Fluidised bed pyrolysis of Moroccan oil shales using the hamburg pyrolysis process

In the present work, the pyrolysis of the Moroccan Timahdit oil shale was studied, using a fluidised bed process. Four experiments were carried out at different temperatures between 520 and 630 °C. By mass balance could be shown that in relation to the kerogen content up to 60 wt.% of oil and 25 wt.% of gas are obtained. These are 40% higher yields compared with the Fischer assay. It was shown that the carbon in the residue, which is much lower (only 12 wt.%) than in the Fischer assay (26 wt.%), explains this difference.     

Some aspects of polymer pyrolysis

Pyrolysis is the important stage of polymer combustion. This process depends on molecular and submolecular structure of polymer as well as conditions of heat affect. It may be realized through the formation of nonvolatile carbonized product. The basic conception of the present work consists in the transformation of macromolecules into carbonized structure which realises by means of formation of the thermodynamically-advantageous intermediate compounds with a system of π-conjugated unsaturated carbon bonds (acyclic or aromatic nature) and by their following conversion into condensed aromatic structures. It has been examined the correlation between the structure and properties of carbonized products and the flammability of polymers.     

Thermoanalytical studies of pitch pyrolysis

Characterization of pitches by thermal analysis techniques is highly relevant to the practical use of these materials, as they undergo heat treatments in all of their utilization processes. The aim of this work was to improve the interpretation of the complex DTA curves of pitches by comparison with model compounds. For this, TG/DTG/DTA was used to study under identical conditions the pyrolysis of a petroleum pitch and a coal tar pitch as well as a number of polycyclic aromatic hydrocarbons. Results were interpreted as a function of the molecular structure, pyrolysis reactivity and graphitizability of cokes from the hydrocarbons. It is concluded that condensation and polymerization, which are the most likely exothermal reactions predominant in petroleum pitches, indicate the presence therein of reactive molecules. Alternatively, endothermal phenomena such as distillation, depolymerization and cracking, predominant in coal tar pitches, suggest the presence of light, little reactive aromatic molecules.Financial support from DGICYT (project PB87-0456) is gratefully acknowledged.     

Modeling pyrolysis kinetics of plastic mixtures

Modeling pyrolysis behavior of waste plastic mixtures is of importance for design and operation of reactors which convert these waste plastics into valuable chemicals. However, because of limited understanding of their degradation behavior even for single component plastic wastes, modeling degradation kinetics of plastic mixtures is a challenging task.In this work, we report modeling of binary and ternary mixture degradation kinetics of polyethylene terephthalate (PET), low density polyethylene (LDPE) and polypropylene (PP). A simple mixing rule approach was used with one cross-kinetic degradation parameter per each binary. Ternary kinetics were completely predictive and showed good agreement with the experimental data.     

The pyrolysis of propane

The pyrolysis of propane plays an important role in determining the combustion properties of natural gas mixtures and offers insight into the cracking patterns of larger fuels. This work investigates propane pyrolysis behind reflected shock waves with a multiwavelength laser-absorption speciation technique. Nine laser wavelengths, sensitive to key pyrolysis species, were used to measure absorbance time histories during the decomposition of 2% propane in argon between 1022 and 1467 K, 3.7-4.3 atm. Absorbance models were developed at each diagnostic wavelength to interrogate common initial conditions, and time histories of all major species are reported at 1250, 1290, 1330, 1370, and 1410 K. Nearly complete carbon recovery observed at lower temperatures enabled the inference of hydrogen formation from atomic conservation, while decaying carbon recovery at high temperatures suggests the formation of allene and 1-butene. The results show systematically faster pyrolysis than predicted by kinetic modeling and motivate further study into the kinetics of propane pyrolysis.     

Pyrolysis of solid waste in a rotary kiln: influence of final pyrolysis temperature on the pyrolysis products

Temperature is one of the most important parameters in pyrolysis reaction. In present work, an externally heated laboratory-scale rotary-kiln pyrolyser was designed and developed. The influence of final pyrolysis temperature (FPT) on the pyrolytic products of solid wastes has been studied. Raising FPT caused increasing gas yield and decreasing semi-coke yield. The average heat value of the gas also changed with FPT. The content of aliphatic hydrocarbons in PE tar increased initially and then decreased with increasing FPT. Parallel to this, the content of aromatic ring changed conversely. FPT had obvious influence on the primary and elemental analysis data of the semi-cokes. The CO₂ reactivity of the semi-cokes also varied with the FPT. The kinetic parameters of the semi-cokes were different for the same material at the different FPT.     

Investigation of pyrolysis kinetics of carboxymethyl hydroxypropyl sesbania gum

The thermal pyrolysis of carboxymethyl hydroxypropyl sesbania gum and hydroxypropyl sesbania gum in air and nitrogen atmospheres were studied in order to establish the thermal stability of carboxymethyl hydroxypropyl sesbania gum. The results indicate that the stability of carboxymethyl hydroxypropyl sesbania gum against pyrolysis is higher than that of hydroxypropyl sesbania gum. The main state of carboxymethyl hydroxypropyl sesbania gum and hydroxypropyl sesbania gum can be assigned as random noncrystalline.We express our thanks to Dr. Yaxiong Xie for his help in this work.     

Shock tube pyrolysis of 1,2,4,5-hexatetraene

1,2,4,5-Hexatetraene (1245HT) is, according to theory, a key intermediate to benzene from propargyl radicals in a variety of flames; however, it has only been experimentally observed once in previous studies of the C3H3 + C3H3 reaction. To determine if it is indeed an intermediate to benzene formation, 1245HT was synthesized, via a Grignard reaction, and pyrolysized in a single-pulse shock tube at two nominal pressures of 22 and 40 bar over a temperature range from 540 to 1180 K. At temperatures T < 700 K, 1245HT converts efficiently to 3,4-dimethylenecyclobutene (34DMCB) with a rate constant of k = 10(10.16) x exp(-23.4 kcal/RT), which is in good agreement with the one calculated by Miller and Klippenstein. At higher temperatures, various C6H6 isomers were generated, which is consistent with theory and earlier experimental studies. Thus, the current work strongly supports the theory that 1245HT plays a bridging role in forming benzene from propargyl radicals. RRKM modeling of the current data set has also been carried out with the Miller-Klippenstein potential. It was found that the theory gives reasonably good predictions of the experimental observations of 1245HT, 1,5-hexadiyne (15HD), and 34DMCB in the current study and in our earlier studies of 15HD pyrolysis and propargyl recombination; however, there is considerable discrepancy between experiment and theory for the isomerization route of 1,2-hexadien-5-yne (12HD5Y) --> 2-ethynyl-1,3-butadiene (2E13BD) --> fulvene.     

油棕废弃物热解的TG-FTIR分析

利用热重分析(TGA)和傅里叶红外光谱(FTIR)联用技术对油棕废弃物的热解特性及其气体产物的释放特性进行了研究，采用一级反应计算了油棕废弃物的热解动力学参数。研究表明，油棕废弃物较易于热解，失重集中在220℃～400℃，其热解活化能较小，约为60kJ/mol；气体产物的析出与生物质的热解失重有着相似的特性，气体产物主要在200℃～400℃析出，主要成分为H2O、CO2、CO、CH4和有机碳水化合物的混合物, 其中CO2和有机混合物的析出温度较低，而CO和CH4的析出温度相对较高。随着温度的进一步升高(>400℃)，除少量的CO2和CO外，无其他气体产物析出。气体产物的析出量与生物质样品的化学组成和结构有关，CO2和有机混合物的析出与生物质的热解失重曲线(DTG)有着相似的特性，是引起油棕废弃物热解失重的主要原因。     

生物质微波干燥及其对热解的影响

通过与常规热风干燥方式比较,研究生物质微波干燥过程及其对热解的影响,以探索在生物质快速热解液化工艺中采用微波干燥技术进行原料预处理的可行性。干燥实验表明,微波炉的干燥速率明显大于烘箱（5倍以上）,同时在微波快速干燥过程中,原料内部的孔隙结构得到了改善。热天平上干燥样品的热解表明,微波干燥处理有利于生物质的热解,特别是纤维素和半纤维素的热解,并且能在一定程度上抑制生物油蒸汽的二次裂解反应,从而使实际流化床热解液化装置中的生物油产率有所提高。研究表明,将微波干燥技术用于生物质热解液化的原料预处理过程在技术上和经济上均具有可行性。     

Wall effects in the pyrolysis of diethylether. A case of hetero-homogeneous pyrolysis at 500°C

The pyrolysis of diethylether has been studied at 500°C and 50 Torr initial pressure in packed vessels (surface-to-volume ratio 11 cm^?1). In untreated vessels the reaction appears to be essentially homogeneous as reported before. On the contrary, it is very sensitive to the walls of PbO-coated or NaOH-treated vessels. Thus most of the initial rates of product formation are increased in the PbO-coated vessel and decreased in the NaOH-treated vessel. The efficiency of the walls has been monitored for several weeks and was shown to decrease slowly with the vessel aging time. These phenomena are interpreted in terms of a free-radical chain mechanism in which a part of the initiation or termination steps occurs at the walls, the propagating steps being homogeneous. The present work clearly proves the existence of hetero-homogeneous chain reactions at 500°C. This new class of reaction could be of practical interest in the design of industrial reactors.     

Catalytic fast pyrolysis of jatropha wastes

In this work, the decomposition behaviors of jatropha wastes (husk, seed shell and branch) have been examined in order to get desired liquid organic compounds, but not undesired inorganic compounds such as CO, CO₂, water and coke. The jatropha wastes exhibit a stepwise degradation pathway which has a slight difference in between samples before and after milling. In the preliminary pyrolysis using quartz reactor and H-ZSM-5(30) catalyst, the liquid products selectivity was seed shell > blanch > husk > seed shell (no catalyst). In the absence of catalyst, the Py-GC/MS analyses for pyrolysis of jatropha wastes show a range of aromatic hydrocarbons, phenols, alcohols and ketones, acids and esters, ethers and aldehydes. Aromatics are predominantly formed above 90% of area percentage by use of catalyst. Of aromatic compounds, xylenes, naphthalenes and toluene are mainly produced. The product selectivity is dependent on both the size of the catalyst pores and the nature of the active sites and one candidate is H-ZSM-5 and the other candidate is β-zeolite. The reaction pathway involves dehydrogenation and dehydroaromatization of aliphatic oxygenates such as alkylcyclohexanol and higher carboxylic acids to form phenol derivatives, which undergo hydrodeoxygenation into toluene and xylenes, followed by dehydroaromatization to give naphthalenes.     

Effects of pyrolysis upgrading temperature on semi-coke explosibility for blast furnace injection

Journal of Thermal Analysis and Calorimetry - The purpose of this work is to understand the semi-coke explosion issues and to improve the safety in semi-coke injection. It shows that the higher...     

Patterns and kinetics of pyrolysis of tobacco under inert and oxidative conditions

The present work is part of a more extensive research carried out in Naples on cigarette combustion. Theoretical and modelling work highlighted the existence of a misdistribution of the gas flow across the cigarette cross-section, which results into locally variable conditions. As a consequence, oxygen-starving versus oxygen-rich conditions do establish in the pre-heat zone of the cigarette, where pyrolysis of cigarette components takes place. More specifically, oxygen-starving conditions should characterize the process of reaction front propagation in the inner part of the cigarette, close to its axis, while oxygen-rich conditions should establish at the cigarette periphery, close to the paper burn line.The present paper addresses the pattern and the kinetics of pyrolysis under inert and under oxidative conditions of three types of tobacco. The experimental work consists of non-isothermal thermogravimetric analysis at heating rates comprised between 5 and 20 °C/min and with different He–oxygen mixtures. Kinetic expressions for the rate of pyrolysis under inert and under oxidative conditions have been obtained for each ingredient investigated.Results, albeit obtained at sample heating rates smaller than those relevant to actual cigarette burning, highlight the profound differences arising under purely pyrolytic or oxy-pyrolytic conditions as regards the number of reaction steps, the rate, the temperature ranges and yields in solid versus gaseous products of thermal decomposition.The effect of inert/oxidative conditions on the chemical composition of the gaseous products of pyrolysis is discussed in a companion paper [O. Senneca, S. Ciaravolo, A. Nunziata, J. Anal. Appl. Pyrol. 78 (2007) 452].     

Polymer packaging waste recycling: study of the pyrolysis of two blends via TGA

Journal of Thermal Analysis and Calorimetry - The aim of this work is the evaluation of thermal degradation temperatures of two polymeric blends constituted by polyethylene PE, polypropylene PP,...     

毛竹在氢气中的催化热解研究

本文以分布广、产量大的速生生物质——毛竹为原料,研究其在H2氛围中、不同反应温度下热解所得产物的产率和分布,并与其在N2氛围中热解的结果进行了比较。结果表明,毛竹在H2气氛中热解,比在N2气氛中更有利于液体产物的生成。两种氛围中温度对液体产物影响的趋势不同,在本文条件下,H2气氛中升高温度始终有利于增加液体产率,使生物质有效转化率提高,在H2中毛竹热解生成甲醇、环丙基甲醇、呋喃甲醛等,这在N2中是不易得到的,但液体产物中含量最高的仍是乙酸。     

The self-inhibited pyrolysis of isobutane

The pyrolysis of isobutane was investigated in the ranges of 770° to 855°K and 20 to 150 Torr at up to 4% decomposition. The reaction is homogeneous and strongly self-inhibited. A simple Rice-Herzfeld chain terminated by the recombination of methyl radicals is proposed for the initial, uninhibited reaction. Self-inhibition is due to abstraction of hydrogen atoms from product isobutene giving resonance-stabilized 2-methylallyl radicals which participate in termination reactions. The reaction chains are shown to be long. It is suggested that a previously published rate constant for the initiation reaction (1) is incorrect and the value k₁ = 10^16.8 exp (?81700 cal mol^?1/RT)s^?1 is recommended. The values of the rate constants for the reactions (4i) (4t) (8) are estimated to be and From a recalculation of previously published data on the pyrolysis of isobutane at lower temperatures and higher pressures, the value k_11c, = 10^9.6 cm³ mol^?1 s^?1 is obtained for the rate constant of recombination of t-butyl. A calculation which is independent of any assumed rate constants or thermochemistry shows that the predominant chain termination reaction is the recombination of two methyl radicals in the conditions of the present work and the recombination of two t-butyl radicals in those of our previous study at lower temperatures and higher pressures.     

Analytical pyrolysis as a characterization technique for monitoring the production of carbon nanofilaments

The main step in the production of carbon nanofilaments is the catalytic nucleation and lengthening of the filament. An undesired parallel step in the production of carbon nanofilaments is their thickening by pyrolitic carbon vapor deposition consisting in an ordered polycondensation of carbon over an existing catalytic carbon nanofilament. The regular characterization of the structure of carbon nanofilaments (coated or not) is by transmission electron microscopy. However, this technique is not affordable in many cases because is expensive and complex. In the present work, the analytical pyrolysis is proposed to obtain clues of the structure of carbon nanofilaments. Several commercial carbon nanofilaments have been analyzed. The samples with a thicker soot layer evolve a higher amount of heavy PAHs in the pyrolysis runs than the ones free of soot. It has been observed that pyrene is a key compound in the pyrolytic carbon vapor deposition process and the resulting formation of soot over the carbon nanofilaments. The aim of this work is to get useful information about the quality of the carbon filaments by a cheap technique, the analytical pyrolysis.     

Porous MoS2 synthesized by ultrasonic spray pyrolysis

The hydrodesulfurization (HDS) activity of molybdenum sulfide-based catalysts is localized to the edges of this layered solid and is, therefore, highly dependent on the technique used to prepare the material. Here, ultrasonic spray pyrolysis (USP) was used to synthesize porous, nanostructured MoS2. Low surface area powders, not useful for catalysis, are generally produced by USP. This work shows that when combined with a dissolvable template, USP is capable of producing high surface area materials. An aqueous solution of ammonium tetrathiomolybdate and colloidal silica was nebulized and pyrolyzed to give a MoS2/SiO2 composite material. Leaching with HF removed the sacrificial SiO2, resulting in a highly porous MoS2 network with surface areas as high as 250 m2/g. Cobalt-promoted MoS2 networks were also synthesized. The thiophene HDS activities of these materials were substantially higher than those of unsupported MoS2 and RuS2 standards, illustrating the enhanced dispersion of the HDS active phase achieved by this synthetic technique.     

Sulphur distribution in the products of waste tire pyrolysis

The aim of the presented work was to investigate the distribution of sulphur in tire pyrolysis products as well as the influence of process parameters (temperature and residence time) on sulphur distribution due to environmental concerns. Among modern methods used for waste tire recycling, pyrolysis is one of the most reasonable alternatives meeting current environmental standards. However, waste tire sulphur content can be a potential drawback for pyrolysis products utilisation as fuels. Sulphur is present in tires in different concentrations, depending on the type and age of the tires. Typical sulphur content in tires is about 1.6 mass %. In this paper, the distribution of sulphur in tire pyrolysis products was investigated. Tire pyrolysis yields three different products: liquid, gaseous, and solid residue composed mostly of carbon black (chars). Temperature and residence time are the two most important parameters affecting the yield and composition of the volatile fraction and they are therefore expected to affect the sulphur content in residues. Pyrolysis experiments were carried out in a laboratory pyrolysis reaction unit in the temperature range of 650°C to 750°C at different residence times: 88.6 s, 80.2 s, and 73.9 s. Liquid and solid products were analysed by elemental analysis and the distribution of total sulphur in tire pyrolysis products was calculated.