Application of analytical pyrolysis for wood fire protection control

The effect of two flame-retardant compositions (A-76% potassium carbonate, B-67% sulphate ammonium) on the process of thermal degradation of wood and the composition of volatile products of pyrolysis has been investigated by the thermogravimetry and analytical pyrolysis methods. It has been shown that the effect of flame retardants manifests itself in the low-temperature region with the formation of more thermally stable intermediate carbonized products. Upon pyrolysis of wood under the action of the composition A, the mechanism of degradation of the lignin component changes, which manifests itself in a more than two-fold increase in the guaiacol and vinylguaiacol contents in the composition of volatile products and the inhibition of the formation of carbohydrates destruction products. It has been found that the composition B has a catalytic action mainly on the process of thermal depolymerization of cellulose, favouring the increase in the formation of levoglucosan and practically does not change the yield of lignin degradation products.     

The pyrolysis of cigarette paper under the conditions that simulate cigarette smouldering and puffing

The combustion properties and pyrolysis behavior of cigarette paper under the pyrolysis conditions of cigarette smouldering were investigated by micro-scale combustion calorimetry (MCC), thermogravimetric analysis coupled to Fourier transform infrared spectrometer (TG-FTIR), respectively. MCC results demonstrated that the combustion and pyrolysis behavior are influenced by heating rate obviously. TG-FTIR results illustrated that the composition of the gaseous products were mainly composed of CO₂, H₂O carbonyl compounds, CO, and methanol. Flash pyrolysis experiment in combination with high performance liquid chromatography (FPy-HPLC) was used to study the pyrolytic formation of eight carbonyl compounds (i.e., formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, crotonaldehyde, methyl ethyl ketone, and butyraldehyde) during the pyrolysis of cigarette paper under the pyrolysis conditions of cigarette puffing. Moreover, the solid char formed after the flash pyrolysis experiments were studied by X-ray photoelectron spectroscopy (XPS). It had been found that the pyrolysis temperature influenced the formation of carbonyl compounds and the composition of char greatly.     

Homogeneous Pyrolysis of α-Naphthol

Homogeneous pyrolysis of -naphthol in argon (1 : 25 volume ratio) at 750-900°C and contact time of 1.5-4.5 s was studied. The conversion and group composition of the liquid products, and component composition of the gaseous pyrolysis products and hydrocarbons were determined; the asphaltenes formed were characterized. The kinetic parameters of -naphthol degradation and formation of methane, hydrogen, and carbon monoxide were calculated; the possible mechanisms of these processes are proposed.     

Pyrolysis behavior of pectin under the conditions that simulate cigarette smoking

In this paper, the formation mechanism of pyrolysis gases released during the pyrolysis of pectin under the conditions that simulate cigarette smouldering was investigated by thermogravimetric analysis coupled to Fourier transform infrared spectrometer (TG-FTIR). Moreover, the combustion behavior of pyrolysis gases was studied by micro-scale combustion calorimetry (MCC). TG-FTIR results illustrated that the composition of the gaseous products was mainly composed of CO₂, H₂O, CO, methanol, methane and carbonyl compounds. MCC results demonstrated that the combustion of pectin was mainly determined by the prolysis gases formed in the temperature range of 200-300 °C. Flash pyrolysis experiment in combination with high performance liquid chromatography (FPy-HPLC) was used to study the pyrolytic formation of eight carbonyl compounds (i.e. formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, crotonaldehyde, methyl ethyl ketone and butyraldehyde) during the pyrolysis of pectin under the pyrolysis conditions of cigarette puffing. Results demonstrated that pyrolysis temperature influenced the formation of acetaldehyde, acrolein, propionaldehyde and butyraldehyde greatly, while nitrogen flow affected the generation of formaldehyde, acetone, crotonaldehyde and methyl ethyl ketone deeply.     

The co-pyrolysis of flame retarded high impact polystyrene and polyolefins

The co-pyrolysis of brominated high impact polystyrene (Br-HIPS) with polyolefins using a fixed bed reactor has been investigated, in particular, the effect that different types of brominated aryl compounds and antimony trioxide have on the pyrolysis products. The pyrolysis products were analysed using FT-IR, GC–FID, GC–MS, and GC–ECD. Liquid chromatography was used to separate the oils/waxes so that a more detailed analysis of the aliphatic, aromatic, and polar fractions could be carried out. It was found that interaction occurs between Br-HIPS and polyolefins during co-pyrolysis and that the presence of antimony trioxide influences the pyrolysis mass balance. Analysis of the Br-HIPS + polyolefin co-pyrolysis products showed that the presence of polyolefins led to an increase in the concentration of alkyl and vinyl mono-substituted benzene rings in the pyrolysis oil/wax resulting from Br-HIPS pyrolysis. The presence of Br-HIPS also had an impact on the oil/wax products of polyolefin pyrolysis, particularly on the polyethylene oil/wax composition which converted from being a mixture of 1-alkenes and n-alkanes to mostly n-alkanes. Antimony trioxide had very little impact on the polyolefin wax/oil composition but it did suppress the formation of styrene and alpha-methyl styrene and increase the formation of ethylbenzene and cumene during the pyrolysis of the Br-HIPS.     

Identification of acrylate copolymers using pyrolysis and gas chromatography

A combination of pyrolysis and gas chromatography were used to investigate thermal degradation products formed from acrylic copolymers containing alkyl acrylate and methacrylate. The method provided an analytical tool for characterizing the chemical composition and structure of the degradation products. Thermal degradation of the synthesized copolymers was analyzed using isothermal (250 °C) pyrolysis–gas chromatography. The degradation process, and the nature and amount of pyrolysis products, provides relevant information about the thermal degradation of acrylic copolymers and the mechanism of pyrolysis. During pyrolysis, the formation of corresponding olefins, alcohols, acrylates and methacrylate was observed.     

Autocatalytic gas-phase dehydrogenation of ethane

Homogeneous gas-phase pyrolysis of ethane by continuous CO₂ laser irradiation was used in our experiments for bulk heating of the reaction mixture. Laser energy was absorbed by ethylene, the main product of ethane dehydrogenation, and transferred to the reaction medium via collisional relaxation. A mechanism of ethane dehydrogenation is suggested to describe the pyrolysis process. The mechanism is autocatalytic in respect of ethylene and includes ethane?Cethylene interaction with the formation of methyl and propyl radicals. Rate constants of elementary reactions, selectivity, and yields of pyrolysis products were determined. The composition of ethane dehydrogenation products determined in the experiments was substantially different from the calculated thermodynamic equilibrium composition.     

The co-pyrolysis of flame retarded high impact polystyrene and polyolefins

The co-pyrolysis of brominated high impact polystyrene (Br-HIPS) with polyolefins using a fixed bed reactor has been investigated, in particular, the effect that different types of brominated aryl compounds and antimony trioxide have on the pyrolysis products. The pyrolysis products were analysed using FT-IR, GC–FID, GC–MS, and GC–ECD. Liquid chromatography was used to separate the oils/waxes so that a more detailed analysis of the aliphatic, aromatic, and polar fractions could be carried out. It was found that interaction occurs between Br-HIPS and polyolefins during co-pyrolysis and that the presence of antimony trioxide influences the pyrolysis mass balance. Analysis of the Br-HIPS + polyolefin co-pyrolysis products showed that the presence of polyolefins led to an increase in the concentration of alkyl and vinyl mono-substituted benzene rings in the pyrolysis oil/wax resulting from Br-HIPS pyrolysis. The presence of Br-HIPS also had an impact on the oil/wax products of polyolefin pyrolysis, particularly on the polyethylene oil/wax composition which converted from being a mixture of 1-alkenes and n-alkanes to mostly n-alkanes. Antimony trioxide had very little impact on the polyolefin wax/oil composition but it did suppress the formation of styrene and alpha-methyl styrene and increase the formation of ethylbenzene and cumene during the pyrolysis of the Br-HIPS.     

Experimental and theoretical study of the pyrolysis of trichlorosilane

Pyrolysis of trichlorosilane (TCS) and copyrolysis of TCS with 1,3-butadiene were studied. The enthalpies and activation energies for the reactions of the products of TCS pyrolysis were found by quantum-chemical calculations. A direct study of the pyrolysis of TCS by mass spectrometry was carried out. Based on the thermochemical parameters found by quantum-chemical calculations and on the results of GLC and mass spectrometry concerning the composition of the pyrolysis products, it was concluded that the pyrolysis of TCS follows a scheme that includes formation of radicals and silylenes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1659–1662, September, 1997.     

Synthesis of carbon nanofibers by catalytic pyrolysis of ethylene in the presence of vapors of volatile components

Catalytic pyrolysis of ethylene was carried out at 700 °C in the presence of vapors of H₂O, EtOH, NH₄OH, PCl₃, (MeO)₃P, Me₂SO₄, (MeO)₃B, and HCl. The composition of solid pyrolysis products was studied using the elemental analysis, X-ray diffraction analysis, and electron microscopy. The composition of the gaseous pyrolysis products was studied using mass spectrometry. The processes in the gas phase were characterized, and the relationship between conditions of ethylene pyrolysis and the structure of formed carbon nanofibers was revealed. The introduction of gaseous additives has a substantial effect on the formation, growth, and structure of the carbon nanofibers formed.     

Pyrolysis of trichlorosilane in the presence of chloroform

The pyrolysis of trichlorosilane in the presence of different amounts of chloroform and the copyrolysis of HSiCl₃ with buta-1,3-diene in the presence of 1 mol.% chloroform were studied. The enthalpies of formation of products resulting from the pyrolysis of HSiCl₃ in the presence of chloroform were calculated by the quantum chemical method. Based on the thermochemical data as well as data from GLC and mass spectrometry, it was concluded from the condensate composition that introduction of chloroform into the zone of pyrolysis of HSiCl₃ favors generation of silylenes.     

Parallels between slow pyrolysis of Estonian oil shale and forest biomass residues

Different types of forest residual biomass, including pine wood, pine bark and spruce needles, and Estonian Kukersite oil shale, were parallelly subjected to the slow pyrolysis in similar conditions. A Fischer assay, modeling industrial semi-coking retorts, was used. Both the yield and the composition of liquid, gaseous and solid products of pyrolysis were determined. FTIR-spectroscopic and chromatographic methods were used to study products group and individual composition. Common and specific features in biomass and oil shale semi-coking have been described. In comparison with oil shale, the biomass yielded less oil and more gas. Specifically large amounts of reaction water and carbon dioxide were obtained in biomass pyrolysis resulting in formation of significantly deoxygenated liquid and solid products. Bio-oils can be distinguished by the solubility in conventional solvents. Kukersite shale oil and the benzene-soluble fractions of different bio-oils were characterized by similar group composition.     

Nonisothermal effects in the process of soot formation in ethylene pyrolysis behind shock waves

The nonisothermal nature of hydrocarbon pyrolysis explains the differences in the critical temperatures of soot formation in the experimental studies of these processes. When reaction heats are taken into account, the critical temperatures become close to 1600 K for all the systems studied. The estimated standard enthalpy of carbon atom formation in the composition of soot particles is δH_{f, z}. ≈ 11 ±6 kJ/mol. A kinetic model is proposed for soot formation in ethylene pyrolysis that describes the experimental data. The calculated temperature of soot particles may differ substantially depending on the choice of a model for energy exchange in collisions.     

1,1,1-Trimethyl-3,3,3-trichlorodisiloxane as a source and a trapping agent for silanones

The pyrolysis of 1,1,1-trimethyl-3,3,3-trichlorodisiloxane (1) was studied and its mechanism involving the formation of dichloro- and dimethylsilanones was proposed. The composition of the condensate from the co-pyrolysis of siloxane i and hexamethyldisiloxane indicated that under the pyrolysis conditions the simplest siloxanes can be both the sources and the trapping agents of silanones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1299–1300, May, 1996.     

混甲酚甲醛炭气凝胶的制备及表征

以混甲酚和甲醛为原料,经溶胶－凝胶民、酸洗老化、超临界干燥得有机气凝胶,密度０．１５０７ｇ／ｃｍ＾３,进一步炭化得炭气凝胶。采用正交试验方法重点考察了炭化工艺条件对炭气凝胶结构和性能的影响,并用ＴＥＭ、ＴＧ、低及附等手段进行了表征。结果表明,炭化工艺条件影响因素顺序为：升温速率〉炭化终温〉维温时间,最佳炭化条件下炭气凝胶密度为０２６０ｇ／ｃｍ＾３,幽静面积人１０２２ｍ＾２／ｇ,平均戏５．６ｍｍ。Ｔ     

Scale-up of microwave heating process for the production of bio-oil from sewage sludge

A pilot-scale microwave heating apparatus was constructed for the production of bio-oil from sewage sludge, and the effects of important microwave processing parameters and chemical additives on the quality and yield of bio-oils were investigated. It was found that bio-oil was mainly formed at the pyrolysis temperature range of 200–400 °C. A higher heating rate (faster pyrolysis) not only increased the yield of bio-oil, but also improved the quality of bio-oil according to the elemental composition and calorific values. The maximum bio-oil yield was 30.4% of organic fraction, obtained from the pyrolysis of original sewage sludge at microwave radiation power of 8.8 kW and final pyrolysis temperature of 500 °C. All of five simple additives (KOH, H₂SO₄, H₃BO₃, ZnCl₂, and FeSO₄) reduced the bio-oil yield, but the composition and property of bio-oil varied with the additive types greatly. KOH, H₂SO₄, H₃BO₃ and FeSO₄ were found to improve the quality of bio-oils remarkably according to the calorific value, density, viscosity and carbon content of bio-oils, but ZnCl₂ treatment went against that. GC–MS analysis of the bio-oils showed that, alkali treatment promoted the formation of alkanes and monoaromatics, while acid treatment favored the formation of heterocyclics, ketones, alcohols and nitriles. Compared with sulfate slat FeSO₄, chloride salt ZnCl₂ was a better catalyst for selective catalytic pyrolysis of sewage sludge. The addition of ZnCl₂ only promoted the formation reactions of a few kinds of nitriles and ketones remarkably. It is technologically feasible to produce bio-oil form microwave-induced pyrolysis of sewage sludge by optimizing pyrolysis conditions and selecting appropriate additives.     

Influence of the interaction of components on the pyrolysis behavior of biomass

There has been much interest in the utilization of biomass-derived fuels as substitutes for fossil fuels in meeting renewable energy requirements to reduce CO₂ emissions. In this study, the pyrolysis characteristics of biomass have been investigated using both a thermogravimetric analyzer coupled with a Fourier-transform infrared spectrometer (TG-FTIR) and an experimental pyrolyzer. Experiments have been conducted with the three major components of biomass, i.e. hemicellulose, cellulose, and lignin, and with four mixed biomass samples comprising different proportions of these. Product distributions in terms of char, bio-oil, and permanent gas are given, and the compositions of the bio-oil and gaseous products have been analysed by gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC). The TG results show that the thermal decomposition of levoglucosan is extended over a wider temperature range according to the interaction of hemicellulose or lignin upon the pyrolysis of cellulose; the formation of 2-furfural and acetic acid is enhanced by the presence of cellulose and lignin in the range 350-500 °C; and the amount of phenol, 2,6-dimethoxy is enhanced by the integrated influence of cellulose and hemicellulose. The components do not act independently during pyrolysis; the experimental results have shown that the interaction of cellulose and hemicellulose strongly promotes the formation of 2, 5-diethoxytetrahydrofuran and inhibits the formation of altrose and levoglucosan, while the presence of cellulose enhances the formation of hemicellulose-derived acetic acid and 2-furfural. Pyrolysis characteristics of biomass cannot be predicted through its composition in the main components.     

Homogeneous Pyrolysis of 1,4-Dimethoxynaphthalene

Homogeneous pyrolysis of 1,4-dimethoxynaphthalene was studied. The yield and group composition of liquid products and the component compositions of the gaseous products and hydrocarbons were determined; the asphaltenes and neutral oxygen-containing compounds were characterized. The kinetic parameters were determined, and possible mechanisms suggested, for decomposition of 1,4-dimethoxynaphthalene with the formation of CH₄, H₂, CO, and CO₂.     

Thermal behavior and pyrolysis products of modified organo-layered silicates as intermediates for in situ polymerization

A systematic study on organo-layered silicate intermediates used for preparing in situ polyethylene nanocomposites was performed by pyrolysis–gas chromatography/mass spectrometry and thermogravimetric analysis. The type and composition of the pyrolysis products gave useful information about mechanism of thermal degradation. The combination of pyrolysis and thermal decomposition data allowed us to describe the evolution of the organoclay structure after the reactive pretreatment steps with alkylaluminoxane cocatalyst and zirconocene or bis(imino)pyridine iron precatalyst, respectively. A proof of the formation of heterogeneous organoclay-immobilized catalyst was obtained.     

Ermittlung des Vernetzungsgrades und Beladungszustandes von Ionenaustauschern auf Kunstharzbasis durch Pyrolyse-Gas-Chromatographie

A special introduction device with switching of carrier gas for improving the reproducibility of pyrolysate composition in pyrolysis gas-chromatography has been described. Its influence on the formation of pyrolysis products and on retention times has been studied on a model substance. The peak area ratios for determining the degree of cross-linking in ion exchangers on styrene-DVB basis can be estimated considerably more accurately with the help of carrier gas switching. Since anion exchangers yield lessα-methylstyrene on pyrolysis than do cation exchangers, their peak area ratios are appreciably larger. Increasing the degree of cross-linking lowers the ratios with the anion exchangers and raises them with the cation exchangers. At 400° C the thermal attack on anion exchangers with styrene-DVB matrix occurs mainly at the active group. The methyl esters or their decomposition products formed from the counter ions are characteristic pyrolysis products. A feature of Dowex 1 is the formation of trimethylamine; of Dowex 2, acetaldehyde. In this way, pyrolysis gas-chromatography enables information about the degree of cross linking and the nature of the anion of ion exchangers, as well as about the matrix, type and structure of the functional group and position of substitution of the anchor group in the matrix to be obtained.