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  • 4519
  • 1
    Publication Date: 2012-02-24
    Description: A diglycidyl ether type epoxy resin from bisphenol A, E-51, was cured by methylhexahydrophthalic anhydride (MeHHPA) and then decomposed in near-critical water without any additives. The effects of the experimental parameters such as the reaction temperature, reaction time, pressure, and feedstock ratio on the percentage of decomposition were investigated to obtain optimized reaction conditions. The results revealed that the percentage of decomposition can be enhanced by increasing either temperature or reaction time. At 260 °C, it initially increased with higher pressure and then decreased dramatically when the pressure further was reduced to the saturated water vapor pressure. The kinetics study of the epoxy decomposition was also carried out by monitoring the glass transition temperature of the solid product using differential scanning calorimetry. The decomposition equation was established and the activation energy was calculated to be 123.5 kJ mol –1 . Epoxy resin cured by an anhydride was successfully decomposed in near-critical water without any additives. The results demonstrated that near-critical water has the potential to serve as promising medium for converting epoxy resin into valuable downstream straw materials at low operating cost.
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  • 2
    Publication Date: 2012-02-24
    Description: Biomass holds great promise as a renewable source of hydrogen and thus as a zero-emission, carbon-neutral, and nearly inexhaustible energy resource. Thermodynamic analysis of biomass hydration is carried out to study the reaction properties considering a series of saccharides as a model. Equilibrium constants and composition are estimated in dependence on the saccharide chain length and temperature. The latter is also studied as a function of the reactant ratios and in the presence of nonreacting additives. Being highly endothermic, the reaction is thermodynamically favorable due to a high entropic contribution. Increase in the saccharide chain length affects the conversion only slightly, so the results for low-molecular-weight saccharides can be transferred to long-chain ones. The hydration of oligosaccharides to hydrogen is evaluated from the equilibrium thermodynamics viewpoint. The reaction is thermodynamically favorable even at mild conditions and is entropically driven. With increasing oligosaccharide chain length, the conversion remains nearly constant. Therefore, results for short chain saccharides can also be applied to long chain sugars such as cellulose.
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  • 3
    Publication Date: 2012-03-14
    Description: Particle synthesis in liquid phase usually requires a subsequent washing step in order to remove undesirable impurities such as unreacted educts, byproducts, solvents and salts. In particular, the washing of mesoporous particles is a challenging task due to large specific surface areas and void volumes. The filter cake washing of mesoporous SiO 2 particles contaminated either with an adsorbing fluorescent dye or sodium sulfate is presented. The effects of wash liquid mass flow rate, mean particle size, and mean pore size on the wash efficiency were investigated. Especially the interaction between impurities and the solid surface, and thereby the initial impurity distribution within the filter cake, led to distinctive washing behaviors. Filter cake washing of porous SiO 2 particles is demonstrated. Major focus was put on the washing behavior and washing efficiency according to the interaction between two types of model impurities and the particle surface. Moreover, the influences of the wash liquid mass flow rate and of particle properties such as particle mean pore size and particle fraction on the wash curves were investigated.
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  • 4
    Publication Date: 2012-03-14
    Description: The effect of temperature has been studied in hydrocracking of light cycle oil (LCO), byproduct of fluidized catalytic cracking (FCC) units on a bifunctional catalyst (Pt-Pd/HY zeolite). The increase in both temperature and H 2 partial pressure have an important attenuating effect on catalyst deactivation, given that they decrease sulfur equilibrium adsorption and enhance hydrocracking of coke precursors. Therefore, the catalyst maintains significant hydrodesulfurization and hydrocracking activity. As the temperature is increased, hydrocracking conversion and naphtha selectivity increase, although there is no significant dearomatization of the medium distillate fraction in the range of the studied experimental conditions. 400 °C is the more suitable temperature for obtaining a high yield of naphtha with a high content of i -paraffins. Valorization of light cycle oil into valuable blending streams (naphtha and medium distillates) can be reached by means of hydrocracking over a Pt-Pd catalyst, supported on a very acid HY zeolite. The effect of temperature as a key factor on conversion, yield, and selectivity of product fractions of interest is determined and evaluated.
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  • 5
    Publication Date: 2012-02-07
    Description: The integrated gasification combined cycle (IGCC) offers the opportunity for precombustion CO 2 capture. However, recent studies using physical absorption for CO 2 separation indicated efficiency penalties only slightly lower than those for postcombustion capture in conventional steam power plants. These efficiency penalties are explained and analyzed. As an alternative, a process using a so-called water-gas shift membrane reactor, which combines hydrogen-selective membranes with water-gas shift reaction, is presented. It is demonstrated that the use of recirculated flue gas from downstream of the heat recovery steam generator as membrane sweep gas results in an overall efficiency loss of only 4.5 %-points (including CO 2 compression to 120 bar) in comparison to an IGCC without carbon capture and storage (CCS). Although the integrated gasification combined cycle technology has advantageous process conditions for carbon capture and storage (CCS), recent studies could not exploit this potential. Simulation results and explanations are given, highlighting how the proper integration of H 2 -selective membranes can reduce the efficiency penalty in comparison to physical absorption-based CCS by about half.
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  • 6
    Publication Date: 2012-02-07
    Description: Simple CO 2 capture in combined solid oxide fuel cell (SOFC) gasification or reforming (of hydrocarbons – fossil or biomass) cycles by condensing the water vapor of the anode exhaust gas after CO shifting and H 2 recycling by a membrane is simulated. High efficiency of about 60 % is demonstrated. The separated CO 2 can be stored in a two-chamber tank at the same pressure and temperature as methane on the two sides of a flexible membrane which divides the tank into chambers since 1 mol CH 4 results in 1 mol CO 2 . In a solid oxide electrolyzer cell (SOEC), CO 2 and steam can be recombined to CH 4 using excess electricity, e.g., produced by wind or solar power, and O 2 is left over. Thus, excess electricity can be stored chemically. Such a cycle allows hybrid vehicles with SOFC as range extender, running as zero-emission vehicles also when using natural gas. Simple CO 2 capture in solid oxide fuel cells (SOFCs) by vapor condensation is simulated. The separated CO 2 can be stored in a two-chamber tank. In a solid oxide electrolyzer cell (SOEC), CO 2 and steam can be recombined to CH 4 and O 2 is left over. Excess electricity can be chemically stored. This cycle allows zero-emission hybrid vehicles with an SOFC as range extender.
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  • 7
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    Publication Date: 2012-12-22
    Description: Boiler-feed pump. Copyright: Sulzer
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  • 8
    Publication Date: 2012-11-03
    Description: An engineering application case study on a two-fluid flow model for the control of industrial drying operations is reported. The mathematical model of this process was numerically solved by a computer code developed in FORTRAN language and was validated through data taken from PVC drying performed in an industrial continuous fluidized-bed dryer. The predicted steady-state outlet temperature and PVC moisture content values agree with the real data observed on the industrial plant. This model was also used to predict the temperature and concentration profiles inside the dryer as a function of time as a response to the disturbances and variations on the PVC water content at the dryer inlet. A two-fluid 1D transient mathematical model to design a drying operation control was developed, validated with data from PVC drying in an industrial continuous fluidized-bed dryer, and applied to simulate responses to disturbance on the PVC moisture content at the dryer inlet. The drying operation could be predicted satisfactorily by this model which due to its simplicity enables fast responses to disturbances in the process.
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  • 9
    Publication Date: 2012-11-03
    Description: The extraction of gold in membrane extractors was theoretically investigated. Extraction of gold in the form of in a solution of n -heptane and synergistic extractants of LIX79+TOPO was studied. The membrane extractor consists of three sections: the tube side, the membrane, and the shell side. Conservation equations were derived for in the membrane module and were numerically solved based on finite element method. Simulations were conducted through solving the momentum and mass transfer equations simultaneously. It was indicated that as the feed flows within the tube side, it moves into the membrane due to the concentration difference, and then gets swept by the moving extractants within the shell side. The distribution of solute concentration in the membrane contactor was obtained. Simulation results showed increasing the feed flow rate reduces the extraction efficiency, while doing the same for the organic phase flow rate does not change the extraction efficiency. Extraction of gold in a solution of n -heptane and synergistic extractants was studied using a membrane extractor consisting of the tube side, the membrane, and the shell side. Simulation results showed that increasing the feed flow rate reduces the extraction efficiency, while doing the same for the organic phase flow rate does not change the extraction efficiency.
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  • 10
    Publication Date: 2012-12-12
    Description: Hydrodynamics characteristics like flow pattern, shear rate distribution, power consumption, axial pumping capacity, mixing time, and mixing efficiency of an ellipse gate (EG) impeller were investigated by experimental and numerical methods. The numerical simulation results were validated by experimental data of power consumption and mixing time. Results indicate that the axial pumping number of the EG impeller is larger than that of any other reported large-scale impeller under laminar regime, and that the shear rate formed by this impeller is less sensitive to Reynolds numbers. In-depth analysis reveals the different function of each part of the EG impeller under different flow regimes. This impeller provides an almost similar mixing efficiency like the double-helical ribbon impeller under laminar regime, but much higher mixing efficiency both under transitional and turbulent flow regimes. An ellipse gate impeller was designed for fermentation processes with varying fluid viscosities in order to cover turbulent to transient or even laminar flow regimes in a reactor. Hydrodynamics characteristics were investigated by experimental and numerical methods, indicating excellent mixing properties of this impeller in a wide range of Reynolds numbers.
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  • 11
    Publication Date: 2012-12-12
    Description: The role that water vapor plays in atmospheric phenomena is extremely important. Saturation of moist air at a given temperature and pressure occurs if its mixing ratio is such that the moist air can coexist in a stable condition with an associated condensed phase at the same temperature and pressure. The saturation mixing ratio is useful to calculate the relative humidity which is a ratio, expressed in percent, of the amount of water vapor in the air (actual mixing ratio) compared to the amount of water vapor the air can hold (saturation mixing ratio). In this work, an attempt has been made to develop a simple-to-use Arrhenius-type function to estimate the mixing ratio for saturated air over water as a function of pressure and temperature. Estimations have been found to be in excellent agreement with the data reported in the literature, with the average absolute deviation being around 0.4 %. A simple correlation is developed to estimate the mixing ratio for saturated air over water as a function of pressure and temperature using an Arrhenius-type asymptotic exponential function. To show the simplicity of the model and the usefulness of the novel predictive tool, the formulation is discussed in a systematic manner.
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  • 12
    Publication Date: 2012-12-12
    Description: Pulsed flow has been widely applied in the past for special applications as in jigging or sorting devices, extraction columns, and fluidized-bed dryers. Recent developments and detailed examinations demonstrate several effects which can be achieved in pulsed operation modes. Here, low-frequency oscillations are considered, providing a more or less uniform phase state along the flow. Secondary flow is induced at obstacles and can be widely controlled by pulsation parameters keeping the backmixing effect low, despite of high transversal mass or heat exchange intensification. At walls, lift forces on particles within the thin boundary layers are beneficial for keeping particles from building deposits on surfaces or on permeable membranes. Broken symmetry devices generate a directed flow even when operated by a harmonically pulsed fluid. At oscillating interfaces, a distinct secondary flow is observed, well-suited to intensify mass transfer. Pulsation of fluids within channels equipped with obstacles allows for intensifying of transverse transport and of heat and mass transfer, independent on the residence time. Special arrangements are even able to induce directional flow despite of harmonic flow drive. It can be assumed that pulsating of fluids opens new fields of still only partly examined effects.
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  • 13
    Publication Date: 2012-12-12
    Description: A multiphase Volume-of-fluid (VOF) model was developed to gain further insights into the reactive flow parameters and electrical capacitance tomography (ECT) measurements on the remediation of hazardous organic pollutants. Low ozone bubble frequencies were obtained for high surface tension fluids, and the liquid viscosity affected the ozone bubbling frequency. The VOF model indicated that the increase of inlet gas velocity enriched the ozone bubble detachment and concomitantly generated larger ozone bubbles, decreasing the detoxification rates. VOF mappings and ECT visualizations of gas-liquid unveiled preferential routes and highlighted the attenuation of the axisymmetric behavior of the ozonation bubble column under high-interaction regimes. Ozonation bubbly flow was investigated through VOF simulations and ECT data. The VOF framework accurately predicted the effect of several physicochemical variables. Gas-liquid velocity distributions were positively correlated with pollutant removal efficiencies. The interstitial flow maps identified by ECT and computed by the VOF model gave rise to unsteady flow patterns.
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  • 14
    Publication Date: 2012-12-12
    Description: A new geometry of liquid-liquid hydrocyclones is proposed seeking to perform the separation of oil emulsified in water. The hydrocyclone performance was investigated by means of a factorial experimental design (2 3 ) leading to a total of ten experiments. The results enabled the determination of empirical mathematical models that describe capacity, total separation efficiency, and flow ratio as a function of oil concentration in the feed inlet, operating pressure drop, and presence or absence of a vortex finder in the geometry. Numerical simulations were also carried out to further understand the flow field characteristics in the studied hydrocyclone. The performance of a new class of liquid-liquid hydrocyclones designed for the separation of dilute aqueous emulsions of oil is presented. The influence of different parameters was studied experimentally and numeri-cal simulations were carried out by CFD techniques. The improvement of this separation technology can contribute to the reduction of environmental impact in the discharge of the produced water.
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  • 15
    Publication Date: 2012-12-12
    Description: A 3D mathematical model is developed to predict the transport of water vapor through porous membranes. The model is based on solving the continuity, momentum as well as energy equations for water in the membrane contactor. The model's equations are numerically solved using the finite element method to obtain the concentration and temperature distributions of water in the membrane contactor. The model findings were in good agreement with experimental data. The proposed 3D model proved to be appropriate for predicting the performance of a membrane evaporator. Simulations were carried out in order to study the influence of different operating parameters and membrane structure on the membrane evaporation effectiveness. The results of simulation indicate that the gas velocity is a favorable parameter in the membrane evaporation process due to its tendency to keep the process far from the thermodynamic equilibrium. A 3D computational fluid dynamics simulation is carried out to predict the dehydration of aqueous solutions by means of a membrane evaporation process. A combined finite element and UFPACK method is applied for simulations. The results indicate good agreement between experimental and simulation results. The proposed model proved to be suitable for predicting the performance of a membrane evaporator.
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  • 16
    Publication Date: 2012-12-12
    Description: Due to its low water solubility and slow dissolution rate, genipin was micronized by an antisolvent precipitation process using ethanol as solvent and n -hexane as antisolvent. The effects of various experimental parameters on the mean particle size (MPS) of micronized genipin were investigated. By analysis of variance, only the concentration of the genipin solution has a significant effect on the MPS in genipin micronization. Under the optimum conditions, micronized genipin with an MPS of 1.8 μm was obtained. The micronized genipin was characterized by various methods, e.g., scanning electron microscopy and thermogravimetry. The analysis results indicated that the chemical structure of micronized genipin was not changed, but the crystallinity was reduced. The dissolution rate and solubility of the micronized genipin were 2.08 and 1.64 times that of the raw drug. In addition, the residual amounts of n -hexane and ethanol were less than the International Conference on Harmonization limit for solvents. Micronized genipin with a mean particle size of 1.8 μm was prepared by the antisolvent precipitation process. The chemical structure of micronized genipin remained unchanged, but the crystallinity was reduced. The dissolution rate and solubility of the micronized genipin were 2.08 and 1.64 times that of the raw drug, and the amounts of residual n -hexane and ethanol were lower than the International Conference on Harmonization limit for solvents.
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  • 17
    Publication Date: 2012-09-26
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  • 18
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    Publication Date: 2012-09-26
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  • 19
    Publication Date: 2012-09-26
    Description: Microbial fuel cells (MFCs), which can directly convert chemical energy in organic matters into electricity, have drawn a lot of attention in the past decades. Recently, MFCs have been integrated with waste-activated sludge (WAS) treatment for recovering energy from WAS. Since 2004, a number of publications regarding this topic have been published. The recent advances in MFCs powered by WAS are critically reviewed. MFC reactor designs, MFC performances, and sludge degradation efficiencies are addressed based on the recent related publications. The challenges and corresponding enhancement measures of MFCs using WAS as fuel are also discussed. Microbial fuel cells (MFCs) are a promising technology for the production of electricity from waste-activated sludge (WAS). A critical review on recent progresses in MFCs powered by WAS summarizes related publications on MFC reactor designs, MFC performan-ces, and sludge degradation efficiencies. Challenges and corresponding enhancement measures of MFCs applying WAS as fuel are discussed as well.
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  • 20
    Publication Date: 2012-09-26
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  • 21
    Publication Date: 2012-09-26
    Description: A new optimization design of the boil-off gas (BOG) reliquefaction process for liquefied ethylene (LEG) vessels is proposed in order to reduce the reliquefaction process energy cost and improve its cold exergy efficiency. The exergy loss of each component is calculated and the efficiency of the available energy utilization is evaluated on the basis of a detailed thermodynamic analysis. The exergy analysis results indicate that the exergy efficiency of the improved BOG reliquefaction process is about 19.0 % higher than that of the existing process, and the amount of refrigerant used in the improved process is reduced by about 44.9 % per hour. The power consumption could be decreased by 16 %. The circulation volumes of the refrigerant and BOG are both significantly reduced, thus lowering the equipment and operation costs of the BOG reliquefaction process. A cost-effective optimization design of the boil-off gas (BOG) reliquefaction process for liquefied ethylene vessels is proposed. The performances of the reliquefaction system and refrigeration cycle are investigated based on the exergy analysis. The exergy efficiency of the improved refrigeration cycle is significantly increased as well as the energy utilization efficiency of the BOG reliquefaction process.
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  • 22
    Publication Date: 2012-09-26
    Description: Cementation is an effective process that meets the requirements of process cleanliness. The performance of the cementation reaction is dictated by a number of variables. In this study, the effects of various parameters on the yields of copper-iron cementation (wire and powder) were investigated. Statistical full factorial designs were used to produce appropriate mixture models for the yields. The experimental designs were done at three different levels of three operating variables, namely initial concentration, temperature, and pH. The optimization studies were carried out with MATLAB 7.0 software. The optimum yields obtained from the predicted models were found to be 0.9916 and 0.9088 for iron wire and powder, respectively, under optimized conditions, and these were in accordance with the experimental observations. Copper cementation is a useful technique for the recovery of copper from a variety of waste solutions. Here, copper cementation on iron substrates in batch process was investigated. Various parameters played a major role on the yield of copper-iron cementation. A statistical full factorial design was carried out and optimization studies were done.
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  • 23
    Publication Date: 2012-09-26
    Description: The search for new adsorbents with enhanced capacity and selectivity, suitable for application on large-scale simulated moving-bed units for separation of p- xylene, requires efficient, reliable, and fast adsorbent characterization methods for this specific separation. Fixed-bed experiments were carried out under the conditions of the Parex process to evaluate a faujasite-type zeolite as adsorbent for the separation of p- xylene from its isomers in the proportions of the real Parex feed stream. The experimental breakthrough curves were used to evaluate the selected adsorbent in terms of nonselective and selective volumes, adsorption capacity, selectivity, and productivity, which can be applied to identify the feasible separation region for different operating conditions. A method based on experimental breakthrough curves for quickly evaluating adsorbents for a defined separation in terms of selective volume, capacity, selectivity and productivity is demonstrated under the conditions of the Parex process. Fixed-bed experiments are carried out in order to assess a barium-exchanged faujasite-type zeolite as adsorbent for the separation of p- xylene from its isomers.
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  • 24
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    Publication Date: 2012-09-26
    Description: Production Plant at Night. Copyright: snapfoto105 – Fotolia.com.
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  • 25
    Publication Date: 2012-09-26
    Description: Hydrophobic interaction and ion exchange chromatography are basic steps in purification of fermentative biopharmaceuticals. An optimization by statistical design of experiments requires a huge amount of feed. An alternative approach is the combination of model parameter determination using small scale experimental model parameter determination (1-mL columns) and rigorous process modeling. Applicability for the prediction of the separation of a fermentation mixture of CHO mammalian cell culture is validated and hence IgG is purified from cell culture supernatant. Hydrophobic interaction chromatography directly combined with ion exchange chromatography is optimized. Any direct integration of those two main unit operations in purification processes is a methodological first step towards total process optimization. The potential for cost reduction and overall yield improvement is demonstrated and this leads to the conclusion that single step optimization is a feigned and not a real optimum. The potential of a model based process design is demonstrated. Hereby, it will be shown that the sum of the single optima of each unit operation is not equal to the total process optimum. Using the example of a combined chromatographic two-step separation the resulting benefits will be pointed out.
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  • 26
    Publication Date: 2012-09-26
    Description: The influence of vibration number Γ, amplitude A , and frequency of vibration f on the fluid dynamic behavior of a vibrofluidized bed operating with inert particles in the transient period of water evaporation and drying of different solutions was evaluated. The solutions investigated were sewage sludge, skimmed milk, and calcium carbonate of three different solids contents. The impact of feed rate and vibration parameters on the dynamic behavior of variables such as pressure drop and inlet air velocity was determined. Based on the results it was verified that the operation at A = 0.015 m improved the bed dynamics and the gas-particle contact in the wetted beds. As different dynamic behaviors may be obtained under the same Γ value, the values of A or f must be informed together with Γ for a complete characterization of vibration effects. The transient period of water evaporation and drying of different solutions was studied to describe the fluid dynamic behavior of a vibrofluidized bed operating with inert particles. The pressure drop and air velocity on the bed were investigated as function of the amplitude, frequency, and dimensionless vibration number.
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  • 27
    Publication Date: 2012-09-26
    Description: Sub-seabed geological storage of CO 2 in the form of gas hydrate is attractive because clathrate hydrate stably exists at low temperature and high pressure, even if a fault occurs by diastrophism like a big earthquake. For the effective design of the storage system it is necessary to model the formation of CO 2 -hydrate. Here, it is assumed that the formation of gas hydrate on the interface between gas and water consists of two stages: gas diffusion through the CO 2 -hydrate film and consequent CO 2 -hydrate formation on the interface, between film and water. Also proposed is the presence of a fresh reaction interface, which is part of the interface between the gas and aqueous phases and not covered with CO 2 -hydrate. Parameters necessary to model the hydrate formation in sand sediment are derived by comparing the results of the present numerical simulations and the measurements in the literature. A mathematical model for the formation of CO 2 -hydrate in sand sediment is proposed for sub-seabed geological storage of CO 2 in the form of gas hydrate, considering gas diffusion through the CO 2 -hydrate film and the presence of a fresh reaction interface. CO 2 -hydrate formation was numerically simulated by solving a heat transfer equation.
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  • 28
    Publication Date: 2012-09-26
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  • 29
    Publication Date: 2012-10-03
    Description: The effects of temperature on the synthesis of 1,1-dibutoxyethane (DBE) in a fixed-bed adsorptive reactor were studied by performing both adsorption/desorption and reaction/regeneration experiments at 15 and 35 °C. The Langmuir-type isotherm parameters at 15 and 35 °C were obtained from the adsorption/desorption experiments. The reaction/regeneration experiments showed an increase in both conversion and productivity with increasing temperature. Isothermal and nonisothermal mathematical models were used to simulate the reactor operation with different Damköhler numbers. The simulated results suggest that the reactor productivity can be improved by using the adiabatic operation mode on the fixed-bed adsorptive reactor, obtaining a productivity for DBE of 71.8 mol kg –1 h –1 . The effects of temperature on the synthesis of 1,1-dibutoxyethane (DBE) in a fixed-bed adsorptive reactor were studied by performing both adsorption/desorption and reaction/regeneration experiments at 15 and 35 °C. Isothermal and nonisothermal mathematical models were used to simulate the reactor operation with different Damköhler numbers. The simulated results suggest that the reactor productivity can be improved by using the adiabatic operation mode on the fixed-bed adsorptive reactor.
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  • 30
    Publication Date: 2012-10-05
    Description: A concentrate of the naturally occurring mineral ilmenite has been found to release small amounts of gas-phase O 2 during chemical-looping combustion experiments at temperatures in the order of 950 °C. This is unexpected, but the effect has been verified by experiments in two different fluidized-bed reactor systems. The O 2 release is small, resulting in approximately 0.1 vol % O 2 in the gas passing through the reactor beds. However, due to the presence of steam as combustion product and as fluidization medium for fuel reactor and loop seals during solid fuel experiments, considerable O 2 concentrations could be obtained if analyzed on dry basis. It is suggested that the reason for the experienced O 2 release could be the presence of small amounts of manganese in the sample or interactions between said impurities and iron or titanium oxides. Ilmenite has been found to release gas phase O 2 during chemical-looping combustion experi-ments. The phenomena manifested itself as an O 2 concentration of 1.0–1.5 vol. % when fluidizing the air reactor with air and the fuel reactor with steam. The O 2 release is small, but due to the presence of steam as fluidization medium, considerable O 2 concen-trations could be obtained if analyzed on dry basis.
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  • 31
    Publication Date: 2012-10-05
    Description: Formation of a gas hydrate with two different gas compositions (natural gas and a mixture of methane-ethane-propane) was investigated using a special method of producing the hydrate from ice. Gas uptake, splitting the fraction of each component between the gas phase and hydrate phase, and purification of methane were studied in the presence of silica-based porous media. Addition of a small amount of colloidal silica media increased considerably the gas storage capacity of the hydrate phase. In the presence of silica-based porous media, the purification factor of CH 4 became significantly higher. The results can provide the basis for the storage of natural gas in hydrate form and application of the hydrate-based gas separation technology to achieve methane with high purity from natural gas. Gas hydrate formation in natural gas and in the ternary gas mixture of CH 4 , C 2 H 6 , and C 3 H 8 was performed with a fixed amount of water with and without the addition of porous media. The addition of colloidal silica media increased substantially the gas storage capacity of the hydrate phase. The purification factor of CH 4 became significantly higher in the presence of silica-based porous media.
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  • 32
    Publication Date: 2012-10-10
    Description: Dealing with calculated three-dimensional flow fields of microchannels, investigations about straight, orifice, z- and y-channels were performed. Computational fluid dynamics was used to gain the flow fields that were the basis of stationary particle tracking performed with more then 5000 seeding points. With the particle tracking, quantification and thus characterization of the acting stresses was performed. The acting stresses (tensile, shear, turbulent and compressive stress) were subsequently used for a comparison with previously conducted dispersion experiments. The dispersion of aluminum oxide agglomerates served as model system. Distributions of stresses and particle sizes could then be compared. As expected, the different stress distributions differ in broadness and level. Although the agreement between experiments and simulations is sufficient, it is still not possible to identify the predominant stress. The microchannels offering the better dispersion results provide higher stresses. Flow fields in a straight, an orifice, a z- and a y-microchannel were investigated. Stationary particle tracking leads to the acting stresses. These stresses (tensile, shear, turbulent and compressive stress) are compared with the results of previously conducted dispersion experiments. Distributions of stresses and particle sizes were compared. Good agreement was found between experiments and simulations, but the predominant mechanism could not be identified.
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  • 33
    Publication Date: 2012-09-25
    Description: The performances of radial-axial flow (Rushton-Maxflo impellers) and axial-radial flow (Maxflo-Rushton impellers) mixers in the laminar-transitional flow regime were experimentally and numerically investigated with Newtonian and non-Newtonian fluids. The rheological properties for a fermentation broth consisting of the fungus Beauveria bassiana were studied under different hydrodynamic conditions in these systems. The bioreactor was a continuous stirred-tank reactor (CSTR), set at different stirring velocities. The rheology of the systems exhibited shear-thinning behavior which was modeled with the power law model. The experimental hydrodynamics and configuration modes were compared and simulated with a model fluid system and by numerical criteria (computational fluid dynamics). The R-M mode was found to be more efficient than the M-R rotating mode in terms of energy and homogenization time. The results will help in the optimization of scale-up production of these fungi. The hydrodynamics of the fungi system Beauveria bassiana is experimentally evaluated for different conditions in a mixing tank with a two-impeller configuration and Newtonian as well as non-Newtonian model fluids. Numerical simulations are essential to understand and optimize these systems. The simulation of streamlines for a radial-axial Rushton-Maxflo impeller configuration is presented.
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  • 34
    Publication Date: 2012-10-05
    Description: Although established in the 1950s, the grindability test according to Zeisel is still one of the most important measurement techniques for the grindability of hard and brittle material. It is used intensively throughout the cement industry for testing clinker and slag, but also for limestone. Test results are applied for mill designing or capacity estimations and often form the basis for contracts for grinding equipment. The accuracy of the test strongly depends on the test parameters but also on the reliability of the employed measurement techniques. Although of high importance to the industry, these measurement techniques are not state-of-the-art. The precise measurement of grinding work by a load cell is introduced which replaces measurement by deflection and protractor. The reliability of the grindability test according to Zeisel is affected by a number of influencing parameters but also by the applied measurement techniques. The precise measurement of the grinding work by a load cell is introduced which replaces the traditional measurement by a protractor. Vibration during the test could be reduced and detailed data of the energy consumption could be obtained.
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  • 35
    Publication Date: 2012-04-15
    Description: β-Galactosidase is an enzyme industrially used to hydrolyze milk lactose, generating dairy products destined for people intolerant to this sugar. Its importance is due to its galactosiltransferase activity. The effects of elution pH and salt gradient volume were evaluated for purification of β-galactosidase by ion exchange chromatography using an experimental design and response surface techniques. The best conditions for purification of β-galactosidase were pH 5.5 with an elution volume of 62.8 mL, obtaining a yield of 85.5 % and a 12-fold increase in the purification factor in a one-step chromatography process. Purification of β-galactosidase by application of a single stage of ion exchange and evaluation of the important process parameters using an experimental design provided good results in the recovery and purification factor that could subsequently be scaled up. In an innovative study, the effects of elution pH and salt gradient volume were evaluated by ion exchange chromatography using an experimental design and response surface techniques for purification of β-galactosidase in only one chromato- graphy step. After optimization, β-galactosidase could be purified effectively with a 12-fold purification factor and 85.5 % recovery in a cost-reducing single step.
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  • 36
    Publication Date: 2012-04-15
    Description: Gas absorption accompanied by an irreversible chemical reaction of first-order or second-order in a liquid layer of finite thickness in plug flow has been investigated. The analytical solution to the enhancement factor has been derived for the case of a first-order reaction, and the exact solution to the enhancement factor has been obtained via numerical simulation for the case of a second-order reaction. The enhancement factor in both cases is presented as a function of the Fourier number and tends to deviate from the prediction of the existing enhancement factor expressions based on the penetration theory at Fourier numbers above 0.1 due to the absence of a well-mixed bulk region in the liquid layer. Approximate enhancement factor expressions that describe the analytical and exact solutions with an accuracy of 5 % and 9 %, respectively, have been proposed. An analytical solution to the enhancement factor was derived for gas absorption with a first-order reaction in a finite liquid layer in plug flow. The exact solution to the enhancement factor was obtained numerically for the case of a second-order reaction. The enhancement factor in both reaction cases tends to deviate from the penetration theory's solution at Fourier numbers above 0.1. Approxi-mate expressions describing the obtained solutions were proposed.
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  • 37
    Publication Date: 2012-04-15
    Description: An integrated continuous process, which combines catalytic distillation and extractive distillation in one column, is investigated for the synthesis of high-purity methylal from methanol and formalin in the presence of a cation-exchange resin catalyst. A feed with methanol:formaldehyde 2:1 molar ratio is chosen to evaluate the effects of operating parameters, such as extractant feeding position, ratio of extractant to feed, reflux ratio, and reboiler temperature, on the continuous synthesis of methylal. Under the optimum operating conditions and with water as extractant, the extractive catalytic distillation process operated continuously, producing a methylal purity of 98.7 % (H 2 O: 〈 1.30 %) with 98.0 % formaldehyde conversion. An integrated continuous process combining catalytic distillation and extractive distillation in one column is applied for high-purity methylal synthesis from methanol and formalin in the presence of a cation-exchange resin catalyst. Under optimum conditions, using water as extractant, the extractive catalytic distillation process provided a methylal purity of 98.7 % with 98.0 % formaldehyde conversion.
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  • 38
    Publication Date: 2012-04-15
    Description: The effect of slow ON-OFF liquid flow modulation on the yield of consecutive reactions is investigated for oxidation of aqueous ethanol solutions using a 0.5 % Pd/Al 2 O 3 commercial catalyst in a laboratory trickle-bed reactor. Experiments with modulated liquid flow rate (MLFR) were performed under the same hydrodynamic conditions (degree of wetting, liquid holdup) as experiments with constant liquid flow rate (CLFR). Thus, the impact of the duration of wet and dry cycles as well as the period can be independently investigated. Depending on cycling conditions, acetaldehyde or acetic acid production is favored with MLFR compared to CLFR. Results suggest both the opportunity and challenge of finding a way to tune the cycling parameters for producing the most appropriate product. ON-OFF liquid flow modulation in a trickle-bed reactor and its impact on the yield of ethanol oxidation in presence of a Pd/Al 2 O 3 catalyst is studied. High cycling frequencies benefit the yield toward the intermediate product, while intermediate frequencies significantly increase the final product yield. As demonstrated, product distribution can be considerably modified through frequency tuning.
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  • 39
    Publication Date: 2012-04-15
    Description: Problems with the pulse-jet bag filter operation have a direct influence on process plant operation and may result in loss of production time. Therefore, long-term stable operation of the plant is desirable for both the manufacturers and operators. The effects of operating parameters are studied experimentally on filter operation with regeneration between the upper and lower pressure drop limits. Many combinations were identified when the filter operation derailed from stable to unstable operation on changing one of the operating parameters. Filtration velocity, pulse pressure, and the upper limit of pressure drop had the potential of creating instability. A threshold detachment overpressure existed below which the operation led to unstable conditions at a certain filtration velocity and which increased with increasing velocity. Long-term stable operation of a filter plant is desirable for both the manufacturers and operators. Filter operation derailed from stable to unstable operation on changing one of the operating parameters under many combinations of operating conditions. A threshold detachment overpressure existed below which the operation led to unstable conditions at a certain filtration velocity and which increased with increasing velocity.
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  • 40
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    Publication Date: 2012-04-15
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  • 41
    Publication Date: 2012-04-15
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  • 42
    Publication Date: 2012-04-15
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  • 43
    Publication Date: 2012-04-15
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  • 44
    Publication Date: 2012-04-15
    Description: IGUS is the International Group of Experts on the Explosion Risks of Unstable Substances. Today, the aim of the group is to exchange information on the behavior of unstable substances and to improve safety in production, storage, transport, and use of these substances. Full members of IGUS work for governments and independent research organizations. Experts from industry can and do attend meetings by invitation. IGUS's 50th anniversary in 2012 gives reason to have a closer look at the questions of how IGUS came to be, what IGUS's aims and objectives were, and how it is organized and working today. Unstable substances stand for energetic materials ranging from explosives as blasting agents, propellants, and pyrotechnics to chemicals as organic peroxides, ammonium nitrate, oxidizers – a special field with respect to testing, classification, and regulation. For 50 years, IGUS, the International Group of Experts on the Explosion Risks of Unstable Substances, successfully takes care for this field.
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  • 45
    Publication Date: 2012-04-15
    Description: A novel capillary-based microfluidic device has been designed to follow the vinyl chloride polymerization reaction. Monodisperse droplets of 200 μm diameter could be obtained by means of a co-flow generation system, each one being considered as a polymerization reactor. Monomer droplets were visualized in a microchannel with a high-speed camera. At the end of the reaction, PVC grains were observed with a scanning electron microscopy technique. Real-time non-invasive Raman measurement was performed on stationary vinyl chloride monomer droplets and provided values of effective reaction orders and rate constants. This microdevice allowed reaction investigation under difficult conditions of pressure and temperature with a minimal amount of reagents. In order to follow the vinyl polymerization reaction, a novel capillary-based microfluidic device has been designed. Real-time non-invasive Raman measurement was performed on stationary vinyl chloride monomer droplets. This microdevice permitted to investigate the reaction under difficult conditions of pressure and temperature with a minimal amount of reagents and in a perfectly safe manner.
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  • 46
    Publication Date: 2012-04-15
    Description: The granulation procedure of a catalyst powder is a crucial step in designing a high-quality catalyst granulate for industrial applications. New granulation processes have been developed that make it possible to form granulates with a very narrow particle size distribution and high sphericity. The innovative granulation techniques offer a great potential to produce layered catalysts with inert cores and an active shell. The novel spherical granules consist of an inexpensive inert core coated with an active catalyst material. New core shell granules with an accurately designed spherical geometry have been synthesized and compared to conventional homogeneous spherical granules of the same shape. The conversion of methanol to olefins has been used as a test reaction to validate the efficiency of these promising granulates. Layered spherical granulates consisting of an inexpensive inert core and a catalytically active zeolite shell were synthesized via a spray granulation technique. These novel granulates showed a better performance in methanol to olefin conversion than conventional homogeneous granulates. Improved conversion efficiency could be demonstrated for synthesized as well as for commercial catalysts.
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  • 47
    Publication Date: 2012-04-15
    Description: Ni-Al 2 O 3 catalyst activity was tested for methane steam reforming using two different reaction systems: a catalyst particle bed (0.42–0.5 mm catalyst particles diluted in SiC) with a surface area-to-volume ratio SA/V of 910 m –1 and a porosity ϵ of 52 % and a catalyst-coated metal monolith with an SA/V of 3300 m –1 and an ϵ of 86 %. Under a steam-to-carbon ratio of 2.5 and at a temperature of 700 °C, the highest specific reaction rates were found for the catalyst-coated monolith. The high SA/V and ϵ, together with the high rate of heat transfer of the metal monolith were found to be responsible of this optimum behavior. However, in both systems, the Ni-Al 2 O 3 catalyst suffered a catalyst deactivation during operation. The potential use of metal monoliths for methane steam reforming activity testing is demonstrated comparing the behavior of a conventional Ni-Al 2 O 3 methane steam reforming catalyst as a bed of catalyst particles and as a catalyst-coated monolith. The monolith configuration provided the highest specific reaction rates due to the high surface area-to-volume ratio, high porosity, and high heat transfer rate.
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  • 48
    Publication Date: 2012-04-15
    Description: As droplets in emulsions are thermodynamically unstable, surfactants are required for their stabilization. However, these additives often are unwanted due to legal restrictions and possible health threats. Gelling of the aqueous phase poses one promising alternative. Only droplet-forming processes like microfluidic devices are known to successfully work so far for stabilization by gelling. As these processes are hard to scale-up and tend to foul, a technical alternative based on commonly used high-pressure homogenization is investigated. A nozzle was adapted by adding a micromixer directly behind the orifice outlet. This allowed gelling and stabilizing the droplets by feeding a cold oil stream immediately after droplet breakup. Up to 40 wt-% droplets with Sauter mean diameters down to the micrometer range could be successfully stabilized. An alternative way in stabilizing emulsion droplets is investigated. The idea of exclusive stabilization by gelling of the droplets was transferred to a high-pressure homogenizer. Stabilization is realized by means of forming a pectin gel matrix in the water droplets directly after droplet disruption. Possibilities for processing of surfactant-free emulsions and limitations of this process are discussed.
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  • 49
    Publication Date: 2012-04-05
    Description: The objective of the present work was to analyze the drying kinetics of silica gel based on an experimental study performed in a thin-layer dryer and a statistical discrimination of the main drying kinetic equations. Most semi-empirical drying kinetics equations presented in the literature are nonlinear; thus, care should be taken when estimating parameters, since in some situations the estimators may not be appropriate. There are procedures available to validate the statistical properties of the least squares estimators of nonlinear models. In this study, five semi-empirical drying kinetics equations were discriminated using measures of curvature and bias. The results showed that the Overhults equation is the best one to describe the drying kinetics of silica gel. The drying kinetics of silica gel was analyzed based on an experimental study performed in a thin-layer dryer and a statistical discrimination of the main drying kinetic equations. Five semi-empirical drying kinetics equations were discriminated using measures of curvature and bias. The Overhults equation is shown to be the best one to describe the drying kinetics of silica gel.
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  • 50
    Publication Date: 2012-04-05
    Description: Experimental studies on the solids holdup of a high-flux circulating fluidized bed (HFCFB) at an operating pressure up to 0.5 MPa were carried out. The effects of operating pressure, solids mass flux and superficial gas velocity on the solids holdup distribution were systematically tested. It was found that the solids holdup at elevated pressure increases with increasing solids mass flux but decreases with increasing superficial gas velocity, which is similar to the trends at atmospheric condition. As a result, the condition of a high-density circulating fluidized bed (HDCFB), i.e., solids holdup in everywhere of the riser is larger than 10 %) is easier to be achieved at elevated pressure than in a HDCFB operated at atmospheric pressure. In the current work, the condition of a full HDCFB with Geldart group B particles has been achieved successfully at 0.5 MPa. Experiments on the flow behavior in a high-flux circulating fluidized bed with Geldart group B particles were carried out at various operating pressures, solids mass fluxes and standard state superficial gas velocities. The influence of operating pressure, solids mass flux and superficial gas velocity on the solids holdup distribution were systematically tested.
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  • 51
    Publication Date: 2012-04-05
    Description: Screening and isolation of a new Bacillus subtilis strain and production of its proteases for leather unhairing are described. B. subtilis strain BLBc 11 was isolated from the aerobic sludge of a tannery. Optimization of enzyme production by this bacterium was carried out using the Plackett-Burman and central composite design. Unhairing and inter-fibrillary removal capabilities were evaluated by scanning electron microscopy and determination of proteoglycans and glycosaminoglycans. Crude enzymatic extracts of B. subtilis BLBc 11 cultures were applied for the unhairing process of hides with excellent results, suggesting that this safe enzymatic preparation can replace the toxic chemicals commonly used in this process. The applicability of unpurified proteolytic extracts from microorganisms isolated from tannery sludge for unhairing of hides was investigated. The Bacillus subtilis BLBc 11 strain turned out to be an excellent producer of such enzymes with hide unhairing capabilities. This safe enzymatic preparation can replace the toxic chemicals commonly used in this process.
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  • 52
    Publication Date: 2012-04-06
    Description: The adsorption of miglitol on the D001 resin in a fixed bed was studied at different flow rates, temperatures, and height-to-diameter ratios ( H / D ). The exhaustion time decreased and the height of the mass transfer zone ( H MTZ ) increased with increasing flow rate. The surface area of the adsorbent increased with decreasing solution flow rate. Breakthrough curves at different flows were described by the Thomas, Yoon–Nelson, and Adams-Bohart models. The rate constants for the kinetic models increased with increasing flow rate. The theoretical and experimental times required for 50 % adsorbate breakthrough slightly differed at varying flow rates. The change trend in the values of the maximum volumetric adsorption capacity was the same as that of the values at the maximum adsorption capacity of the D001 resin. The temperature did not obviously affect the breakthrough curves. The slope of the breakthrough curve decreased and the H MTZ increased with increasing H / D ratio. The adsorption capacities of the fixed bed for H / D = 7.6 and 0.7 were greater than that for H / D  = 1.5. The adsorption of miglitol on the D001 resin in a fixed bed was studied. Breakthrough curves at different flows were described by the Thomas, Yoon-Nelson, and Adams-Bohart models. The aim was to provide the theoretical basis and technical support for further separation investigations, to reduce the cost of miglitol synthesis and to provide guidance in technical designs of miglitol purification.
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  • 53
    Publication Date: 2012-04-13
    Description: A thermodynamic analysis is performed with a Gibbs free energy minimization method to compare the conventional steam reforming of ethanol (SRE) process and sorption-enhanced SRE (SE-SRE) with three different sorbents, namely, CaO, Li 2 ZrO 3 , and hydrotalcite-like compounds (HTlc). As a result, the use of a CO 2 adsorbent can enhance the hydrogen yield and provide a lower CO content in the product gas at the same time. The best performance of SE-SRE is found to be at 500 °C with an HTlc sorbent. Nearly 6 moles hydrogen per mole ethanol can be produced, when the CO content in the vent stream is less than 10 ppm, so that the hydrogen produced via SE-SRE with HTlc sorbents can be directly used for fuel cells. Higher pressures do not favor the overall SE-SRE process due to lower yielding of hydrogen, although CO 2 adsorption is enhanced. The current research status of thermodynamic analysis on ethanol steam reforming (SRE) and sorption-enhanced SRE (SE-SRE) is surveyed. Hydrotalcite-like compounds (HTlc), CaO, and Li 2 ZrO 3 as three typical CO 2 sorbents for SE-SRE are compared for the first time. The simulated results agree well with other publications.
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  • 54
    Publication Date: 2012-04-15
    Description: This work introduces a modified space-time conservation element/solution element (CE/SE) method for the simulation of the dynamic behavior of a pilot-scale hydrocracking reactor. With this approach, a four-lump dynamic model including vacuum gas oil (VGO), middle distillate, naphtha and gas is solved. The proposed method is capable of handling the stiffness of the partial differential equations resulting from the hydrocracking reactions. To have a better judgment, the model is also solved by the finite difference method (FDM), and the results from both approaches are compared. Initially, the absolute average deviation of the cold dynamic simulation using the CE/SE approach is 8.98 %, which is better than that obtained using the FDM. Then, the stability analysis proves that for achieving an appropriate response from the dynamic model, the Courant number, which is a function of the time step size, mesh size and volume flow rate through the catalytic bed, should be less than 1. Finally, it is found that, following a careful selection of these parameters, the CE/SE solutions to the hydrocracking model can produce higher accuracy than the FDM results. A four-lump dynamic model including vacuum gas oil, middle distillate, naphtha and gas was developed. To solve it, a modified space-time conservation element and solution element method was introduced to simulate the dynamic behavior of a pilot-scale hydrocracking reactor. The approach was evaluated by comparing its results with those obtained by applying the finite difference method.
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  • 55
    Publication Date: 2012-04-15
    Description: A thermodynamic analysis is performed with a Gibbs free energy minimization method to compare the conventional steam reforming of ethanol (SRE) process and sorption-enhanced SRE (SE-SRE) with three different sorbents, namely, CaO, Li 2 ZrO 3 , and hydrotalcite-like compounds (HTlc). As a result, the use of a CO 2 adsorbent can enhance the hydrogen yield and provide a lower CO content in the product gas at the same time. The best performance of SE-SRE is found to be at 500 °C with an HTlc sorbent. Nearly 6 moles hydrogen per mole ethanol can be produced, when the CO content in the vent stream is less than 10 ppm, so that the hydrogen produced via SE-SRE with HTlc sorbents can be directly used for fuel cells. Higher pressures do not favor the overall SE-SRE process due to lower yielding of hydrogen, although CO 2 adsorption is enhanced. The current research status of thermodynamic analysis on ethanol steam reforming (SRE) and sorption-enhanced SRE (SE-SRE) is surveyed. Hydrotalcite-like compounds (HTlc), CaO, and Li 2 ZrO 3 as three typical CO 2 sorbents for SE-SRE are compared for the first time. The simulated results agree well with other publications.
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  • 56
    Publication Date: 2012-04-15
    Description: Screening and isolation of a new Bacillus subtilis strain and production of its proteases for leather unhairing are described. B. subtilis strain BLBc 11 was isolated from the aerobic sludge of a tannery. Optimization of enzyme production by this bacterium was carried out using the Plackett-Burman and central composite design. Unhairing and inter-fibrillary removal capabilities were evaluated by scanning electron microscopy and determination of proteoglycans and glycosaminoglycans. Crude enzymatic extracts of B. subtilis BLBc 11 cultures were applied for the unhairing process of hides with excellent results, suggesting that this safe enzymatic preparation can replace the toxic chemicals commonly used in this process. The applicability of unpurified proteolytic extracts from microorganisms isolated from tannery sludge for unhairing of hides was investigated. The Bacillus subtilis BLBc 11 strain turned out to be an excellent producer of such enzymes with hide unhairing capabilities. This safe enzymatic preparation can replace the toxic chemicals commonly used in this process.
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  • 57
    Publication Date: 2012-04-15
    Description: Experimental studies on the solids holdup of a high-flux circulating fluidized bed (HFCFB) at an operating pressure up to 0.5 MPa were carried out. The effects of operating pressure, solids mass flux and superficial gas velocity on the solids holdup distribution were systematically tested. It was found that the solids holdup at elevated pressure increases with increasing solids mass flux but decreases with increasing superficial gas velocity, which is similar to the trends at atmospheric condition. As a result, the condition of a high-density circulating fluidized bed (HDCFB), i.e., solids holdup in everywhere of the riser is larger than 10 %) is easier to be achieved at elevated pressure than in a HDCFB operated at atmospheric pressure. In the current work, the condition of a full HDCFB with Geldart group B particles has been achieved successfully at 0.5 MPa. Experiments on the flow behavior in a high-flux circulating fluidized bed with Geldart group B particles were carried out at various operating pressures, solids mass fluxes and standard state superficial gas velocities. The influence of operating pressure, solids mass flux and superficial gas velocity on the solids holdup distribution were systematically tested.
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  • 58
    Publication Date: 2012-04-15
    Description: The objective of the present work was to analyze the drying kinetics of silica gel based on an experimental study performed in a thin-layer dryer and a statistical discrimination of the main drying kinetic equations. Most semi-empirical drying kinetics equations presented in the literature are nonlinear; thus, care should be taken when estimating parameters, since in some situations the estimators may not be appropriate. There are procedures available to validate the statistical properties of the least squares estimators of nonlinear models. In this study, five semi-empirical drying kinetics equations were discriminated using measures of curvature and bias. The results showed that the Overhults equation is the best one to describe the drying kinetics of silica gel. The drying kinetics of silica gel was analyzed based on an experimental study performed in a thin-layer dryer and a statistical discrimination of the main drying kinetic equations. Five semi-empirical drying kinetics equations were discriminated using measures of curvature and bias. The Overhults equation is shown to be the best one to describe the drying kinetics of silica gel.
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  • 59
    Publication Date: 2012-04-15
    Description: The adsorption of miglitol on the D001 resin in a fixed bed was studied at different flow rates, temperatures, and height-to-diameter ratios ( H / D ). The exhaustion time decreased and the height of the mass transfer zone ( H MTZ ) increased with increasing flow rate. The surface area of the adsorbent increased with decreasing solution flow rate. Breakthrough curves at different flows were described by the Thomas, Yoon–Nelson, and Adams-Bohart models. The rate constants for the kinetic models increased with increasing flow rate. The theoretical and experimental times required for 50 % adsorbate breakthrough slightly differed at varying flow rates. The change trend in the values of the maximum volumetric adsorption capacity was the same as that of the values at the maximum adsorption capacity of the D001 resin. The temperature did not obviously affect the breakthrough curves. The slope of the breakthrough curve decreased and the H MTZ increased with increasing H / D ratio. The adsorption capacities of the fixed bed for H / D = 7.6 and 0.7 were greater than that for H / D  = 1.5. The adsorption of miglitol on the D001 resin in a fixed bed was studied. Breakthrough curves at different flows were described by the Thomas, Yoon-Nelson, and Adams-Bohart models. The aim was to provide the theoretical basis and technical support for further separation investigations, to reduce the cost of miglitol synthesis and to provide guidance in technical designs of miglitol purification.
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  • 60
    Publication Date: 2012-04-15
    Description: A new approach for process intensification through process simplification is proposed. This approach is based on a mass-integration framework for reducing the number of processing steps for grassroots and retrofit designs. Two procedures are presented based on graphical and mathematical programming techniques. The process simplification task is aimed at synthesizing process configurations that involve the least number of processing steps while yielding a certain product from a set of raw materials. The new concepts of maximum extendible zones and product paths are introduced and incorporated into the design procedure. The solution identifies the simplest processes along with their configuration, stream distribution, and basic performance data. A new systematic approach to process simplification is presented. The objective is to convert the raw materials to products in the least number of processing steps. This involves choosing the proper technologies, unit type, unit size, operating conditions, and materials. A methylethylketone process is used as a case study to demonstrate the benefits of applying the proposed process simplification approach.
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  • 61
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    Wiley
    Publication Date: 2012-04-15
    Description: Lippe Natural Gas Compressor Station. Courtesy of WINGAS GmbH & Co. KG.
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  • 62
    Publication Date: 2012-04-15
    Description: The electro-Fenton (EF) process is a promising method combining electrochemical reactions and Fenton's reagent. In this hybrid process, the electrical current induces the in situ generation of H 2 O 2 via reduction of oxygen, and the catalytic reaction is propagated by Fe 2+ regeneration, which can take place by reduction of Fe 3+ with H 2 O 2 , hydroperoxyl radical, organic radical intermediates, or directly at the cathode. Recent advances in the EF process are discussed and several key variables analyzed, including electrode material, initial pH, and Fenton's reagents, in order to extend the applicability of this technology. A brief survey of the electro-Fenton (EF) process for the removal of different pollutants is presented. Special attention is focused on improving the technology by optimization of the fundamental variables governing the process, including pH, electrode material, and identity of Fenton's reagents in order to extend the applicability of this process.
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  • 63
    Publication Date: 2012-04-15
    Description: Particle synthesis in liquid phase usually requires a subsequent washing step in order to remove undesirable impurities such as unreacted educts, byproducts, solvents and salts. In particular, the washing of mesoporous particles is a challenging task due to large specific surface areas and void volumes. The filter cake washing of mesoporous SiO 2 particles contaminated either with an adsorbing fluorescent dye or sodium sulfate is presented. The effects of wash liquid mass flow rate, mean particle size, and mean pore size on the wash efficiency were investigated. Especially the interaction between impurities and the solid surface, and thereby the initial impurity distribution within the filter cake, led to distinctive washing behaviors. Filter cake washing of porous SiO 2 particles is demonstrated. Major focus was put on the washing behavior and washing efficiency according to the interaction between two types of model impurities and the particle surface. Moreover, the influences of the wash liquid mass flow rate and of particle properties such as particle mean pore size and particle fraction on the wash curves were investigated.
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  • 64
    Publication Date: 2012-04-15
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  • 65
    Publication Date: 2012-04-12
    Description: Crystallization is a suitable process for selective separation of a target ion since ions can be removed and recovered as purified and stable materials. Methods of recovery and recycling of phosphate and fluoride ions have been investigated to determine the optimum crystallization conditions like supersaturation, temperature, pH, impurities, and kind of solvents. As a result, by selecting the optimum crystal operation conditions for each wastewater composition, spherical-shape crystals with desired purity and size are obtained and generation of sludge is minimized. Recovery and recycling of phosphate and fluoride ions are investigated to determine the optimum crystallization conditions in terms of supersaturation, temperature, pH, impurities, and kind of solvents. By selecting the optimum crystal operation condition for each wastewater composition, spherical-shape crystals with desired purity and size are obtained and generation of sludge is minimized.
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  • 66
    Publication Date: 2012-04-15
    Description: Manufacturing of polysilicon by chemical vapor deposition from SiHCl 3 in a fluidized-bed reactor was studied. The effects of reaction temperature, H 2 /SiHCl 3 ratio, gas velocity, and seed particle loading were evaluated. The outlet gas composition was analyzed by gas chromatography. The physical features of the product particles were determined by scanning electron microscopy and laser particle size analyzer. Well-grown product particles were obtained. The temperature and H 2 /SiHCl 3 ratio significantly affected conversion, yield, and selectivity, which were less affected by gas velocity and seed particle loading at higher temperatures. The surface reaction kinetics determined the product yield only at lower temperatures, and thermodynamic equilibrium was approached at temperatures above 900 °C. The preparation of polysilicon from trichlorosilane by chemical vapor deposition was studied in a lab-scale fluidized-bed reactor. A well-grown polysilicon product was obtained. The temperature and H 2 /SiHCl 3 ratio significantly affected conversion, yield, and selectivity which were less influenced by gas velocity and seed particle loading at higher temperatures.
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  • 67
    Publication Date: 2012-04-15
    Description: Interfacial void-free mixed-matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano-zeolites and tested for gas separation purposes. Fabrication of a void-free polymer-zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO 2 /N 2 and CO 2 /CH 4 selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO 2 /CH 4 and CO 2 /N 2 at the three examined feed pressures of 4, 8 and 12 atm. Homogeneous mixed-matrix membranes (MMMs) based on polyimide-zeolite nanocrystal composites were developed using an optimized manufacturing approach to improve the interfacial compatibility between the zeolite and the polymer matrix for selective gas separation. The permeabilities and selectivities of the MMMs toward CO 2 , CH 4 and N 2 gases were studied at different feed pressures.
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  • 68
    Publication Date: 2012-04-15
    Description: This review highlights selected examples of photochemical transformations in microflow reactors. The main advantages of microflow reactors over conventional batch systems are superior light penetrations, controlled reaction times, precise temperature control and removal of photoproducts from the irradiated area. These features typically result in higher conversions or yields, improved selectivity, enhanced energy efficiencies and reductions of solvent volumes and consequently waste. Different types of homogeneous and heterogeneous reactions are presented, showing the superiority of microflow photochemistry over batch processes. Following the famous Lab on a chip approach, synthetic organic photochemistry has also been miniaturized. The combination of microscopic dimensions and flow conditions offers exciting advantages for photochemical reactions. Using selected highlights from the literature, this review aims to demonstrate the superiority of microflow photochemistry over conventional batch techniques.
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  • 69
    Publication Date: 2012-04-15
    Description: A discrete bubble model has been developed taking into account multiple bubble-bubble interactions and a delayed coalescence method. The obtained simulation results were compared with experimental data reported in literature. The simulation results predicted by the developed model indicate clearly that the multiple interactions of bubbles lead to more reasonable results than those predicted by a binary interaction model. In addition, two types of interaction models were applied and predicted results were compared. The frequency of gas bubbles passing through the bed cross section versus bed height follows the same trend as the experimental data. A new modified discrete bubble model has been developed for freely bubbling fluidized beds. The influence of two various types of bubble-bubble interaction models on the bubble behavior were investigated and a new coalescence method based on the wake angle of gas bubbles was applied. It was found that the delayed coalescence method predicts bubble behavior better than the sudden coalescence method.
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  • 70
    Publication Date: 2012-04-15
    Description: Significant progress has been made in developing formulations for protein and drug encapsulation and delivery. The most frequently used method is the emulsion/solvent removal technology, where microencapsulation of proteins in polymeric matrices can be easily achieved with a simple stirrer setup. However, it remains a challenge to produce protein-encapsulated formulations with high encapsulation efficiencies. The emulsion/solvent removal technique and the relevant formulation and process parameters that govern the protein encapsulation processes are reviewed. A new encapsulation method of using foam as a delivery medium during the preparation of protein-loaded microparticles is proposed. The foam characteristics of direct relevance to protein encapsulation are discussed. The unique properties of foam could enhance intermolecular interactions and access to internal pore surfaces, thus making them superior compared to traditional methods employing aqueous liquid phases during protein encapsulation. The emulsion/solvent removal technique for production of protein-loaded microparticles including the relevant formulation and process parameters governing protein encapsulation are reviewed. A new encapsulation method using foam as a delivery medium for preparation of protein-loaded microparticles is proposed. The foam characteristics of direct relevance to protein encapsulation are discussed.
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  • 71
    Publication Date: 2012-04-15
    Description: Nanoseeds of BZSM-5 zeolite with a narrow particle size distribution of 100–200 nm were successfully prepared under mild hydrothermal conditions. Thin and oriented BZSM-5 membranes of 3–4 μm, prepared at low temperature, were manufactured and examined for the separation of 5 wt-% ethanol/water mixtures. Separation factor and flux were 13.93 and 1.11 kg m –2 h –1 , respectively. The temperature of synthesis showed a remarkable influence on the morphology, crystal orientation and separation performance of the membranes. The thinner a,b-oriented membrane showed a higher separation performance than the thicker h0h-oriented one. Nanoseeds of BZSM-5 zeolite with a narrow particle size distribution were prepared under mild hydrothermal conditions. Thin and oriented BZSM-5 membranes were manufactured and examined for the separation of 5 wt-% ethanol/water mixtures. The temperature of synthesis showed a remarkable influence on the morphology, crystal orientation and separation performance of the membranes.
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  • 72
    Publication Date: 2012-04-15
    Description: Biomass holds great promise as a renewable source of hydrogen and thus as a zero-emission, carbon-neutral, and nearly inexhaustible energy resource. Thermodynamic analysis of biomass hydration is carried out to study the reaction properties considering a series of saccharides as a model. Equilibrium constants and composition are estimated in dependence on the saccharide chain length and temperature. The latter is also studied as a function of the reactant ratios and in the presence of nonreacting additives. Being highly endothermic, the reaction is thermodynamically favorable due to a high entropic contribution. Increase in the saccharide chain length affects the conversion only slightly, so the results for low-molecular-weight saccharides can be transferred to long-chain ones. The hydration of oligosaccharides to hydrogen is evaluated from the equilibrium thermodynamics viewpoint. The reaction is thermodynamically favorable even at mild conditions and is entropically driven. With increasing oligosaccharide chain length, the conversion remains nearly constant. Therefore, results for short chain saccharides can also be applied to long chain sugars such as cellulose.
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  • 73
    Publication Date: 2012-04-15
    Description: A synthesis of diethyl carbonate through transesterification of propylene carbonate and ethanol, coproducing useful propylene glycol, was carried out in the presence of sodium ethoxide as catalyst. The effects of reaction parameters such as catalyst concentration, mole ratio of ethanol to propylene carbonate and reaction temperature on the transesterfication reaction were investigated. The results showed that the reaction is reversible with a propylene carbonate equilibrium conversion of about 64 % at an ethanol to propylene carbonate mole ratio of 8.0 and a reaction temperature of 303 K. A kinetic model was proposed based on the reaction mechanism. The model parameters were estimated by the Runge-Kutta method. The statistical test showed that the model calculation results were in good agreement with the experimental data. A synthesis of diethyl carbonate through transesterification of propylene carbonate and ethanol, coproducing useful propylene glycol, was carried out in the presence of sodium ethoxide as catalyst. The effects of reaction parameters such as catalyst concentration, mole ratio of ethanol to propylene carbonate and reaction temperature on the transesterfication reaction were investigated.
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  • 74
    Publication Date: 2012-04-15
    Description: Crystallization is a suitable process for selective separation of a target ion since ions can be removed and recovered as purified and stable materials. Methods of recovery and recycling of phosphate and fluoride ions have been investigated to determine the optimum crystallization conditions like supersaturation, temperature, pH, impurities, and kind of solvents. As a result, by selecting the optimum crystal operation conditions for each wastewater composition, spherical-shape crystals with desired purity and size are obtained and generation of sludge is minimized. Recovery and recycling of phosphate and fluoride ions are investigated to determine the optimum crystallization conditions in terms of supersaturation, temperature, pH, impurities, and kind of solvents. By selecting the optimum crystal operation condition for each wastewater composition, spherical-shape crystals with desired purity and size are obtained and generation of sludge is minimized.
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  • 75
    Publication Date: 2012-04-15
    Description: Convective heat transfer characteristics of microencapsulated phase change material slurries (MPCSs) flowing in a circular tube under constant heat flux are studied and a feasible heat transfer model is presented. The heat transfer coefficient of MPCS and the wall temperature of the circular tube are simulated. The simulation results agree qualitatively with the experimental results. The effects of Stefan (Ste) number, mass concentration, phase change temperature range, and Reynolds (Re) number on heat transfer characteristics are discussed. The results indicate that the Ste-number and mass fraction are the most important parameters influencing heat transfer properties compared to the phase change temperature range and Re-number which less affect these characteristics. The heat transfer characteristics of microencapsulated phase change slurries are analyzed and the effects of Stefan number, mass concentration, and Reynolds number are discussed. The phase change process, Stefan number, and mass fraction influence these heat transfer characteristics significantly. The heat transfer coefficient increases with higher Reynolds numbers.
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  • 76
    Publication Date: 2012-04-15
    Description: A novel chemical soft-sensor approach for the prediction of the melt index (MI) in the propylene polymerization industry is presented. The MI is considered as one of the important variables of quality that determine the product specifications. Thus, a reliable estimation of the MI is crucial in quality control. An accurate optimal predictive model of MI values with the relevance vector machine (RVM) is proposed, where the RVM is employed to build the MI prediction model; a modified particle swarm optimization (MPSO) algorithm is then introduced to optimize the parameter of the RVM, and the MPSO-RVM model is thereby developed. An online correcting strategy (OCS) is further carried out to update the modeling data and to revise the model's parameter self-adaptively whenever model mismatch happens. Based on the data from a real polypropylene production plant, a detailed comparison is carried out among the least squares support vector machine (LS-SVM), RVM, MPSO-RVM, and OCS-MPSO-RVM models. The research results reveal the prediction accuracy and validity of the proposed approach. A chemical soft-sensor approach for the prediction of the melt index (MI) in the propylene polymeriza-tion industry is presented. The relevance vector machine (RVM) is employed to build the MI prediction model. A modified particle swarm optimization algorithm is then introduced to optimize the parameter of the RVM and an online correcting strategy is carried out to update the modeling data.
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  • 77
    Publication Date: 2012-04-15
    Description: The selectivity and conversion of the sulfuric acid-catalyzed Beckmann rearrangement of cyclohexanone oxime, dissolved in cyclooctane, to ϵ-caprolactam are determined in a microreactor for conditions with a high concentration of ϵ-caprolactam. The microreactor consists of a low-temperature mixing zone followed by a high-temperature reaction zone. The mixing is conducted in a split-and-recombine micromixer and a microchannel at 65 °C, followed immediately by a second microchannel at 100–127 °C to obtain complete conversion. Under these conditions a selectivity of 99 % is achieved. The residence time of the reactants in the microreactor setup is about 10 s. In literature, a selectivity of about 95 % for the same reaction in a similar setup is reported, but at a uniform temperature of 120–130 °C for mixing and reaction. So, suppressing the reaction during mixing is a major tool to enhance the selectivity to ϵ-caprolactam. Selectivity and conversion of the sulfuric acid-catalyzed Beckmann rearrangement of cyclohexanone oxime, dissolved in cyclooctane, to ϵ-caprolactam are determined in a microreactor consisting of a low-temperature mixing zone followed by a high-temperature reaction zone. Under these conditions, with a residence time of the reactants of just ∼10 s, complete conversion and a selectivity of 99 % are found.
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  • 78
    Publication Date: 2012-04-15
    Description: The integrated cold box and demethanizer system as one of the most critical production sections in an ethylene plant couples multistage refrigeration and cryogenic separation to extract hydrogen and methane from the cracked gas feed. Ethylene and the heavier components are liquefied for recovery in the downstream process. During separation, ethylene contained in the methane and hydrogen streams is accounted as the product loss which in reality is significant. To reduce the ethylene loss with energy consumption consideration, a systematic methodology has been developed to optimize the process operation of the integrated cold box and demethanizer system. It covers rigorous simulation model development and validation, sensitivity analysis, operational optimization, and result analysis. The optimization results demonstrate the significant economic benefits of the proposed methodology. The integrated cold box and demethanizer system in ethylene plants consumes huge amounts of energy and causes significant ethylene product loss. A systematic methodology has been developed to optimize the process operation of this system, so as to minimize the total ethylene product loss under consideration of energy consumptions.
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  • 79
    Publication Date: 2012-04-15
    Description: In order to enhance the uniformity of the radial solids distribution and thereby the performance of industrial circulating fluidized-bed (CFB) risers, an approach by using the air jet from the riser circumference is proposed. The Eulerian-Eulerian computational fluid dynamics (CFD) model with the kinetic theory of granular flow is adopted to simulate the gas-solids two-phase flow in a CFB riser with fluid catalytic cracking (FCC) particles. The numerical results indicate that by employing the circumferential air jet approach under appropriate jet velocities, the maximum solids concentration in the near-wall region can be greatly reduced, the entrance region can be shortened, and the uniformity of the flow structure can be significantly improved. A circumferential air jets approach is proposed to improve the uniformity of lateral or radial solids concentration distributions mainly in the fully developed region. A comprehensive numerical study on the effects of this approach on the flow structure of gas-solids two-phase flows in a circulating fluidized-bed (CFB) riser is conducted. The results could permit optimal designs and operations of CFBs.
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  • 80
    Publication Date: 2012-04-15
    Description: Response surface methodology was employed to optimize the conditions of supercritical CO 2 extraction of the oil from freeze-dried onion powder. The effects of pressure, temperature and extraction time on the yield of oil were investigated. The maximum extraction yield of 4.69 ± 0.04 g/kg dry basis was achieved at a pressure of 20.6 MPa, a temperature of 40.6 °C, a time of 260 min, a CO 2 flow rate of 22 L h –1 , and an entrainer ratio of 0.1 mL absolute ethanol per gram dry basis. The chemical composition of the oil was analyzed by gas chromatography-mass spectrometry. The most representative compounds of the essential oil were organosulfur-containing compounds and, among these, the main constituents were methyl 5-methylfuryl sulfide (18.30 %), methyl 3,4-dimethyl-2-thienyl disulfide (11.75 %) and 1-propenyl propyl disulfide (9.72 %). The effects of the extraction parameters of pressure, temperature and extraction time on the yield of onion oil from freeze-dried onion powder using the supercritical fluid extraction method and CO 2 as the extraction solvent were evaluated. The extraction conditions were optimized using response surface methodology.
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  • 81
    Publication Date: 2012-04-15
    Description: A reduced model by proper orthogonal decomposition (POD) and Galerkin projection methods for steady-state heat convection is established on a nonuniform grid. It was verified by thousands of examples that the results are in good agreement with the results obtained from the finite volume method. This model can also predict the cases where model parameters far exceed the sample scope. Moreover, the calculation time needed by the model is much shorter than that needed for the finite volume method. Thus, the nonuniform POD-Galerkin projection method exhibits high accuracy, good suitability, and fast computation. It has universal significance for accurate and fast prediction. Also, the methodology can be applied to more complex modeling in chemical engineering and technology, such as reaction and turbulence. The POD projection method for the steady-state heat convection problem was extended to a non-uniform grid. This model can predict many complex conditions up to as many as eleven variables, regardless of whether these variables are within the sample scope or even if the distributions of boundary conditions obey different laws to the samples.
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  • 82
    Publication Date: 2012-04-15
    Description: The leaching kinetics of spent nickel oxide catalysts in HCl and aqua regia solution is described. The considered parameters affecting nickel recovery are particle size, reaction time, acid concentration, and reaction temperature. Nickel could be extracted with HCl by ∼87.41 % and with aqua regia by ∼81.01 % using a spent catalyst with 200 mesh particle size at a reaction temperature of 100 °C. The reaction time was 360 min and the concentrations of HCl and aqua regia were 37 % and 80 %, respectively. The leaching kinetics indicates that shrinking sphere and diffusion were the rate-controlling processes during the reactions with HCl and aqua regia, respectively. The activation energies for HCl and aqua regia were determined as 24.04 and 19.03 kJ mol –1 , respectively. The kinetics of leaching nickel from spent nickel oxide catalysts in HCl and aqua regia solutions as well as process parameters affecting nickel recovery were investigated. The leaching kinetics indicates that shrinking sphere and diffusion were the rate-controlling processes during the reaction for HCl and aqua regia, respectively.
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  • 83
    Publication Date: 2012-04-13
    Description: Pyrolytic lignin is attributed to the instability of bio-oil but is a potential chemical material. To improve the stability and increase the economic viability of bio-oil, high- and low-molecular-mass pyrolytic lignin (HMM and LMM) were obtained using solvent extraction. The microstructure of pyrolytic lignin was examined by Fourier transform infrared spectrometry (FTIR). The dissimilar absorption intensities indicated the different content of corresponding functional groups in HMM and LMM. The pyrolysis behavior of HMM and LMM was studied by thermogravimetry coupled with FTIR. Obviously pyrolytic lignin undergoes three weight loss stages. Pyrolytic lignin contributes to the instability of bio-oil; however, it is also discussed as a potential chemical material. In order to improve the stability of bio-oil high- (HMM) and low-molecular-mass (LMM) pyrolytic lignins were obtained by solvent extraction. The microstructures, pyrolysis behavior, and gas generation of HMM and LMM were investigated by thermogravimetry-FTIR.
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  • 84
    Publication Date: 2012-04-13
    Description: Manufacturing of polysilicon by chemical vapor deposition from SiHCl 3 in a fluidized-bed reactor was studied. The effects of reaction temperature, H 2 /SiHCl 3 ratio, gas velocity, and seed particle loading were evaluated. The outlet gas composition was analyzed by gas chromatography. The physical features of the product particles were determined by scanning electron microscopy and laser particle size analyzer. Well-grown product particles were obtained. The temperature and H 2 /SiHCl 3 ratio significantly affected conversion, yield, and selectivity, which were less affected by gas velocity and seed particle loading at higher temperatures. The surface reaction kinetics determined the product yield only at lower temperatures, and thermodynamic equilibrium was approached at temperatures above 900 °C. The preparation of polysilicon from trichlorosilane by chemical vapor deposition was studied in a lab-scale fluidized-bed reactor. A well-grown polysilicon product was obtained. The temperature and H 2 /SiHCl 3 ratio significantly affected conversion, yield, and selectivity which were less influenced by gas velocity and seed particle loading at higher temperatures.
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  • 85
    Publication Date: 2012-04-13
    Description: An integrated continuous process, which combines catalytic distillation and extractive distillation in one column, is investigated for the synthesis of high-purity methylal from methanol and formalin in the presence of a cation-exchange resin catalyst. A feed with methanol:formaldehyde 2:1 molar ratio is chosen to evaluate the effects of operating parameters, such as extractant feeding position, ratio of extractant to feed, reflux ratio, and reboiler temperature, on the continuous synthesis of methylal. Under the optimum operating conditions and with water as extractant, the extractive catalytic distillation process operated continuously, producing a methylal purity of 98.7 % (H 2 O: 〈 1.30 %) with 98.0 % formaldehyde conversion. An integrated continuous process combining catalytic distillation and extractive distillation in one column is applied for high-purity methylal synthesis from methanol and formalin in the presence of a cation-exchange resin catalyst. Under optimum conditions, using water as extractant, the extractive catalytic distillation process provided a methylal purity of 98.7 % with 98.0 % formaldehyde conversion.
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  • 86
    Publication Date: 2012-04-13
    Description: This work introduces a modified space-time conservation element/solution element (CE/SE) method for the simulation of the dynamic behavior of a pilot-scale hydrocracking reactor. With this approach, a four-lump dynamic model including vacuum gas oil (VGO), middle distillate, naphtha and gas is solved. The proposed method is capable of handling the stiffness of the partial differential equations resulting from the hydrocracking reactions. To have a better judgment, the model is also solved by the finite difference method (FDM), and the results from both approaches are compared. Initially, the absolute average deviation of the cold dynamic simulation using the CE/SE approach is 8.98 %, which is better than that obtained using the FDM. Then, the stability analysis proves that for achieving an appropriate response from the dynamic model, the Courant number, which is a function of the time step size, mesh size and volume flow rate through the catalytic bed, should be less than 1. Finally, it is found that, following a careful selection of these parameters, the CE/SE solutions to the hydrocracking model can produce higher accuracy than the FDM results. A four-lump dynamic model including vacuum gas oil, middle distillate, naphtha and gas was developed. To solve it, a modified space-time conservation element and solution element method was introduced to simulate the dynamic behavior of a pilot-scale hydrocracking reactor. The approach was evaluated by comparing its results with those obtained by applying the finite difference method.
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  • 87
    Publication Date: 2012-04-13
    Description: Gas absorption accompanied by an irreversible chemical reaction of first-order or second-order in a liquid layer of finite thickness in plug flow has been investigated. The analytical solution to the enhancement factor has been derived for the case of a first-order reaction, and the exact solution to the enhancement factor has been obtained via numerical simulation for the case of a second-order reaction. The enhancement factor in both cases is presented as a function of the Fourier number and tends to deviate from the prediction of the existing enhancement factor expressions based on the penetration theory at Fourier numbers above 0.1 due to the absence of a well-mixed bulk region in the liquid layer. Approximate enhancement factor expressions that describe the analytical and exact solutions with an accuracy of 5 % and 9 %, respectively, have been proposed. An analytical solution to the enhancement factor was derived for gas absorption with a first-order reaction in a finite liquid layer in plug flow. The exact solution to the enhancement factor was obtained numerically for the case of a second-order reaction. The enhancement factor in both reaction cases tends to deviate from the penetration theory's solution at Fourier numbers above 0.1. Approxi-mate expressions describing the obtained solutions were proposed.
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  • 88
    Publication Date: 2012-04-13
    Description: β-Galactosidase is an enzyme industrially used to hydrolyze milk lactose, generating dairy products destined for people intolerant to this sugar. Its importance is due to its galactosiltransferase activity. The effects of elution pH and salt gradient volume were evaluated for purification of β-galactosidase by ion exchange chromatography using an experimental design and response surface techniques. The best conditions for purification of β-galactosidase were pH 5.5 with an elution volume of 62.8 mL, obtaining a yield of 85.5 % and a 12-fold increase in the purification factor in a one-step chromatography process. Purification of β-galactosidase by application of a single stage of ion exchange and evaluation of the important process parameters using an experimental design provided good results in the recovery and purification factor that could subsequently be scaled up. In an innovative study, the effects of elution pH and salt gradient volume were evaluated by ion exchange chromatography using an experimental design and response surface techniques for purification of β-galactosidase in only one chromato- graphy step. After optimization, β-galactosidase could be purified effectively with a 12-fold purification factor and 85.5 % recovery in a cost-reducing single step.
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  • 89
    Publication Date: 2012-04-15
    Description: Pyrolytic lignin is attributed to the instability of bio-oil but is a potential chemical material. To improve the stability and increase the economic viability of bio-oil, high- and low-molecular-mass pyrolytic lignin (HMM and LMM) were obtained using solvent extraction. The microstructure of pyrolytic lignin was examined by Fourier transform infrared spectrometry (FTIR). The dissimilar absorption intensities indicated the different content of corresponding functional groups in HMM and LMM. The pyrolysis behavior of HMM and LMM was studied by thermogravimetry coupled with FTIR. Obviously pyrolytic lignin undergoes three weight loss stages. Pyrolytic lignin contributes to the instability of bio-oil; however, it is also discussed as a potential chemical material. In order to improve the stability of bio-oil high- (HMM) and low-molecular-mass (LMM) pyrolytic lignins were obtained by solvent extraction. The microstructures, pyrolysis behavior, and gas generation of HMM and LMM were investigated by thermogravimetry-FTIR.
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  • 90
    Publication Date: 2012-04-15
    Description: Precipitation of silver nanocrystals was carried out in a poly(acrylic) acid (PAA) solution by using a single-jet crystallizer. The influence of the feeding rate, the injection position and the PAA dosage on the crystal size distribution (CSD) was clarified. The precipitated silver nanocrystals agglomerate with each other, forming an agglomerated microcrystal. In the presented case, smaller feeding rates caused smaller crystal sizes and narrower CSD widths. PAA, which is a water-soluble polyelectrolyte, successfully inhibited agglomeration and crystal growth, and decreased the crystal size and the CSD width. Thus, this idea may also facilitate the production of other nano-/microcrystalline particles. Precipitation of silver nanocrystals was carried out in a poly(acrylic) acid (PAA) solution by using a single-jet crystallizer. The influence of the feeding rate, the injection position and the PAA dosage on the crystal size distribution was determined and a mechanism of crystal growth in the presence of PAA is proposed.
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  • 91
    Publication Date: 2012-04-15
    Description: An approximate analysis of gas absorption with instantaneous reaction in a liquid layer of finite thickness in plug flow is presented. An approximate solution to the enhancement factor for the case of unequal diffusivities between the dissolved gas and the liquid reactant has been derived and validated by numerical simulation. Depending on the diffusivity ratio of the liquid reactant to the dissolved gas ( γ ), the enhancement factor tends to be either lower or higher than the prediction of the classical enhancement factor equation based on the penetration theory ( E i , pen ) at Fourier numbers typically larger than 0.1. An empirical correlation valid for all Fourier numbers is proposed to allow a quick estimation of the enhancement factor, which describes the prediction of the approximate solution and the simulation data with a relative error below 5 % under the investigated conditions ( γ = 0.3–4, E i , pen = 2–1000). An approximate solution to the enhancement factor for gas absorption accompanied by an instantaneous reaction in a liquid layer of finite thickness in plug flow was derived mathematically for unequal reactant diffusivities. The enhancement factor is shown as a function of the Fourier number, where the classical enhancement factor equation based on the penetration theory can only be applied at Fourier numbers 〈0.1.
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  • 92
    Publication Date: 2012-04-15
    Description: A diglycidyl ether type epoxy resin from bisphenol A, E-51, was cured by methylhexahydrophthalic anhydride (MeHHPA) and then decomposed in near-critical water without any additives. The effects of the experimental parameters such as the reaction temperature, reaction time, pressure, and feedstock ratio on the percentage of decomposition were investigated to obtain optimized reaction conditions. The results revealed that the percentage of decomposition can be enhanced by increasing either temperature or reaction time. At 260 °C, it initially increased with higher pressure and then decreased dramatically when the pressure further was reduced to the saturated water vapor pressure. The kinetics study of the epoxy decomposition was also carried out by monitoring the glass transition temperature of the solid product using differential scanning calorimetry. The decomposition equation was established and the activation energy was calculated to be 123.5 kJ mol –1 . Epoxy resin cured by an anhydride was successfully decomposed in near-critical water without any additives. The results demonstrated that near-critical water has the potential to serve as promising medium for converting epoxy resin into valuable downstream raw materials at low operating cost.
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  • 93
    Publication Date: 2012-04-15
    Description: The effect of temperature has been studied in hydrocracking of light cycle oil (LCO), byproduct of fluidized catalytic cracking (FCC) units on a bifunctional catalyst (Pt-Pd/HY zeolite). The increase in both temperature and H 2 partial pressure have an important attenuating effect on catalyst deactivation, given that they decrease sulfur equilibrium adsorption and enhance hydrocracking of coke precursors. Therefore, the catalyst maintains significant hydrodesulfurization and hydrocracking activity. As the temperature is increased, hydrocracking conversion and naphtha selectivity increase, although there is no significant dearomatization of the medium distillate fraction in the range of the studied experimental conditions. 400 °C is the more suitable temperature for obtaining a high yield of naphtha with a high content of i -paraffins. Valorization of light cycle oil into valuable blending streams (naphtha and medium distillates) can be reached by means of hydrocracking over a Pt-Pd catalyst, supported on a very acid HY zeolite. The effect of temperature as a key factor on conversion, yield, and selectivity of product fractions of interest is determined and evaluated.
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  • 94
    Publication Date: 2012-04-15
    Description: The isothermal kinetics of ethanol adsorption from aqueous solution onto a zeolite type carbon molecular sieve (CMS-3A) under conventional heating (CH) and microwave heating (MWH) was investigated. The adsorption kinetics is described by the model of a phase-boundary controlled reaction for both heating modes. The activation energy ( E a ) for the adsorption process under MWH is lower than under CH while the preexponential factor (ln A ) is higher. Ethanol adsorption is a kinetically complex process whose complexity changes with the mode of heating. The established decrease in E a and increase in ln A under MWH compared to CH is explained with the increase in the ground vibrational level of the – OH twisting vibrations in the ethanol molecule and with the decrease in its anharmonicity factor which is caused by the selective resonant transfer of energy from CMS-3A to the OH oscillators. A detailed comparative analysis of the kinetics of isothermal adsorption of ethanol from aqueous solution onto a carbon molecular sieve under conventional and microwave heating was performed. Aiming to establish and explain the influence of microwave heating on the kinetics of ethanol adsorption, this study focuses on the effects of microwave reaction conditions on a kinetic model, the values of the kinetic parameters and the kinetic complexity of the investigated process.
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  • 95
    Publication Date: 2012-08-25
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  • 96
    Publication Date: 2012-08-25
    Description: Reactive crystallization for separation and recovery of divalent metal ions from wastewater using a semi-batch crystallizer has been developed. In this process, metal carbonates are produced by reacting metal sulfate solution with sodium carbonate solution. Nickel and copper ions are crystallized under particular initial pH conditions but the product shapes are not regular. Consequently, sphere seeds have been used as nucleus-generating agents and their growth mechanism has been examined. When providing a particular amount of seeds before crystallization, metal substances piled up on the surface of the seeds, maintaining the form sphere, and the production of fines was restricted. The metal removal rate through reactive crystallization was ∼99.9 % on average. This operation proved to be suitable for application in industrial wastewater treatment and for recycling of metal materials. A reactive crystallization method for separation and recovery of divalent metal ions from wastewater using a semi-batch crystallizer has been developed which is effective for both effluent purification and metal recycling. Metal removal rates of around 99.9 % on average could be achieved. Applying optimum amounts of seeds, the production of fines was restricted and regular product shapes were attained.
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  • 97
    Publication Date: 2012-08-25
    Description: The material behavior of elastic-plastic zeolite 4A granules has been experimentally studied using compression tests. The influence of particle size and moisture content has been investigated. Furthermore, the specific fracture energy distribution and the distribution of the equivalent breakage velocity at impact on a rigid target have been determined. In order to investigate the mechanical behavior of zeolite 4A granules compression tests until primary breakage have been carried out. The influence of particle size and moisture content on the force-displacement curve has been analyzed. Moreover, the specific fracture energy distribution and the distribution of the equivalent velocity have been determined.
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  • 98
    Publication Date: 2012-08-25
    Description: Nanostructured particles made from polystyrene and zinc oxide are synthesized by precipitation in miniemulsions and miniemulsion polymerization. There are two main applications for miniemulsions: the formation of sub-micron or nano-sized reactors for the precipitation of inorganic nanoparticles and the use of sub-micron or nano-sized droplets as templates for nanostructured particles. The latter includes the formation of the desired structures within a monomer droplet, which then is polymerized without changing its size or structure during the process. In this research article two approaches to combine both processes are presented: The zinc oxide nanoparticles are precipitated in an inverse miniemulsion of water droplets in a continuous monomer phase. The resulting miniemulsion is either distilled and the nanoparticles are forced into the monomer phase or the miniemulsion is used directly without distillation. In both cases the particle loaded monomer droplets are afterwards polymerized to hybrid nanoparticles. The focus is on the technological challenges in producing nano-sized, hybrid particles, especially in regard to continuous processing. A process for the encapsulation of zinc oxide in polystyrene is developed. The zinc oxide nanoparticles are precipitated in an inverse miniemulsion of water droplets in a continuous monomer phase. The resulting miniemulsion is transferred into a direct miniemulsion, and the particle loaded monomer droplets are afterwards polymerized to hybrid nanoparticles.
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  • 99
    Publication Date: 2012-08-25
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  • 100
    Publication Date: 2012-08-25
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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