石灰岩对褐煤模拟地下气化残焦物化性质的影响

基于煤炭地下气化过程中石灰岩可能影响煤焦的组成和结构,借助煤炭地下气化模拟实验系统对不同石灰岩掺量(质量分数为0-30%)的褐煤进行水蒸气气化,并采用低温N_2吸附-脱附、XRD和FT-IR等分析手段研究石灰岩对褐煤模拟地下气化残焦的组成、比表面积及孔结构特征、微晶结构和表面官能团等物理化学性质的影响。结果表明,石灰岩对煤焦的元素组成有较大影响。石灰岩可促使煤焦中的微孔向中孔发育,增大煤焦的比表面积和孔容积;当石灰岩掺量从0增加到30%时,煤焦的比表面积增大21.91%,介孔率增加21.49个百分点。XRD分析表明,钙的存在破坏煤焦的芳香结构,使煤焦无序化程度增加,晶面间距(d_(002))增大,抑制煤焦的石墨化发展倾向。FT-IR分析表明,石灰岩存在下,煤焦的羟基官能团减少。     

传递函数在石灰石分解研究中的应用

本文应用高温气固悬浮试验台架对石灰石的分解动力学过程进行了研究,并利用试验系统的传递函数对检测数 据进行了修正,从而获取了石灰石在反应器中的真实动态分解数据。试验结果表明采用传递函数对试验数据进行修正是必 要的,所得结果对于工业应用以及设计具有一定的参考价值。     

A novel approach to consolidation of historical limestone: the calcium alkoxides

Potential utilization of calcium alkoxides as stone consolidants was considered. Reaction of Ca(OCH₃)₂, Ca(OCH₂CH₃)₂(CH₃CH₂OH)₄ and Ca[OCH(CH₃)₂]₂ with the atmosphere in different experimental conditions was studied. The reaction produced CaCO₃ and two different pathways seem to be involved, the first taking place through CO₂ insertion into the Ca–O bond of Ca(OR)₂ species with formation of an alkylcarbonate derivative, subsequently transformed into CaCO₃ through ROH elimination; the second takes place through hydrolysis of Ca(OR)₂ to Ca(OH)₂, which is then carbonated to CaCO₃. The vaterite/calcite ratios found in the final CaCO₃ vary considerably with the experimental conditions adopted. Investigations demonstrated the potentiality of Ca(OCH₃)₂ to act as a stone consolidant. In fact, impregnation of a porous substrate, simulating the deteriorated stone, with a methanol solution of Ca(OCH₃)₂, produced a crystalline vaterite film, which gradually filled all the pores and cavities of substrate and seems to fulfil the necessary requirements for a consolidant. Copyright © 2008 John Wiley & Sons, Ltd.     

单轴压缩条件下溶蚀礁灰岩细观变形破坏特征研究

礁灰岩的溶蚀对海洋工程和岛礁工程的稳定性有明显的影响.孔隙型溶蚀是礁灰岩常见的溶蚀方式.本文通过构建随机溶蚀孔洞的离散元模型,模拟孔洞型溶蚀礁灰岩的细观变形破坏特征,分析其变形破坏规律与裂隙演化特征.结果 表明,基于随机聚类算法构建的溶蚀礁灰岩离散元模型能够很好地模拟孔洞型溶蚀作用,且其变形破坏特征具有明显的规律;随着溶蚀率的增加,溶蚀礁灰岩单轴应力应变曲线由单峰型逐渐转变为双峰型或多峰型,破坏特征由脆性破坏逐渐转变为塑性破坏;随着溶蚀率的增加,礁灰岩单轴抗压强度和弹性模量都逐渐减小,抗压强度呈指数函数下降,弹性模量呈线性函数下降,而泊松比则表现为先增后降,说明试样在高溶蚀率时主要发生结构性破坏;随着溶蚀率增加,礁灰岩的宏观破裂面逐渐消失,由于溶蚀孔洞的相互作用,导致了起源于孔洞周围的裂隙开始萌生,并逐渐贯通,最终导致试样发生整体宏观破坏.本研究成果可为深入认识海洋工程和岛礁工程中溶蚀礁灰岩的变形破坏特征提供理论参考.     

Modelling Unsaturated Moisture Transport in Heterogeneous Limestone

The influence of macro-scale heterogeneities on the imbibition process is investigated for Savonnières, a French layered limestone. Free uptake experiments are performed both parallel and perpendicular to the bedding. It is found that the position of the different layers, and the exact material properties inside each layer can significantly influence the imbibition process. The experimental results are compared with numerical simulations. For the flow simulations, moisture permeability of the different layers is obtained with the upscaling technique presented in Part 1. Good agreement between simulations and experiments validate the proposed upscaling from meso to macroscopic scale.     

石灰石颗粒分解的动力学模型研究

本文应用热重法对石灰石在氮气气氛、不同升温速率下的分解动力学进行了研究,采用普适积分法、微分方程法以及多重速率扫描Kissinger法相结合的方式求解动力学参数,确定反应机理模型。研究结果表明石灰石分解反应符合相边界反应的收缩圆柱体模型,采用三种方式相结合的动力学处理方法可以有效的进行动力学模式函数的选取。     

用于流化床燃烧脱硫的石灰石的反应活性评价和测试研究

对用于燃煤流化床燃烧脱硫的脱硫剂石灰石的反应活性进行了研究，提出了易于进行数学处理的石灰石硫盐化模型，得出了评价石灰石反应活性的两个指标－最大转化率和反应速率常数。研究方法除采用了传统的热天平法和鼓泡流化床外，还根据循环流化床燃烧技术的特点，发展了提出了湍流床法和石英棉法，并进行了不同试验条件下的实验研究，对不同反应活性温度技术进行了试验比较。     

Physico-Chemistry of the Limestone Sulphation Process

Aspects of the mechanism of the overall reaction between CaCO₃/CaO and SO₂/SO₃ under oxidizing conditions are discussed. The limestone and lime sulphation processes were carried out in a thermobalance under conditions relevant to atmospheric fluidized bed combustion. Sulphated samples, prepared in the form of cross-section particles, were examined in a scanning electron microscope by energy-dispersive X-ray and back-scattered electron imaging. Photomicrographs are presented. The reaction proceeded from the outer surface of the particles and along the pores. Surface textural changes during the reaction were considered. The layer of products was identified as controlling both the rate and extent of limestone/lime sulphation. In the products, two sulphur-bearing solids (CaSO₄ and CaS) were identified. The presence of CaS, which may cause difficulties in practice, is attributed to CaSO₃ disproportionation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Influence of lime-containing additives on the thermal behaviour of ammonium nitrate

Ammonium nitrate (AN) is one of the main nitrogen fertilizers used in fertilization programs. However, AN has some serious disadvantages — being well soluble in water hardly 50% of the N-species contained are assimilated by plants. The second disadvantage of AN is associated with its explosive properties. The aim of this paper was to clarify the influence of different lime-containing substances — mainly Estonian limestone and dolomite — as internal additives on thermal behaviour of AN. Commercial fertilizer grade AN was under investigation. The amount of additives used was 5, 10 or 20 mass%, or calculated on the mole ratio of AN/(CaO, MgO)=2:1 in the blends. Experiments were carried out under dynamic heating condition up to 900°C (10°C min⁻¹) in a stream of dry air or N₂ by using Setaram Labsys 2000 equipment coupled to Fourier transform infrared spectrometer (FTIR). The results of analyses of the gaseous compounds evolved at thermal treatment of neat AN indicated some differences in the decomposition of AN in air or in N₂. At the thermal treatment of AN’s blends with CaCO₃, MgCO₃, limestone and dolomite samples the decomposition of AN proceeds through a completely different mechanism — depending on the origin and the content of additives, partially or completely, through the formation of Mg(NO₃)₂ and Ca(NO₃)₂.     

Non-isothermal kinetic analysis and feasibilty study of medium grade crude oil field

In this research, non-isothermal kinetics and feasibility study of medium grade crude oil is studied in the presence of a limestone matrix. Experiments were performed at a heating rate of 10°C min⁻¹, whereas the air flow rate was kept constant at 50 mL min⁻¹ in the temperature range of 20 to 600°C (DSC) and 20 to 900°C (TG). In combustion with air, three distinct reaction regions were identified in all crude oil/limestone mixtures, known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). The activation energy values were in the order of 5–9 kJ mol⁻¹ in LTO region and 189–229 kJ mol⁻¹ in HTO region. It was concluded that the medium grade crude oil field was not feasible for a self-sustained combustion process.