• Title/Summary/Keyword: Pyrolysis/GC/MS

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Characterization of Degradation features and Degradative Products of Poplar Wood(Populus alba${\times}$glandulosa) by Flow Type-Supercritical Water Treatment (초임계수에 의한 현사시 목분의 분해특성 및 분해산물 분석)

  • Choi Joon-Weon;Lim Hyun-Jin;Han Kyu Sung;Kang Ha-Young;Choi Don-Ha
    • Journal of Korea Foresty Energy
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    • v.24 no.1
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    • pp.39-46
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    • 2005
  • In this study, the possibility of sugar conversion of poplar wood(Populus $alba{\times}rglandulosa$) and their degradation features of major wood components were characterized using flow type supercritical water treatment system. The finely ground poplar wood meals were treated for 2min. under subcritical condition$(23MPa,\;275^{\circ}C\;and\;325^{\circ}C)$ and supercritical condition $(23MPa,\;375^{\circ}C\;and\;415^{\circ}C)$. respectively. The degradation products of poplar wood meals appeared brownish colors, including undegraded solids. Increasing the temperature of the system, the degradation rate of poplar wood meals was accelerated and reached up to $94\%\;at\;375^{\circ}C$. The total amount of reducing sugars in degradation products determined by DNS method were gradually lowered when the temperature condition became severe. This indicated that the reducing sugars formed were further degraded to kan derivatives by certain side reaction such as pyrolysis under higher temperature. In order to characterize degradation features of lignin, the degradation products were extracted with ethylacetate and the organic phases were subjected to GC-MS analysis. Main lignin degradation products were identified to vanillin, guaiacol, syrinaldehyde, 4-prophenyl syringol and dihydrosinapyl alcohol, which could be formed by the cleavage of ether linkages in lignin polymers by high temperature condition.

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Characterization of Poly(methyl methacrylate)-tin (IV) Chloride Blend by TG-DTG-DTA, IR and Pyrolysis-GC-MS Techniques

  • Arshad, Muhammad;Masud, Khalid;Arif, Muhammad;Rehman, Saeed-Ur;Saeed, Aamer;Zaidi, Jamshed Hussain
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3295-3305
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    • 2011
  • Thermal behavior of poly (methyl methacrylate) was analyzed in the presence of tin (IV) chloride. Five different proportions - polymer to additive - were selected for casting films from common solvent. TG, DTG and DTA were employed to monitor thermal degradation of the systems. IR and py-GC-MS helped identify the decomposition products. The blends start degrading at a temperature lower than that of the neat polymer and higher than that of the pure additive. Complex formation between tin of additive and carbonyl oxygen (pendent groups of MMA units) was noticed in the films soon after the mixing of the components in the blends. The samples were also heated at three different temperatures to determine the composition of residues left after the expulsion of volatiles. The polymer, blends and additive exhibited a one step, two-step and three-step degradation, respectively. $T_0$ is highest for the polymer, lowest for the additive and is either $60^{\circ}C$ or $70^{\circ}C$ for the blends. The amount of residue increases down the series [moving from blend-1 (minimum additive concentration) to blend-5 (maximum additive concentration)]. For blend-1, it is 7% of the original mass whereas it is 16% for blend-5. $T_{max}$ also goes up as the concentration of additive in the blends is elevated. The complexation appears to be the cause of observed stabilization. Some new products of degradation were noted apart from those reported earlier. These included methanol, isobutyric acid, acid chloride, etc. Molecular-level mixing of the constituents and "positioning effect" of the additive may have brought about the formation of new compounds. Routes are proposed for the appearance of these substances. Horizontal burning tests were also conducted on polymer and blends and the results are discussed. Activation energies and reaction orders were calculated. Activation energy is highest for the polymer, i.e., 138.9 Kcal/mol while the range for blends is from 51 to 39 Kcal/mol. Stability zones are highlighted for the blends. The interaction between the blended parts seems to be chemical in nature.

A Study on Fire Explosion Characteristics via Physico-chemical Analysis of Petroleum Residues (석유 부산물의 물리화학적 분석을 통한 화재폭발 특성연구)

  • Kim, Hyeonggi;Lee, Young-Seak
    • Applied Chemistry for Engineering
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    • v.30 no.5
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    • pp.556-561
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    • 2019
  • In this study, the physical and chemical analyses of petroleum residues (pyrolized fuel oil, PFO) were conducted and major components were selected to investigate their fire and explosion characteristics. Major component distribution areas of the PFO were identified via the GC-SIMDIS and MALDI-TOF analyses. In addition, the qualitative analysis of major component distribution areas was performed by GC-MS analysis. Major components of pyrolysis residue were selected based on the results of various analyses such as EA, SARA and TGA. As a result, benzene, toluene and xylene were selected as major components. Finally, the process hazard analysis software tool (PHAST) analysis was performed to investigate the range of maximum damage effect in case of fire and explosion. Toluene presented the highest risk due to the radiation effect of $227kW/m^2$ and 118 m in the case of jet fire. Xylene and benzene showed the maximum radiant heat values of 114 and $151kW/m^2$, respectively. It was also confirmed from the analysis of pasquill stability and wind speed that the radiant heat increased up to 55% according to wind speed in benzene, which was considered to be a main factor increasing the influence range.

Investigation of Physicochemical Properties of Bio-oils Produced from Pitch Pine (Pinus rigida) at Various Temperatures (열분해 온도에 따른 리기다소나무 바이오오일의 물리·화학적 특성 평가)

  • Kim, Tae-Seung;Kim, Jae-Young;Oh, Shin-Young;Hwang, Hye-Won;Choi, Joon-Weon
    • Journal of the Korean Wood Science and Technology
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    • v.40 no.3
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    • pp.204-211
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    • 2012
  • In this study, fast pyrolysis of pitch pine (Pinus rigida) was performed in a fluidized bed reactor under the temperature ranges between 400 and $550^{\circ}C$ at the residence time of 1.9 sec. Essential pyrolytic products (bio-oil, biochar, and gas) were produced and their yield was clearly influenced by temperature. The maximum yield of bio-oil was observed to 64.9 wt% (wet basis) at the temperature of $500^{\circ}C$. As pyrolysis temperature increased, the yield of biochar decreased from 36.8 to 11.1 wt%, while gas amount continuously increased from 16.1 to 33.0 wt%. Water content as well as heating value of bio-oils were obviously sensitive to the pyrolysis temperature. The water contents in the bio-oil clearly decreased from 26.1 ($400^{\circ}C$) to 11.9 wt% ($550^{\circ}C$), with increasing the fast pyrolysis temperature, while their higher heating values were increased from 16.6 MJ/kg to 19.3 MJ/kg. According to GC/MS analysis, 22 degradation compounds were identified from the bio-oils and 10 compounds were derived from carbohydrate, 12 compounds were derived from lignin.

A case study of verifying a suicide by carbon monoxide intoxication committed by burning an ignition charcoal briquette (착화탄 연소에 의한 일산화탄소 중독사에서 자살입증에 관한 사례연구)

  • Sung, Tae-myung;Jo, Ju-ik;Ahn, Phil-sang
    • Analytical Science and Technology
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    • v.28 no.6
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    • pp.398-408
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    • 2015
  • Carbon monoxide (CO) intoxication, arising from CO from an ignited charcoal briquette (ICB), is a popular means of committing suicide in Korea. Most CO intoxications are related to suicide attempts; however, the possibility of a homicide disguised as a suicide cannot be ruled out. Therefore, forensic investigation of the deceased and the crime scene is crucial to confirm that the deceased committed suicide. Detection of the components of an ICB on the objects suspected of being contacted by the deceased, such as the hands, nostrils, and doorknobs, is essential for linking the crime scene to the victim in the case of suicides by ignited ICBs. The traces from an ICB were analyzed by investigating the morphological characteristics and obtaining elemental compositions. The ICBs were completely different from blackened wood, as detected by discriminant analysis with the elements of carbon and oxygen. We analyzed one case of CO intoxication to demonstrate an excellent procedure for verifying whether a suicide occurred with an ICB. We employed SEM-EDX for the analysis of an ICB, microscope-FT/IR and pyrolysis-GC/MS for a partly burnt resin-type substance, GC/MS for diphenhydramine (a sleeping drug), and GC/TCD for the CO-Hb level. We detected traces of an ICB on the hands, nostrils, and doorknobs, which were all discriminated into an ICB group. Detection of ICB traces from the nostrils could indicate that the deceased started the fire themselves to commit suicide. The partially burnt black material was analyzed as an acrylronitrilestyrene polymer, which is normally used to make bags for carrying or wrapping and could be assumed to have been used to transport the ICB. Diphenhydramine, a sleeping drug, was detected at a level of 2.3 mg/L in the blood, which was lower than that in fatal cases (8-31 mg/L; mean 16 mg/L). A CO-Hb level of 79% was found in the blood, which means that the cause of death was CO intoxication. The steps shown here could represent an ideal method for reaching a verdict of suicide by CO intoxication produced by burning an ICB in a sealed room or a car.

Thermochemical Sulfate Reduction Simulation Experiments on the Formation and Distribution of Organic Sulfur Compounds in the Tuha Crude Oil

  • Yue, Changtao;Li, Shuyuan;Song, He
    • Bulletin of the Korean Chemical Society
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    • v.35 no.7
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    • pp.2057-2064
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    • 2014
  • Thermochemical sulfate reduction (TSR) was conducted in autoclave on the system of crude oil and $MgSO_4$ at different temperatures. Gas chromatography pulsed flame photometric detector (GC-PFPD) was used to detected the composition of organic sulfur compounds in oil phase products. The results of the analysis indicate that with increased temperature, the contents of organic sulfur compounds with high molecular weight and thermal stability, such as benzothiophenes and dibenzothiophenes, gradually became dominated. In order to gain greater insight into the formation and distribution of organic sulphur compounds from TSR, positive ion electrospray Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used in detecting the detailed elemental composition and distribution of them. The mass spectra showed that the mass range of sulfur compounds was 200-550 Da. Four sulfur class species, $S_1$, $N_1S_1$, $O_1S_1$ and $O_2S_1$, were assigned in the positive-ion spectrum. Among the identified sulfur compounds, the $S_1$ class species was dominant. The most abundant $S_1$ class species increase associated with the DBE value and carbon number increasing which also indicates the evolution of organic sulfur compounds in TSR is from the labile series to the stable one. In pure blank pyrolysis experiments with crude oil cracking without TSR, different composition and distribution of organic sulfur compounds in oil phase products were seen from mass spectra in order to evaluate their pyrolysis behaviors without $MgSO_4$. FT-IR and XRD were used in analyzing the products of solid phases. Two distinct crystallographic phases MgO and $MgSO_4$ are found to coexist in the products which demonstrated the transformation of inorganic sulfur compounds into organosulfur compounds exist in TSR.

Effect of Particle Size and Moisture Content of Woody Biomass on the Feature of Pyrolytic Products (급속열분해 공정에서 바이오매스의 입자크기와 수분 함량이 열분해 산물의 특성에 미치는 영향)

  • Hwang, Hyewon;Oh, Shinyoung;Kim, Jae-Young;Lee, Soomin;Cho, Taesu;Choi, Joon Weon
    • Journal of the Korean Wood Science and Technology
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    • v.40 no.6
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    • pp.445-453
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    • 2012
  • In this study the effects of particle size and water content on the yields and physical/chemical properties of pyrolytic products were investigated through fast-pyrolysis of yellow poplar. Water content was critical parameters influencing the properties of bio-oil. The yields of bio-oil were increased with decreasing water content. However, the yield of pyrolytic product was not clearly influenced by feedstock's particle size. The water content, pH and HHV (Higher Heating Value) of bio-oil were measured to 20~30%, 2.2~2.4 and 16.6~18.5MJ/kg, respectively. The water content of feedstock was clearly influenced to water content of bio-oil. In terms of bio-char, HHV of them were measured to 26.2~30.1 MJ/kg with high content of carbon over 80%.

Pyrolysis Characteristics of CCL(Copper Clad Laminate) Based Paper/Phenolic Resin Composites (종이/페놀수지가 주성분인 동박적층판(Copper Clad Laminate)의 열분해 특성)

  • Song, Jae-Hun;Kim, Seung-Do;Ahn, Hyun-Cheol;Kim, Gyung-Soo;Kim, Sang-Bum;Jung, Jae-Sung;Gong, Sung-Ho;Cho, Young-Gae
    • Journal of Korean Society of Environmental Engineers
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    • v.29 no.9
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    • pp.1013-1019
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    • 2007
  • Electronic wastes have increased tremendously. However, any reliable treatment methodologies have rarely been established. Electronic wastes have posed serious disposal problem due to their physico-chemical stability. This paper investigated the application possibility of pyrolysis for the purpose of recycling the p-CCL(phenol based Copper Clad Laminate). Thermogravimetric analysis(TGA) was used to investigate the thermal decomposition pattern of p-CCL. We elucidated the characteristics of pyrolysis by-products at operating temperatures of 280, 350 and $600^{\circ}C$. GC/MS and FT-IR were used to characterize the liquid by-products along with general characterization methods such as Ultimate Analysis, Proximate Analysis and Heating Value, whereas general characterization methods were only introduced for the solid by-products. At a heating rate of $5^{\circ}C$/min, TGA curves exhibited three decomposition stages: (1) low-temperature decomposition region$(<280^{\circ}C)$, (2) medium temperature region$(280\sim350^{\circ}C)$ and (3) high-temperature region$(>350^{\circ}C)$. The major compounds of liquid by-products at low- and medium-temperatures were accounted for by water and phenol, whereas branched phenols and furans were major compounds at high-temperatures. As the temperature increases, volatile quantities decreased but the fixed carbon increased. High heating values of solid by-products($7,400\sim7,600$ kcal/kg) would suggest that the solid by-products could be applicable as fuel. In addition, high fixed carbon but low ash content of the solid by-products offered an implication that they are capable of being upgradable for adsorbent after applying appropriate activating process.

The Recovery of Carbon Fiber from Carbon Fiber Reinforced Epoxy Composites for Train Body (철도차량용 폐 복합소재에서의 탄소섬유 회수)

  • Lee, Suk-Ho;Lee, Cheul-Kyu;Kim, Yong-Ki;Kim, Jung-Seok;Ju, Chang-Sik
    • Proceedings of the KSR Conference
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    • 2008.11b
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    • pp.406-415
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    • 2008
  • Recently, the amount of thermosetting plastic wastes have increased with the production of reinforced plastic composites and causes serious environmental problems. The epoxy composites, one of the versatile thermosetting plastics with excellent properties, cannot be melted down and remolded as what is done in the thermoplastic industry. In this research, a series of experiments that recovers carbon fibers from carbon fiber reinforced epoxy composites for train body was performed. We experimentally examined various decomposition processes and compared their decomposition efficiencies and mechanical property of recovered carbon fibers. For the prevention of tangle of recovered carbon fibers, each composites specimen was fixed with a Teflon supporter and no mechanical mixing was applied. Decomposition products were analyzed by scanning electron microscope (SEM), gas chromatography mass spectrometer (GC-MS), and universal testing machine (UTM). Carbon fibers could be completely recovered from decomposition process using nitric acid aqueous solution, liquid-phase thermal cracking and pyrolysis. The tensile strength losses of the recovered carbon fibers were less than 4%.

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Example of Air Exposure Assessment for Fire Extinguishing Agent Residues (소화약제 잔류물질에 대한 공기 중 노출평가 사례)

  • Daesung Lim
    • Journal of Korean Society of Occupational and Environmental Hygiene
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    • v.34 no.1
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    • pp.14-17
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    • 2024
  • Objectives: This is a case of air exposure assessment conducted after researchers complained of headaches and odor due to residual substances from fire extinguishing agents spread throughout the laboratory due to a malfunction of the fire extinguishing facility. Methods: A component analysis was conducted on the residual substances of a fire extinguishing agent spread in a laboratory using Py-GC-MS (pyrolysis gas chromatography mass spectrometry) at the research institute's own central equipment research center. As a result of the component analysis, several types of substances were detected. Among these, five types of substances subject to work environment measurement in the aromatic hydrocarbon series, which can affect headaches and odor, were selected as substances subject to exposure assessment in the air, and the measurement and analysis methods of the target substances were conducted in accordance with the KOSHA Guide for each substance. Conclusions: The measurement results showed that all 5 types of substances were not detected at locations A, B, and C. This is believed to be the result of the residual substances in the fire extinguishing agent being measured when approximately two months had elapsed after being exposed to the test bench, and the substances already exposed had volatilized and disappeared. In this survey, it is believed that the measurement process is more important than the measurement results.