贝壳固硫过程热重研究

利用LCT-2型热天平对贝壳的固硫反应过程进行了实验研究。探讨了贝壳在含SO2模拟烟气气氛下的固硫能力、温度特性及SO2浓度对其钙利用率的影响特性;并利用JXA-840扫描电镜实验观察了贝壳与石灰石微观结构特性的主要差别。结果表明:贝壳具有良好的微观结构特性和固硫反应活性,其最佳固硫反应温度比石灰石高出约100℃,大部分贝壳更适合作900~1000℃温度下的燃煤固硫剂。     

石灰石闪蒸改性及脱硫性能的试验研究

本文对3种不同产地的石灰石进行了闪蒸改性处理,对改性石灰石颗粒的孔径分布进行了测定,研究了压力、温度等参数对石灰石闪蒸改性的影响。并在气流反应器上对闪蒸后的样品进行了硫化试验。结果表明,在一定的压力和温度下,闪蒸处理能够增大石灰石颗粒的微孔孔径,并使石灰石样品的脱硫性能得到较大提高。     

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.     

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。     

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。     

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。     

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.     

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.     

D-T中子源n-γ密度测井规律的蒙特卡罗模拟

根据D-T反应中子的能谱和角分布数据,建立了中子源模型;根据石灰岩地层标准刻度井群数据,建立了井模型。采用MCNP程序模拟了井中中子和射线的输运,得到了不同地层密度、不同源距处NaI探测器中的混合能谱和非弹能谱。在混合能谱2.5~4.5 MeV能区开窗,混合射线相对计数随源距的变化曲线显示,源距应选择在20~80 cm,密度与混合射线计数之间呈现非线性关系。在非弹能谱1.0~8.0 MeV能区开窗,非弹射线相对计数随源距的变化数据显示,源距应选择在20~40 cm或80 cm附近,密度与非弹射线计数之间成近似线性关系。