Thermal Hydrolysis Reaction Research Articles

The role of ubiquitous metal ions in degradation of microplastics in hot-compressed water

Hydrothermal processing (HTP) is an efficient thermochemical technology to achieve sound treatment and resource recovery of sewage sludge (SS) in hot-compressed subcritical water. However, microplastics (MPs) and heavy metals can be problematic impurities for high-quality nutrients recovery from SS. This study initiated hydrothermal degradation of representative MPs (i.e., polyethylene (PE), polyamide (PA), polypropylene (PP)) under varied temperatures (180–300 °C) to understand the effect of four ubiquitous metal ions (i.e., Fe3+, Al3+, Cu2+, Zn2+) on MPs degradation. It was found that weight loss of all MPs in metallic reaction media was almost four times of that in water media, indicating the catalytic role of metal ions in HTP. Especially, PA degradation at 300 °C was promoted by Fe3+ and Al3+ with remarkable weight loss higher than 95% and 92%, respectively, which was ca. 160 °C lower than that in pyrolysis. Nevertheless, PE and PP were more recalcitrant polymers to be degraded under identical condition. Although higher temperature thermal hydrolysis reaction induced severe chain scission of polymers to reinforce degradation of MPs, Fe3+ and Al3+ ions demonstrated the most remarkable catalytic depolymerization of MPs via enhanced free radical dissociation rather than hydrolysis. Pyrolysis gas chromatography-mass spectrometry (Py GC–MS) was further complementarily applied with GC–MS to reveal HTP of MPs to secondary MPs and nanoplastics. This fundamental study highlights the crucial role of ubiquitous metal ions in MPs degradation in hot-compressed water. HTP could be an energy-efficient technology for effective treatment of MPs in SS with abundant Fe3+ and Al3+, which will benefit sustainable recovery of cleaner nutrients in hydrochar and value-added chemicals or monomers from MPs.

Deep dewatering of sewage sludge and simultaneous preparation of derived fuel via carbonaceous skeleton-aided thermal hydrolysis

To simultaneously solve problems of high water content and poor fuel performance hindering sludge incineration, carbonaceous skeleton-aided thermal hydrolysis was firstly developed in this study. Results showed that thermal hydrolysis could break sludge particle and release bound water. Sawdust as a typical carbonaceous skeleton improved permeability of sludge, decreased the specific resistance to filtrate significantly and lowered effective thermal hydrolysis temperature from 180 °C to 150 °C. The water content of sawdust-aided 150 °C hydrolysis sludge reached 42.2% after dewatered at 1 MPa. Zeta potential was not always linked to sludge dewatering performance after carbonaceous skeleton-aided thermal hydrolysis. The changes of zeta potential-pH in sawdust-aided thermal hydrolysis at different temperature, which was affected by aliphatic acid and acetic acid derived from sludge and sawdust respectively, were vector sums of that in hydrolysis alone. Zeta potential-pH vector relations and filtrate composition revealed that sawdust could interact with sludge and accelerate thermal hydrolysis reaction. Maillard reaction was the main color reaction in thermal hydrolysis consuming protein and polysaccharide in EPS. There were two stages for the combustion of derived fuel. Thermal hydrolysis could homogenize the sludge and reduce the temperature intervals between two stages. More fixed carbon, higher heating values and comprehensive combustibility index suggested a better combustion performance of derived fuel.

열가수분해 반응을 이용한 조류인플루엔자(AI) 감염 가금류의 사체처리 및 연료화

열가수분해 반응을 이용한 조류인플루엔자(AI) 감염 가금류의 사체처리 및 연료화

병열 1차 반응속도식을 이용한 유기성 슬러지 수열탄화 반응온도별 메탄생산퍼텐셜 평가

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-VSadded 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.

도계폐기물의 열가수분해 반응에 따른 열전달 특성 연구

The purpose of this study was performed to quantitatively measure the thermal conductivity of poultry slaughter waste with variation of reaction temperature for optimal design of thermal hydrolysis reactor. We continuously quantified the thermal conductivity of dehydrated sludge related to the reaction temperature. As the reaction temperature increased, the dehydrated sludge is thermally liquefied under high temperature and pressure by the thermal hydrolysis reaction. Therefore, the bond water in the sludge cells comes out as free water, which changes the dehydrated sludge from a solid phase to slurry of a liquid phase. As a result, the thermal conductivity of the its sludge was more than 2.11 times lower than that of the water at . However, the thermal conductivity of the sludge approached to of water at , experimentally substantiating liquefaction of the dehydrated sludge. Therefore, we confirmed that the change in physical properties due to thermal hydrolysis appears to be an important factor for heat transfer efficiency. And the thermal conductivity function related to reaction temperature was derived to give the boundary condition for the optimal design of the thermal hydrolysis reactor. The consistency of the calculated function was 99.69%.

열가수분해 반응을 이용한 가축분뇨 슬러지의 연료화에 관한 연구

ABSTRACT Livestock sludge contains high concentration of organic matter and some heavy metals. In case of discharging into the sea, it might have negative effects in the environment. In this study thermal hydrolysis reaction was applied for livestock sludge to determine the fuelization possibility and obtain the best operation conditions. Livestock sludges were thermally hydrolyzed at temperature range 170∼210 ℃ in sealed high-temperature reactors. Liquid products and dewatered cakes were analyzed. The operation at 190℃ was found to be best effective condition. High heating value and low heating value were 5,050 kcal/kg and 4,740 kcal/kg, respectively. Therefore, fuelization of livestock sludge using thermal hydrolysis reactor is found to be highly effective.Keywords : Livestock Sludge, Thermal Hydrolysis, Fuelization, Dewatered Cake, Heating Value 초 록 가축분뇨 슬러지는 유기물의 농도가 높고 일부 중금속이 높은 농도로 혼합되어 있어 해양에 배출될 경우 환경에 부정적인 영향을 끼칠 수 있다. 본 연구에서는 가축분뇨 슬러지 처리에 열가수분해 기술을 적용 http://dx.doi.org/10.17137/korrae.2015.23.3.051

Thermal conductivity characteristics of dewatered sewage sludge by thermal hydrolysis reaction

The purpose of this study is to quantify the thermal conductivity of sewage sludge related to reaction temperature for the optimal design of a thermal hydrolysis reactor. We continuously quantified the thermal conductivity of dewatered sludge related to the reaction temperature. As the reaction temperature increased, the dewatered sludge is thermally liquefied under high temperature and pressure by the thermal hydrolysis reaction. Therefore, the bound water in the sludge cells comes out as free water, which changes the dewatered sludge from a solid phase to slurry in a liquid phase. As a result, the thermal conductivity of the sludge was more than 2.64 times lower than that of the water at 20℃. However, above 200℃, it became 0.704 W/m•°C, which is about 4% higher than that of water. As a result, the change in physical properties due to thermal hydrolysis appears to be an important factor for heat transfer efficiency.ImplicationsThe thermal conductivity of dewatered sludge is an important factor the optimal design of a thermal hydrolysis reactor. The dewatered sludge is thermally liquefied under high temperature and pressure by the thermal hydrolysis reaction. The liquid phase slurry has a higher thermal conductivity than pure water.

Reaction mechanism and kinetics analysis of the phase transformation of TiO2 from the anatase phase to the rutile phase

The kinetic mechanism of the phase transformation of TiO2 from the anatase phase to the rutile phase was investigated. TiO2 powders were prepared with different pH value of the starting solution via the thermal hydrolysis method in this study. The pH values of the starting solutions have significant effects on the phase transformation temperatures of the thermal hydrolysis reaction. As the reaction temperatures were raised, the conversion from the anatase phase to the rutile phase was increased. A core–shell morphology of the prepared TiO2 samples was suggested via the signals of the anatase phase and the rutile phase in UV–vis spectrum analysis. Through the isothermal heating process of the reaction kinetics, the controlling reaction in the phase transformation process from the anatase phase to the rutile phase was determined to be the three-dimensional phase boundary controlled process. The activation energy of the phase transformation was increased with an increase in the pH value of the starting solution.

Thermal properties and chemical changes in blend melt spinning of cellulose acetate butyrate and a novel cationic dyeable copolyester

AbstractA novel cationic dyeable copolyester (MCDP) containing purified terephthalate acid (PTA), ethylene glycol (EG), 2‐methyl‐1,3‐propanediol (MPD), and sodium‐5‐sulfo‐isophthalate (SIP) was synthesized via direct esterification method. The chemical structure of modified cationic dyeable polyester (MCPD) was confirmed by FTIR and 1H‐NMR. The thermal properties of MCDP and cellulose acetate butyrate (CAB) blends with different blend ratios were investigated by DSC. The results revealed that MCDP and CAB were immiscible polymer blends, and the glass transition temperature of CAB in blend fibers was higher than that of CAB in blend chips because of the strengthening hydrogen bonding. The chemical changes of MCDP and CAB in blend melt spinning were analyzed. It was found that the thermal hydrolysis reaction of ester side groups of CAB occurred in blend melt spinning, which resulted in that the acid gas was produced and the hydroxyl group content of CAB was increased. Furthermore, the moisture absorption of blend fibers was improved about three times than pure MCDP fiber even after washing 30 times. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Effects of operational conditions on sludge degradation and organic acids formation in low-critical wet air oxidation

Wet air oxidation processes are to treat highly concentrated organic compounds including refractory materials, sludge, and night soil, and usually operated at supercritical water conditions of high temperature and pressure. In this study, the effects of operational conditions including temperature, pressure, and oxidant dose on sludge degradation and conversion into subsequent intermediates such as organic acids were investigated at low critical wet oxidation conditions. The reaction time and temperature in the wet air oxidation process was shown an important factor affecting the liquefaction of volatile solids, with more significant effect on the thermal hydrolysis reaction rather than the oxidation reaction. The degradation efficiency of sludge and the formation of organic acids were improved with longer reaction time and higher reaction temperature. For the sludge reduction and the organic acids formation under the wet air oxidation, the optimal conditions for reaction temperature, time, pressure, and oxidant dose were shown approximately 240 °C, 30 min, 60 atm, and 2.0 L/min, respectively.