• Korean Chemical Engineering Research
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• v.50 no.3
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• pp.391-397
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• 2012

The depletion of conventional oil reserves and the increasing energy need in developing countries such as China and India result in exceeding oil demand over supply. As a solution of the problem, the efficient utilization of heavy oil has been receiving more and more interest. In order to utilize heavy oil, upgrading processes are required. Among the upgrading processes, thermal decomposition is thought to be relatively simple and economical. In this study, to understand basic characteristics of thermal decomposition of heavy oil, we conducted pyrolysis experiments of deasphalted oil (DAO) produced by a solvent deasphalting process. DAO is a mixture of many components and consists mainly of materials of carbon number 20~40. For the comparison with results of DAO pyrolysis, additional pyrolysis experiments with single materials of carbon number 30 ($C_{30}H_{62}$, $C_{30}H_{58}O_4S$, $C_{30}H_{63}O_3P$) were conducted. Pyrolysis experiments were carried out non-isothermally with variation of heating rate (10, 50, $100^{\circ}C$/min) in a thermogravimetric analyzer. Average pyrolysis activation energy determined by using Arrhenius method, Ingraham and Marrier method, and Coats and Redfern method was 72~99 kJ/mol. In the activation energy calculated by Ozawa-Flynn-Wall method, DAO had wider variation than other single materials.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.506-512
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• 2013

Biomass and low-grade coals are known to be better potential sources of energy compared to crude oil and natural gas since these materials are readily available and found to have large reserves, respectively. Gasification of these carbonaceous materials produced syngas for chemical synthesis and power generation. Woodchip, sawdust and lignite were gasified with steam in a thermobalance reactor under atmospheric pressure in order to evaluate their kinetic rate information. The effects of gasification temperature ($600{\sim}900^{\circ}C$) and partial pressure of steam (20~90 kPa) on the gasification rate were investigated. The three different types of gas-solid reaction models were applied to the experimental data to predict the behavior of the gasification reactions. The modified volumetric model predicted the conversion data well, thus the model was used to evaluate kinetic parameters in this study. The observed activation energy of biomass, sawdust and lignite gasification reactions were found to be in reasonable range and their rank was found to be sawdust > woodchip > lignite. The expression of apparent reaction rates for steam gasification of the three solids was proposed to provide basic information on the design of coal gasification processes.

• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.500-505
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• 2013

In this study, we investigated the kinetics of gas hydrate formation in the presence of ionic liquid (IL). Hydroxyethyl-methyl-morpholinium chloride (HEMM-Cl) was chosen as a material for the promotion effect test. Phase equilibrium curve for $CH_4$ hydrate with aqueous IL solution was obtained and its induction time and consumed amount of $CH_4$ gas were also measured. Aqueous solutions containing 20~20,000 ppm of HEMM-Cl was prepared and studied at 70 bar and 274.15 K. To compare the measured results to those of the conventional promoter, sodium dodecyl sulfate was also tested at the same condition. Result showed that the hydrate equilibrium curve was shifted toward higher pressure and lower temperature region. In addition, the induction time on $CH_4$ hydrate formation in the presence of IL was not shown. The amount of consumed $CH_4$ was increased with the whole range of tested concentration of IL and the highest consumption of $CH_4$ happened at 1,000 ppm of HEMM-Cl. HEMM-Cl induced and enhanced the $CH_4$ hydrate formation with a small amount of addition. Obtained result is expected to be applied for the development of technologies such as gas storage and transport using gas hydrates.

• Korean Chemical Engineering Research
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• v.45 no.6
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• pp.604-610
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• 2007

Characteristics of steam gasification and combustion of naphtha tar pitch, which is the bottom product of naphtha cracking process, were investigated by using the thermo gravimetric analyzer to develop the technology for obtaining syngas by using the naphtha tar pitch as a carbon source. Friedman's and Ozawa-Flynn-Wall method were used to calculate activation energy, reaction order and frequency factor of reaction rate constant for both of steam gasification and combustion. The activation energy of combustion of naphtha tar pitch based on the fractional conversion by Friedman's method was in the range of 41.58 ~ 68.14 kJ/g-mol when the fractional conversion level was in the range of 0.2~0.6, but 183.07~191.17 kJ/g-mol when the conversion level was 0.9~1.0, respectively. In case of steam gasification of naphtha tar pitch, the activation energy was in the range of 31.87~44.87 kJ/g-mol in the relatively lower conversion level (0.2~0.6), but 70.63~87.79 kJ/g-mol in the relatively higher conversion level (0.8~0.95), respectively. Those results exhibited that the steam gasification as well as combustion would occur by means of two steps such as devolitilization followed by combustion or gasification.

• Korean Chemical Engineering Research
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• v.46 no.5
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• pp.931-937
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• 2008

Rigorous multiscale modelling and simulation of the MTR for WGSR was carried out to accurately predict the behavior of process variables and the reactor performance. The MTR consists of 4 fixed bed tube reactors packed with heterogeneous catalysts, as well as surrounding shell part for the cooling purpose. Considering that fluid flow field and reaction kinetics give a great influence on the reactor performance, employing multiscale methodology encompassing Computational Fluid Dynamics (CFD) and process modeling was natural and, in a sense, inevitable conclusion. Inlet and outlet temperature of the reactant fluid at the tube side was $345^{\circ}C$ and $390^{\circ}C$, respectively and the CO conversion at the exit of the tube side with these conditions approached to about 0.89. At the shell side, the inlet and outlet temperature of the cooling fluid, which flows counter-currently to tube flow, was $190^{\circ}C$ and $240^{\circ}C$. From this heat exchange, the energy saving was achieved for the flow at shell side and temperature of the tube side was properly controlled to obtain high CO conversion. The simulation results from this research were accurately comparable to the experimental data from various papers.

• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.177-182
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• 2011

A diketo-type ligand was synthesized by the Knoevenagel condensation reaction of thiophene-2-aldehyde with acetylacetone, subsequently its transition metal complexes with Cu(II), Ni(II), and Co(II) chlorides were also prepared. All the complexes were characterized by various physico-chemical methods. The molar conductivity data reveals ionic nature for the complexes. The electronic spectrum and the EPR values suggest square planar geometry for the Cu(II) ion. Interaction of the Cu(II) complex with CTDNA (calf thymus DNA) was studied by absorption spectral method and cyclic voltammetry. The $k_{obs}$ values versus [DNA] gave a linear plot suggesting psuedo-first order reaction kinetics. The cyclic voltammogram of the Cu(II) complex reveals a quasi-reversible wave attributed to Cu(II)/Cu(I) redox couple for one electron transfer with $E_{1/2}$ values -0.240 V and -0.194 V. respectively. On addition of CTDNA, there is a shift in the $E_{1/2}$ values 168 mV and 18 mV respectively and decrease in Ep values. The shift in $E_{1/2}$ values in the presence of CTDNA suggests strong binding of Cu(II) complex to the CTDNA.

• Clean Technology
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• v.20 no.4
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• pp.425-432
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• 2014

The effect of two important parameters of a catalytic membrane reactor (CMR), hydrogen selectivity and hydrogen permeance, coupled with an Ar sweep flow and an operating pressure on the performance of a water gas shift reaction in a CMR has been extensively studied using a one-dimensional reactor model and reaction kinetics. As an alternative pre-combustion $CO_2$ capture method, the feasibility of capturing a pressurized and concentrated $CO_2$ in a retentate (a shell side of a CMR) and separating a purified $H_2$ in a permeate (a tube side of a CMR) simultaneously in a CMR was examined and a guideline for a hydrogen permeance, a hydrogen selectivity, an Ar sweep flow rate, and an operating pressure to achieve a simultaneous capture of a concentrate $CO_2$ in a retentate and production of a purified $H_2$ in a permeate is presented. For example, with an operating pressure of 8 atm and Ar sweep gas for rate of $6.7{\times}10^{-4}mols^{-1}$, a concentrated $CO_2$ in a retentate (~90%) and a purified $H_2$ in a permeate (~100%) was simultaneously obtained in a CMR fitted with a membrane with hydrogen permeance of $1{\times}10^{-8}molm^{-2}s^{-1}Pa^{-1}$ and a hydrogen selectivity of 10000.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.34 no.12
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• pp.1101-1109
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• 2010

We investigated the combustion rate and kinetic rate of char when burning in oxygen-enriched atmospheres with either an $N_2$ or $CO_2$ bath gas in a drop tube furnace. The experiments were performed with sub-bituminous coal (Adaro) and bituminous coal (Coal valley) under atmospheric pressure conditions. Two different coals were investigated over 12 to 30 vol% oxygen and furnace temperatures of 900, 1100, and $1300^{\circ}C$. For both coals, the particle temperature and overall reaction rate are lower in the $CO_2$ bath gas. However, analysis of single-particle data shows that the surface-specific burning rate of char oxidation is similar in both gases. In addition, the kinetic rate and activation energy for each coal were similar for both gases. Generally, the particle temperature and overall reaction rate of sub-bituminous coal are higher than those of bituminous coal.

• Elastomers and Composites
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• v.37 no.2
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• pp.79-85
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• 2002

Ethyl-branched polyethylene [PE(2)] containing 2mole% ethyl branch and three ethylene-propylene rubbers (EPR's) having the same ethylene(E)-propylene(P) molar ratio(E/P=50/50) with different stereoregularity, that is, random EPR (r-EPR), alternating-EPR (alt-EPR) and isotactic-alternating-EPR (iso-alt-EPR) were mixed for the investigation or their properties depending on the stereoregularity. Crystallinity of the prepared blends decreased with increasing content of amorphous EPR because of a decrease in both the degree of annealing and kinetics of diffusion of the crystallizable polymer content. With blend composition, crystallinity was reduced with the stereoregularity in EPR. The thermodynamic interaction parameter(x) for the three blend systems approximately equals to zero near the melting point. These systems were determined to be miscible on a molecular scale near or above the crystalline melting point or the crystalline PE(2). From the measurement of $T_m$ vs. $T_c$, the behavior of PE(2) is mainly due to a diluent effect of EPR component. The spherulite size measured by small angle light scattering (SALS) technique depended upon blend composition, and stereoregularity of EPR. The size of spherulite was enlarged with the content of rubbery EPR and the decrease of stereoregularity in EPR.

• Elastomers and Composites
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• v.34 no.2
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• pp.135-146
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• 1999

The thermal degradation kinetics of SBR and tire were studied using a conventional thermogravimetric analysis in the stream nitrogen at a heating rate of 5, 10, 15, $20^{\circ}C/min$, respectively. Thermogravimetric curves and their derivatives were analyzed using various analytical methods to determine the kinetic parameters. The degradation of the SBR and tire was found to be a complex process which has multi-stages. The Friedman method gave average activation energies for the SBR and tire of 247.53kJ/mol and 230.00kJ/mol, respectively. Mean-while, the Ozawa method Eave 254.80kJ/mol and 215.76kJ/mol. It would appear that either. Friedman's differential method or Ozawa's integral method provided satisfactory mathematical approaches to determine the kinetic parameters for the degradation of the SBR and tire. Approximately 86% and 55% of oil products were obtained at a final temperature of $700^{\circ}C$ and a heating rate of $20^{\circ}C/min$ for the SBR and tire respectively.