Evaluation of pyrolysis and combustion products from foundry binders: potential hazards in metal casting

The aim of this paper is the comparison of the thermal destruction course of one of the commercially available binders applied in the ALPHASET technology in dependence of the temperature, heating rate and the character of the atmosphere (inert, oxidising or reducing). The thermogravimetric analysis/differential scanning calorimetry/Fourier-transform infrared spectroscopy (TG/DSC/FTIR) system allowed for real-time analysis of the composition and intensity of gases emitted during slow heating in the inert and oxidising atmospheres. In addition, the TG/DTG/DSC investigation of the binder was performed in the reducing atmosphere. The pyrolysis gas chromatography coupled with mass spectrometry system allowed for the analysis of gases evolved at very fast heating in the inert atmosphere (pyrolysis) as a function of temperature. It has been proven that the type and amount of the gases emitted is highly dependent on the temperature, heating rate and the atmosphere in which it is performed. The highest versatility of harmful volatiles is produced during heating in the inert atmosphere. This type of atmosphere is present in the closest proximity of the liquid metal. Thus, to reduce the risk of exposure of the foundry workers, the extraction of the casting should be done under the hood, and sufficient personal protective equipment should be used.

     

Gas Evolution from the Pyrolysis of Jordan Oil Shale in A Fixed-bed Reactor

Jordan oil shale from El-Lajjun deposit was pyrolysed in a fixed-bed pyrolysis reactor and the influence of the pyrolysis temperature between 400 to 620°C and the influence of the pyrolysis atmosphere using nitrogen and nitrogen/steam on the product yield and gas composition were investigated. The gases analysed were H₂, CO, CO₂ and hydrocarbons from C₁ to C₄. The results showed for both nitrogen and nitrogen/steam that increase the pyrolysis bed temperature from 400 to 520°C resulted in a significant increase in the oil yield, after which temperature the oil yield decreased. The alkene/alkane ratio including ethene/ethane, propene/propane, and butene/butane ratios, can be used as an indication of pyrolysis temperature and the magnitude of cracking reactions. Increasing alkene/alkane ratio occurring with increasing pyrolysis temperature. The alkene/alkane ratio for nitrogen/steam pyrolysis atmosphere was lower than the one found under nitrogen atmosphere. This revised version was published online in July 2006 with corrections to the Cover Date.     

Experimental and kinetic investigation of the pyrolysis,combustion, and gasification of deoiled asphalt

The pyrolysis, combustion, and gasification behaviors of deoiled asphalt were studied by a thermogravimetric analyzer and the kinetics were also analyzed using a multi-stage first-order integral model. All the experiments were conducted at non-isothermal conditions with heating rates range of 10–40 K min^?1 under N₂ (pyrolysis), air (combustion), or CO₂ (gasification) atmosphere, respectively. The results showed that, for pyrolysis, the reaction mainly occurred between 498 and 798 K and could be divided into two stages: the first was caused by the volatilization of small molecules and the second probably due to the cracking reactions. For combustion, the mass loss process could be divided into three stages: the devolatilization and oxidation first, the ignition and combustion of the volatiles second, and finally the combustion of the formed char. Under CO₂ atmosphere, the mass loss behavior was similar with that of the N₂ atmosphere at lower temperatures, but when the temperature was higher than 1,233 K, the gasification reaction obviously happened. The results of kinetic investigation showed that the multi-stage first-order integral method agreed well with the above experiments.     

Investigation of the evolved gases from Sulcis coal during pyrolysis under N2 and H2 atmospheres

The evolution of gases and volatiles during Sulcis coal pyrolysis under different atmospheres (N₂ and H₂) was investigated to obtaining a clean feedstock of combustion/gasification for electric power generation. Raw coal samples were slowly heated in temperature programmed mode up to 800 °C at ambient pressure using a laboratory-scale quartz furnace coupled to a Fourier transform infrared spectrometer (FTIR) for evolved gas analysis. Under both pyrolysis and hydropyrolysis conditions the evolution of gases started at temperature as low as 100 °C and was mainly composed by CO and CO₂ as gaseous products. With increasing temperature SO₂, COS, and light aliphatic gases (CH₄ and C₂H₄) were also released. The release of SO₂ took place up to 300 °C regardless of the pyrolysis atmosphere, whilst the COS emissions were affected by the surrounding environment. Carbon oxide, CO₂, and CH₄ continuously evolved up to 800 °C, showing similar release pathways in both N₂ and H₂ atmospheres. Trace of HCNO was detected at low pyrolysis temperature solely in pure H₂ stream. Finally, the solid residues of pyrolysis (chars) were subjected to reaction with H₂ to produce CH₄ at 800 °C under 5.0 MPa pressure. The chars reactivity was found to be dependent on pyrolysis atmosphere, being the carbon conversions of 36% and 16% for charN₂ and charH₂, respectively.     

Explosive degradation of woody biomass under the presence of metal nitrates

The influence of various metal nitrates (Fe, Ni, Cu, Zn, etc.) has been studied in the pyrolysis of woody biomass under inert atmosphere. Pyrolysis samples have been prepared by impregnation of wood with aqueous solution of the salts as well as by mechanical mixing of powders of wood and nitrates. Thermogravimetric analysis showed that the addition of nickel, copper and zinc nitrates reduced significantly the decomposition temperature of wood below 150 °C. The decomposition of wood completes explosively at the temperature. The pyrolysis products have been analysed by GC–MS and XRD methods. Preliminary result of the quantitative analysis of emitted NO_x gas in the pyrolysis treatment is also presented.     

Thermal degradation and evolved gas analysis of thiourea-formaldehyde resin (TFR) during pyrolysis and combustion

Thiourea formaldehyde resin (TFR) has been synthesized by condensation of thiourea and formaldehyde in acidic medium and its thermal degradation has been investigated using TG-FTIR-MS technique during pyrolysis and combustion. The results revealed that the thermal decomposition of TFR occurs in three steps assigned to drying of the sample, fast thermal decomposition of polymers, and further cracking. The similar TG and DTG characteristics were found for the first two stages during pyrolysis and combustion. The combustion process was almost finished at 680?°C, while during pyrolysis a total mass loss of 93 wt% is found at 950?°C. The release of volatile products during pyrolysis are NH₃, CS₂, CO, HCN, HNCS, and NH₂CN. The main products in the second stage are NH₃ CO₂, CS₂, SO₂, and H₂O during combustion. In the next stage, the combustion products mentioned above keep on increasing, but some new volatiles such as HCN, COS etc., are identified. Among the above volatiles, CO₂ is the dominant gaseous product in the whole combustion process. It is found that the thermal degradation during pyrolysis of TFR produced more hazardous gases like HCN, NH₃, and CO when compared with combustion in similar conditions.     

Thermal degradation and evolved gas analysis of epoxy (DGEBA)/novolac resin blends (ENB) during pyrolysis and combustion

The thermal degradation of epoxy (DGEBA) and phenol formaldehyde (novolac) resins blend was investigated by using thermogravimetric analysis (TGA) coupled with Fourier transform infrared spectroscopy and mass spectroscopy. The results of TGA revealed that the thermal degradation process can be subdivided into four stages: drying the sample, fast and second thermal decomposition, and further cracking process of the polymer. The total mass loss of 89.32 mass% at 950 °C is found during pyrolysis, while the polymer during the combustion almost finished at this temperature. The emissions of carbon dioxide, aliphatic hydrocarbons, carbon monoxide, etc., while aromatic products, are emitted at higher temperature during combustion and pyrolysis. It was observed that the intensities of CO₂, CO, H₂O, etc., were very high when compared with their intensities during pyrolysis, attributed to the oxidation of decomposition product.     

水城褐煤热解的气体产物析出特征及甲烷的生成反应类型研究

利用傅里叶红外光谱仪研究了煤中主要官能团的分布,利用热重-质谱联用（TG/MS）在10℃/min的条件下研究了水城褐煤的热解行为,获得了煤热解主要挥发分气体（H₂、CH₄、H₂O、CO、CO₂）生成的速率曲线。采用分峰拟合的方法将甲烷的生成速率曲线分解为五个峰,通过化学动力学分析,结合煤的结构特性、热解特性及其他挥发分气体的生成特征,认为甲烷的生成主要由一个脱吸附过程和四个化学反应组成。     

A comparative study on the thermal decomposition of some transition metal maleates and fumarates

Thermal decomposition of M(mal/fum)·xH₂O (M=Mn, Co, Ni) has been studied in static air atmosphere from ambient to 500°C employing TG-DTG-DTA, XRD and IR spectroscopic techniques. After dehydration the anhydrous maleate salts decompose to metal oxalate in the temperature range of 320–360°C, which at higher temperature undergo an abrupt oxidative pyrolysis to oxides. The anhydrous fumarate salts have been found to decompose directly to oxide phase. A comparison of thermal analysis reveals that fumarates are thermally more stable than maleates.     

Microstructure and electrical properties of BaTiO<Subscript>3</Subscript> and (Ba,Sr)TiO<Subscript>3</Subscript> ferroelectric thin films on nickel electrodes

Nickel thin films have been sputtered on standard Si/SiO₂ substrates with TiO₂ as an adhesive layer. The thermal stability of these substrates was analyzed. SEM images show an increase in grain size with annealing temperature. They were found to be stable till 800°C, beyond which the nickel layer disintegrated. These substrates were used for deposition of BaTiO₃ and (Ba,Sr)TiO₃ dielectric thin films under a reducing atmosphere. The dielectric thin films were processed with various pyrolysis and annealing temperatures in order to optimize the dielectric properties. Increased pyrolysis temperatures showed an increase in the grain size. Results on these nickelised substrates were finally compared with dielectric films deposited on platinized silicon substrates under identical conditions but crystallized in an oxygen atmosphere.     

Product distribution in pyrolysis of cellulose in a microfluidized bed

A study of flash pyrolysis of cellulose was carried out in the temperature range from 313 to 770°C in a microfluidized bed. Chemical analysis was done for gaseous and liquid products using gas chromatography. Levoglucosan was measured after silylation of the tar fraction. In the fluidized bed, residence times were of the order of 1 s, while heating rates were estimated at higher than 100,000°C/s for cellulose particles of 60 μm diameter and about 1000°C/s for cellulose particles having about 0.6 mm mean particle diameter. No pronounced effects of particle size were observed. Logarithms of product yields as wt.% of sample correlate linearly with bed temperature. Transitions in these curves are observed between 500 and 600°C corresponding roughly to decomposition of levoglucosan. Effects of atmosphere were also studied by comparing the effect of various atmospheres (CO, CO₂, H₂ + N₂) with pure N₂. Only a slight effect was noted on the product distribution. It appears that levoglucosan, a major product obtained from the slow pyrolysis of cellulose, is not a primary product under flash pyrolysis conditions.     

Analytical and thermal investigations of new solid Y(III) and La(III) complexes

New compounds with formulae Y(2,4′-bpy)_1.5Cl₃·8H₂O (I), Y(2,4′-bpy)_0.5Br₃·8H₂O (II), La(2,4′-bpy)Cl₃·5H₂O (III) and La(2,4′-bpy)_1.5Br₃·5H₂O (IV) were prepared and characterized by chemical and elemental analysis, IR spectroscopy and powder X-ray diffraction. The thermal properties of compounds in the solid state were studied using TG-DTA techniques under dry air atmosphere. The thermal behavior of investigated compounds was studied in the temperature range 298–1273 K. They are stable up to 323 K. The complexes decompose in several stages, accompanied by endo- and exothermic effects. In all cases, the first step of pyrolysis is partial or total dehydration. When the temperature rises, deamination takes place. The solid final products of decomposition are Y₂O₃ and La₂O₃, respectively. Additionally, for all complexes mass spectrometry was used to analyze principal volatile thermal decomposition and fragmentation products evolved during pyrolysis under dry air atmosphere.

     

Low temperature pyrolysis of carboxymethylcellulose

Unlike the common high temperature pyrolysis of carboxymethylcellulose (CMC) targeting activated carbon, this study investigates the pyrolytic behaviour of plain CMC at low temperatures ranging between 260 and 300 °C. Preliminary experiments were conducted using differential scanning calorimetry to define the temperature range necessary for the process. Low-temperature pyrolysis was then simulated using thermogravimetric analysis under inert atmosphere. Investigations reveal that a minimum holding temperature of 260 °C is required for an isothermal process, at which pyrolysis is terminated after around 26 min. Increasing exposure temperature reduces pyrolysis time. Within the range of the investigated sample and CMC particle size, no significant effects could be measured regarding the decomposition behaviour. The resulting char was further analysed using X-ray diffraction and Fourier transform infrared spectroscopy. Visual inspection was conducted using scanning electron microscopy. Upon pyrolysis, originally longitudinally shaped CMC was found to be converted into spherical particles of functionalised amorphous carbon with an average particle size of 41 µm.     

Solid/liquid- and vapor-phase interactions between cellulose- and lignin-derived pyrolysis products

Solid/liquid- and vapor-phase interactions between cellulose- and lignin (Japanese cedar milled wood lignin)-derived pyrolysis products were studied under the conditions of N₂/600 °C/40–80 s. A dual-space closed ampoule reactor was used to eliminate the solid/liquid-phase interactions, and careful comparison of the resulting data with those of the pyrolysis of the mixed samples gave some insights into the solid/liquid- and vapor-phase interactions separately. With the solid/liquid-phase interactions, the tar yields from both cellulose and lignin increased with the decreasing yields of the char fractions in a short pyrolysis time of 40 s (primary pyrolysis stage). Most of the identified tar components from cellulose and lignin increased in their yields. The vapor-phase interactions were significant at a longer pyrolysis time of 80 s (secondary reaction stage) when the methoxyl groups of the lignin-derived volatiles were cleaved homolytically. The vapor-phase interactions accelerated the gas formation from the cellulose-derived volatiles with suppressing the vapor-phase char formation of the lignin-derived volatiles. The yields of methane and catechols from lignin also increased greatly instead of the formation of o-cresols. Most of these influences are explained with a proposed interaction mechanism, in which the cellulose-derived volatiles act as H-donors while the lignin-derived volatiles (radicals) act as H-acceptors.     

Gas-phase pyrolysis mechanism and kinetics of 3-chloroquadricyclane

The gas-phase pyrolysis of 3-chloroquadricyclane [1] was investigated over the temperature range 513–550 K at one atm in helium. The initial pyrolysis step is the isomerization of 3-chloroquadricyclane to 7-chloronorbornadiene (E_a=39.63±1.40 kcal/mole, log A=15.18±0.58). 7-chloronorbornadiene rearranges (623–660 K) to exclusively produce benzyl chloride (E_a=48.05±1.10 kcal/mole, log A=15.82±0.38). This two step mechanism affords fewer reactions than the unsubstituted quadricyclane system in the gas phase. The production of a benzene derivative from the chlorinated norbornadiene is a reaction pathway contained in the unsubstituted norbornadiene and other 7-substituted pyrolysis mechanisms. © 1997 John Wiley & Sons, Inc.     

STUDY ON THE GASEOUS PRODUCTS OF HIGH TEMPERATURE PYROLYSIS OF ACRYLONITRILE POLYMERS BY ON-LINE FTIR METHOD

The gaseous products of high temperature pyrolysis (300℃ to 960℃) of aerylonitrile polymers were measured continuously under nitrogen atmosphere by on-line Fourier Transform Infrared Spectroscopic method (FTIR). From the variations of characteristic peaks it was found that the nitrogen of macromolecules evolved were mainly in the form of hydrogen cyanide and ammonia. During the pyrolysis amorphous carbonaceous element was formed, and crosslinked to form network structure. Three kinds of samples were used for comparison. The experimental results show that the gaseous products of volatile small molecules were HCN, NH_3, CH_4, C_2H_6 and cyanide. CO and CO_2 were also formed when copolymers of PAN were thermally pyrolyzed.     

UV assisted pyrolysis of solution deposited BiFeO<Subscript>3</Subscript> multiferroic thin films. Effects on microstructure and functional properties

BiFeO₃ thin films were processed on platinized silicon substrate via chemical solution deposition. Short wave UV assisted pyrolysis was conducted in oxygen atmosphere in order to obtain a fine and homogeneous grain structure. Phase pure thin films with a pronounced (100) texture were obtained at a fairly low annealing temperature of 600°C. For comparison specimens processed without UV assisted pyrolysis were also investigated. It is shown that UV assisted pyrolysis leads to a substantial improvement of leakage resistance properties. Polarization switching could also be obtained using capacitance-voltage (C-V) curves. The leakage current was investigated as a function of temperature. Interpretation in terms of Frenkel-Poole mechanism leads to a high trap depth in the range of 2.4 eV which is attributed to the creation of Fe²⁺ centres. For both microstructures investigated well saturated magnetization loops were obtained with a remnant magnetization of 2Mr = 5.4 emu/cm³ and a coercive fields in the range of 2Hc = 200 Oe. Slightly higher saturation magnetization 2Ms of 55.4 emu/cm³ was obtained for UV assisted pyrolysis in comparison to 45.8 emu/cm³ for the thin films processed without UV.     

The synthesis of few-walled carbon nanotubes by the catalytic pyrolysis of methane and the kinetics of their accumulation

The kinetic dependences of the accumulation of carbon during pyrolysis of CH₄ mixed with H₂ on an Mo-Co/MgO catalyst with the atomic ratio Mo: Co: Mg = 3: 1: 76 at atmospheric pressure, temperature 900°C, and various CH₄ and H₂ partial pressures were determined by direct thermogravimetric measurements in combination with electron microscopic examination. The main solid pyrolysis products were found to be carbon nanotubes with two to five walls. The outside diameter of nanotubes changed from ～3 to 9 nm. A kinetic model of the accumulation of carbon was suggested. The model took into account the formation of two products, nanotubes and carbon deposited on their surface, process reversibility, and catalyst deactivation by nanotubes formed.     

Thermogravimetric analysis on gasification reactivity of Hailar lignite

Comparative studies on the Hailar lignite pyrolysis/gasification characteristics at N₂/CO₂ atmosphere and the influence of inherent mineral matters, external ash and pyrolysis temperature on its reactivity during gasification at CO₂ atmosphere were conducted by non-isothermal thermogravimetric analysis, FTIR, and X-ray diffraction (XRD) analysis. Thermogravimetric test results show that the atmosphere of N₂ or CO₂ almost has no effects on the pyrolysis behavior, and the gasification reaction under CO₂ atmosphere occurs over 943?K at the heating rate of 40?K?min^?1. The external ash prepared at 1173 and 1223?K shows a certain catalytic effect on promoting the gasification reaction, although the inherent mineral matters of Hailar lignite are found in stronger catalytic effects on gasification than the external ash. The lignite gasification reactivity decreases with increasing pyrolytic temperature between 1073 and 1273?K.     

Thermal analyses of Ohio bituminous coals

A suite of twenty-one bituminous coal samples from Ohio were analyzed by differential scanning calorimetry (DSC) and non-isothermal thermogravimetry (TG) techniques. Three regions of endothermic activity may be distinguished in the DSC scans in an inert atmosphere. The first peak (25–150°C) corresponds to loss of moisture from the coal, a second, very broad endotherm peaking in the range 400–500°C corresponds to devolatilization of the organic matter and a partially resolved endotherm at temperatures above 550°C probably corresponds to cracking and coking processes subsequent to the pyrolysis step. Evidence obtained from experiments with sealed pans suggest an autocatalytic effect exerted by the pyrolysis products. The use of the DSC technique to quantify the volatile matter content of coal seems less reliable than the proximate analyses obtained from non-isothermal TG in inert and O₂ atmospheres. Good agreement with ASTM values is observed by the latter method for a range of volatile matter and ash content.