The chemical kinetics of steam reforming of polystyrene (PS) and polypropylene (PP) pyrolysis oil were studied using a ruthenium-based catalyst. The experiments were performed in a tubular flow reactor at temperatures of 530-680°C, Weight Hourly Space Velocities (WHSVs) of 0.453-7.916 h−1, and different steam and pyrolysis oil gas-phase concentrations. The activation energy of steam reforming of polypropylene oil and polystyrene oil is 136 and 142 kJ/mol, respectively. The reaction orders of polypropylene and polystyrene oils were 0.42 and 0.37, respectively. Conversions of polypropylene and polystyrene oils were 2.0-50.3 and 1.9-45.3%, respectively. Indeed, a Langmuir-Hinshelwood (LH) mechanism requiring the dissociative adsorption of pyrolysis oil and steam at two different sites on plastics appeared to be the most plausible pathway for the steam reforming reaction.

Converting biomass to biocrude oil has been extensively studied worldwide as a renewable energy technology and a solution to global warming caused by overuse of fossil fuels because it is a carbon neutral fuel that originates from biomass and, thus, could help prevent climate change. Fast pyrolysis is an effective technology for producing biocrude-oil, and woody biomass is usually used as feedstock. Although many studies have been performed with this feedstock, high production cost and low higher heating value (HHV) have frequently reported as challenging barriers to commercialization. Thus, coffee ground residue was selected as an alternative feedstock to overcome this barrier due to its higher HHV than other biomasses, as well as an expected improvement in the recycling rate of organic waste from many coffee shops. A kinetic study on the thermal decomposition reaction of ground coffee residue was carried out previously to investigate pyrolysis characteristics by thermogravimetric analysis, and its kinetic parameters were studied using two calculation models. A bubbling-fluidized-bed reactor was used for fast pyrolysis and the yield and characteristics of the biocrudeoil from ground coffee residue were investigated at reaction temperatures of 400-600°C. The activation energy of the decomposition reaction was calculated separately to be 41.57 kJ/mol and 44.01-350.20 kJ/mol with the above two methods. The highest biocrude-oil content was about 51.7wt% at 550°C.

산업발달로 인한 화석 연료의 급격한 사용으로 기후변화와 연료고갈 문제가 대두되고 있어 폐기물자원화 및 신재생에너지에 대한 관심이 급증하고 있다. 선행되어온 연구들은 바이오매스나 플라스틱의 대체연료 가능성 연구들로 국한되어 진행되었다. 폐플라스틱 필름의 경우 많은 연구가 진행되어 왔으나, 현재 발생되는 폐플라스틱 필름에 관한 연구는 미비한 상황이다. 많은 폐플라스틱 필름의 발생량에 비해 절반정도를 웃도는 재활용처리 비율은 다른 폐플라스틱 필름 처리방안 마련이 필요하다는 점을 시사한다. 열분해를 이용한 오일 및 화학원료 생산에 대한 관심이 높아지고 있다. 따라서 본 연구에서는 폐플라스틱 필름의 물리･화학적 특성 분석 및 열중량분석기를 통한 동역학분석과 파이롤라이저-가스크로마토그래피 /질량분석기를 이용한 반응 생성물 분석하여 폐플라스틱 필름의 열분해 공정 도입 가능성을 추가 확인하고자 한다. 또한 현재 배출되는 폐플라스틱 필름류의 열분해 특성과 어떤 성분이 생성되는지 알아보고 공정설계 기초자료로 활용되고자 폐플라스틱 필름의 열분해 특성연구를 수행하였다.

폐 바이오매스의 열 화학적 전환 공정 중 하나인 급속열분해 공정은 공정변수에 따라 열분해 생성물의 수율 및 특성이 변화한다. 급속 열분해 반응이 이루어지는 반응기는 전체 급속 열분해 공정의 핵심이며, 폐 바이오매스의 급속열분해 반응을 위해서는 1,000~10,000℃/s의 빠른 열전달 속도, 500℃의 열분해 반응온도, 1~2초이내의 열분해 생성물 체류시간이 요구된다. 따라서 이를 실현하기 위한 급속열분해 반응기 개발에 많은 연구가 진행되었다. 현재 개발되어 사용 중인 대표적인 급속열분해 반응기는 기포 유동층, 순환유동층, 분사층, Augur형, 융해열분해, 진공열분해 등의 반응기가 있다. 이중 분사층 반응기는 기체-고체 간의 열 및 물질전달이 우수하고, dilute spouted bed regime 에서는 반응기 내 열분해 가스의 체류시간이 짧아 오일의 수율을 기존 유동층 반응기 보다 증가시킬 수 있는 장점이 있다. 분사층 급속열분해 반응기 내 폐 바이오매스의 급속 열분해 반응은 기체-고체간의 수력학적 특성과 열전달 특성에 영향을 받는다. 따라서 분사층 급속열분해 반응기의 최적 설계와 운전을 위해서는 반응기 내 수력학적 특성과 열전달 특성에 대한 정보가 필요하다. 그러나 현재까지 분사층의 운전조건에 따른 분사층 내 열전달 특성에 대한 연구는 부족한 실정이다. 따라서, 본 연구에서는 분사층 내 열전달 특성 연구를 위하여 열전달 센서를 설계/제작하였으며, 제작된 열전달 센서를 통하여 분사층내 기체-고체간의 열전달 특성을 측정하였다. 분사층 내 기체-고체간의 열전달 실험은 공탑 속도, Geldart 입자분류, bed 높이를 실험변수로 하여 실험을 수행하였으며, 실험을 통하여 실험변수에 따른 분사층 내 기체-고체간의 열전달 계수의 변화를 연구하였다.

Non-CO2 온실가스인 염화불화탄소(Chlorofluorocarbons, CFCs)와 수소염화불화탄소(Hydro-Chlorofluorocarbons, HCFCs)는 오직 인류의 경제(산업) 활동에 의해 발생하며 인체에 무해하고 안정한 물질이기 때문에 냉매, 분사제, 발포제 등 여러 분야에서 다양하게 사용되었지만 오존층 파괴물질으로 국제협약인 몬트리올 의정서에 의해 생산과 사용이 규제되었다. 이에 대한 대체물질로써 수소화불화탄소(Hydrofluorocarbons, HFCs)와 과불화탄소(Perfluorinated compounds, PFCs)가 개발되었지만 여전히 높은 지구온난화지수(Global Warming Potential, GWP)를 지닌 것으로 알려져 있다. 또한 국내 HFCs 소비량은 꾸준히 증가하고 있는 추세로 HFCs 중 전기･전자제품 및 자동차에 99% 이상 냉매로 사용되는 HFC-134a(1,1,1,2-Tetrafluouroethane, CH2FCF3)는 물리･화학적으로 안정된 난처리성 물질로써 처리 시 많은 에너지(높은 온도)가 필요하며, 강산으로 알려진 불산(Hydrogen fluoride, HF)의 발생으로 처리시설의 부식을 야기시킨다. 이에 따라 HFC-134a의 안정적이고 효율적인 분해 기술 개발을 위한 연구가 필요하다 사료되며 본 연구는 수직형 관형흐름 반응기를 이용한 촉매열분해를 적용하여 촉매별 HFC-134a 분해효율 연구하고, 각 촉매별 열분해 반응 생성물의 비교를 통해 HFC-134a의 촉매열분해 특성을 알아보고자 하였다.

자동차 산업 발달로 인하여 해마다 증가하는 폐타이어 발생과 그에 따른 처리에 관한 문제는 날로 심각해지고 있다. 폐타이어는 연소 시 오염물질 발생으로 인한 2차 환경오염을 야기하므로 보다 안정적으로 재생 에너지화 하는 폐기물 처리 방법에 대한 기술개발 중요성이 날로 증대되고 있다. 또한 국내 폐타이어의 주 이용 분야가 시멘트 킬른 또는 단순 소각에 의한 열원으로의 이용이 약 60%를 차지한다는 점에서 폐타이어의 재생에너지원으로서 경제성을 향상 시키는 요구가 나타나고 있다. 따라서 폐타이어 재생 에너지화의 경제성 문제를 해결하기 위하여 부가가치를 높이는 기술 개발이 절실히 요구되고 있다. 폐타이어를 자원화 하는 열분해 기술은 무산소 조건에서 400~600℃ 정도의 반응온도로 폐타이어를 가열하여 고분자 물질을 분해하는 친환경적인 공정으로, 열분해오일, 카본블랙, 철심과 같은 열분해 부산물의 회수를 통하여 경제성 또한 높일 수 있는 이점을 가지고 있다. 이에 따라 본 연구에서는 폐타이어의 재생 에너지화 연구를 위하여 폐타이어의 열분해 특성 연구를 수행하였다. 폐타이어의 열분해는 기체-고체간 열 및 물질 전달이 우수한 원뿔형 분사층 반응기를 사용하여 실험을 수행하였다. 폐타이어 열분해 실험은 열분해 반응온도와 시료의 투입속도를 실험 변수로 선정하여 실험을 수행하였으며, 실험 조건별로 생산된 열분해 오일의 물리-화학적 특성을 분석하여 폐타이어 열분해 오일의 특성을 연구하였다.

The chemical kinetics of the steam reforming of the pyrolysis oil of polypropylene (PP) over a ruthenium-based catalyst has been examined as a function of pyrolysis oil and steam partial pressures at various temperatures. The activation energy of steam reforming over Ru/Al2O3 catalyst is 136 kJ/mol, and the reaction orders of pyrolysis oil and steam are 0.42 and 0.24, respectively. Fitting the experimental data to the Langmuir?Hinshelwood expression shows that the steamreforming reaction probably proceeds via the dissociative adsorption of pyrolysis oil and steam on two different sites.

This paper assesses the feasibility of producing fuel energy from sewage sludge via four processes: microwave-induced pyrolysis/gasification and conventional pyrolysis/gasification. Both pyrolysis and gasification produced gas, char, and tar. The gas produced for the gasification contained mainly hydrogen and carbon monoxide with a small amount of methane and hydrocarbons (C2H4, C2H6, C3H8). However, the gasification produced higher carbon monoxide instead of the hydrogen. The microwave gasification generated higher heavy tar compared to other processes. As a light tar, benzene generated higher value for both the pyrolysis and gasification. The sludge char showed a vitreous-like texture for the microwave process and a deep crack shape for the conventional heating process. These results indicate that the gas produced from the microwave processes of wet sewage sludge might be usable as a fuel energy source, but this would require removal of the condensable PAH tars. The sludge char produced could also be used as a solid fuel or adsorbent.

For material recovery of black carbon and pyrolysis oil, pyrolysis is considered as an alternative to combustion-based technologies for treatment of waste tire. This study investigated the heat transfer optimization in a pyrolysis reactor for waste tire chips with a capacity of 24 t/d. The reactor was required to have a larger heat transfer rate from hot gas to tire chips in the early stage of pyrolysis, whereas the rate in the later stage should be lower. This was to prevent thermal cracking of heavy compounds in the pyrolysis vapor and to improve the quality of black carbon. CFD was applied to analyze the flow and heat transfer in the complex geometry of the reactor for a total of nine design cases. It was found that modifications to control the distribution of gas flow rate along the reactor are more effective for the present reactor than adjusting the measures for heat transfer enhancement (such as fins). The ideal design improvement was to divide the reactor into two gas sections for a separate control of the flow rate, and to remove the fins of which its alignment perpendicular to the flow inhibits the hot gas from approaching the tube of tire chips.

Fast pyrolysis is one of the most viable and commonly used thermochemical conversion technologies which can be applied to both fossil-based and bio-based wastes. The conical spouted bed reactor is an alternative to fluidized beds and has been proven to be a versatile reactor for waste biomass fast pyrolysis, which allows obtaining high bio-oil yields because of its high heat and mass transfer rates and very short residence times. Understanding of the stable hydrodynamic operation range of the conical spouted bed is important for operation of fast pyrolysis reactor. This study characterizes the hydrodynamics of conical spouted bed using the analysis of pressure fluctuation signals. Stable hydrodynamic operation rages were identified by evaluation of pressure drop curve and FFT analysis. The stable operation range of a conical spouted bed was maintained while dominant frequency is 10 Hz. This appears to be promising cost-effective tool for precess control especially in fast pyrolysis systems.

Refuse plastic fuel (RPF) as materials for the recycling processes (Materiel Recycling) present difficulties with the mixing, the demolishing, the molding and the drying steps. While using RDF as a fuel by pyrolysis, accompanying tar and soot causes many problems like clogging, the corrosion and the erosion of the chloride channel. Using the intermittent pyrolysis equipment during the decomposition of the RPF gases H2, CH4, CO and among the by-products of Cl2 and HCl, Tar is produced in a large quantity. With understanding the by-products decomposition system of the Cl2, H2, Tar and the gases H2, CH4, CO we can understand the nature of the generation of the products. The experimental conditions were chosen according to the temperature of the decomposition (300 ~ 900oC), While varying RPF 2 g, pyrolysis temperature 700oC during a holding time of 32 min : the H2 gas 1.71%, CH4 2.54%, CO 4.63%, Cl2 12.86 ppm, HCl 30.2 ppm were composed. Also light tar benzene 18.45 g/m3, naphthalene 0.86 g/m3, anthracene 0.09 g/m3, pyrene 0.04 g/m3, gravimetric tar 31.8 g/m3, and char 0.45 g was formed.

This paper attempted to elucidate pyrolysis reaction characteristics of waste paper laminated phenolic-printed circuit board (p-PCB). Thermogravimetric analysis was performed for the pyrolysis kinetic analysis of waste p-PCB and Pyrolyzer-gas chromatography/mass spectrometry (Py-GC/MS) was also employed to analyze the product distribution of waste p-PCB pyrolysis reaction under isothermal condition (230, 350, 600oC). Kinetic analysis and isothermal Py-GC/MS results showed that the pyrolysis reaction of waste p-PCB has three reaction temperature regions: 1) low temperature decomposition region (< 280oC), 2) medium temperature decomposition region (280 ~ 380oC), 3) high temperature decomposition region (> 380oC). At the first region, triphenyl phosphate used as fire retardant, water, and phenol were vaporized. At the second region, phenolic resin, tetrabromobisphenol-A (TBBA), and laminated paper are decomposed and produce phenols, brominated compounds, and levoglucosan which were the specific pyrolysis reaction products of phenolic resin, TBBA, and laminated paper, respectively. In the final region, cresol and alkyl benzene were detected which can be considered as the decomposition products of phenolic resin. By above results, pyrolysis reaction pathway of waste p-PCB is accounted for a series reaction with four independent reactions of phosphate based frame retardant, TBBA, laminated paper, and phenolic resin.

Waste heavy oil sludge is considered oil waste that can be utilized as a renewable energy source. In this study, an attempt has been made to convert the mixtures of waste heavy oil sludge and sawdust into solid biomass fuels. The solid fuel pellets from waste heavy oil sludge and sawdust could be manufactured only with a press type pelletizer. The mixing ratios of waste heavy oil sludge and sawdust capable of manufacturing a solid fuel pellet were 30 : 70, 40 : 60 and 50 : 50. Ultimate analysis result revealed that these mixtures had C 50.21 ~ 54.77%, H 10.25 ~ 12.66%, O 25.84 ~ 34.83%, N 1.01 ~ 1.04%, S 1.03 ~ 1.07%. With increasing the mixing ratio of waste heavy oil sludge, the carbon and hydrogen content in solid fuel pellets were increased, while the oxygen content was decreased. But the nitrogen and sulfur content in solid fuel pellets did not show much difference. Their lower heating values ranged from 4,780 kg/kcal to 5,530 kg/kcal. The density of the solid fuel pellets was increased from 0.63 g/cm3 to 0.85 g/cm3 with increasing the mixing ratio of waste heavy oil sludge and the collapse of the solid fuel pellets occurred at a moisture content of 21%. As the mixing ratio of waste heavy oil sludge in the solid fuel pellets was increased, the reaction of thermal cracking became faster. It was also observed that the solid fuel pellets were thermally decomposed in two steps and their DTG curves were simpler with increasing the mixing ratio of waste heavy oil sludge. The activation energy and the pre-exponential factor of the solid fuel pellets ranged from 18.90 kcal/mol to 21.36 kcal/mol and from 201 l/sec to 8,793 l/sec, respectively. They were increased with increasing the mixing ratio of waste heavy oil sludge.

In this study, activation energy of lignite, RPF and a sample mixed both of them was obtained through kinetics characteristics analysis in pyrolysis in order to identify the applicability of RPF as an assistant fuel. TGA (Thermogravimetric analysis) was conducted with follow experimental conditions; in a nitrogen atmosphere, gas flow rate of 20 ml/min, heating rate of 5 ~ 50oC/min, and maximum hottest temperature of 800oC. As a result of TGA, it showed that pyrolysis of samples mixed with 20% and 10% of RPF were more stable than other mixed ratio, and 20% of RPF was the most similar with lignite in activation energy.

The large amount of waste oil sludge was generated from waste oil purification process, oil bunker, or the ocean plant. Although it has high calorific values, it should be treated as a designated waste. During the recycling process of construction and demolition wastes or the trimming process of woods, a lot of sawdust is produced. In this study, the feasibility of BOF (biomass and waste oil sludge fuel) as a renewable energy source was estimated. For manufacturing a BOF, a press type pelletizing was better than an extruder type and also 40 ~ 60% of mixing ratio in waste oil sludge was appropriate to produce a pellet. The pellet was 13 mm in diameter and 20 mm in length. There was no fixed carbon in waste oil sludge, and its carbon content and higher heating value were 63.90% and 9,110 kcal/kg, respectively. With an increse of mixing ratio of sawdust, the carbon content and heating value of the BOF were dropped, but fixed carbon content was increased. The heating value of BOF was in the range of 6,400 ~ 7,970 kcal/kg at the mixing ratio of 40 ~ 60% in waste oil sludge. It means that the BOF can be classified as the 1stgrade solid fuel. In TGA experiment carried out at heating rate of 10oC/min and under nitrogen atmosphere, thermal decomposition of sawdust was occurred in two steps, but waste oil sludge was destructed in one step. The initiated cracking temperature of sawdust and waste oil sludge was 300 and 280oC in respective and after 450oC the thermal decomposition process of sawdust was slowly progressed by 800oC in contrast to waste oil sludge. Thermal decomposition of waste oil sludge was finished around 600oC. It can be considered that this difference is due to the fixed carbon content. Thermal decomposition pattern for the pellet of mixing ratio over 50% in waste oil sludge was similar to that for waste oil sludge and thermal cracking was occurred between 300 and 350oC. As the mixing ratio of waste oil sludge in the pellet increased, the reaction of thermal cracking became fast.

In this study those currently operating pyrolysis oil plant were selected for the investigation. The yield of the oil andfuel was assessed for its use as fuel and the char component analysis, and the reaction time to collect contaminantscollected and analyzed. As the result, about 40% of the oil was yielded and oil could be used as an alternative fuel. Char’sleaching test analysis result was satisfied with the landfill standard. And emission of Dioxin and pollutants was analyzed.The highest concentration of dioxin was 0.7347ng I-TEQ/Sm3. The result satisfied the requirement however the emissionconcentration was changed depending on the input Fuel. Therefore the appropriate pollution control facility should berequired.

Pyrolysis of biomass is the thermal decomposition of its carbohydrate structures into numerious hydrocarboncompounds, light gases and carbon-rich solid residue. Understanding the pyrolysis characteristics is essential asfundamental data for various thermo-chemical conversion of biomass. This study investigated slow pyrolysis of fourIndonesian biomass (sugarcane bagasse, cocopeat, palm kernel shell (PKS), umbrella tree) for a temperature range of300~600oC. With increase in temperature, all samples showed a decrease in the biochar yield as more compounds werereleased as vapors increasing the bio-oil and gas yields. The biochar became more carbon-rich with a carbon content of85% or higher at 500oC. However, the product yields and properties showed large variations between the samples.Cocopeat had the highest biochar yield, while wood and baggasse had the highest bio-oil yield. Despite the low massyields, the biochar of wood and bagasse had the best quality in terms of macro-pore and micro-pore development, whichis a key property for its applications as adsorbent, soil ameliorator, as well as fuel. The bio-oil did not have a sufficientlyhigh HHV for use as main fuel, but could be utilized through co-firing or slurry production with biochar. In the lightgases, CO and CO2 were dominant, but could be burned on-site to supply the heat required for pyrolysis.

In order to obtain the optimal design of a char removal cyclone, the effect of the vortex finder height and inlet shapeon its performance are numerically carried out. The pressure drop and collection efficiency are calculated for four differentcyclones with different vortex finder heights and inlet shapes. To validate the present numerical process, the calculatedpressure drops for two types of cyclones are compared with experimental results and the results show a good agreementbetween experimental and numerical results. From the results, increasing the height of the vortex finder, the collectionefficiency is increased. As for cyclone inlet shapes, the tangential one is characterized by lower efficiency compared withthe volute counterpart. The current result can be used for the design of cyclones with high collection efficiency, especiallyfor removing tiny char which is generated during fast pyrolysis process of waste biomass.

In the present study, lab-scale fast pyrolysis reactor (1kg/hr) using lignocellulosic waste biomass was numerically modeledwith various reaction mechanism and the calculation results were compared. Three kinds of reaction mechanisms were appliedsuch as three-step mechanism, two-stage, semi global mechanism and Broido-Shafizadeh mechanism to simulate chemicalreactions in the fast pyrolysis reactor. The fast pyrolysis reactor was modeled as function of mass fraction and reactiontemperature following each reaction mechanism. Especially, the reaction temperature is one of important factors to determinebio-oil yield. Hence, in this study, reaction rates and yield of fast pyrolysis products were compared with varying reactiontemperature for the three kinds of reaction mechanism. The variation of reaction rate for two-stage, semi global mechanismand Broido-Shafizadeh mechanism showed very similar pattern but, three-step mechanism has different trend because theeffect of secondary reaction was missing. The yield of tar was increased before reaching maximum tar yield at 430oC and520oC for two-stage, semi global mechanism and Broido-Shafizadeh mechanism, respectively then decreased as temperaturerises more. But, the yield of tar was increased continuously for three-step mechanism as temperature rises. The yield of non-condensable gas and char was increased as temperature rises for three kinds of reaction mechanisms.

This study described characteristics of product gases emitted during high temperature pyrolysis of sewage sludge in the temperature range of 800 ~ 1,200oC for determining the possibility of energy recovery as one of the sewage sludge treatment methods. Char yield of each sewage sludge decreased with increasing reaction temperature until 1,000oC during pyrolysis experiment, but above 1,000oC it is nearly constant due to the total release of volatile matter contained in samples. Major gas components emitted from high temperature pyrolysis experiment of sewage sludges are CO2, H2, CO, and CH4. These major combustible gases except CO2 can be used as major energy source. Also major sulfur-containing gases known as the pollutant gas emitted during high temperature pyrolysis experiments are H2S, COS, and CS2. The principal sulfur gaseous product is H2S and concentrations of H2S and CS2 increases with increasing temperature, but in the case of COS its concentration is nearly constant with variation of temperature. So efficient treatment of sulfurcontaining gases emitted from thermal treatment of sewage sludge should be needed.