• Korean Journal of Environmental Agriculture
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• v.35 no.2
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• pp.128-136
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• 2016

BACKGROUND: Hydrothermal carbonization reaction is the thermo-chemical energy conversion technology for producing the solid fuel of high carbon density from organic wastes. The hydrothermal carbonization reaction is accompanied by the thermal hydrolysis reaction which converse particulate organic matters to soluble forms (hydro-thermal hydrolysate). Recently, hydrothermal carbonization is adopted as a pre-treatment technology to improve anaerobic digestion efficiency. This research was carried out to assess the effects of hydro-thermal reaction temperature on the methane potential and anaerobic biodegradability in the thermal hydrolysate of organic sludge generating from the wastewater treatment plant of poultry slaughterhouse .METHODS AND RESULTS: Wastewater treatment sludge cake of poultry slaughterhouse was treated in the different hydro-thermal reaction temperature of 170, 180, 190, 200, and 220℃. Theoretical and experimental methane potential for each hydro-thermal hydrolysate were measured. Then, the organic substance fractions of hydro-thermal hydrolysate were characterized by the optimization of the parallel first order kinetics model. The increase of hydro-thermal reaction temperature from 170℃ to 220℃ caused the enhancement of hydrolysis efficiency. And the methane potential showed the maximum value of 0.381 Nm³ kg^-1-VS_added in the hydro-thermal reaction temperature of 190℃. Biodegradable volatile solid(VSB) content have accounted for 66.41% in 170℃, 72.70% in 180℃, 79.78% in 190℃, 67.05% in 200℃, and 70.31% in 220℃, respectively. The persistent VS content increased with hydro-thermal reaction temperature, which occupied 0.18% for 170℃, 2.96% for 180℃, 6.32% for 190℃, 17.52% for 200℃, and 20.55% for 220℃.CONCLUSION: Biodegradable volatile solid showed the highest amount in the hydro-thermal reaction temperature of 190℃, and then, the optimum hydro-thermal reaction temperature for organic sludge was assessed as 190℃ in the aspect of the methane production. The rise of hydro-thermal reaction temperature caused increase of persistent organic matter content.

• Journal of the Korea Organic Resources Recycling Association
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• v.25 no.1
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• pp.35-45
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• 2017

In order to improve the anaerobic digestion efficiency of the sewage sludge, the methane potential of the hydrolysate generated from the hydro-thermal reaction at 170, 180, 190, 200, 210, $220^{\circ}C$ was analyzed and the constitutional characteristics of the organic materials were estimated by dividing organic materials of hydro-thermal hydrolysate into easily biodegradable, decomposition resistant, and non-biodegradable organic materials applying the parallel first order kinetics model. The ultimate methane potential of sewage sludge hydro-thermal hydrolysate increased to 0.39, 0.39, 0.40, 0.44, 0.45, and $0.46Nm^3/kg-VS_{added}$ as hydro-thermal reaction temperature increased from 170, 180, 190, 200, 210, $220^{\circ}C$. It has been shown that the organic matter of sewage sludge is solubilized to increase the content of biodegradable organic material($VS_B$). The easily degradable organic matter($VS_e$) content was highest at hydro-thermal reaction temperature of 200 and $210^{\circ}C$, and optimum hydro-thermal reaction temperature for organic matter solubilization of sewage sludge was in the range of $200{\sim}210^{\circ}C$. In addition, the amount of biodegradable organic material($VS_B$) and easily biodegradable organic matter ($VS_e$) in the hydrolysate of sewage sludge was the highest at hydro-thermal reaction temperature of $200^{\circ}C$.

• Journal of the Korea Organic Resources Recycling Association
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• v.28 no.4
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• pp.23-33
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• 2020

Marine algae(Macro algae) are easily bio-degradable, and by-products are available as feed and fertilizer. The biomass of marine algae has higher CO2 absorption capacity than the wood system, and is highly valuable in use due to its fast growth speed and wide cultivation area without special cost for raw material production. In 2018, Marine algae production was 1,722,486ton, such as Saccharina japonica, Undaria pinnatifida and Porphyra tenera, the large amounts of by-products have been generated in the food processing facilities for commercialization. In this study, Saccharina japonica, Undaria pinnatifida were collected in the south coast region and Porphyra tenera was collected in the west coast region. The theoretical methane potential and biochemical methane potential(BMP) were analyzed, and Modified Gompertz model and Parallel first order kinetics model were adopted for the interpretation of the cumulative methane production curves. The theoretical methane potential of Saccharina japonica, Undaria pinnatifida and Porphyra tenera were 0.393, 0.373 and 0.435 N㎥/kg-VS, respectively. BMP obtained by the Modified gompertz model 0.226, 0.227, and 0.241 N㎥/kg-VS for Saccharina japonica, Undaria pinnatifida and Porphyra tenera, respectively. And BMP obtained by the Parallel first order kinetics model were 0.220, 0.243, and 0.240 N㎥/kg-VS for Saccharina japonica, Undaria pinnatifida and Porphyra tenera, respectively.

• Journal of the Korea Organic Resources Recycling Association
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• v.30 no.1
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• pp.13-21
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• 2022

Mushroom waste medium refers to the waste biomass generated after mushroom cultivating. And, the burden of treatment on mushroom farmhouse is increasing due to the absence of appropriate treatment method and increase of treatment costs of the mushroom waste medium. In this study, in order to assess the energy value of mushroom waste medium by an anaerobic digestion, methane potential and anaerobic organic matter decomposition characteristics were investigated. The theoretical methane potential(B_th) of mushroom medium(MM) was 0.481 Nm³-CH₄/kg-VS_added, and the B_th of mushroom waste medium(MWM) was 0.451 Nm³-CH₄/kg-VS_added. The biochemical methane potential(B_u-exp) of MWM was increased by 18% from 0.155 for MM to 0.183 Nm³-CH₄/kg-VS_added for MWM. In the reaction kinetics analysis by the Modified Gompertz model, the maximum methane production rate(R_m) was increased from 4.59 for MM to 7.21 mL/day for MWM and the lag growth phase time(λ) was decreased from 2.78 for MM to 1.96 days for MWM. In the reaction kinetics analysis by the parallel first order kinetics model, the easily degradable organic matter(VS_e) content was increased by 5.89% and the persistently degradable organic matter(VS_p) content was 2.03% in MWM, and the non-degradable organic matter(VS_NB) content was decreased by 7.85%. Therefore, it was evaluated that the anaerobic digestion efficiency of MWM was increased. The anaerobic digestion efficiency of MWM was assessed to be more improved than that of MM.

• Bulletin of the Korean Chemical Society
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• v.16 no.2
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• pp.143-148
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• 1995

Ketene (CH2CO) adsorption on Ag(111) has been studied in ultrahigh vacuum using electron energy loss spectroscopy and temperature programmed desorption. Ketene adsorbs molecularly on Ag(111) at temperatures below 126 K. The coverage increases linearly with exposure until saturation. No multilayer formation and no shift in desorption temperature with coverage were observed, indicating a lack of attractive interaction between adsorbate molecules. The desorption activation energy is estimated to be 7.8 kcal/mol by assuming first order kinetics and a pre-exponential factor of 1013 sec-1. The adsorption geometry of ketene on the surface is determined from the relative intensities of the vibrational energy loss peaks. The CCO axis of CH2CO is found to be almost parallel to (∼4°away from) the surface and the molecular plane is almost perpendicular to the surface (∼3°tilt).

• Korean Journal of Soil Science and Fertilizer
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• v.48 no.6
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• pp.602-609
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• 2015

In order to enhance a biogas production by the hydro-thermal pre-treatment of piggery manure, the effects of hydro-thermal reaction temperature at thermal hydrolysis of piggery manure on the methane potential and anaerobic biodegradability of thermal hydrolysate were analyzed. The increase of hydro-thermal reaction temperature from $170^{\circ}C$ to $220^{\circ}C$ caused the enhancement of hydrolysis efficiency, and most of organic matters were present in soluble forms. However, the methane potentials ($B_u-TCOD$) of hydrolysate were decreased from 0.239 to $0.188Nm^3kg^{-1}-TCOD_{added}$ by increasing hydro-thermal reaction temperature from $170^{\circ}C$ to $220^{\circ}C$, and also the anaerobic biodegradability (DTCOD) decreased from 74.6% to 58.6% with increase of hydro-thermal reaction temperature. The increase of hydro-thermal reaction temperature from $170^{\circ}C$ to $220^{\circ}C$ resulted in the decrease of easily biodegradable organic matter content, while persistent organic matter contents increased.

• Bulletin of the Korean Chemical Society
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• v.9 no.5
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• pp.298-303
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• 1988

Kinetic studies on cupric ion ($Cu^{2+}$) oxidation of 1-benzyl- and 1-aryl-1,4-dihydronicotinamides (XNAH) in aqueous solution were performed. In the presence of dioxygen ($O_2$), the reaction followed first order kinetics with respect to both XNAH and $Cu^{2+}$. The oxidation reaction was found to be independent and parallel to the acid-catalyzed hydration reaction of XNAH. The catalytic role of $Cu^{2+}$ for the oxidation of XNAH in the presence of $O_2$ was attributed to $Cu^{2+}/Cu^+$ redox cycle by the reactions with XNAH and $O_2$. The second order rate constants of the Cu2+ oxidation reaction kCu, and acid-catalyzed hydration reaction $k_H$ were strongly dependent on the nature of the substituents in 1-aryl moiety. The slopes of log $k_{Cu}$ vs log $K_H$ and log $k_{Cu}$ vs ${\sigma}_p$ of the substituents plots were 1.64 and -2.2, respectively. This revealed the greater sensitivity of the oxidation reaction rate to the electron density on the ring nitrogen than the hydration reaction rate. A concerted two-electron transfer route involving XNAH-$Cu^{2+}$ complex was proposed for mechanism of the oxidation reaction.

• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.476-482
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• 1988

Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

• Journal of the Korean Chemical Society
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• v.46 no.1
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• pp.57-63
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• 2002

The hydropurification reaction of CTA (crude terephthalic acid) was carried out with hydrogen over PdRu/CCM (carbon-carbonaceous composite material) catalyst in a batch reactor at high temperature. The first order kinetics of hydropurification is confirmed with the linear dependence of ln(4-CBA; 4-carboxybenzaldehyde) with reaction time. The reaction condition studied is thought to represent the hydropurification well because of the linear dependence of catalytic activity on the catalyst weight. The p-toluic acid (p-tol) in solid and liquid increases with the conversion of reaction or the decrease of 4-CBA. However, the benzoic acid (BA) concentration does not depend much on the conversion. The AT (alkali transmittance) does not depend on the 4-CBA when the concentration is higher than about 0.2% which shows the 4-CBA, in itself, does not cause the coloring effect. The AT of PTA depends inversely with the concentration of 4-CBA when the 4-CBA is less than about 0.15%. This may show the coloring materials are removed in parallel with the hydrogenation of 4-CBA. The (0.3%Pd-0.2%Ru)/CCM shows larger residual catalytic activity than a commercial catalyst, 0.5%Pd/C, after using in a commercial reactor even though the former has smaller fresh activity than the latter. The palladium and ruthenium in PdRu/CCM show the synergetic effect in activity when the ruthenium concentration is about $0.2{\sim}0.35$ wt%. It may be supposed that the PdRu/CCM catalyst can be a promising candidate to replace the commercial Pd/C catalyst.

• Journal of the Korea Organic Resources Recycling Association
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• v.31 no.4
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• pp.13-28
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• 2023

This study assessed the biochemical methane potential (B_u-P) of three grass species-Poa pratensis (PP), Zoysia japonica (ZJ), and Agrostis stolonifera (AS). B_u-P values were determined as 0.330 Nm³/kg-VS_added for PP, 0.297 Nm³/kg-VS_added for ZJ, and 0.261 Nm³/kg-VS_added for AS. Notably, PP exhibited superior suitability for methane production. The investigation also examined the impact of silage storage duration on PP grass clippings, revealing a 19% decline in B_u-P from an initial value of 0.269 Nm³/kg-VS_added on day 0 to 0.217 Nm³/kg-VS_added on day 180. Throughout the storage period, there were significant increases in neutral detergent fiber (NDF), acid detergent fiber (ADF), and crude protein (CP) contents, rising from 67.59%, 39.68%, and 3.02% on day 0 to 77.12%, 54.65%, and 6.24% on day 180, respectively. These findings highlight the influence of storage duration on the anaerobic digestibility of PP grass clippings. To effectively utilize grass clippings as a renewable resource for methane production, further studies considering factors such as initial moisture content, pretreatment methods, and potential effects of residual pesticides are necessary to optimize anaerobic digestion efficiency for herbaceous biomass.