Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Effect of Wood Welding Process on Chemical Constituents of Australian Eucalyptus

Thermochemical changes occurring during wood welding were investigated in Eucalyptus saligna and Eucalyptus pilularis. Unwelded reference wood and material from welded interface were compared via Py-GC/MS, thermogravimetric analyses, X-ray photoelectron spectroscopy, and attenuated total reflection Fourier transform infrared spectroscopy to explain differences in mechanical properties of welded wood between species. It appeared that the species originally containing more condensed substructures also provided stronger joints. The condensation index after welding allowed validating that the adhesive properties of lignin are more accessible in such species. The presence of more carbonyl functions, attributed to carbohydrate solicitation during welding process, potentially made lignin less accessible. Changes following welding were evidenced by the contribution of extractive compounds, fatty acid chains, and terpenoids, possibly reacting with hydroxyl groups and leading to adhesive properties by chemical linkage through new covalent bonds formation. Results corroborate the better mechanical properties of E. saligna, providing stronger joints possibly due to more accessible adhesive properties by esterification between lignin and fatty acid.     

Mechanisms of synthesis gas production via thermochemical cycles over La0·3Sr0·7Co0·7Fe0·3O3

La_0·3Sr_0·7Co_0·7Fe_0·3O₃ (LSCF3773) was chosen as an oxygen carrier material for synthesis gas production and synthesized using ethylene-diamine-tetra-acetic acid (EDTA) citrate-complexing method. LSCF exhibited a pure cubic structure where 110 and 100 plane diffractions were active for CO₂ splitting, while 111 was more favored by H₂O splitting. Overall oxygen storage capacity (OSC) of LSCF was 4072 μmol/g_cat. During the reduction process, regular cations (Co⁴⁺, Fe⁴⁺), polaron cations (Co³⁺, Fe³⁺) and localized cations (Co²⁺, Fe²⁺) were achieved when the LSCF was reduced at 500, 700 and 900 °C, respectively. The strength of the active sites depended on reduction temperatures. An increase in oxidation temperature enhanced H₂ production at temperature ranging from 500 °C to 700 °C while effected CO production at 900 °C. H₂O and CO₂ was competitively split during the oxidation step, especially at 700 °C. The activation energy of each reaction was ordered as; CO₂ splitting > H₂O splitting > CO₂ adsorption, supporting the above evidence where H₂ and CO production were found to increase when the operating temperature was increased.     

Study of the refractory used in a submerged arc furnace in the copper-making industry

A cost driver in the copper-making industry is the periodical relining of the furnaces because of wear. This paper presents thermochemical calculations (using the FactSage^™ database) focused on the evaluation of the slag-refractory chemical interaction in a submerged arc furnace (SAF) used for slag-cleaning operations. This evaluation was made under different conditions: slag-refractory volume ratio, oxygen partial pressure, and different types of slag. The new phases formed as a consequence of the slag-refractory chemical interaction were identified and quantified. To support the theoretical calculations based on thermochemistry, a postmortem study was carried out on a SAF used at the Atlantic Copper Smelter (Spain) after a 6-year campaign (4.5 mill. t. slag processed). Refractory samples were taken from different locations on the wall and analyzed using a scanning electron microscope equipped with an Energy Dispersive Spectroscopy system.     

Enthalpies of formation of selected Pd2YZ Heusler compounds

Standard enthalpies of formation of selected ternary Pd-based Heusler type compositions Pd₂YZ (Y = Cu, Hf, Mn, Ti, Zr; Z = Al, Ga, In, Ge, Sn) were measured using high temperature direct synthesis calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the Heusler compounds are, Pd₂HfAl (−81.6 ± 2.4); Pd₂HfGa (−79.9 ± 2.9); Pd₂HfIn (−76.4 ± 1.4); Pd₂HfSn (−77.6 ± 1.6); Pd₂MnSn (−54.6 ± 3.1); Pd₂TiGa (−65.6 ± 3.6); Pd₂TiIn (−69.9 ± 2.1); Pd₂TiSn (−78.6 ± 2.4); Pd₂ZrAl (−85.3 ± 3.0); Pd₂ZrGa (−76.2 ± 1.9); Pd₂ZrIn (−85.1 ± 3.9); Pd₂ZrSn (−92.2 ± 3.1); for the B2 compounds, Pd₂MnAl (−87.1 ± 3.0); Pd₂MnGa (−54.5 ± 1.7); Pd₂MnIn (−41.0 ± 2.5); Pd₂TiAl (−81.4 ± 1.9); for the tetragonal compound Pd₂CuAl (−55.2 ± 3.0) and for the orthorhombic compound Pd₂CuSn (−43.1 ± 2.3). Values were compared with those from published first principles calculation and the Open Quantum Materials Database (OQMD). Lattice parameters of these compounds were determined by X-ray diffraction analysis (XRD). Microstructures were identified using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Selected alloys were annealed at various temperatures to investigate phase transformations and phase relationships.     

混油泥浆化学热洗法无害化处置研究

泥浆体系中混油泥浆是对环境影响较为严重的一种泥浆。泥浆中油含量较高,是较难解决的问题之一,也是制约油田企业环境质量提高和可持续发展的一大难题。随着新工艺新材料的发展,混油泥浆处理技术也持续发展,本研究将化学破乳处理法中反应温度、反应时间、破乳剂的加量等参数进行调整,研究了不同条件下液体的处理效果。     

基于钙循环的Mn-Mg修饰石灰石流态化储热及磨损特性研究

以石灰石、Mn(CH3COO)2•4H2O和Mg(CH3COO)2•4H2O为原料，采用浸渍法制备了Mn-Mg修饰石灰石，研究了其在流态化下的钙循环储热性能和颗粒磨损特性。结果表明：Mn的掺入提高了CaO的储热反应速率，有助于减缓石灰石储热转化率随循环次数增加而衰减，最佳Mn/Ca摩尔比为5∶100；Mn和Mg的共同掺入使Mn-Mg修饰石灰石具有更稳定的循环储热性能，最佳Mn/Mg/Ca摩尔比为5∶8∶100；最佳条件下，Mn-Mg修饰石灰石第20次循环储热转化率分别比天然石灰石和Mn修饰石灰石提高54%和30%，其20次储热循环磨损率比Mn修饰石灰石仅增加5%。     

光热驱动多孔氧化铈热化学循环解水制氢非热质平衡模型

热化学循环太阳燃料技术过程所涉及的多孔介质中复杂反应及热质传递过程,尚未建立较为完善的数学模型。以多孔氧化铈热化学循环解水过程为研究对象,将颗粒尺度的氧输运与宏观尺度的热质输运相耦合,提出完整的光热驱动条件下多孔介质非热质平衡模型,实验数据对比验证了动力学及热质输运模型的可靠性,分析了两种尺度(颗粒及床层)下,非热平衡效应、入射辐射热流、反应物浓度对动态过程的影响。入射辐射在床层的体积效应下,轴向的温度梯度使得缺陷反应的热力学平衡控制最大氧空位浓度出现在床层前侧,在缺陷反应的动态过程中,氧化过程相较于还原反应更快,提高多孔载氧体反应器的产物H₂浓度应主要从还原阶段中反应过程及条件出发。可为该类问题的建模和过程设计提供较为完整的理论基础和参考路径。     

Thermodynamic modeling of the germanium–manganese system

Based on a careful review of the literature, the Ge–Mn system is modeled using the Calphad method. The liquid is described using an associate model regarding to physicochemical observations. The phases cub_a13, fcc_a1 and bcc_a2 are modeled as substitution solutions using the Redlich–Kister formalism. The Mn₁₁Ge₈, Mn₅Ge₃, LT_Mn₅Ge₂ and LT_Mn₃Ge are treated as stoichiometric compounds and the non-stoichiometry of Mn₃Ge, Mn₅Ge₂ and Mn₂Ge are respectively described as (Mn)_0.75(Ge,Mn)_0.25, (Ge,Mn)_0.714 (Ge,Mn)_0.286 and (Ge,Mn)_0.667 (Ge,Mn)_0.333. The results are in good agreement with the set of experimental data which is carefully selected. Finally, a few experimental data which could be checked are indicated.     

Metal sulfate decomposition using green Pd-based catalysts supported on γAl2O3 and SiC: A common step in sulfur-family thermochemical cycles

Thermochemical water splitting cycles (TWSCs) are processes with the potential for large-scale production of carbon-free hydrogen. Among these, the sulfur-family thermochemical cycles are considered the most promising due to both, the use of readily affordable chemical reagents and the temperature required to thermally decompose oxygenated sulfur compounds, which is achievable by solar means. Indeed, solar heat assisted metal sulfate decomposition is a key step, where catalysis can be employed to reduce decomposition temperature. Here we present a green route to synthesize Ag-Pd and Fe-Pd intermetallic alloy catalysts supported over γ-Al₂O₃ and Si-C by a microwave-assisted method using glycerol both as a solvent and as a reducing and stabilizing agent. The obtained supported catalysts were physicochemically characterized. Fe-Pd/Al₂O₃ catalyst exhibited the best performance, abating the zinc sulfate decomposition temperature by ca. 85 °C in comparison with other reported catalysts.