on a glass substrate, or by using channels filled with a soft metal alloy or an electrolyte. This device found its use in screening of enzymatic reactions and sorting of individual fluorescently labelled microorganisms. The authors acknowledge the support from the Grant Agency of the Czech Republic (GA16-07965S) and Ministry of Education, Youth and Sports of the Czech Republic (LO1212) together with the European Commission (ALISI No. CZ.1.05/2.1.00/01.0017).
An Alternative Nano Design Strategy by Neutralized AMPS and Soy Bean Lecithin to Form Nanoparticles
Paclitaxel is used in treatment of different cancer types mainly breast, ovarian, lung and Kaposi’s sarcoma. It is poorly soluble in water; therefore, currently used formulations tremendously show side-effects and high toxicity. Encapsulation of the drug in a nano drug carrier which causes both reducing side effects and increasing drug activity is a desired new approach for the nano-medicine to target the site of cancer. In this study, synthesis of a novel nano paclitaxel formulation made of a new amphiphilic monomer was followed by the investigation of its pharmacological properties. UV radical polymerization was carried out by using the monomer Lecithin-2-Acrylamido-2-methylpropane (L-AMPS) and the drug-spacer, to obtain sterically high stabilized, biocompatible and biodegradable phospholipid nanoparticles, in which the drug paclitaxel (Pxl) was encapsulated (NanoPxl). Particles showed high drug loading capacity (68%) and also hydrodynamic size less than 200 nm with slight negative surface charge. The drug release profile was obtained and in vitro cytotoxicity test was performed on MCF-7 cell line. Consequently, these data indicated that paclitaxel loaded Lecithin-AMPS/PCL-MAC nanoparticles can be considered as a new, safe and effective nanocarrier for the treatment of breast cancer.
Effects of Potential Chloride-Free Admixtures on Selected Mechanical Properties of Kenya Clay-Based Cement Mortars
The mechanical performance of hydrated cements pastes mainly depends on its compressive strength, setting time and soundness. These properties are crucial in the construction industry. Time, strength and soundness are key mechanical parameters considered during construction. Low 28 day compressive strength and long setting times are some of the major impediments to the production and diverse use of Pozzolana Based Cements despite numerous technological and environmental benefits associated with it. The study investigated the effects of potential chloride-free admixtures in calcined clay- Portland cement blends to achieve high early compressive strength and shorter setting times in a sound cement paste. The test cement was made by blending calcined clays with Ordinary Portland Cement (OPC) at replacement levels from 35 to 50 percent by mass of the OPC to make test cement labeled PCC for the purposes of this study. Mortar prisms were cast with and without activators. Solutions of Na2SO4, NaOH, Na2SiO3 and Na2CO3 containing 0.5M, 1.5M, 2M and 2.5M were separately added during casting as the admixtures. PCC samples were separately subjected to different curing temperatures at 20, 30 and 40 °C on for 24 hours then cured in water. Compressive strength was determined at 2, 7 and 28 days of casting. Both initial and final setting times, soundness of the cement as well as the standard consistency of all test cement categories was determined in the usual manner. For comparison purposes, commercial Portland Pozzolana cement (PPC) and Ordinary Portland Cement (OPC) were also investigated without activators under similar conditions. X-Ray Florescence (XRF), X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) were used for chemical and mineralogical analysis. Mercury Intrusion Porosimeter (MIP) and Scanning Electron Microscope (SEM) were used to study the microstructure of the hardened paste. The results indicated that addition of 0.5M, 1.5M, 2M and 2.5M significantly increased the 2nd and 7th day compressive strength but minimal increase on the 28th day strength. Thermal curing significantly increased the 2nd and 7th day compressive strength of PCC. However elevated curing temperatures lead to minimal improvement of 28th day compressive strength. Addition of the said activators significantly reduced both initial and final setting time. Water demand increased with increased amount of clay in the test cement. The expansion for the cement samples was below 10mm. Mineralogical tests indicate that N-A-S-H is formed in addition to C-S-H. The microstructure of the hardened cement paste reveal dense packing of secondary cementious gels when the activators are used. In conclusion, use of activators improves 28 day compressive strength by 20 percent for the clay content between 35 to 50 percent. All the activator solutions produced optimum compressive strength at 2M. Na2SO4 produced the highest increase in compressive strength while incorporation of NaOH leads to the shortest setting time.
Solvent Extraction and Spectrophotometric Determination of Palladium (II) Using P-Methylphenyl Thiourea as a Complexing Agent
A precise, sensitive, rapid and selective method for the solvent extraction, spectrophotometric determination of palladium (II) using para-methylphenyl thiourea (PMPT) as an extractant is developed. Palladium (II) forms yellow colored complex with PMPT which shows an absorption maximum at 300 nm. The colored complex obeys Beer’s law up to 90.0 µg/ml of palladium. The molar absorptivity and Sandells sensitivity were found to be 0.843 x 103 L mole-1cm-1 and 0.125μg mol-1 cm-2 respectively. The optimum conditions for the extraction and determination of palladium have been established by monitoring the various experimental parameters. The precision of the method has been evaluated and the relative standard deviation has been found to be less than 0.5%. The proposed method is free from interference from large number of foreign ions. The method has been successfully applied for the determination of palladium from alloy, synthetic mixtures corresponding to alloy samples.
Free Radical Scavenging Potency of Guava (Psidiumguajava) Fruit from District Khairpur Mir’S
The district Khairpur Mir’s, Pakistan was focus of our research and two stages (i.e. semi ripening and post ripening stages) of guava (Psidiumguajava) fruits were selected from each area on the basis of their variable genotype in terms of size, color and ripening stage. After the vigorous sample collection, physical parameters (weight, length, diameter, volume, density and moisture content of the fruit) were calculated and tabulated comprehensively and all the physical parameters were found to be least for semi ripening stage compared to post ripening stage. The pH values obtained for semi ripening stages were more acidic than post ripening stages which stated that pH increased from semi to post ripening stage of guava fruit. A total of six (06) extracts were made by using different solvents (water, methanol and water:methanol). The qualitative analysis were performed to examine different class of compounds i.e. anthroquinone, flavonoids, phenols, steriods and Tri-terpenoids presents. The free radical scavenging potency of all the extracts was determined by using DPPH and hydroxyl method using ascorbic acid as standard. In general the IC50 values calculated by DPPH assay were found to be less than that of hydroxyl method. It has been found that all the extracts had impressive antioxidant potency, but between them semi ripening stage of guava fruit revealed greater extent of potency to pair up free radicals by using DPPH assay and hydroxyl radical scavenging method.
Blending Effects on Crude Oil Stability: An Experimental Study
This study is a part of investigating the possibility of blending two crude oils obtained from Libyan oil fields, namely crude oil (A) and crude oil (B) with different ratios, prior to blending the crude oils have to be compatible in order to avoid phase out and precipitation of asphaltene from the bulk of crude. The physical properties of both crudes such as density, viscosity, pour point and sulphur content were measured according to (ASTM) method. To examine the stability of both crudes and their blends, the oil compatibility model using microscopic, colloidal instability index (CII) using SARA analysis and asphaltene stabilization test using Turbiscan tests were conducted in the Libyan Petroleum Institute laboratories.
Compatibility tests were carried out with both crude oils, the insolubility number (IN), and the solubility blending number (SBN), for both crude oils and their blends were calculated. The criteria for compatibility of any blend is that the volume average solubility blending number (SBN) is greater than the insolubility number (IN) of any component in the blend, the results indicated that both crudes were compatible.
To support the results of compatibility tests the SARA analysis was done for the fractional determination of (saturates, aromatics, resins and asphaltenes) content. From this result, the colloidal Instability index (CII) and resin to asphaltenes ratio (R/A) were calculated for crudes and their blends.
The results show that crude oil (B) which has higher (R/A) and lower (CII) is more stable than crude oil (A) and as the ratio of crude (B) increases in the blend the (CII) and (R/A) were improved, and the blends becomes more stable.
Asphaltene stabilization test was also conducted for the crudes and their blends using Turbiscan MA200 according to the standard test method ASTM D7061-04, the Turbiscan shows that the crude (B) is more stable than crude (A) which shows a fair tendency.
The (CII) and (R/A) were compared with the solubility number (SBN) for each crude and the blends along with Turbiscan results.
The solubility blending number (SBN) of the crudes and their blends show that the crudes are compatible, also by comparing (R/A) and (SBN) values of the blends, it can be seen that they are complements of each other. All the experimental results show that the blends of both crudes are more stability.
Removal of Vanadium from Effluents Using Tamarindous indica Seed Powder as a Natural Ion Exchanger
In the study, removal of Vanadium from aqueous solution using Tamarindous indica seeds powder has been investigated. The effect of pH, contact time, exchanger dose and temperature has been studied at ambient temperature (25°C +2°C). The equilibrium process has been described by the Langmuir isotherm model with adsorption capacity for vanadium. The Tamarindous indica seeds are subjected to different modification (Formaldehyde and sulphuric acid treatment). The adsorption capacity of Tamarindous indica seed powder for metal ion adsorption was obtained. The maximum exchange level attained was 99% at pH 3 with exchanger dose 2.0 g and contact time 60 min. Method is applied for removal of vanadium from industrial effluents.
Modified Graphene Oxide in Ceramic Composite
At present intensive scientific researches of ceramics, cermets and metal alloys have been conducted for improving materials physical-mechanical characteristics. In purpose of increasing impact strength of ceramics based on alumina, simple method of graphene homogenization was developed. Homogeneous distribution of graphene (homogenization) in pressing composite became possible through the connection of functional groups of graphene oxide (-OH, -COOH, -O-O- and others) and alumina superficial OH groups with aluminum organic compounds. These two components connect with each other with -O-Al–O- bonds, and by their thermal treatment (300–500°C), graphene and alumina phase are transformed. Thus, choosing of aluminum organic compounds for modification is stipulated by the following opinion: aluminum organic compounds fragments fixed on graphene and alumina finally are transformed into an integral part of the matrix. By using of other elements as modifier on the matrix surface (Al2O3) other phases are transformed, which change sharply physical-mechanical properties of ceramic composites, for this reason, effect caused by the inclusion of graphene will be unknown. Fixing graphene fragments on alumina surface by alumoorganic compounds result in new type graphene-alumina complex, in which these two components are connected by C-O-Al bonds. Part of carbon atoms in graphene oxide are in sp3 hybrid state, so functional groups (-OH, -COOH) are located on both sides of graphene oxide layer. Aluminum organic compound reacts with graphene oxide at the room temperature, and modified graphene oxide is obtained: R2Al-O-[graphene]–COOAlR2. Remaining Al–C bonds also reacts rapidly with surface OH groups of alumina. In a result of these process, pressing powdery composite [Al2O3]-O-Al-O-[graphene]–COO–Al–O–[Al2O3] is obtained. For the purpose, graphene oxide suspension in dry toluene have added alumoorganic compound Al(iC4H9)3 in toluene with equimolecular ratio. Obtained suspension has put in the flask and removed solution in a rotary evaporate presence nitrogen atmosphere. Obtained powdery have been researched and used to consolidation of ceramic materials based on alumina. Ceramic composites are obtained in high temperature vacuum furnace with different temperature and pressure conditions. Received ceramics do not have open pores and their density reaches 99.5 % of TD. During the work, the following devices have been used: High temperature vacuum furnace OXY-GON Industries Inc (USA), device of spark-plasma synthesis, induction furnace, Electronic Scanning Microscopes Nikon Eclipse LV 150, Optical Microscope NMM-800TRF, Planetary mill Pulverisette 7 premium line, Shimadzu Dynamic Ultra Micro Hardness Tester DUH-211S, Analysette 12 Dynasizer and others.
Effect of Liquid Additive on Dry Grinding for Desired Surface Structure of CaO Catalyst
Grinding method was used to control the active site and to improve the specific surface area (SSA) of calcium oxide (CaO) derived from scallop shell as a sustainable resource. The dry grinding of CaO with acetone and tertiary butanol as a liquid additive was carried out using a planetary ball mill with a laboratory scale. The experiments were operated by stepwise addition with time variations to determine the grinding limit. The active site of CaO was measured by X-Ray Diffraction and FT-IR. The SSA variations of products with grinding time were measured by BET method. The morphology structure of CaO was observed by SEM. The use of liquid additive was effective for increasing the SSA and controlling the active site of CaO. SSA of CaO was increased in proportion to the amount of the liquid additive and the grinding time. The performance of CaO as a solid base catalyst for biodiesel production was tested in the transesterification reaction of used cooking oil to produce fatty acid methyl ester (FAME).
Synthesis, Characterization and Antibacterial Properties of 3-Hydroxy-2-[3-(2/3/4-Methoxybenzoyl)Thioureido]Butyric Acid
A series of methoxybenzoylthiourea amino acid derivatives have been successfully synthesized and characterized via typical spectroscopic and analytical techniques namely FTIR, H and 13C NMR spectrometry and UV-Visible. The title compounds were obtained from the reactions between 2/3/4-methoxybenzoyl isothiocyanate with threonine. The FTIR spectra of the compounds indicated that six significant bands of interest namely (N-H), v(O-H), v(C=O-OH), v(C=O-NH), v(C=C) aromatic and v(C=S) and the values were observed within the range. The 1H NMR spectra for the compounds show the expected protons for OCH3 at the range δH 3.8-4.0 ppm, C=S-NH at δH 11.1-11.5 ppm and C=O-NH at 10.0-11.5 ppm. While, the 13C NMR spectra show resonances of OCH3, C=O-NH, C=O-OH and C=S at δC 55.0-57.0 ppm, 165.0-168.0 ppm, 170.0-171.0 ppm and 180.0-182.0 ppm, respectively. UV-Vis spectra showed two absorption bands and both were assigned to the n-π* and π-π* transitions. Mass spectra for all of the compounds showed the presence of molecular ion [M]+ peaks at m/z 312, which are in agreement to the calculated molecular weight. The antibacterial activities for all of the compounds were screened against Staphylococcus aureus, Staphylococcus epidermidis, Salmonella typhimurium and Eschericia coli. However, no activity was observed.
Spectrophotometric Determination of Photohydroxylated Products of Humic Acid in the Presence of Salicylate Probe
Humic substances produce reactive oxygene species such as hydroxyl, phenoxy and superoxide radicals by oxidizing in a wide pH and reduction potential range. Hydroxyl radicals, produced by reducing agents such as antioxidants and/or peroxides, attack on salicylate probe, and form 2,3-dihydroxybenzoate, 2,4-dihydroxybenzoate and 2,5-dihydroxybenzoate species. These species are quantitatively determined by using HPLC Method. Humic substances undergo photodegradation by UV radiation. As a result of their antioxidant properties, they produce hydroxyl radicals. In the presence of salicylate probe, these hydroxyl radicals react with salicylate molecules to form hydroxylated products (dihidroxybenzoate isomers). In this study, humic acid was photodegraded in a photoreactor at 254 nm (400W), formed hydroxyl radicals were caught by salicylate probe. The total concentration of hydroxylated salicylate species was measured by using spectrophotometric CUPRAC Method. And also, using results of time dependent experiments, kinetic of photohydroxylation was determined at different pHs. This method has been applied for the first time to measure the concentration of hydroxylated products. It allows to achieve the results easier than HPLC Method.
Comparison of the Distillation Curve Obtained Experimentally with the Curve Extrapolated by a Commercial Simulator
True Boiling Point distillation is one of the most common experimental techniques for the determination of petroleum properties. This curve provides information about the performance of a petroleum in terms of its cuts. The experiment is performed in a few days. Others techniques are used to determine the properties faster, with software that calculate the distillation curve when they are known a few information about crude oil. In order to evaluate the accuracy of distillation curve prediction, eight points of the TBP curve and specific gravity curve (348 K and 523 K) were inserted in the Hysys Oil Manager and the extended curve was evaluated up to 748 K. The methods were able to predict the curve with accuracy of 0.6 % - 9.2% error (Software X ASTM), 0.2% - 5.1% error (Software X Spaltrohr).
CO2 Utilization by Reverse Water-Shift and Fischer-Tropsch Synthesis for Production of Heavier Fraction Hydrocarbons in a Container-Sized Mobile Unit
Carbon capture and utilization (CCU) are one of the key topics in mitigation of CO2 emissions. There are many different technologies that are applied for the production of diverse chemicals from CO2 such as synthetic natural gas, Fischer-Tropsch products, methanol and polymers. Power-to-Gas and Power-to-Liquids concepts arise as a synergetic solution for storing energy and producing value added products from the intermittent renewable energy sources and CCU. VTT is a research and technology development company having energy in transition as one of the key focus areas. VTT has extensive experience in piloting and upscaling of new energy and chemical processes. Recently, VTT has developed and commissioned a Mobile Synthesis Unit (MOBSU) in close collaboration with INERATEC, a spin-off company of Karlsruhe Institute of Technology (KIT, Germany). The MOBSU is a multipurpose synthesis unit for CO2 upgrading to energy carriers and chemicals, which can be transported on-site where CO2 emission and renewable energy are available. The MOBSU is initially used for production of fuel compounds and chemical intermediates by combination of two consecutive processes: reverse Water-Gas Shift (rWGS) and Fischer-Tropsch synthesis (FT). First, CO2 is converted to CO by high-pressure rWGS and then, the CO and H2 rich effluent is used as feed for FT using an intensified reactor technology developed and designed by INERATEC. Chemical equilibrium of rWGS reaction is not affected by pressure. Nevertheless, compression would be required in between rWGS and FT in the case when rWGS is operated at atmospheric pressure. This would also require cooling of rWGS effluent, water removal and reheating. For that reason, rWGS is operated using precious metal catalyst in the MOBSU at similar pressure as FT to simplify the process. However, operating rWGS at high pressures has also some disadvantages such as methane and carbon formation, and more demanding specifications for materials. The main parts of FT module are an intensified reactor, a hot trap to condense the FT wax products, and a cold trap to condense the FT liquid products. The FT synthesis is performed using cobalt catalyst in a novel compact reactor technology with integrated highly-efficient water evaporation cooling cycle. The MOBSU started operation in November 2016. First, the FT module is tested using as feedstock H2 and CO. Subsequently, rWGS and FT modules are operated together using CO2 and H2 as feedstock of ca. 5 Nm3/hr total flowrate. On spring 2017, The MOBSU unit will be integrated together with a direct air capture (DAC) of CO2 unit, and a PEM electrolyser unit at Lappeenranta University of Technology (LUT) premises for demonstration of the SoletAir concept. This would be the first time when synthetic fuels are produced by combination of DAC unit and electrolyser unit which uses solar power for H2 production.
Optimization of Doping Process Parameters of Cerium Vanadate Doped with Be, Mg, Ca, Sr, and Ba Ions
In this research, Taguchi method was applied to determine optimum parameters of doping process of cerium vanadate with Be, Mg, Ca, Sr, and Ba ions. Percentage and type of doping ions are used as parameters in optimization process applied as orthogonal array to decrease the number of experiments. The calculated unit cell volume by Rietveld Refinement analysis via X-ray diffraction data (XRD) were used to confirm the formation of doped cerium vanadates. ANOVA method was applied to determine the effectiveness of the parameters.
Coarse-Grained Computational Fluid Dynamics-Discrete Element Method Modelling of the Multiphase Flow in Hydrocyclones
Hydrocyclones are widely used to classify particles by size in industries such as mineral processing and chemical processing. The particles to be handled usually have a broad range of size distributions and sometimes density distributions, which has to be properly considered, causing challenges in the modelling of hydrocyclone. The combined approach of Computational Fluid Dynamics (CFD) and Discrete Element Method (DEM) offers convenience to model particle size/density distribution. However, its direct application to hydrocyclones is computationally prohibitive because there are billions of particles involved. In this work, a CFD-DEM model with the concept of the coarse-grained (CG) model is developed to model the solid-fluid flow in a hydrocyclone. The DEM is used to model the motion of discrete particles by applying Newton’s laws of motion. Here, a particle assembly containing a certain number of particles with same properties is treated as one CG particle. The CFD is used to model the liquid flow by numerically solving the local-averaged Navier-Stokes equations facilitated with the Volume of Fluid (VOF) model to capture air-core. The results are analyzed in terms of fluid and solid flow structures, and particle-fluid, particle-particle and particle-wall interaction forces. Furthermore, the calculated separation performance is compared with the measurements. The results obtained from the present study indicate that this approach can offer an alternative way to examine the flow and performance of hydrocyclones
Development of Hydrophobic Coatings on Aluminum Alloy 7075
High performance requirement of aircrafts and marines industry demands to cater major industrial problems like wetting, high-speed efficiency, and corrosion resistance. These problems can be resolved by producing the hydrophobic surfaces on the metal substrate. By anodization process, the surface of AA 7075 has been modified and achieved a rough surface with a porous aluminum oxide (Al2O3) structure at nano-level. This surface modification process reduces the surface contact energy and increases the liquid contact angle which ultimately enhances the anti-icing properties. Later the Silane and Polyurethane (PU) coatings on the anodized surface have produced a contact angle of 130°. The results showed a good water repellency and self-cleaning properties. Using SEM analysis, micrographs revealed the round nano-porous oxide structure on the substrate. Therefore this technique can help in increasing the speed efficiency by reducing the friction with the outer interaction and can also be declared as a green technique since it is user-friendly.
Functionalization of Polypropylene with Chiral Monomer for Improving Hemocompatibility
Polypropylene (PP) is one of the most commonly used plastics because of its low density, outstanding mechanical properties, and low cost. However, its drawbacks such as low surface energy, poor dyeability, lack of chemical functionalities, and poor compatibility with polar polymers and inorganic materials, have restricted the application of PP. To expand its application in biomedical materials, functionalization is considered to be the most effective way. In this study, PP was functionalized with a chiral monomer, (S)-1-acryloylpyrrolidine-2-carboxylic acid ((S)-APCA), by free-radical grafting in the solid phase. The grafting degree of PP-g-APCA was determined by chemical titration method, and the chemical structure of functionalized PP was characterized by FTIR spectroscopy, which confirmed that the chiral monomer (S)-APCA was successfully grafted onto PP. Static water contact angle results suggested that the surface hydrophilicity of PP was significantly improved by solid phase grafting and assistance of surface water treatment. Protein adsorption and platelet adhesion results showed that hemocompatibility of PP was greatly improved by grafting the chiral monomer.
Study on the Carboxymethylation of Glucomannan from Porang
Chemical modification process on glucomannan from porang via carboxymethylation have been conducted. The process was done in two stages, the alkalization, and the carboxymethylation. The alkalization was done by adding NaOH solution into the medium which was contained glucomannan and then stirred it in ambient temperature for thirty minutes. The carboxymethylation process was done by adding sodium mono chloroacetate solution into the alkalization product. The carboxymethylation process was conducted for a certain time, and the product was then analyzed for determining the degree of substitution. In this research, the influence of medium to the degree of substitution was studied. Three different medium were used, namely water, 70% ethanol, and 90% ethanol. The results show that 70% ethanol was a better medium than two others because give a higher degree of substitution. Using 70% ethanol as a medium, the experiments for studying the influence of temperature on the carboxymethylation stages were conducted. The results show that the degree of substitution at 65°C is higher than at 45°C.
Improved Mechanical Properties and Osteogenesis in Electrospun Poly L-Lactic Ultrafine Nanofiber Scaffolds Incorporated with Graphene Oxide
Recently, the applications of graphene oxide in fabricating scaffolds for bone tissue engineering have been received extensive concern. In this work, poly l-lactic/graphene oxide composite nanofibers were successfully fabricated by electrospinning. The morphology structure, porosity and mechanical properties of the composite nanofibers were characterized using different techniques. And mouse mesenchymal stem cells were cultured on the composite nanofiber scaffolds to assess their suitability for bone tissue engineering. The results indicated that the composite nanofiber scaffolds had finer fiber diameter and higher porosity as compared with pure poly l-lactic nanofibers. Furthermore, incorporation of graphene oxide into the poly l-lactic nanofibers increased protein adsorptivity, boosted the Young’s modulus and tensile strength by nearly 4.2-fold and 3.5-fold, respectively, and significantly enhanced adhesion, proliferation, and osteogenesis in mouse mesenchymal stem cells. The results indicate that composite nanofibers could be excellent and versatile scaffolds for bone tissue engineering.
Virus Adsorption by Using Photo-Crosslinked PVA Based Electrospun Nanofiber Membranes
The aim of the study is to reveal the capability of virus adsorption of electrospun nanofiber membranes (ENMs) fabricated by in situ photo-crosslinking-electrospinning technique. Poly(vinyl alcohol) (PVA) and polyethyleneimine (PEI) were modified with glycidyl methacrylate (GMA), enabling the polymer to cross-link upon UV exposure during the electrospinning process. An optimized composition prepared from m-PVA and m-PEI polymer solutions was successfully electrospun and obtained ENMs with 0.48 µm of the mean flow pore size and 90 nm of the minimum nanofiber diameter. The membrane resistance of ENMs was found 5.18×109 (1/m) which is suitable for water filtration applications when compared with commercial microfiltration membranes (e.g., 1.90×1010 (1/m) of PCTE). The water stable ENMs showed 98 % retention of MS2 over the microfiltration. Moreover, adsorption studies showed that Freundlich isotherm model fitted better and the maximum adsorption capacity (Qmax) was found 3.71 E+6 pfu/mg.
Theoretical and Experimental Investigations of
Binary Systems for Hydrogen Storage
Hydrogen is a promising energy carrier, compatible with the sustainable energy concept. In this context, solid-state hydrogen-storage is the key challenge in developing hydrogen economy. The capability of absorption of large quantities of hydrogen makes intermetallic systems of particular interest. In this study, efforts have been devoted to the theoretical investigation of binary systems with constraints consideration. On the one hand, besides considering hydrogen-storage, a reinvestigation of crystal structures of the palladium-arsenic system shows, with experimental validations, that binary systems could still currently present new or unknown relevant structures. On the other hand, various binary Mg-based systems were theoretically scrutinized in order to find new interesting alloys for hydrogen storage. Taking the effect of pressure into account reveals a wide range of alternative structures, changing radically the stable compounds of studied binary systems. Similar constraints, induced by Pulsed Laser Deposition, have been applied to binary systems, and results are presented.
Economic Assessment of CO2-Based Methane, Methanol and Polyoxymethylene Production
Carbon dioxide (CO2) utilization might be a promising way to substitute fossil raw materials like coal, oil or natural gas as carbon source of chemical production. While first life cycle assessments indicate a positive environmental performance of CO2-based process routes, a commercialization of CO2 is limited by several economic obstacles up to now. We, therefore, analyzed the economic performance of the three CO2-based chemicals methane and methanol as basic chemicals and polyoxymethylene as polymer on a cradle-to-gate basis. Our approach is oriented towards life cycle costing. The focus lies on the cost drivers of CO2-based technologies and options to stimulate a CO2-based economy by changing regulative factors. In this way, we analyze various modes of operation and give an outlook for the potentially cost-effective development in the next decades. Biogas, waste gases of a cement plant, and flue gases of a waste incineration plant are considered as CO2-sources. The energy needed to convert CO2 into hydrocarbons via electrolysis is assumed to be supplied by wind power, which is increasingly available in Germany. Economic data originates from both industrial processes and process simulations. The results indicate that CO2-based production technologies are not competitive with conventional production methods under present conditions. This is mainly due to high electricity generation costs and regulative factors like the German Renewable Energy Act (EEG). While the decrease in production costs of CO2-based chemicals might be limited in the next decades, a modification of relevant regulative factors could potentially promote an earlier commercialization.
Assessment of Korea's Natural Gas Portfolio Considering Panama Canal Expansion
South Korea cannot import natural gas in any form other than LNG because of the division of South and North Korea. Further, the high proportion of natural gas in the national energy mix makes this resource crucial for energy security in Korea. Expansion of Panama Canal will allow for reducing the cost of shipping between the Far East and U.S East. Panama Canal expansion can have significant impacts on South Korea. Due to this situation, we review the natural gas optimal portfolio by considering the uniqueness of the Korean Natural gas market and expansion of Panama Canal.
In order to assess Korea’s natural gas optimal portfolio, we developed natural gas portfolio model. The model comprises two steps. First, to obtain the optimal long-term spot contract ratio, the study examines the price level and the correlation between spot and long-term contracts by using the Markowitz, portfolio model. The optimal long-term spot contract ratio follows the efficient frontier of the cost/risk level related to this price level and degree of correlation. Second, by applying the obtained long-term contract purchase ratio as the constraint in the linear programming portfolio model, we determined the natural gas optimal import portfolio that minimizes total intangible and tangible costs.
Using this model, we derived the optimal natural gas portfolio considering the expansion of Panama Canal. Based on these results, we assess the portfolio for natural gas import to Korea from the perspective of energy security and present some relevant policy proposals.
Technology Valuation of Unconventional Gas R&D Project Using Real Option Approach
The adoption of information and communication technologies (ICT) in all industry is growing under industry 4.0. Many oil companies also are increasingly adopting ICT to improve the efficiency of existing operations, take more accurate and quicker decision making and reduce entire cost by optimization. It is true that ICT is playing an important role in the process of unconventional oil and gas development and companies must take advantage of ICT to gain competitive advantage. In this study, real option approach has been applied to Unconventional gas R&D project to evaluate ICT of them. Many unconventional gas reserves such as shale gas and coal-bed methane(CBM) has developed due to technological improvement and high energy price. There are many uncertainties in unconventional development on the three stage(Exploration, Development, Production). The traditional quantitative benefits-cost method, such as net present value(NPV) is not sufficient for capturing ICT value. We attempted to evaluate the ICT valuation by applying the compound option model; the model is applied to real CBM project case, showing how it consider uncertainties. Variables are treated as uncertain and a Monte Carlo simulation is performed to consider variables effect.
Acknowledgement—This work was supported by the Energy Efficiency & Resources Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20152510101880) and by the National Research Foundation of Korea Grant funded by the Korean Government (NRF-205S1A3A2046684).
The Growth Role of Natural Gas Consumption for Developing Countries
Carbon emissions have emerged as global concerns. Intergovernmental Panel of Climate Change (IPCC) have published reports about Green House Gases (GHGs) emissions regularly. United Nations Framework Convention on Climate Change (UNFCCC) have held a conference yearly since 1995. Especially, COP21 held at December 2015 made the Paris agreement which have strong binding force differently from former COP. The Paris agreement was ratified as of 4 November 2016, they finally have legal binding. Participating countries set up their own Intended Nationally Determined Contributions (INDC), and will try to achieve this. Thus, carbon emissions must be reduced. The energy sector is one of most responsible for carbon emissions and fossil fuels particularly are. Thus, this paper attempted to examine the relationship between natural gas consumption and economic growth. To achieve this, we adopted the Cobb-Douglas production function that consists of natural gas consumption, economic growth, capital, and labor using dependent panel analysis. Data were preprocessed with Principal Component Analysis (PCA) to remove cross-sectional dependency which can disturb the panel results. After confirming the existence of time-trended component of each variable, we moved to cointegration test considering cross-sectional dependency and structural breaks to describe more realistic behavior of volatile international indicators. The cointegration test result indicates that there is long-run equilibrium relationship between selected variables. Long-run cointegrating vector and Granger causality test results show that while natural gas consumption can contribute economic growth in the short-run, adversely affect in the long-run. From these results, we made following policy implications. Since natural gas has positive economic effect in only short-run, the policy makers in developing countries must consider the gradual switching of major energy source, from natural gas to sustainable energy source. Second, the technology transfer and financing business suggested by COP must be accelerated. Acknowledgement—This work was supported by the Energy Efficiency & Resources Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20152510101880) and by the National Research Foundation of Korea Grant funded by the Korean Government (NRF-205S1A3A2046684).