Study of the thermal decomposition of solids in a fluidized bed,III

The influence of the air humidity upon the thermal decomposition of diammonium hydrogen phosphate was studied in a fluidized bed, under isothermal conditions. It was found that the increase of the decomposition rate is influenced directly by the partial pressure of the water vapour in the air, and indirectly by the working temperature. The moisture effect is explained by the salt hydrolysis in the water condensed on the grain surface. The energy of activation of the thermal decomposition decreases when the air humidity increases.     

Study of the thermal decomposition of solids in a fluidized bed,II

In order to eliminate the errors of the TG method with a static layer, and to determine the influence of the heating rate, the composition of the carrier gas and the particle size of the solids, a method of thermal gas evolution from a fluidized bed (FTGE) with continuous and linear increase of temperature was worked out and the thermal decomposition of diammonium hydrogen phosphate was followed. This method gives reproducible results and makes possible the determination of the apparent activation energies and kinetic parameters.

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Zusammenfassung Um die Fehler der TG Methode unter fixierten Verhältnissen zu eliminieren, den Einfluß der Temperaturerhöhung, der Zusammensetzung des Trägergases und des Ausmaßes der Festkörper zu klären, wurde eine thermogasanalytische Methode im fluidisierten Bett (FTGE) mit kontinuierlichem und linearem Temperaturanstieg entwickelt und die thermische Zersetzung des Diammonium-biphosphates verfolgt. Man erhielt mit dieser Methode reproduzierbare Ergebnisse. Sie ist zur Bestimmung der scheinbaren Aktivierungsenergien und kinetischer Parameter geeignet.

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Résumé Dans le but d'éliminer les erreurs des procédés thermogravimétriques avec couches fixes, et de mettre en évidence l'influence de la vitesse d'échauffement de la composition du gaz porteur et de la dimension des solides, on a développé une méthode d'analyse des gaz dégagés, avec lit fluidifié et élévation de la température continue et linéaire. On a suivi ainsi la décomposition thermique de (NH₄)₂HPO₄. Cette méthode donne des résultats reproductibles et rend possible la détermination des énergies d'activation apparentes et des paramètres cinétiques.

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Some parts presented at the IIIrd Analytical Conference, Budapest, 1970     

Study on the thermal decomposition of solids in fluidized bed

Reliable thermodynamic parameters for the thermal decomposition of diammonium hydrogenphosphate [(NH₄)₂HPO₄] may be obtained using a fluidized bed. For the same size of particle, at the same temperature, but for different carrier gases, the rate constant and activation energy increase in the following order: air, methane, hydrogen. For the same carrier gas (air) the rate constant increases when the particle size decreases.     

Investigation of thermal decomposition of solids

Practical aspects of the studies of stages of thermal dissociation of solids, of the kinetics of the stages, and of utilization of general regularities of the process for verification of kinetic studies are discussed.

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Zusammenfassung Die praktischen Aspekte der Untersuchungen über die Stufen der thermischen Dissoziation von Festkörpern und ihrer Kinetik weiterhin über die Anwendungsmöglichkeiten der RegelmÄssigkeiten der Verifikation der kinetischen Untersuchungen werden erörtert.

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Role of vapour oversaturation in the thermal decomposition of solids

Elementary thermochemical calculations show that in all cases of formation of solid product in the process of the congruent dissociative vaporization of reactants, the equilibrium partial pressure of the main product greatly exceeds its saturation vapour pressure, and therefore causes the appearance of vapour oversaturation. The oversaturation is responsible for the formation and growth of nuclei, their shape and position, the transfer of condensation energy to the reactant, the existence of induction and acceleration decomposition periods, the reaction localization, the epitaxial/topotaxy effects and the nanocrystal structure of the solid product. Variations in the energy transfer explain an increase of the molar enthalpy with temperature and the decelerating influence of melting on the rate of decomposition.     

The thermal decomposition of ammonium metavanadate,III

The kinetics and thermodynamics of the thermal decomposition of ammonium metavanadate (AMV) are combined with the structural information available for AMV, for the important decomposition intermediate, ammonium hexavanadate (AHV), and for vanadium pentoxide, the product of the decomposition in non-reducing atmospheres, to enable the atomic movements involved in the course of decomposition to be discussed in detail.The decomposition of AMV involves scission of the V-G chains in the AMV structure (accompanied by simultaneous evolution of gaseous ammonia and water) with subsequent rearrangement and cross-linking of discrete units, based on V₃O ₈ ^– , to form AHV. Further decomposition to V₂O₅ is a similar but less ordered process.

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Zusammenfassung Die Kinetik und thermische Zersetzung von Ammoniummetavanadat (AMV) wurden mit der zu erhaltenden Information über die Strukturen des AMV, des wichtigen Zwischenproduktes der Zersetzung, des Ammoniumhexavanadats (AHV) sowie des Vanadiumpentoxids verbunden. Das in nichtreduzierenden Atmosphären erhaltene Zersetzungsprodukt wurde eingehend erörtert um die in der Zersetzung mit inbegriffenen Atombewegungen zu studieren.Bei der Zersetzung von AMV spielt eine Spaltung der V- O-Ketten in der Struktur des AMV mit (welche durch eine gleichzeitige Entwicklung von gasförmigen Ammoniak und Wasser begleitet wird), dieser folgt eine Neuordnung und Raumvernetzung diskreter Einheiten auf V₃O ₈ ^– -Basis um zur Bildung von AHV zu führen. Die weitere Zersetzung zu V₂O₆ ist ein ähnlicher, obwohl weniger geordneter Vorgang.

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Résumé On a rapproché les données structurales du métavanadate d'ammonium (MVA) avec celles relatives à la cinétique et à la thermodynamique de la décomposition thermique du MVA, pour étudier le produit intermédiaire important de la décomposition, l'hexavanadate d'ammonium (HVA) et le pentoxyde de vanadium. On discute en détail le produit de la décomposition obtenu en atmosphère non réductrice afin d'obtenir des données sur les mouvements atomiques mis en jeu pendant la décomposition.La décomposition du MVA s'effectue avec scission des chaines V—O dans la structure du MVA, accompagnée d'un dégagement de gaz ammoniac et d'eau et suivie d'un réarrangement et d'une réticulation d'unités discrètes V₃O ₈ ^– , pour former HVA. La décomposition ultérieure en V₂O₅ suit un processus similaire mais moins bien ordonné.

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Financial support from the National Institute for Metallurgy, Johannesburg, and the South African Council for Scientific and Industrial Research is gratefully acknowledged.     

Kinetic analysis of reversible thermal decomposition of solids

The isoconversional method was used to elucidate the kinetics of reversible solid-state reactions occurring under nonisothermal linear heating. The characteristic dependencies of the effective activation energy (E) on the extent of conversion (W) were established for two model processes: a reversible first-order reaction and a reversible reaction followed by an irreversible one. For the first process, E is almost independent of W and varies between the activation energy of the direct and inverse reaction. For the second, process with an endothermic reversible step, the dependence of E on W is of decreasing shape. The effective activation energy is limited by the sum of the activation energy of the irreversible reaction and the enthalpy of the reversible reaction, at low conversions, and by the activation energy of the irreversible reaction at high conversions. Analyses of the kinetic data for the dehydration of crystalhydrates, as well as other processes proceeding through a reversible step, show the dependencies of E on W characteristic of a reversible reaction followed by an irreversible one. © 1995 John Wiley & Sons, Inc.     

Thermal decomposition of potassium tetraborate tetrahydrate to anhydrous potassium tetraborate in a fluidized bed

Production of anhydrous potassium tetraborate from potassium tetraborate tetrahydrate (PTT) was investigated in a controlled fluidized bed calcinatory (FBC). Single step calcination gives a puffed product with very low bulk density and the calcination of potassium tetraborate tetrahydrate is incomplete since agglomeration starts at temperature higher than 250 °C. Effect of the temperature on the bulk density of the product obtained at the end of single step is given and compared with theoretical calculation. In order to obtain anhydrous potassium tetraborate, dehydration should be carried out at least two stages. The most important step dominating the final bulk density is the first step. Dehydration of potassium tetraborate tetrahydrate up to 85% K₂B₄O₇ content and temperature lower than 150 °C in the first step gives commercial available product at final stage. As a result, both puffed and denser anhydrous potassium tetraborate of 99.5% purity with bulk density around 0.4 and 0.7 g cm⁻³ has been produced by two and three stage calcinations.     

Hydrogen production by catalytic decomposition of methane using a Fe-based catalyst in a fluidized bed reactor

Catalytic decomposition of methane using a Fe-based catalyst for hydrogen production has been studied in this work. A Fe/Al2O3 catalyst previously developed by our research group has been tested in a fluidized bed reactor (FBR). A parametric study of the effects of some process variables,including reaction temperature and space velocity,is undertaken. The operating conditions strongly affect the catalyst performance. Methane conversion was increased by increasing the temperature and lowering the space velocity. Using temperatures between 700 and 900℃ and space velocities between 3 and 6LN/(gcat·h),a methane conversion in the range of 25%-40% for the gas exiting the reactor could be obtained during a 6 hrun. In addition,carbon was deposited in the form of nanofilaments (chain like nanofibers and multiwall nanotubes) with similar properties to those obtained in a fixed bed reactor.     

流化床中甲烷裂解制氢与催化剂再生过程研究

对流化床中甲烷裂解制氢与催化剂再生过程进行了研究。选用25Ni/CuAl2O3和75Ni/CuAl2O3两种催化剂,分别在500℃和650℃进行甲烷裂解制氢与催化剂再生,反应与再生过程的温度与时间保持相同,催化剂再生时采用空气进行再生,气体流量均为370mL/min（STP）。实验结果表明,镍质量分数较低时催化剂表现出较好的稳定性,温度增加催化剂的稳定性降低。甲烷转化率随操作周期呈下降趋势,在500℃制氢与再生操作达到第五周期时,甲烷转化率趋于稳定。对切换时间的影响研究表明,切换时间存在一个最佳值,即切换5min时甲烷裂解制氢效率最高。对生成碳产品进行了XRD和TEM表征,并对实验结果进行了讨论。     

Comparison of methods concerning the selection of a function describing the thermal decomposition of solids

Determination of the kinetic parameters of the thermal decomposition of solids usually requires a knowledge of the function describing the mechanism of decomposition. Research was made to obtain a method that enables the selection of one of the 16 functions used in the literature in such a way that it best describes experimental data in the isothermal measurements. The results obtained indicate that the best fit of experimental and calculated data is gained by using the weighted least-squares method with the equation g(α) = kt + b and using criteria based on the minimization of the difference between α_exp and α_calc     

Thermodynamic,kinetic and surface texture factors in the production of active solids by thermal decomposition

The production of an active solid by thermal decomposition of some precursor material usually an oxysalt is only one way of producing such a material. The activity of any solid resides at the surface albeit some of the surface may be internal or in the decomposition process a reaction interface. The peculiar property of any solid phase is that to describe it properly one must cite the pre-history of the material, and it can be shown that the pre-history of any solid phase is mainly that of altering the surface and textural properties. This fact influences the application of thermodynamic and kinetics to processes involving the solid phase. This becomes more evident in the case of active solids where a larger proportion of chemical species than usual resides at or near the surface. This is evidenced by the existence of many or more active solids in an amorphous phase and the possible co-existence of different types of solid phase. In this review, the usefulness of normal solid phase structural determination is discussed and the manner in which thermal analysis can be used to determine thermodynamic and kinetic parameters.

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Zusammenfassung Die Herstellung eines aktiven Feststoffes durch thermische Zersetzung einiger Präkursorsubstanzen, meistens eines Oxysalzes, ist nur der eine Weg zur Herstellung solcher Substanzen. Die Aktivität der Feststoffe besteht an ihrer Oberfläche, obwohl sich ein Teil der Oberfläche auch im Innern oder bei Zersetzungsprozessen an der Reaktionsgrenzfläche befinden kann. Die eigentümliche Eigenschaft einiger Feststoffphasen besteht darin, da\ man, um sie richtig beschreiben zu können, die Vorgeschichte der Substanz berücksichtigen mu\ und es kann gezeigt werden, da\ die Vorgeschichte einer Substanz hauptsächlich die der Veränderung der Oberflache und der Feinstruktur ist. Diese Tatsache beeinflu\t die Anwendung von Thermodynamik und Reaktionskinetik bei Prozessen mit Feststoffen. Dies ist besonders bei aktiven Feststoffen offensichtlich, bei denen an oder in der Nähe der Oberfläche verhältnismä\ig mehr chemische Stoffe vorkommen als üblicherweise. Dies wird durch die Existenz von vielen oder mehreren aktiven Feststoffen in einer amorphen Phase und durch die mögliche Koexistenz verschiedenartiger Festphasen bezeugt. In vorliegendem überblick wird die Nützlichkeit der Strukturbestimmung normaler Feststoffphasen sowie die Art der möglichen Anwendung der Thermoanalyse bei der Bestimmung thermodynamischer und kinetischer Parameter diskutiert.

     

循环流化床燃煤锅炉中的汞迁移研究

采用美国环保署颁布的吸附剂吸附汞采样方法30B(USEPA 40 CFR Part 60 30B)采集燃煤烟气中汞。选择一循环流化床燃煤机组进行现场采样,吸附剂吸附烟囱处烟气中的汞、入炉煤样、锅炉底灰、静电除尘器飞灰等样品同时采集。对该机组中汞质量平衡率进行衡算,通过汞质量平衡率说明了汞采样方法的准确性和有效性。评价了汞在飞灰、底灰和烟气中的分布,循环流化床锅炉底灰中对脱汞的贡献率仅0.55%,飞灰脱除汞的效率高达83.37%,剩余的16.08%的汞排放入大气环境,表明循环流化床机组是有效控制汞的清洁煤燃烧技术。     

PVC塑料流化床气化试验研究

为开发城市生活垃圾低污染流化床气化与旋风燃烧熔融技术,研究了垃圾中广泛存在的PVC塑料在流化床内的气化特性与污染物生成机理。不同温度和过量空气系数下进行了流化床PVC气化试验,分析了不同工况对PVC中Cl转化为HCl的影响。实验结果表明,反应高于600 ℃、过量空气系数大约0.4时,Cl转化为HCl的选择性达到95％以上;气化效率达到22％～25％,气化气热值达到2 000 kJ/m3～2 300 kJ/m3。反应高于700 ℃,PVC流化床气化生烟量明显减少,过量空气系数0.6时,生烟量减少到PVC质量的10％左右。提出的HCl析出与生烟机理较好地解释了试验结果,为城市生活垃圾气化熔融技术提供了相关基础数据与污染物生成及控制方法。     

Sulphur capture in fluidized bed boilers: The effect of reductive decomposition of CaSO4

Sulphur capture by lime was studied in a 16 MW stationary fluidized bed boiler (FBB). A marked fall-off in sulphur capture was noted at temperatures above about 880 °C. The proposed explanation is that the combustion produces reducing conditions in the particle phase, and thus allows for a reductive decomposition of CaSO₄. This explanation is supported by (i) thermodynamics showing the instability of CaSO₄ under reducing conditions; (ii) in-bed oxygen measurements indicating reducing conditions in the particle phase; (iii) the observed fall-off in sulphur capture with temperature, which is not seen in laboratory tests under oxidizing conditions or in a circulating FBB, where the sorbent particles experience oxidizing conditions to a greater extent; (iv) the observation that the temperature dependence of the sulphur emission is very strong even when the net sulphur capture is zero provided always that CaSO₄ is present and (v) literature data indicating the rate of the proposed reaction.     

On the possibilities of theoretical analysis of kinetics of the thermal decomposition of solids

The main reasons for changes in the environment surrounding us are discussed on the basis of thermodynamics of irreversible processes. Subsequently, relations between thermodynamics of irreversible processes and chemical kinetics are shown, then the possibilities of theoretical determination of rate constants on the framework of the modified RRKM theory are presented. These latter considerations are supplemented by a discussion concerning the possibilities of determining the activation barriers and structural changes (necessary to account for entropy changes upon reaction) in molecules kept on the surface of crystalline phases by combination of quantum chemistry methods for isolated molecules with those reflecting the influence of the environment (i.e. interaction within the lattice). Finally, the future of theoretical methods in examining the reactivity of solid state systems is briefly discussed.     

木屑在鼓泡流化床和循环流化床中气化特性的对比研究

对木屑在内径分别为0.3m×0.3m的鼓泡流化床气化炉（BFBG）和内径0.4m的循环流化床气化炉(CFBG)中的气化特征进行了对比,重点考察了当量比对生物质气化特性的影响。实验结果表明,在相同当量比下,由于CFBG操作气速明显高于BFBG,床内强烈的气固传热传质,使得CFBG可以获得较高的热解速率,同时可以使 CFBG在较高温度下运行。较高的运行温度不仅有利于二次裂解气化反应,使可燃气体质量明显好于BFBG,同时也减少了燃气中焦油的量。在较低气化当量比下(ER≤0.28),CFBG比BFBG可以获得更高的气体产率、碳转化率和气体效率;在较高当量比下,(ER＞0.28),CFBG和BFBG的气体产率、碳转化率和气体效率则相差不大。     

Parallel consecutive reactions in a fluidized catalyst bed

The two-phase model of Werther is applied to a parallel consecutive triangular reaction scheme. An analytical solution is obtained and used to predict the performance of a fluidized bed reactor producing maleic anhydride from benzene oxidation. The model predictions agree with experimental data. The model is also useful for examining the sensitivity of various parameters, thus guiding the direction of future experiments.