콜타르로부터 탄소섬유 제조를 위한 프리커서용 석탄계 핏치의 제조

고효준,박창욱,조효행,유미정,김명수,임연수,Ko, Hyo Joon,Park, Chang Uk,Cho, Hyo Hang,Yoo, Mi Jung,Kim, Myung-Soo,Lim, Yun-Soo 한국재료학회 2013 한국재료학회지 Vol.23 No.5

Coal tar is the primary feedstock of premium graphitizable carbon precursor. Coal tars are residues formed as byproducts of thermal treatments of coal. Coal tar pitches were prepared through two different heat treatment schedules and their properties were characterized. One was prepared with argon and oxidation treatment with oxygen; the other was prepared with oxygen treatment at low temperature and then argon treatment at high temperature; both used coal tar to prepare coal tar pitches. To modulate the properties, different heat treatment temperatures ($300{\sim}400^{\circ}C$) were used for the coal tar pitches. The prepared coal tar pitches were investigated to determine several properties, such as softening point, C/H ratio, coke yield, and aromaticity index. The coal tar pitches were subject to considerable changes in chemical composition that arose due to polymerization after heat treatment. Coal tar pitch showed considerable increases in softening point, C/H ratio, coke yields, and aromaticity index compared to those characteristics for coal tar. The contents of gamma resin, which consists of low molecular weight compounds in the pitches and is insoluble in toluene, showed that the degree of polymerization in the pitches was proportional to C/H ratio. Using an oxidizing atmosphere like air to prepare the pitches from coal tar was an effective way to increase the aromaticity index at relatively low temperature.

Pyrolyzed Fuel Oil/Coal-tar 혼합원료의 열중합 반응에 따른 Pitch 제조 특성

이은별 ( Eunbyul Lee ),김형기 ( Hyeong Gi Kim ) 한국공업화학회 2020 공업화학 Vol.31 No.3

본 연구에서는 PFO와 Coal-tar의 구조와 열 중합 거동 분석을 통해 PFO와 Coal-tar으로 구성된 혼합 원료의 피치 합성 간 제조 특성을 확인하였다. 원소분석과 FT-IR 분석을 통해, PFO와 Coal-tar 각각 0.355, 0.818로 방향족화도 수치를 확인하였다. 또한, PFO와 Coal-tar의 열중량 분석을 통해 질량 감소곡선의 차이를 확인하였으며, 이러한 현상은 방향족 화도와 관능기 함량에 따른 구조적 안정성에 기인한 것으로 판단된다. 피치 제조 특성은 PFO를 원료로 사용한 피치가 혼합원료로부터 제조된 피치보다 평균적으로 낮은 수율과 높은 연화점을 보임을 확인하였다. 특히 유사한 연화점을 가지는 P360 (138.5 ℃)과 B420 (141.4 ℃)을 비교하였을 때, 두 피치의 탄화수율은 각각 29.89, 49.03 wt%로 Coal-tar가 혼합된 경우 약 20 wt% 향상됨을 확인하였다. 이러한 결과는 다량의 알킬기를 포함하여 높은 피치 중합 반응성을 가지는 PFO와 높은 열적 안정성을 가지는 Coal-tar의 혼합에 기인한 것으로 판단된다. In this study, blended feedstock derived pyrolyzed fuel oil (PFO) and coal-tar was prepared to produce a pitch by thermal polymerization reaction for manufacturing artificial graphite materials. The aromaticity value of 0.355 and 0.818 was obtained for PFO and coal-tar, respectively. In addition, PFO and coal-tar exhibited the difference tendency of weight loss curve for thermogravimetric analysis, which is related to the structural stability depending on the aromaticity and functional groups. The production characteristics confirmed that the pitch derived PFO showed lower production yield and higher softening point than that using blended feedstock. In particular, when comparing P360 (138.5 ℃) and B420 (141.4 ℃) having similar softening points, the production yields of both pitches exhibited 29.89 and 49.03 wt%, respectively. This is mainly due to the blending of PFO and coal-tar having high pitch polymerization reactivity including a large amount of alkyl groups and coal-tar having high thermal stability. This phenomenon indicated that the increased production yield is because of a synergic effect of both the high reactivity of PFO and thermal stability of coal-tar.

콜타르 피치를 취급하는 근로자의 광독성 피부질환

정철,임현술,김두희,성열오,Jung, Cheol,Lim, Hyun-Sul,Kim, Doo-Hie,Sung, Yeol-Oh 대한예방의학회 1997 예방의학회지 Vol.30 No.1

Interview survey and dermatological examination have been performed to investigate the health problems of workers continuously exposed to coal-tar pitch. The phototoxicity of coal-tar pitch was confirmed by the photopatch tests for six healthy adults. The main results are followings; 1. There was no special history of allergic diseases in both the exposed and non-exposed group. 2. The frequency of the phototoxic dermatosis and the coal-tar acne in the exposed group was significantly greate.(p<0.05) than that of the control group. In the exposed group, the phototoxic dermatosis and the coal-tar acne were observed in nine workers(90%) and seven workers(70%), respectively. However, those, disease were not observed in the control group. 3. Five results(83%) were positive to the photopatch test for coal-ta. pitch 48 hours after UVA irradiation. But the lesion was subsiding 72 hours after UVA irradiation. 4. Malignant cancers were not reported among workers ever exposed to coal-tar pitch. In conclusion, it appears that workers exposed to coal-tar pitch have high risks of phototoxic dermatosis and coal-tar acne. A health policy should be provided to prevent phototoxic dermatosis among coal-tar pitch workers. More studies are required to determine malignancy.

열분해유/콜타르 혼합비가 피치계 활성탄의 수율 및 물성에 미치는 영향

유태웅 ( Tae Ung Yoo ),서상완 ( Sang Wan Seo ),임지선 ( Ji Sun Im ),이수홍 ( Soo Hong Lee ),송우진 ( Woo Jin Song ),강석창 ( Seok Chang Kang ) 한국공업화학회 2024 공업화학 Vol.35 No.2

피치계 활성탄의 수율 향상을 위해 열분해유와 콜타르를 혼합하여 피치를 합성하고, 합성된 피치를 물리적 활성화하여 활성탄을 제조하였다. 피치는 콜타르를 열분해유 대비 0~20%로 달리하여, 380~420 ℃에서 3 h 반응하여 합성하였다. 합성된 피치는 80~260 ℃ 사이의 연화점을 가졌고, 10~40% 범위의 수율을 나타냈다. 모든 합성온도에서 콜타르 혼합비율이 증가할수록 수율이 증가하고, 연화점이 감소함을 확인하였다. 합성된 피치 중 연화점이 230~260 ℃ 사이의 피치를 선정하여 물성을 고찰하였다. 열분해유만으로 제조된 피치에 비해 콜타르가 함유된 피치가 저비점에서 휘발분이 많고, 잔탄량이 높았다. 이는 콜타르와 열분해유의 조성에 따른 차이로, 방향족 성분이 많은 콜타르와 지방족 성분이 많은 열분해유의 영향임을 확인하였다. 선정된 피치를 관형 반응기에서 950 ℃까지 승온하고, 1 h 동안 수증기로 물리적 활성화하였다. 콜타르가 포함된 활성탄이 열분해유만으로 제조된 활성탄에 비해 높은 수율과 미세기공율을 나타냈다. 본 연구에서는 피치 원료 혼합에 의한 활성탄 수율 증가 효과를 확인하고, 콜타르 혼합 비율에 따른 물리적 활성화 특성을 고찰하였다. In order to produce high-yield pitch-based activated carbon, pitch was synthesized by blending pyrolysis fuel oil (PFO) and coal-tar. Pitch was synthesized by varying the amount of coal-tar from 0~20% compared to PFO and reacting at 380~420 ℃ for 3 h. The synthesized pitch had a softening point between 80 and 260 ℃, and yields ranged from 10 to 40%. At all synthesis temperatures, as the coal-tar blending ratio increased, the yield increased and the softening point decreased. After considering the selected pitches (softening points: 230~260 ℃), pitches containing coal-tar were more volatile at a low boiling point and had a higher residual carbon content. This is a difference in the composition of coal-tar and PFO, and it was confirmed that coal-tar has a lot of aromatics and PFO has a lot of aliphatics. The selected pitch was heated to 950 ℃ in a tubular reactor and physically activated with steam for 1 hour. Activated carbon containing coal-tar showed higher yield and microporosity compared to only PFO. In this study, the effect of increasing activated carbon yield by blending pitch raw materials was confirmed, and the physical activation characteristics according to the coal-tar mixing ratio were examined.

환경친화적 콜탈에나멜의 개발

이진욱,이의수,이명천 동국대학교 산업기술연구원 1998 산업기술논문집 Vol.11 No.-

콜탈에나멜의 수송관 코팅제로서의 요구물성을 충족시키면서, 유해한 fume의 발생을 최소화하는 환경 친화적인 저 휘발성 콜탈에나멜을 개발하였다. 이는 기존의 coal tar enamel의 주원료인 coal tar를 사용하지 않고, 휘발분의 유출량이 상대적으로 적은 물성을 가진 원료인 heavy oil, middle pitch, coal만의 혼합으로 가능하였으며, 제품을 휘발분 실험한 결과 휘발분이 평균 36.7%가 낮은 환경 친화적인 제품을 만들 수 있었다. 저 휘발성 콜탈에나멜을 제조시 얻은 물성 data로부터 heavy oil과 pitch의 투입비(%), coal의 투입량(weight%), 그리고 원료 heavy oil의 ASTM 유출량을 독립변수로 하여 연화점과의 상관관계식을 도출하였으며, 이로부터 얻어지는 연화점으로부터 침입도를 예측할 수 있는 관계식을 유도하였다. 이들 관계식은 향후 신제품 개발시, 공정을 최적화시키기 위한 원료 배합비의 결정을 위한 기준으로 사용될 수 있다. For easement of working environmental problem we developed low fume coal tar enamel(CTE), which is made by mixing of low volatile materials, i.e heavy oil, middle pitch and coal. The new CTE product not only meets the required physical properties as the protective coatings for steel pipe but has volatilities by average 36.7% lower than existing CTE. As a guide for manipulation of operation conditions we derived a correlated equation of softening point from independent manufacturing variables such as projection ratio of heavy oil and pitch(%), projection weight (%), and ASTM effluent quality of heavy oil. And we also derived a correlated equation for prediction of penetration point from softening point. These equations can be used to predict the optimal mixing ratio of raw materials

석탄계 타르의 열처리 중 압력변화에 따른 변성 콜타르 핏치의 미세구조 및 물성 변화

고효준,정성모,한지훈,박창욱,김명수,임연수,Ko, Hyo Joon,Chung, Sung Mo,Han, Ji Hoon,Park, Chang Uk,Kim, Myung-Soo,Lim, Yun-Soo 한국재료학회 2014 한국재료학회지 Vol.24 No.6

Coal-tar pitch, a feedstock which can be heat-treated to create graphite, is composed of very complex molecules. Coal-tar pitch is a precursor of many useful carbon materials (e.g., graphite, carbon fibers, electrodes and matrices of carbon/carbon composites). Modified coal-tar pitch (MCTP) was prepared using two different heat-treatment methods and their properties were characterized and compared. One was prepared using heat treatment in nitrogen gas; the other was prepared under a pressure of 350 mmHg in air. The MCTPs were investigated to determine several properties, including softening point, C/H ratio, coke yield, formation of anisotropic mesophase and viscosity. The MCTPs were subject to considerable changes in chemical composition due to condensation and polymerization in the used-as-received coal-tar pitch after heat-treatment under different conditions. The MCTPs showed considerable increases in softening point, C/H ratio, and coke yield, compared to those of as-received coal-tar pitch. The MCTP formed by heat-treatment in nitrogen showed isotropic phases below $350^{\circ}C$ for 1 h of soaking time. However, MCTP heat-treated under high pressure (350 mmHg) showed isotropic phases below $300^{\circ}C$, and showed anisotropic phases above $350^{\circ}C$, for 1 h of soaking time. The viscosity of the MCTPs increased with increase in their softening points.

Evaluation of ocular irritancy of coal-tar dyes used in cosmetics employing reconstructed human cornea-like epithelium and short time exposure tests

Lee, M.,Nam, K.T.,Kim, J.,Lim, S.E.,Yeon, S.H.,Lee, B.,Lee, J.Y.,Lim, K.M. Pergamon ; Elsevier Science Ltd 2017 Food and chemical toxicology Vol.108 No.1

Coal-tar dyes in cosmetics may elicit adverse effects in the skin and eyes. Countries, like the US, have banned the use of coal-tar dyes in cosmetics for the eye area due to the potential for ocular irritation. We evaluated the eye irritation potential of 15 coal-tar dyes permitted as cosmetic ingredients in reconstructed human cornea-like epithelium (RhCEs [EpiOcular(TM) and MCTT HCE(TM)]) tests and the short time exposure (STE) test. Eosin YS, phloxine B, tetrachlorotetrabromofluorescein, and tetrabromofluorescein were identified as irritants in RhCEs; dibromofluorescein and uranine yielded discrepant results. STE enabled further classification in accordance with the UN Globally Harmonized System of Classification and Labelling of Chemicals, as follows: eosin YS as Cat 2; phloxine B, Cat 1; and tetrachlorotetrabromofluorescein and tetrabromofluorescein, Cat ½. STE indicated dibromofluorescein (irritant in EpiOcular(TM)) and uranine (irritant in MCTT HCE(TM)) as No Cat, resulting in the classification of ''No prediction can be made.'' based on bottom-up approach with each model. These results demonstrated that in vitro eye irritation tests can be utilized to evaluate the potential ocular irritancy of cosmetic ingredients and provide significant evidence with which to determine whether precautions should be given for the use of coal-tar dyes in cosmetics or other substances applied to the eye area.

A Numerical Study on Coal Devolatilization of Bituminous Coal Using CPD Model

Ryang Gyoon Kim(김량균),Byoung Hwa Lee(이병화),Chung Hwan Jeon(전창환),Young June Chang(장용준),Ju Hun Song(송주헌) 대한기계학회 2008 대한기계학회 춘추학술대회 Vol.2008 No.11

The coal considerably is the energy resource which is important with the new remarking energy resource. The coal conversion has two processes which are coal devolatilization and char oxidation. Coal devolatilization is important because it describes up to 70% weight loss and has been shown that nitrogen contribute 60 to 80% of the total NOx produced. The chemical percolation devolatilization(CPD) model is used here to describe coal devolatilization. The model was developed to describe coal devolatilization behavior of rapidly heated coal based on characteristics of the chemical structure of the parent coal. This paper describes CPD model in detail and makes an analysis of Shenhua coal(bituminous) which is used calculated 13-C NMR(carbon - nuclear magnetic resonance).

콜타르를 취급하는 근로자에서 발생한 폐암 1예

임현술,이관 東國大學校醫學硏究所 2004 東國醫學 Vol.11 No.2

콜타르는 폐암, 피부암 등을 유발하는 발암물질로 우리나라에서 콜타르에 의한 암이 보고 된 적은 없었다. 저자들은 26년간 콜타르를 취급한 48세 남자 근로자에서 발생한 비소세포성 폐암에 대하여 작업력과 폐암과의 관련성을 파악하고자 하였다. 환자는 1976년 7월 10일 모 화학공장에 취직하여 원료 반입, 제품 출하 및 장치 관리를 담당하였다. 2001년 10월 경 우측 경부 림프절이 촉지되었으며, 동년 12월 26일 비소세포성 폐암으로 진단을 받은 후 2002년 12월 20일에 명예 퇴직하였다. 환자는 26년간 저유시설 관리업무를 담당하는 과정에서 콜타르에 노출된 사실이 확인되었고, 하루 3시간 10분 정도는 발암물질 특히, 콜타르에 노출될 가능성이 있었다. 2.5~5갑년의 흡연력이 있지만, 흡연량이 적고, 젊은나이에 금연하였기 때문에 폐암의 발생은 다른 원인에 의하거나 발암물질과 상승작용을 하였을 가능성이 높다. 방향족탄화수소에 대한 농도 측정과 동료 근로자들의 암 발생 현황은 정확히 파악할 수 없었지만, 업무와 관련되어 발병하였을 가능성이 높아 콜타르에 의한 직업성 폐암으로 인정되었다. 본 증례로 미루어 콜타르에 노출된 근로자에 대하여 노출을 감소시키기 위한 제도적이고 현실적인 대책을 적극적으로 수립하여야 한다. 뿐만 아니라 철저한 작업환경개선 및 관리, 철저한 보호구 착용 및 금연을 실천하여 암 발생을 감소시키기 위하여 노력하여야 한다. 또한 암을 조기 발견하기 위한 방안을 모색하기위해서 다환방향족 탄화수소에 대한 농도 측정과 발암물질에 노출된 근로자에 대하여 건강진단을 강화하여야 한다. We report a case of lung cancer (non-small cell carcinoma) occurred to worker handled coal tar. The author reviewed his clinical features, job contents and measured work environments etc. The worker was a 48-year-old male who had worked in a chemical company for 26 years from 1976 to 2002. He has been engaged in taking fuel, shipping goods and managing equipments. He had exposed to coal tar, benzene and toluene during for manage establishment storage of oil for 26 years. He worked without safety precautions such as a protective mask. We concluded that the lung cancer occurred to this case was an occupational disease due to exposure to coal tar. To prevent occupational cancer in a worker exposed to coal tar, we must improve the engineering procedure, begin comprehensive medical surveillance and biological monitoring for polycyclic aromatic hydrocarbons, educate workers an risks and increase awareness of safety regulations in the workplace.

국내원전에 매설된 콜타르 코팅 배관의 음극방식과 FEM법을 이용한 방식성능 시뮬레이션

장현영 ( H. Y. Chang ),김기태 ( K. T. Kim ),임부택 ( B. T. Lim ),김경수 ( K. S. Kim ),김재원 ( J. W. Kim ),박흥배 ( H. B. Park ),김영식 ( Y. S. Kim ) 한국부식방식학회 2017 Corrosion Science and Technology Vol.16 No.3

Coal tar-coated pipes buried in a domestic nuclear power plant have operated under the cathodic protection. This work conducted the simulation of the coating performance of these pipes using a FEM method. The pipes, being ductile cast iron have been suffered under considerably high cathodic protection condition beyond the appropriate condition. However, cathodic potential measured at the site revealed non-protected status. Converting from 3D CAD data of the power plant to appropriate type for a FEM simulation was conducted and cathodic potential under the applied voltage and current was calculated using primary and secondary current distribution and physical conditions. FEM simulation for coal tar-coated pipe without defects revealed over-protection condition if the pipes were well-coated. However, the simulation for coal tar-coated pipes with many defects predict that the coated pipes may be severely degraded. Therefore, for high risk pipes, direct examination and repair or renewal of pipes are strongly recommended.