Analysis of Carbonization Behavior of Hydrochar Produced by Hydrothermal Carbonization of Lignin and Development of a Prediction Model for Carbonization Degree Using Near-Infrared Spectroscopy(열수 탄화 공정을 거친 리그닌 하이드로차(hydrochar)의 탄화 거동 분석과 근적외선 분광법을 이용한 예측 모델 개발)

( Un Taek Hwang ),( Junsoo Bae ),( Taekyeong Lee ),( Sung-yun Hwang ),( Jong-chan Kim ),( Jinseok Park ),( In-gyu Choi ),( Hyo Won Kwak ),( Sung-wook Hwang ),( Hwanmyeong Yeo ) 한국목재공학회 2021 목재공학 Vol.49 No.3

In this paper, we investigated the carbonization characteristics of lignin hydrochar prepared by hydrothermal carbonization and established a model for predicting the carbonization degree using near-infrared spectroscopy and partial least squares regression. The carbon content of the hydrothermally carbonized lignin at the temperature of 200 ℃ was higher by approximately 3 wt% than that of the untreated sample, and the carbon content tended to gradually increase as the heating time increased. Hydrothermal carbonization made lignin more carbon-intensive and more homogeneous by eliminating the microparticles. The discriminant and predictive models using near-infrared spectroscopy and partial least squares regression approppriately determined whether hydrothermal carbonization has been applied and predicted the carbon content of hydrothermal carbonized lignin with high accuracy. In this study, we confirmed that we can quickly and nondestructively predict the carbonization characteristics of lignin hydrochar manufactured by hydrothermal carbonization using a partial least squares regression model combined with near-infrared spectroscopy. 본 논문에서는 열수 탄화(hydrothermal carbonization)에 의해 제조된 리그닌 하이드로차의 탄화 특성을 조사하였고, 근적외선 분광법과 부분 최소 제곱(partial least squares) 회귀를 이용하여 탄화 거동을 예측하기 위한 모델을 수립하였다. 온도 200℃에서 열수 탄화된 리그닌의 탄소 함량은 무처리 시료 보다 약 3 wt% 높았으며 가열 시간이 증가할수록 탄소 함량도 서서히 증가하는 경향이 나타났다. 열수 탄화는 리그닌을 더욱 탄소 집약적으로 변화시키고 마이크로 파티클을 제거하여 더욱 균질한 특성을 부여하였다. 근적외선 분광법과 부분 최소 제곱 회귀를 이용한 판별 및 예측 모델은 수열 탄화의 적용 여부를 완벽히 구분했으며 높은 정확도로 열수 탄화 리그닌의 탄소 함량을 예측하였다. 본 연구로부터 근적외선 분광법과 결합된 부분 최소 제곱 회귀 모델을 이용하여 열수 탄화에 의해 제조된 리그닌 하이드로차의 탄화 특성을 빠르고 비파괴적으로 예측할 수 있다는 것이 확인되었다.

Pressure Effects on the Morphology Development of C/C Composites During Carbonization

Hyeok-Jong Joo,Seung-Hee Ryu,Hun-Seung Ha 한국탄소학회 2001 Carbon Letters Vol.1 No.3

It is well known that the fabrication process of carbon/carbon composites is very complex. Above all, the carbonization process have major effect on the morphology development of carbon matrix. Carbon/carbon composites of 4-directional fiber preform were fabricated using the coal tar based pitch as a matrix precursor in this study. According to carbonization pressure of 1 bar, 100 bar, 600 bar, and 900 bar, morphological changes of cokes and matrix of composites were discussed. As the carbonization pressure increased to 600 bar, the flow pattern morphology of bulk mesophse was well developed. On the contrary, mosaic pattern morphology was found in case of 900 bar of carbonization pressure. It is confirmed that the carbonization pressure have profound effect on the degree of graphitization and crystal size of carbon matrix. Even in the highly densified carbon/carbon composites, large voids were still found in the matrix pocket region.

Formation of Isotropic Carbon Matrix in Carbon/Carbon Composites Derived from Pitch

Chong-Jin Ahn,In-Seo Park,Hyeok-Jong Joo 한국탄소학회 2010 Carbon Letters Vol.11 No.4

To manufacture a carbon/carbon composite the coal tar pitch was used as the matrix precursor and the PAN (polyacrylonitrile)-based carbon fiber was used as the reinforcing material to weave 3-directional preform. For pressure carbonization HIP equipment was used to produce a maximum temperature of 1000℃ and a maximum pressure of 100 MPa. The carbonization was induced by altering the dwell temperature between 250℃ and 420℃, which is an ideal temperature for the moderate growth of the mesophase nucleus that forms within the molten pitch during the pressure carbonization process. The application of high pressure during the carbonization process inhibits the mesophase growth and leads to the formation of spherical carbon particles that are approximately 30 nm in size. Most particles were spherical, but some particles were irregularly shaped. The spread of the carbon particles was larger on the surface of the carbon fiber than in the interior of the matrix pocket.

Effect of kneading and carbonization temperature on the structure of the carbon block for thermally conductive bulk graphites

An Donghae,김경훈,Lim Chaehun,이영석 한국탄소학회 2021 Carbon Letters Vol.31 No.6

Artifcial graphites have been used in various applications, for example, as anode materials for Li-ion batteries, C/C composites, and electrodes for aluminum smelting, due to their unique mechanical strength and high thermal and electrical conductivity. Artifcial graphites can be manufactured by a series of kneading, molding, carbonization and graphitization processes with an additional impregnation process. In this study, the infuence of the process variables in the kneading and carbonization/graphitization process on the properties of the resulting carbon block was systemically investigated. During the kneading process, the optimum kneading temperature was 90 °C higher than the softening point of the binder pitch; thus, the binder pitch reached its maximum fuidity. On the other hand, during the carbonization and graphitization process, the structural properties of carbon blocks prepared at diferent heat treatment temperatures were examined and their structural change and evolution were closely described according to the temperature and divided into low-temperature carbonization and high-temperature carbonization/graphitization. Based on this study, we expect to provide a better understanding of setting the parameters for thermally conductive carbon block manufacturing.

Nd:YAG Laser 직접 각인을 이용한 Carbon 스트레인 센서

주동현,윤상우,김주한,박우태,Joo, Donghyun,Yoon, Sangwoo,Kim, Joohan,Park, Woo-Tae 한국마이크로전자및패키징학회 2018 마이크로전자 및 패키징학회지 Vol.25 No.1

Nd:YAG Laser를 이용하여 polyimide film에 탄화(carbonization)를 진행하여 Carbon을 생성하여 저가의 센서를 간단한 제조과정으로 만들었다. 이를 통하여 유연한 저가형 압저항 센서의 특성에 관한 연구를 수행하였다. 기존에 많은 연구들이 Polyimide에 $10.6{\mu}m$의 파장을 가지는 $CO_2$ laser를 이용하여 carbonization을 하여 센서를 제작하였다. 본 논문에서는 polyimide film에 $1.064{\mu}m$의 파장을 가지는Nd:YAG laser를 이용하여 carbonization(탄화공정)을 진행하였다. 또한 Nd:YAG laser를 사용하여 polyimide film위에 직접 탄화시키며 carbon을 생성하는 최적의 전력밀도($W/cm^2$)과 속도(scan rate) 조건 조합을 찾아 해상도를 높였다. $CO_2$ laser를 사용하였던 기존의 선행연구에서는 carbon생성의 최소 선폭이 $140{\sim}220{\mu}m$의 길이를 가졌지만, 본 연구에서는 카본의 생성되는 선폭이 $35{\sim}40{\mu}m$으로 축소시켰다. 이번 연구에서 제작된 센서의 초기 면저항은 $100{\sim}300{\Omega}/{\square}$ 이였다. 곡률 반경 21 R 로 인장을 하였을 때 저항이 30% 줄어들었고, 이를 통하여 계산된 게이지 팩터는 56.6이였다. 본 연구는 압저항 센서를 제조하기 위한 단순하고, 매우 유연하고 저렴한 공정을 제공한다. Nd:YAG laser was used to carbonize polyimide films to produce carbon films. This is a simple manufacturing process to fabricate low cost sensors. By applying this method, we studied characteristics of flexible and low-cost piezoresistive. Previously, many studies focused on carbonization of polyimide using $CO_2$ laser with wavelength of $10.6{\mu}m$. In this paper, carbonization (carbonization process) was performed on polyimide films using an Nd:YAG laser with a wavelength of $1.064{\mu}m$. In order to increase the resolution, we optimized the laser conditions of the power density ($W/cm^2$) and the beam scan rate. In previous studies using $CO_2$ laser, the minimum line width was $140{\sim}220{\mu}m$ but in this study, carbon line width was reduced to $35{\sim}40{\mu}m$. The initial sheet resistance of the carbon sensor was $100{\sim}300{\Omega}/{\square}$. The resistance decreased by 30% under stretched with a curvature radius of 21 R. The calculated gauge factor was 56.6. This work offers a simple, highly flexible, and low-cost process to fabricate piezoresistive sensors.

Pressure Effects on the Morphology Development of C/C Composites During Carbonization

Joo, Hyeok-Jong,Ryu, Seung-Hee,Ha, Hun-Seung 한국탄소학회 2001 Carbon Letters Vol.1 No.3

It is well known that the fabrication process of carbon/carbon composites is very complex. Above all, the carbonization process have major effect on the morphology development of carbon matrix. Carbon/carbon composites of 4-directional fiber preform were fabricated using the coal tar based pitch as a matrix precursor in this study. According to carbonization pressure of 1 bar, 100 bar, 600 bar, and 900 bar, morphological changes of cokes and matrix of composites were discussed. As the carbonization pressure increased to 600 bar, the flow pattern morphology of bulk mesophse was well developed. On the contrary, mosaic pattern morphology was found in case of 900 bar of carbonization pressure. It is confirmed that the carbonization pressure have profound effect on the degree of graphitization and crystal size of carbon matrix. Even in the highly densified carbon/carbon composites, large voids were still found in the matrix pocket region.

Investigation of Narrow Pore Size Distribution on Carbon Dioxide Capture of Nanoporous Carbons

Long-Yue Meng,박수진 대한화학회 2012 Bulletin of the Korean Chemical Society Vol.33 No.11

Nanoporous carbons with a high specific surface area were prepared directly from thermoplastic acrylic resin as carbon precursor and MgO powder as template by carbonization over the temperature range, 500-1000 °C. The effect of the carbonization temperature on the pore structure and CO2 adsorption capacity of the obtained porous carbon was examined. The textural properties and morphology of the porous carbon materials were analyzed by N2/−196 °C and CO2/0 °C adsorption/desorption isotherms, SEM and TEM. The CO2 adsorption capacity of the prepared porous carbon was measured at 25 °C and 1 bar and 30 bar. The specific surface area increased from 237 to 1251 m2/g, and the total pore volumes increased from 0.242 to 0.763 cm3/g with increasing the carbonization temperature. The carbonization temperature acts mainly by generating large narrow micropores and mesopores with an average pore size dependent on the level of carbonization of the MgO-templated nanoporous carbons. The results showed that the MgO-templated nanoporous carbons at 900 °C exhibited the best CO2 adsorption value of 194 mg/g at 1 bar.

Investigation of Narrow Pore Size Distribution on Carbon Dioxide Capture of Nanoporous Carbons

Meng, Long-Yue,Park, Soo-Jin Korean Chemical Society 2012 Bulletin of the Korean Chemical Society Vol.33 No.11

Nanoporous carbons with a high specific surface area were prepared directly from thermoplastic acrylic resin as carbon precursor and MgO powder as template by carbonization over the temperature range, $500-1000^{\circ}C$. The effect of the carbonization temperature on the pore structure and $CO_2$ adsorption capacity of the obtained porous carbon was examined. The textural properties and morphology of the porous carbon materials were analyzed by $N_2/-196^{\circ}C$ and $CO_2/0^{\circ}C$ adsorption/desorption isotherms, SEM and TEM. The $CO_2$ adsorption capacity of the prepared porous carbon was measured at $25^{\circ}C$ and 1 bar and 30 bar. The specific surface area increased from 237 to $1251m^2/g$, and the total pore volumes increased from 0.242 to $0.763cm^3/g$ with increasing the carbonization temperature. The carbonization temperature acts mainly by generating large narrow micropores and mesopores with an average pore size dependent on the level of carbonization of the MgO-templated nanoporous carbons. The results showed that the MgO-templated nanoporous carbons at $900^{\circ}C$ exhibited the best $CO_2$ adsorption value of 194 mg/g at 1 bar.

배추를 이용한 활성탄 제조에 관한 연구

이성헌,이봉헌,박흥재 한국환경과학회 2001 한국환경과학회지 Vol.10 No.5

In recent years, the demand of activated carbon has been increasing steadily because of the environmental problems. Among them waste and water treatment and removal of poisonous gas were involved. Therefore, in this study, activated carbon was made from the waste chinese cabbage and measured the iodine adsorption ability, carbonization yield, and activation yield of the produced activated carbon. The result showed that the carbonization yield was decreased when carbonization temperature was increased and that the optimal carbonization temperature was 600℃. The optimal concentration of NaOH for removing ash in the raw sample was 1∼2N. The range of iodine adsorption number of activated carbon using chinese cabbage at 600℃ carbonization was 610.82㎎/g to 1019.58㎎/g. The activation result of carbonization sample showed that the optimal activation condition was the carbonization at 400℃ and the activation at 700℃. So the production of activated carbon using chinese cabbage was possible in the aspect of reuse of resource and decrease of environmental pollution compared to the commercial activated carbon.

하수슬러지의 수열탄화를 통한 고형연료 탄화 특성

한성국,김문일 유기성자원학회 2023 유기물자원화 Vol.31 No.2

Most of the sewage sludge is organic waste containing a large amount of organic substances decomposable by microorganisms by biological treatment. As for existing sewage sludge treatment methods, reduction and fuel conversion are being carried out using technologies such as drying, incineration, torrefaction, carbonization. However, the disadvantage of high energy consumption has been pointed out as latent heat of 539 kcal/kg is consumed based on drying. Therefore, in this study, we intend to produce solid fuel through hydrothermal carbonization(HTC), which is a thermochemical treatment. To evaluate the value of solid fuel, the characteristics of carbonization and fuel ratio were analyzed. As a result, as the hydrothermal carbonization reaction temperature increased, the lower heating value also increased by about 500 kcal/kg due to the increase in the degree of carbonization. H/C, O/C, ratio showed a decreasing trend from 1.78, 0.46 to 1.57, 0.32. When the ratio of ash to combustible content (fixed carbon + volatile) of dry sludge was 0.25 or more, it was derived that the degree of carbonization and calorific value did not increase even when hydrothermal carbonization was performed. 하수슬러지의 대부분은 생물학적 처리에 의한 미생물에 의해 분해 가능한 유기물질을 다량 함유하고 있는유기성 폐기물이다. 기존의 하수슬러지 처리방법으로는 건조, 소각, 반탄화 그리고 탄화 등의 기술을 이용하여감량화 및 연료화를 진행하고 있다. 그러나, 건조를 기반으로 하여 539kcal/kg의 잠열이 소비됨으로 에너지 소비가높은 단점이 지적되고 있다. 따라서 본 연구에서는 열화학적 처리인 수열탄화(HTC)를 통해 고형연료를 생산하고자한다. 고형연료의 가치를 평가하기 위하여 탄화도 및 연료비의 특성을 분석하였다. 그 결과 수열탄화 반응온도가증가할수록 탄화도의 상승으로 저위발열량도 약 500kcal/kg 상승하였다. H/C, O/C, Ratio는 1.78, 0.46에서 1.57, 0.32로감소하는 경향을 보였다. 건조슬러지의 가연분(고정탄소+휘발분) 대비 회분(Ash)의 비율이 0.25 이상으로 나타날경우는 수열탄화를 진행하여도 탄화도 및 발열량의 증가되지 않는다는 것을 도출하였다.