• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2615-2620
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• 2014

Ni/$La_2O_3$ with a high dispersion was prepared by reduction of $La_2O_3$ perovskite oxide to examine the catalytic activity for the $CO_2-CH_4$ reaction. The Ni/$La_2O_3$ catalyst was found to be highly active for the reaction. The ratios of $H_2$/CO were measured in a flow of the reaction mixture containing $CO_2/CH_4$/Ar using an on-line gas chromatography system operated at 1 atm and found to be varied with temperature between 0.66 and 1 in the temperature range of $500-800^{\circ}C$. A kinetic study of the catalytic reaction was performed in a static reactor at 40 Torr total pressure of $CO_2/CH_4/N_2$ by using a photoacoustic spectroscopy technique. The $CO_2$ photoacoustic signal varying with the concentration of $CO_2$ during the catalytic reaction was recorded as a function of time. Rates of $CO_2$ disappearance in the temperature range of $550-700^{\circ}C$ were obtained from the changes in the $CO_2$ photoacoustic signal at early reaction stage. The plot of ln rate vs. 1/T showed linear lines below and above $610^{\circ}C$. Apparent activation energies were determined to be 10.4 kcal/mol in the temperature range of $550-610^{\circ}C$ and 14.6 kcal/mol in the temperature range of $610-700^{\circ}C$. From the initial rates measured at $640^{\circ}C$ under various partial pressures of $CO_2$ and $CH_4$, the reaction orders were determined to be 0.43 with respect to $CO_2$ and 0.33 with respect to $CH_4$. The kinetic results were compared with those reported previously and used to infer a reaction mechanism for the Ni/$La_2O_3$-catalyzed $CO_2-CH_4$ reaction.

• Clean Technology
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• v.26 no.3
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• pp.221-227
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• 2020

When the waste solid fuel (SRF, Bio-SRF) is burnt in a boiler, a problem occurs in the combustion process involving the alkali components (Na, K) contained in large amounts in the fuel. The alkaline component has a low melting point, which usually forms low melting point salt in the temperature of the furnace, with the resulting low melting point salts attaching to the heat pipe to form a clinker. Various additives are used to suppress clinker generation, and the additive based on the kaolinite has alkali-aluminum-silica to inhibit the clinker. In this study, the reactivity of the additives based on the kaolinite was compared. The additives utilized were R-kaolinite, B-kaolinite, and A-kaolinite. Also silica and MgO were sourced as the comparison group. The experimental group was employed as a laboratory-scale batch horizontal reactor. The additive and alkaline salts were reacted at a weight ratio of 1 : 1, and the reaction temperature was performed at 900 ℃ for 10 hours. The first measurement of HCl occurring during the experiment was performed 30 minutes after the detection tube was used, and the process was repeated every hour after the experiment. After the reaction, solid residues were photographed for characterization analysis by means of an optical microscope. The reaction characteristics of the kaolinite were confirmed based on the analysis results.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.77-77
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• 2016

Thin films synthesized by plasma processes have been widely applied in a variety of industrial sectors. The structure control of thin film is one of prime factor in most of these applications. It is well known that the structure of this film is closely associated with plasma parameters and species of plasma which are electrons, ions, radical and neutrals in plasma processes. However the precise control of structure by plasma process is still limited due to inherent complexity, reproducibility and control problems in practical implementation of plasma processing. Therefore the study on the fundamental physical properties that govern the plasmas becomes more crucial for molecular scale control of film structure and corresponding properties for new generation nano scale film materials development and application. The thin films are formed through nucleation and growth stages during thin film depostion. Such stages involve adsorption, surface diffusion, chemical binding and other atomic processes at surfaces. This requires identification, determination and quantification of the surface activity of the species in the plasma. Specifically, the ions and neutrals have kinetic energies ranging from ~ thermal up to tens of eV, which are generated by electron impact of the polyatomic precursor, gas phase reaction, and interactions with the substrate and reactor walls. The present work highlights these aspects for the controlled and low-temperature plasma enhanced chemical vapour disposition (PECVD) of Si-based films like crystalline Si (c-Si), Si-quantum dot, and sputtered crystalline C by the design and control of radicals, plasmas and the deposition energy. Additionally, there is growing demand on the low-temperature deposition process with low hydrogen content by PECVD. The deposition temperature can be reduced significantly by utilizing alternative plasma concepts to lower the reaction activation energy. Evolution in this area continues and has recently produced solutions by increasing the plasma excitation frequency from radio frequency to ultra high frequency (UHF) and in the range of microwave. In this sense, the necessity of dedicated experimental studies, diagnostics and computer modelling of process plasmas to quantify the effect of the unique chemistry and structure of the growing film by radical and plasma control is realized. Different low-temperature PECVD processes using RF, UHF, and RF/UHF hybrid plasmas along with magnetron sputtering plasmas are investigated using numerous diagnostics and film analysis tools. The broad outlook of this work also outlines some of the 'Grand Scientific Challenges' to which significant contributions from plasma nanoscience-related research can be foreseen.

• Korean Chemical Engineering Research
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• v.49 no.5
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• pp.510-515
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• 2011

The pyrolytic reaction of 1,1-dichloroethylene($CH_2CCl_2$) has been conducted to investigate thermal decomposition of chlorocarbon and product formation pathways under hydrogen reaction environment. The reactions were studied in a isothermal tubular flow reactor at 1 atm total pressure in the temperature range $650{\sim}900^{\circ}C$ with reaction times of 0.3~2.0 sec. A constant feed molar ratio $CH_2CCl_2:H_2$ of 4:96 was maintained through the whole experiments. Complete decay(99%) of the parent reagent, $CH_2CCl_2$ was observed at temperature near $825^{\circ}C$ with 1 sec. reaction time. The important decay of $CH_2CCl_2$ under hydrogen reaction environment resulted from H atom cyclic chain reaction by abstraction and addition displacement. The highest concentration (28%) of $CH_2CHCl$ as the primary product was observed at temperature $700^{\circ}C$, where up to 46% decay of $CH_2CCl_2$ was occurred. The secondary product, $C_2H_4$ as main product was detected at temperature above $775^{\circ}C$. The one less chlorinated ethylene than parent increase with temperature rise subsequently. The HCl and dechlorinated hydrocarbons such as $C_2H_4$, $C_2H_6$, $CH_4$ and $C_2H_2$ were the main products observed at above $825^{\circ}C$. The important decay of $CH_2CCl_2$ resulted from H atom cyclic chain reaction by abstraction and addition displacement. The important pyrolytic reaction pathways to describe the features of reagent decay and intermediate product distributions, based upon thermochemical and kinetic principles, were suggested.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1052-1060
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• 1999

Tire and raw material of tire, i.e., SBR were degraded using pyrolysis process. The yield of pyrolytic oil was increased and that of gas was decreased with increase of operating temperature in pyrolysis. And the yield of pyrolytic oil was increased and that of gas and char was decreased with increase of heating rate. The maximum oil yields of SBR and tire were 86% and 55% each at $700^{\circ}C$ with a heating rate of $20^{\circ}C/min$. The number average molecular weight ranges of SBR and tire were 740~2486, 740~1719, and the calorific value of SBR and tire was 39~40 kJ/g. The oil components were consisted of mostly 50 aromatic compounds. The particle size was decreased and the surface area was increased with increase of operating temperature, and the BET surface area was $47{\sim}63m^2/g$. The optimum condition of pyrolysis was the temperature of $700^{\circ}C$ with heating rate of $20^{\circ}C$, and the reactor was continuously purged with inert gas to sweep the evolved gases from the reaction zone.

• 한국신재생에너지학회:학술대회논문집
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• 2005.11a
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• pp.561-566
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• 2005

Polycrystalline silicon films were deposited using hot wire CVD (HWCVD). The deposition of silicon thin films was approached by the theory of charged clusters (TCC). The TCC states that thin films grow by self-assembly of charged clusters or nanoparticles that have nucleated in the gas phase during the normal thin film process. Negatively charged clusters of a few nanometer in size were captured on a transmission electron microscopy (TEM) grid and observed by TEM. The negatively charged clusters are believed to have been generated by ion-induced nucleation on negative ions, which are produced by negative surface ionization on a tungsten hot wire. The electric current on the substrate carried by the negatively charged clusters during deposition was measured to be approximately $-2{\mu}A/cm^2$. Silicon thin films were deposited at different $SiH_4$ and $H_2$ gas mixtures and filament temperatures. The crystalline volume fraction, grain size and the growth rate of the films were measured by Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The deposit ion behavior of the si1icon thin films was related to properties of the charged clusters, which were in turn controlled by the process conditions. In order to verify the effect of the charged clusters on the growth behavior, three different electric biases of -200 V, 0 V and +25 V were applied to the substrate during the process, The deposition rate at an applied bias of +25 V was greater than that at 0 V and -200 V, which means that the si1icon film deposition was the result of the deposit ion of charged clusters generated in the gas phase. The working pressures had a large effect on the growth rate dependency on the bias appled to the substrate, which indicates that pressure affects the charging ratio of neutral to negatively charged clusters. These results suggest that polycrystalline silicon thin films with high crystalline volume fraction and large grain size can be produced by control1ing the behavior of the charged clusters generated in the gas phase of a normal HWCVD reactor.

• Journal of Animal Science and Technology
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• v.45 no.4
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• pp.641-648
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• 2003

In a batch mode treatment process, which electrolyzes the wastewater after derivation of N-P crystal formation and recovery, the characteristics of pollutant removal induced with the changes of loading rate and hydraulic retention time were studied. $MgCl_2$ was used as Mg source for the formation of struvite and the molar ratio of $MgCl_2$ to $PO_4^{3-}$ in influent was 1.3. When analyzing the average treatment efficiencies and removal characteristics obtained from four separate operations (Run I, II, III, IV), removal efficiencies of PO43- was not function of its loading rate. Under a condition of sufficient aeration and Mg source provided, over 88% of $PO_4^{3-}$ was eliminated by the formation of MAP without any pH adjustment, in spite of loading rate variation. An optimum-loading rate of NH4-N to achieve high removal efficiency was approximately $100g/m^3/d$. Below that loading rate, the removal of NH4-N was proportional to the loading rate into the system, and hence stable and high removal efficiency, over 90%, was achieved. However, when the loading rate increased over that rate, removal efficiency began to drop and fluctuate. Removal efficiency of TOCs was dependant upon the hydraulic retention time ($r^2$=0.97), not upon the loading rate. Stable and high color removal (94%) was obtained with 2 days of HRT in electrolysis reactor.

• Korean Journal of Environmental Agriculture
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• v.35 no.2
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• pp.121-127
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• 2016

BACKGROUND: Anaerobic digestion is the most feasible technology because not only the energy embedded in organic matters can be recovered, but also they are stabilized while being degraded. This study carried out to improve methane yield of slaughterhouse wastewater treatment sludge cake by the thermal pre-treatment prior to anaerobic digestion.METHODS AND RESULTS: Slaughterhouse wastewater treatment sludge cake was pre-treated by the closed hydrothermal reactor at reaction temperature of 190℃. BMPs (Biochemical methane potential) of the thermal hydrolysate was tested in the different S(Substrate)/I(Inoculum) ratio conditions. COD(Chemical oxygen demand) and SCOD(Soluble chemical oxygen demand) contents of thermal hydrolysate were 10.99% and 10.55%, respectively, then, the 96.00% of COD was remained as a soluble form. The theoretical methane potential of thermal hydrolysate was 0.51 Nm³ kg^-1-VS_added. And BMPs were decreased from 0.56 to 0.22 Nm³ kg^-1-VS_added when S/I ratio were increased from 0.1 to 2.0 in the VS content basis. Those were decreased from 0.32 to 0.13 Nm³ kg^-1-COD_added when S/I ratio were increased from 0.1 to 2.0 based on COD content. The anaerobic degradability of VS basis have showed 196.9%, 102.2%, 80.7%, 67.4%, and 39.4% in S/I ratios of 0.1, 0.3, 0.5, 1.0, and 2.0, respectively. Also the COD of 119.6%, 76.3%, 70.1%, 69.0%, and 43.1% were degraded anaerobically in S/I ratios of 0.1, 0.3, 0.5, 1.0, and 2.0, respectively.CONCLUSION: BMPs obtained in the S/I ratios of 0.1 and 0.3 was overestimated by the residual organic matters remaining at the inoculum. And inhibitory effect was observed in the highest S/I ratio of 2.0. The optimum S/I ratios giving reasonable BMPs might be in the range of 0.5 and 1.0 in S/I ratio. Therefore VS biodegradability of thermal hydrolysate was in 67.4-80.7% and COD biodegradability showed 69.0-70.1%.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.11
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• pp.1146-1153
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• 2008

Numerical simulation was carried out to study the trichloroethylene (TCE) degradation by permeable reactive barrier (PRB), and revealed the effect of concentration of TCE, iron medium mass, and concentration of iron-reducing bacteria (IRB). Newly developed model was based on axial dispersion reactor model with chemical and biological reaction terms and was implemented using MATLAB ver R2006A for the numerical solutions of dispersion, convection, and reactions over column length and elapsed time. The reaction terms include reactions of TCE degradation by zero-valent iron (ZVI, Fe$^0$) and ferrous iron (Fe$^{2+}$). TCE concentration in the column inlet was maintained as 10 mg/L. Equation for Fe$^0$ degradation includes only TCE reaction term, while one for Fe$^{2+}$ has chemical and biological reaction terms with TCE and IRB, respectively. Two coupled equations eventually modeled the change of TCE concentration in a column. At Fe$^0$ column, TCE degradation rate was found to be more than 99% from 60 hours to 235 hours, and declined to less than 1% in 1,365 hours. At the Fe$^{2+}$ and IRB mixed column, TCE degradation rate was equilibrated at 85.3% after 210 hours and kept it constant. These results imply that the ferrous iron produced by IRB has lowered the TCE degradation efficiency than ZVI but it can have higher longevity.http://kci.go.kr/kciportal/ci/contents/ciConnReprerSearchPopup.kci#

• Journal of Korean Society of Environmental Engineers
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• v.27 no.10
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• pp.1108-1113
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• 2005

Advanced oxidation process involving $O_3/H_2O_2$ was used to eliminate 1,4-dioxane and to enhance the biodegradability of dioxane-contaminated water. Oxidation process was carried out in a bubble column reactor under different pH and $H_2O_2$ concentrations. The removal efficiencies of 1,4-dioxane were investigated at hydrogen peroxide concentration between 40 and 120 mg/L. At the same pH, removal efficiencies of 1,4-dioxane increased with increasing initial $H_2O_2$ concentration. There was a linear relationship between initial concentration of $H_2O_2$ and the amount of consumed $O_3$. It was observed that the high $H_2O_2$ concentration accelerated the generation of hydroperoxy ions(${HO_2}^-$) and hydroxyl radicals($OH{\cdot}$). Hydrogen peroxide enhanced the decomposition of 1,4-dioxane and the biodegradability of the solution.