Korean Journal of Chemical Engineering (v.29, #12)

Upgrading of biofuel by the catalytic deoxygenation of biomass by Chang Hyun Ko; Sung Hoon Park; Jong-Ki Jeon; Dong Jin Suh; Kwang-Eun Jeong; Young-Kwon Park (1657-1665).
Biomass can be used to produce biofuels, such as bio-oil and bio-diesel, by a range of methods. Biofuels, however, have a high oxygen content, which deteriorates the biofuel quality. Therefore, the upgrading of biofuels via catalytic deoxygenation is necessary. This paper reviews the recent advances of the catalytic deoxygenation of biomass. Catalytic cracking of bio-oil is a promising method to enhance the quality of bio-oil. Microporous zeolites, mesoporous zeolites and metal oxide catalysts have been investigated for the catalytic cracking of biomass. On the other hand, it is important to develop methods to reduce catalyst coking and enhance the lifetime of the catalyst. In addition, an examination of the effects of the process parameters is very important for optimizing the composition of the product. The catalytic upgrading of triglycerides to hydrocarbon-based fuels is carried out in two ways. Hydrodeoxygenation (HDO) was introduced to remove oxygen atoms from the triglycerides in the form of H2O by hydrogenation. HDO produced hydrogenated biodiesel because the catalysts and process were based mainly on well-established technology, hydrodesulfurization. Many refineries and companies have attempted to develop and commercialize the HDO process. On the other hand, the consumption of huge amounts of hydrogen is a major problem hindering the wide-spread use of HDO process. To solve the hydrogen problem, deoxygenation with the minimum use of hydrogen was recently proposed. Precious metal-based catalysts showed reasonable activity for the deoxygenation of reagent-grade fatty acids with a batch-mode reaction. On the other hand, the continuous production of hydrocarbon in a fixed-bed showed that the initial catalytic activity decreases gradually due to coke deposition. The catalytic activity for deoxygenation needs to be maintained to achieve the widespread production of hydrocarbon-based fuels with a biological origin.
Keywords: Bio-oil; Biodiesel; Catalytic Cracking; Triglyceride; Hydrodeoxygenation

Use of biologically designed gold nanowire for biosensor application by Sung-Hee Shin; Gha-Young Kim; Joonmok Shim; Jungok Kim; Hor-Gil Hur; Don-Jung Lee; Jong-In Song; Seung-Hyeon Moon (1666-1669).
A highly sensitive tyrosinase (TYR)-based amperometric biosensor is prepared using biologically designed gold nanowires (AuNWs) for pesticide detection. The AuNWs were synthesized by dodecapeptide Midas-11 and were modified with the formation of self-assembled monolayer (SAM), followed by covalent binding with TYR. The prepared TYR-AuNWs-SPCE (screen printed carbon electrode) was compared with bare, AuNWs-, modified-AuNWs-SPCE by the measurement of cyclic voltammetry. The quantitative relationship between the inhibition percentage and the pesticide concentration at the TYR-AuNWs-SPCE was obtained by measuring the current response in various concentrations of pesticides. The reasonable detection range of parathion was determined to be 0.1 ppt through 10 ppb (R 2 =0.990) with 0.087 ppt of detection limits. The higher sensitivity and wider detection range of the TYR-based biosensor was achieved by the use of biologically synthesized AuNWs.
Keywords: Tyrosinase; Gold Nanowire; Peptide; Amperometric Biosensor; Pesticide

This work presents a theoretical prediction of the cage occupancy of CH4 in small cages and the heat of dissociation for THF-CH4 hydrate using the predictive Soave-Redlich-Kwong group contribution method combined with the UNIFAC model. The predicted cage occupancy of CH4 gradually increases with increasing pressure, indicating that the CH4 molecules could readily be encaged in the small 512 cages of the sII hydrate framework stabilized by THF molecules. The molar enthalpy of encagement of CH4 in the small 512 cages of the sII clathrate hydrate is estimated to be 26.7±1.7 kJ mol−1.
Keywords: Gas Hydrate; Guest; Cage Occupation; Heat of Dissociation; Methane; Tetrahydrofuran

The volatile organic compounds (VOCs) contained in coconut shell are wasted in the carbonization process of coconut shell due to the difficulty of recovery. The VOCs recovery is useful and necessary, because the VOCs are a sustainable energy source, and the recovery is an economically feasible project. A simulation model of the VOC recovery process from coconut shell using a rotary kiln is developed to investigate the process characteristics and the role of model parameters. The model includes the energy and material balances for the processing solid and the gas in the kiln. The validity of the proposed model is partially examined with the experimental results. From the simulation, the dominant heat transfer mechanism is determined for the understanding of the process operation. In addition, the optimal operating conditions of the rotary kiln are found for the use in the design and control of the kiln.
Keywords: Process Model; VOC Recovery; Rotary Kiln; Heat Transfer

The existing internally heat-integrated distillation column with the problem of utilizing a compressor is modified to propose a new heat-integrated distillation column without the compressor. Two identical columns of a conventional binary distillation are implemented to the heat integration. The energy used in the reboiler is recovered by the internal heat integration between the stripping section of one of the columns at lower pressure and the rectifying section of the other higher pressure column. The heat integration is similar to double-effect distillation, but internal heat integration requires less pressure elevation. The performance of energy saving and thermal efficiency improvement of the proposed system is evaluated with the two examples of the benzene-toluene and methanol-ethanol processes. The performance comparison indicates that the proposed system requires 17.4% less of reboiler duty for the benzene-toluene process and 15.8% less of heating duty for the methanol-ethanol process. The thermal efficiencies are 16.3% and 23.8% for the benzene-toluene and methanol-ethanol processes, respectively. Elimination of the compressor makes the column operation easy and the separate reboilers and condensers for the two columns in the proposed system provide flexible control, when the controllability of the proposed system is compared with that of the existing internally heat-integrated distillation column.
Keywords: Heat-integrated Distillation; Energy-efficient Distillation; Internal Heat Integration; Double-effect Distillation

The onset of viscous fingering in a radial Hele-Shaw cell was analyzed by using linear theory. In the selfsimilar domain, the stability equations were derived under the normal mode analysis. The resulting stability equations were solved analytically by expanding the disturbances as a series of orthogonal functions and also numerically by employing the shooting method. It was found that the long wave mode of disturbances has a negative growth rate and the related system is always stable. For the limiting case of the infinite Péclet number, Pe→∞, the analytically obtained critical conditions are R c =11.10/ $sqrt {Pe} $ and n c =0.87 $sqrt {Pe} $ . For Pe≥100, these stability conditions explain the system quite well.
Keywords: Viscous Fingering; Radial Flow; Hele-Shaw Cell; Spectral Analysis; Numerical Shooting Method

Effect of acid type in WO X clusters on the esterification of ethanol with acetic acid by Jae Ryul Park; Byoung Kyu Kwak; Dae Sung Park; Tae Yong Kim; Yang Sik Yun; Jongheop Yi (1695-1699).
Tungsten oxide clusters supported on silica (WO X /SiO2) with different W loading levels and the effect of acid type on the esterification of acetic acid with ethanol were examined. The catalysts were characterized using various techniques (XRD, Raman spectroscopy, NH3-TPD and FT-IR) to investigate the crystallinity and the nature of the acid sites. The change in the composition of two tungsten oxide species (polytungstate and crystalline WO3) leads to the change of Lewis acid to Brønsted acid ratio. Importantly, the ratio of the two different acid types has a substantial effect on the catalytic activity. The fraction of Lewis acid to total acid sites rapidly changed from 23% to 77% due to the presence of crystalline WO3. Where the Lewis acid sites accounted for 55% of the total acid sites, the WO X /SiO2 catalyst showed the highest catalytic activity among the prepared catalysts.
Keywords: Esterification; Tungsten Oxide; WO X /SiO2 ; Ethyl Acetate

A non-petroleum approach for the catalytic synthesis of methyl acrylate via methoxycarbonylation of acetylene with carbon monoxide and methanol as nucleophilic reagent has been studied under various conditions. Pd(OAc)2/2-PyPPh2/p-tsa was found to be a highly efficient catalytic system. The types of phosphorus ligands and their concentration was a determinative factor for catalytic activity. Mono-dentate phosphorus ligand such as triphenylphosphine has no activity while 2-(diphenylphosphino)pyridine with a mixed N-P bidentate structure has an excellent activity. Catalytic performance of acids depends on their acidic strength and coordinative property. Among all acidic promoters, p-toluenesulfonic acid displayed an excellent performance. Other parameters such as solvent polarity and initial pressure of carbon monoxide have also important influences on the hydroesterification of acetylene. It is beneficial for the reaction that the solvents have a high polarity. At low pressure of carbon monoxide, to high active palladium catalyst, the reaction easily proceeded. However, at high pressure of carbon monoxide, acetylene will transfer from solution to gas phase, resulting in lower conversion of acetylene. In addition, due to steric hindrance of alcohols, methanol has a highest activity in hydroesterification of acetylene in low carbon alcohols. Under the optimal reaction conditions, 99.5% of acetylene conversion and 99.7% of selectivity toward methyl acrylate as well as 2,502 h−1 TOF were achieved.
Keywords: Palladium Acetate; N-P Ligands; Methoxycarbonylation; Methyl Aacrylate; Acetylene

A reactor has been developed to produce high quality fatty acid methyl esters (FAME) from waste cooking palm oil (WCO). Continuous transesterification of free fatty acids (FFA) from acidified oil with methanol was carried out using a calcium oxide supported on activated carbon (CaO/AC) as a heterogeneous solid-base catalyst. CaO/AC was prepared according to the conventional incipient-wetness impregnation of aqueous solutions of calcium nitrate (Ca(NO3)2·4H2O) precursors on an activated carbon support from palm shell in a fixed bed reactor with an external diameter of 60 mm and a height of 345 mm. Methanol/oil molar ratio, feed flow rate, catalyst bed height and reaction temperature were evaluated to obtain optimum reaction conditions. The results showed that the FFA conversion increased with increases in alcohol/oil molar ratio, catalyst bed height and temperature, whereas decreased with flow rate and initial water content in feedstock increase. The yield of FAME achieved 94% at the reaction temperature 60 °C, methanol/oil molar ratio of 25: 1 and residence time of 8 h. The physical and chemical properties of the produced methyl ester were determined and compared with the standard specifications. The characteristics of the product under the optimum condition were within the ASTM standard. High quality waste cooking palm oil methyl ester was produced by combination of heterogeneous alkali transesterification and separation processes in a fixed bed reactor. In sum, activated carbon shows potential for transesterification of FFA.
Keywords: Biodiesel; Waste Cooking Palm Oil; Heterogeneous Catalysis; Fixed Bed Reactor

Rheology and fuel properties of slurries of char and bio-oil derived from slow pyrolysis of cassava pulp residue and palm shell by Chaiyot Tangsathitkulchai; Piyarat Weerachanchai; Malee Tangsathitkulchai (1713-1721).
Three bio-oil samples, namely, raw bio-oil from pyrolysis of cassava pulp residue (CPR), separated oil phase and aqueous phase of bio-oil from pyrolysis of palm shell (PS), were used as suspending media for preparing slurries of bio-oil and the co-product char. Rheologies of all tested slurries exhibited pseudoplasticity with yield stress and the degree of this non-Newtonian behavior depended on such parameters as slurry type, solid concentration, particle size and slurry temperature. Overall, char/bio-oil slurries gave better fuel properties including higher pH and reasonably high calorific value (18–32 MJ/kg) as compared to their bio-oil properties. Combustion of char/bio-oil slurries occurred in the temperature range similar to their solid char combustion and without ignition delay.
Keywords: Bio-oil; Biomass; Char; Slurry Rheology; Pyrolysis

Photocatalytic degradation of azo dye using TiO2 supported on spherical activated carbon by Ji-Won Yoon; Mi-Hwa Baek; Ji-Sook Hong; Chang-Yong Lee; Jeong-Kwon Suh (1722-1729).
TiO2 supported on spherical activated carbon (TiO2/SAC) was prepared through an ion-exchange method followed by a heat-treatment process. The adsorption characteristic of TiO2/SAC was evaluated using azo dye methyl orange (MO) as a target substance, and the photocatalytic degradation of MO under UV irradiation was also discussed. A synergistic effect of both the adsorption capacity of activated carbon and the photoactivity of TiO2 on the removal of MO from aqueous solution was observed. Experimental results revealed that the photocatalytic degradation of MO improved with increasing photocatalyst dosage and followed a pseudo-first order kinetic. After five-cycle runs, TiO2/SAC still exhibited relatively high photocatalytic characteristic for the degradation of MO. Besides, the prepared TiO2/SAC can be helpful in the easy separation of photocatalyst from solution after photocatalysis of MO. Furthermore, the use of liquid chromatography/mass spectrometry (LC/MS) technique, identified three intermediates as degradation products during the photocatalytic reaction of MO with TiO2/SAC.
Keywords: Titanium Dioxide; Photocatalytic Degradation; Spherical Activated Carbon; Azo Dye; Methyl Orange

Abstract-To selectively adsorb indium(III) in industrial wastewater coexisting with zinc(II), the surface of sawdust was modified into phosphate groups through chemical reaction. Among various manufacturing methods, phosphorylated sawdsust made from using non-grinding sawdust with same ratio (based on volume) of H3PO4 and distilled water had a very high selectivity to indium(III), which shows removal efficiency of about 90% with 1.0 g at pH 3.5. Meanwhile, in case of zinc(II), there is almost no adsorption onto phosphorylated sawdust. The surface condition and phosphorus content of phosphorylated sawdust were analyzed by scanning electron microscopy (SEM) photograph and energy dispersive x-ray (EDX) spectrum. Also, the effects of loading of adsorbent and time on selective adsorption characteristics of indium(III) were investigated.
Keywords: Indium(III); Sawdust; Phosphate; Selectivity; Adsorption

Low cost adsorbents obtained from ash for copper removal by Maria Harja; Gabriela Buema; Daniel-Mircea Sutiman; Corneliu Munteanu; Daniel Bucur (1735-1744).
We investigated the utilization of ash and modified ash as a low-cost adsorbent to remove copper ions from aqueous solutions such as wastewater. Batch experiments were conducted to determine the factors affecting adsorption of copper. The influence of pH, adsorbent dose, initial Cu2+ concentration, type of adsorbent and contact time on the adsorption capacity of Cu2+ from aqueous solution by the batch adsorption technique using ash and modified ash as a low-cost adsorbent were investigated. The optimum pH required for maximum adsorption was found to be 5. The results from the sorption process showed that the maximum adsorption rate was obtained at 300 mg/L when a different dosage of fly ash was added into the solution, and it can be concluded that decreasing the initial concentration of copper ion is beneficial to the adsorption capacity of the adsorbent. With the increase of pH value, the removal rate increased. When the pH was 5, the removal rate reached the maximum of over 99%. When initial copper content was 300 mg/L and the pH value was 5, the adsorption capacity of the zeolite Z 4 sample reached 27.904 mg/g. The main removal mechanisms were assumed to be the adsorption at the surface of the fly ash together with the precipitation from the solution. The adsorption equilibrium was achieved at pH 5 between 1 and 4 hours in function of type of adsorbent. A dose of 1: 25 g/mL of adsorbent was sufficient for the optimum removal of copper ions. For all synthesized adsorbents the predominant mechanism can be described by pseudo-second order kinetics.
Keywords: Adsorption Capacity; Ash; Copper ions; Kinetic; Zeolite

Thermal reaction studies of diluted mixture (1%) of chloroform (CHCl3) under each argon (Ar) and hydrogen (H2) reaction atmosphere have been investigated to examine the effect of reaction atmosphere on decomposition of CHCl3 and product distributions. The experimental results were obtained over the temperature range 525–900 °C with reaction times of 0.3–2.0 sec. at 1 atm by utilizing an isothermal tubular flow reactor. Complete destruction (>99%) of the parent reagent, CHCl3 was observed near 675 °C under H2 reaction atmosphere (CHCl3/H2 reaction system) and 700 °C under Ar reaction atmosphere (CHCl3/Ar reaction system) with 1 sec reaction time. The CHCl3 pyrolysis yielded more conversion in H2 atmosphere than in Ar atmosphere. Major products in CHCl3/Ar reaction system were C2Cl4, CCl4, C2HCl3 and HCl over a wide temperature range. Hydrocarbon was not found in CHCl3/Ar reaction system. Major products of CHCl3/H2 reaction system observed were CH2Cl2, CH3Cl, CH4, C2Cl4, C2HCl3, C2H2Cl2, C2H3Cl and HCl at 600 °C with 1 sec. reaction time. Non-chlorinated hydrocarbons such as CH4, C2H4 and C2H6 were the major products at above 850 °C. Product distributions were distinctly different in Ar and H2 reaction atmospheres. The H2 gas plays a key role in acceleration of reagent decay and formation of non-chlorinated light hydrocarbons through hydrodechlorination process. The important reaction pathways, based on thermochemical and kinetic principles, to describe the features of reagent decay and intermediate formation under each Ar and H2 reducing reaction atmosphere were investigated.
Keywords: Thermal Decomposition; Chloroform; Hydrogen; Argon; Reaction Pathway

Kinetics, mechanism, isotherm and thermodynamic analysis of adsorption of cadmium ions by surface-modified Strychnos potatorum seeds by Ponnusamy Senthil Kumar; Rangasamy Gayathri; Chandrasekaran Senthamarai; Muthukumar Priyadharshini; Panimayam Sebastina Anne Fernando; Ramakrishnan Srinath; Vaidyanathan Vinoth Kumar (1752-1760).
The surface-modified Strychnos potatorum seeds (SMSP) were used as an effective low-cost adsorbent for the removal of cadmium ions from aqueous solution. SMSP was characterized by Fourier transform infrared spectroscopy and scanning electron microscopic analyses. The effect of operating variables such as solution pH, adsorbent dose, contact time, initial cadmium ions concentration and temperature on the removal of cadmium ions were studied in a batch mode adsorption operation. The optimum conditions for the adsorption of cadmium ions onto the SMSP were found to be: pH of 5.0, SMSP dose of 2 g/L, contact time of 30min, temperature of 30 °C for an initial cadmium ions concentration of 100 mg/L. Kinetic data were analyzed using the pseudo-first order and pseudo-second order kinetic equations, intraparticle diffusion model, Boyd kinetic model and shrinking core model. The characteristic parameters for each model have been estimated. Adsorption of cadmium ions onto the SMSP follows the pseudo-second order kinetic model. The rate-limiting steps in the adsorption process were found to be external and internal diffusion. Equilibrium data were well described by the Langmuir isotherm model than the Freundlich isotherm model, which yields a maximum monolayer adsorption capacity of 200 mg/g. Thermodynamic parameters such as standard free energy change, enthalpy change and entropy change were also estimated. The results show that the removal of cadmium ions by the SMSP was found to be spontaneous and exothermic.
Keywords: Adsorption; Cadmium Ions; Isotherms; Kinetics; Mechanism; Thermodynamics

Biological synthesis of gold nanoparticles by Bacillus subtilis and evaluation of increased antimicrobial activity against clinical isolates by A. Thirumurugan; S. Ramachandran; Neethu Anns Tomy; G. J. Jiflin; G. Rajagomathi (1761-1765).
Biological sources of microorganisms and plants are playing a major role in the reduction of metallic nanoparticles such as silver and gold, as it emerges as an eco-friendly and exciting approach in nanotechnology. We report on the biological synthesis of gold nanoparticles using the culture supernatant of Bacillus subtilis and its effect on increased antibacterial and antifungal activities against clinically isolated organism. When the supernatant of Bacillus subtilis was added to HAuCl4 aqueous solution, HAuCl4 was reduced as Au+ ions, which confirmed the presence of nanoparticles by the color change of pale yellow to purple. The minimum and maximum peaks were observed at 24th and 120th hours by UV-Visible spectroscopy. The combined antibacterial and antifungal activities with various antibiotics were observed against clinical isolates.
Keywords: AuNP’s; Bacillus subtilis ; UV-visible Spectroscopy; Antimicrobial Activity; Antibiotics

A new electrochemical biosensor for hydrogen peroxide using HRP/AgNPs/cysteamine/p-ABSA/GCE self-assembly modified electrode by Ali Shokuhi Rad; Mohsen Jahanshahi; Mehdi Ardjmand; Ali-Akbar Safekordi (1766-1770).
An electrochemical hydrogen peroxide biosensor was designed by immobilizing horseradish peroxidase (HRP) on Ag nanoparticles/cysteamine/p-aminobenzene sulfonic acid/glassy carbon (GC) electrode. Ag nanoparticles can act as tiny conduction centers on electrodes that adsorb redox enzymes, facilitating the transfer of electrons with no requiring any loss of biological activity. The forerunner film was first electropolymerized on the glassy carbon electrode with p-aminobenzene sulfonic acid (p-ABSA) by cyclic voltammetry. The cysteamine (CA) was bound on the surface of the film by electrostatic force, then Ag nanoparticles were immobilized on the cysteamine monolayer, and lastly HRP was adsorbed onto the surfaces of the Ag nanoparticles. A dramatic decrease in the overvoltage of H2O2 was observed with improved sensitivity, which makes the modified electrodes of great promise for oxidase-based amperometric biosensors. The biosensor responded to H2O2 in the linear range from 1.2×106 mol/L to 9.8×103 mol/L with a detection limit of 1.1×108 mol/L. Moreover, the obtained biosensor exhibited good accuracy and high sensitivity.
Keywords: AgNP; Hydrogen Peroxide; Cycteamamin; Biosensor; Cyclic Voltammetry

Silver nanoparticles are used in many industries due to their disinfection and antibacterial properties. Biological methods of nanoparticle synthesis have been suggested as possible ecofriendly alternatives to chemical and physical methods. In this study, biologically synthesized silver nanoparticles using Magnolia kobus leaf extract were coated on the surface of latex foam products using dip coating (exposure to nanoparticle solution) or ultrasonic treatment. SEM image of the treated foam showed that silver nanoparticles were uniformly coated on the surface of latex foam. Antibacterial properties were tested by counting viable Escherichia coli cells after 24 h growth in shake flask cultures containing latex foams coated with silver nanoparticles. Foams coated with silver nanoparticles showed higher antibacterial activities compared with foams untreated. Smaller silver nanoparticles synthesized at higher temperature showed higher antibacterial activity due to the larger specific surface area and higher content of silver nanoparticles. The growth of E. coli decreased with increasing the concentration of silver nanoparticles. Ultrasonic treatment showed higher adsorption and lower desorption of silver nanoparticles to and from the foams compared with dip coating, resulting in higher antibacterial activity.
Keywords: Silver Nanoparticles; Antibacterial Activity; Latex Foam; Biological Synthesis; Magnolia kobus

Synthesis and characterization of nanocomposite MCM-48-PEHA-DEA and its application as CO2 adsorbent by Mansoor Anbia; Vahid Hoseini; Sakineh Mandegarzad (1776-1781).
Three nanocomposites containing MCM-48-35PEHA-15DEA (35 and 15 as weight percent of amine addition), MCM-48-30PEHA-20DEA and MCM-48-25PEHA-25DEA of mesoporous silica MCM-48 modified by the mixture of pentaethylenehexamine (PEHA) and diethanolamine (DEA) have been synthesized and used to study the adsorption of carbon dioxide (CO2). They are characterized by low angle x-ray diffraction (XRD), Fourier transform infrared (FT-IR) and Brunauer-Emmet-Teller (BET) analysis. MCM-48-35PEHA-15DEA (as optimized adsorbent) shows CO2 adsorption capacity of 0.51 (m·mol CO2/g-adsorbent) at 1 bar and 298 K, much higher than CO2 adsorption capacity on polyethyleneimine, pyrrolidinepropyl and polymerized aminopropyl loaded MCM-48.
Keywords: CO2 Adsorption; Nanocomposite; MCM-48; Amine Modified

The waste material NCL coal dust was used as adsorbent for removal of Cr(VI) from aqueous solutions under batch adsorption experiments. The maximum removal of 99.97% was recorded at pH 2. The time required to attain equilibrium was found to be 60 min. Adsorption kinetics was described by the Lagergren equation. The value of the rate constant of adsorption was found to be 0.0615 min−1 at 16 mg dm−3 initial concentration and 298 K. The applicability of the Langmuir and Freundlich equations for the present system was also tested at different temperatures: 298, 313, and 328 K. Both thermodynamic parameters and temperature dependence indicated the endothermic nature of Cr(VI) adsorption on coal dust. The results showed that NCL coal dust is a promising adsorbent for the removal of Cr(VI) from aqueous solutions.
Keywords: Coal Dust; Adsorption Dynamics and Isotherms; Cr(VI); Thermodynamic Parameters

Nano-assisted inclusion separation of alkali metals from basic solutions was reported by inclusion-facilitated emulsion liquid membrane process. The novelty of this study is the application of nano-baskets of calixcrown in the selective and efficient separation of alkali metals as both the carrier and the surfactant. For this aim, four derivatives of diacid calix[4]-1,2-crowns were synthesized, and their inclusion-extraction parameters were optimized including the calixcrown scaffold (13, 4 wt%) as the carrier/demulsifier, the commercial kerosene as diluent in membrane, sulphonic acid (0.2 M) and ammonium carbonate (0.4 M) as the strip and the feed phases, the phase and the treat ratios of 0.8 and 0.3, mixing speed (300 rpm), and initial solute concentration (100mg/L). The selectivity of membrane over more than ten interfering cations was examined and the results revealed that under the optimized operating condition, the degree of inclusion-extraction of alkali metals was as high as 98–99%.
Keywords: Nano-basket; Inclusion; Calixcrown; Emulsion Liquid Membrane

The multiple tube preparation of a silica membrane using a porous α-alumina tube as a support tube was carried out by chemical vapor deposition (CVD) to scale up the membrane reactor. A porous alumina tube with a pore size of 100 nm was modified by chemical vapor deposition using tetraethoxysilane as an Si source. The single-component permeance of H2 and N2 in the prepared silica membrane that was achieved by a multiple tube membrane preparation system was measured at 300–600 °C. Hydrogen permeance of the modified membrane at a permeation temperature of 600 °C was 5×10−8 mol·Pa−1·m−2·s−1. H2/N2 selectivity at 600 °C was about 32. It was confirmed that permeance of H2 and N2 and the selectivity for H2 to N2 in the prepared silica membrane by the multiple tube membrane preparation system had almost the same value compared to those of the silica membrane prepared by the single-tube system.
Keywords: Inorganic Membrane; Silica-alumina Membrane; Chemical Vapor Deposition; Multiple Layered Membrane Preparation; Hydrogen Permselectivity

Highly nanoporous nickel oxide electrodes were obtained by electrodeposition accompanied by hydrogen evolution reaction and the selective electrochemical dealloying of copper from Ni-(Cu) porous foam. The nanoporous nickel oxide electrodes consequently have numerous dendritic morphologies composed of nanopores with 20–30 nm diameters. The specific capacitances were 428 F g−1 for as-deposited Ni-(Cu) foam electrode and 1,305 F g−1 for nanoporous nickel-oxide electrode after dealloying process, respectively. This indicates increased surface area by dealloying process leads to innovative increase of specific capacitance.
Keywords: Nanoporous NiO Foam Electrode; Dendritic Structure; Hydrogen Evolution Reaction; Electrochemical Dealloying; Supercapacitors

Rheological behavior of sun protection compositions during formulation by Maria Karsheva; Silviya Georgieva; Silvia Alexandrova (1806-1811).
Rheological properties of cosmetic products are related to the products’ sensory attributes and to performance. In literature there is a lack of information on the influence of physicochemical interactions during processing of complex systems. This study is focussed on the interactions between the ingredients of cosmetic compositions during formulation in respect to their flow behavior. The rheological behavior of model cosmetic compositions based on polyvinyl alcohol solutions and containing natural plant extracts in glycerol and olive oil, UV screens (TiO2), synthetic UV absorber, emulsifier (Carbopol 2050), preservative (Bronopol) and fragrance was studied. The flow properties of compositions containing natural UV absorbers were compared to those of compositions with synthetic ones. All the compositions exhibited shear thinning rheological behavior that can be described by the power-law rheological model. It was proved that the emulsifier’s addition thickens the compositions; the addition of Bronopol leads to slight degree of thixotropy avoided by pre-shearing the samples for one minute. The fragrance addition in EtOH solution lowers the composition’s apparent viscosity; the addition of fine TiO2 as UV-screen even in quite tiny quantity of 0.2% mass increases the consistency of basic 10% PVA samples, lowering in the same time the flow index. The compositions containing glycerol extracts are more stable than those with olive oil extracts and they preserve their properties longer.
Keywords: Rheology; Sun Protection Cosmetics; Natural Plant Extracts

Simultaneous removal of H2S and COS using Zn-based solid sorbents in the bench-scale continuous hot gas desulfurization system integrated with a coal gasifier by Young Cheol Park; Sung-Ho Jo; Ho-Jung Ryu; Jong-Ho Moon; Chang-Keun Yi; Yongseung Yoon; Jeom-In Baek (1812-1816).
A bench-scale continuous hot gas desulfurization system using Zn-based solid sorbents was developed to remove H2S and COS simultaneously in a 110 Nm3/h of real coal-gasified syngas. The bench-scale unit, which consisted of a fast fluidized-bed type desulfurizer and a bubbling fluidized-bed type regenerator, was integrated with a 3 ton/day-scale coal gasifier installed at the Institute for Advanced Engineering. The solid sorbents, which consisted of 50 wt% of ZnO for sulfides sorption and 50 wt% of supporters for mechanical strength, were manufactured by a spray drying method and supplied by Korea Electric Power Corporation Research Institute. The bench-scale unit was designed to operate at the high temperature of above 500 °C and the high pressure of 19 kgf/cm2 gauge. Integration of the bench-scale unit with a coal gasifier was first performed to investigate the operation stability of the integrated system. And the long-term continuous operation above 30 h was performed to analyze the desulfurization performance of the bench-scale unit. The concentration of both H2S and COS in the syngas was measured by a continuous UV gas analyzer and an online gas chromatograph and that of both H2S and COS after desulfurization was measured by an online gas chromatograph. Through the above 30-h continuous operation, the sulfur removal reached up to 99.9%.
Keywords: Hot Gas Desulfurization; Solid Sorbents; Bench-scale Unit; Integration with a Coal Gasifier; IGCC