热解条件对淮南煤焦孔隙结构的影响

用N2等温吸附(77 K)法考察了热解条件对淮南煤焦孔隙结构的影响.测量了淮南原煤、淮南快焦和淮南慢焦的BET比表面积,并由BJH模型计算得到了孔容积、平均孔径及孔径分布.结果表明,快速热解和慢速热解都可以使煤孔隙结构发达,加速孔的生成和发展,且热解温度越高,趋势越明显,但慢速热解对煤焦孔隙结构的影响更加显著.应用分形维数的概念,结合吸附/脱附曲线得到了煤焦的分形维数,结果表明快速热解和慢速热解都可以增加煤焦的分形维数.     

油页岩半焦与锯末混烧过程孔隙结构变化研究

利用氮等温吸附脱附法研究了燃烧过程对油页岩半焦和锯末混合物表面孔隙结构特性的影响,并应用分形维数来定量描述混合物表面形态的复杂程度。结果表明:混合物各个孔径范围内的孔体积较半焦明显减少,在失水段尤为明显,燃烧前期表面孔隙以中微孔为主,后期以中大孔和大孔为主;混合物的中微孔结构在挥发分燃烧阶段得到充分发展,比表面积在显著增大,对反应进程具有促进作用。通过FHH方程线性回归得到的分形维数反映出混合物内部孔隙的立体化程度比半焦更高,燃烧阶段化学反应及力学作用的交替影响,引起分形维数随温度而变化。     

生物质颗粒孔隙结构在热解过程中的变化

利用氮气等温吸附/脱附法（-196℃）和扫描电镜（SEM）等研究了热解过程中生物质颗粒孔隙结构的演化规律,并用分形维数来描述焦颗粒内部孔隙表面形态的复杂程度。结果表明,热解温度对生物质焦的孔结构和表面形态有显著影响。热解过程中孔网络结构在发生演变,孔的形状发生了一定变化,且孔径有先变小后变大的趋势。高温导致焦颗粒发生塑性变形,使得孔隙扩大和孔表面更加光滑。随着温度的升高,生物质焦的BET比表面积先增大后减小,500℃以前,孔容积的变化规律与比表面积相近。通过分形FHH方程回归得到的分形维数能较好地表征颗粒内部孔隙表面的分形特征。其分形特征与热解温度密切相关,分形维数的变化与BET比表面积有一定关联。     

燃烧过程中石油焦表面形态的变化

用氮气等温吸附/脱附法对石油焦燃烧过程中表面形态的变化进行了分析.通过BET法和t-plot法对不同燃尽率的石油焦进行了比表面积和孔容积的测定.结果表明,石油焦燃烧过程中孔隙结构变得发达,比表面积和孔容积较原样明显增大且变化趋势基本一致.验证了石油焦燃烧具有分形动力学的行为特征,用FHH模型求得燃烧中表面分形维数值接近3,表明燃烧反应是在空间网格结构的内、外部同时发生的;同时发现,石油焦表面分形维数与比表面积和孔容积在变化趋势上存在明显差异.     

基于分形理论的油页岩有效扩散系数研究

以直径为1.6—2 mm柳树河油页岩为原料,采用扫描电镜法与氮吸附法得出油页岩吸附-脱附等温线,孔径分布曲线等;分析了油页岩内部孔隙结构,计算出孔道弯曲分形维数与孔隙面积分形维数,并研究油页岩内部的有效扩散系数。结果表明:油页岩吸附-脱附曲线属于Ⅲ型等温线,是一种典型的二端都开放的管状毛细孔型结构的多孔物质;其含有较发达孔隙,孔径分布为0.4—40 nm;油页岩孔道弯曲分形维数越小,孔道越平坦,孔隙面积分形维数为2.464;油页岩有效扩散系数与其内部结构和操作温度有关,温度越高,粒径越小,有效扩散系数越大。     

谷壳热解过程中颗粒孔隙结构分形特性

由于颗粒相本身的复杂特性,因此研究者多是对生物质颗粒定性或就某一方面进行描述。借助分形理论可以对颗粒物理结构进行全面而精确的表征。本文利用分形BET方程,基于非线性最小二乘法,提出一种新的分形维数计算途径。该方法是根据多层吸附理论,对氮气等温吸附/脱附法测定的数据分析,直接获得表征整个吸附范围的颗粒分形维数,同时回归得到吸附过程中的吸附层数。分析表明,该方法计算得到的分形维数在数学层面上可以很好地表征颗粒内部微孔特征,同时通过对计算得到的吸附层数分析发现该计算结论也能被多层吸附理论解释,表明该方法在物理层面上也符合实际情况。利用该方法计算得到谷壳在快速热解条件下焦颗粒分形维数的变化。     

干馏终温对油砂半焦表面特性的影响

利用氮气等温吸附脱附法和电镜扫描研究了印尼油砂干馏热解过程中半焦表面特性的变化,并利用分形维数来定量描述半焦表面形态的复杂程度。结果表明,半焦BET比表面积与孔容积随干馏终温的变化趋势相近,均呈现先增大后减小的趋势。通过FHH方程回归得到的分形维数能够较好地反映半焦内部孔隙结构的分形特性,挥发分的吸出、塑性变形、气体产物的逸出以及油蒸汽的再凝结造成的闭孔效应的多种作用的交替影响,使分形维数在不同的温度区间有不同的变化趋势。电镜扫描能够直观地观察到半焦表面的孔结构特征,利用Matlab编程分析电镜图片得到的盒子维数与氮吸附数据拟合得到的FHH分形维数变化趋势基本一致。     

Ru/Al2O3催化剂表面分形分析

利用静态氮吸附仪在-196.15 ℃液氮气氛中,测定Ru/Al2O3催化剂的比表面积以及孔结构参数,研究了催化剂的孔容-孔径分布和吸附-脱附等温线。基于FHH多层吸附模型,利用全吸附数据计算出Ru/Al2O3催化剂的表面分形维数。结果表明,3种Ru/Al2O3催化剂的表面分形维数均约2.4,分形维数与比表面积和总孔体积无直接关联。     

用氮气吸附法研究二甲醚催化剂表面分形维数

在77K下对四种二甲醚催化剂进行N2吸附—脱附等温线测定,得到了催化剂的孔结构参数,研究了其孔径分布、比表面积、等温线形态变化,并利用等温吸附数据计算其分形维数。结果表明,四种催化剂分形维数在2～3之间,将催化剂颗粒机械成型得到的片剂都具有分形特性,但其分形维数与比表面积和孔容积没有直接联系。     

混煤热解过程中的表面形态

以管式电炉为热解室,改变热解终温,在惰性气氛下对无烟煤与烟煤的混煤进行快速加热条件下的热解。采用低温氮气吸附方法研究混煤焦表面形态的变化规律。通过对吸附等温线的分析,表明煤焦具有连续、完整的孔隙结构,无定形孔的存在使得吸附迴线存在不闭合的状态。随着热解终温的升高,混煤焦的比表面积先增加后减小;随着烟煤掺混比例的增加,混煤焦的微孔容积和表面积也先增加后减小,A1B2混煤焦具有最大微孔容积和表面积。对煤焦孔隙的分形研究发现煤焦孔隙分形维数与微孔结构关系密切。混煤焦表面形态的变化规律体现了混煤热解的独立性以及相互作用。     

煤焦气化过程中的分形特征

将分形理论的概念应用到煤焦气化研究中 .煤焦气化过程孔结构参数间的变化规律符合一定的分形关系 ,气化速率越大 ,分形维数也越大 ,但是分形理论并不适用于所有煤焦气化过程研究 ,只有那些孔容积绝大部分由中小孔构成的煤焦才符合分形规律 .     

Fractal characteristic of three Chinese coals

Experimental and theoretical investigation about coal/char structure is presented. Surface structures of parent coal and char with different burn-off ratios were analyzed. We introduced the fractal theory into Scanning Electron Microscopy image analysis and utilize the particle surface fractal dimension (D_ps) to quantitatively describe the surface character of coal/char particles. D_ps of three Chinese coals reach their maximum in the 35-45 wt% char burn-off interval and then decrease with increasing carbon burn-off ratio. The inner-pore information of coal/char particles was determined by N₂ isotherm adsorption/desorption. Using fractal BET model, internal surface fractal dimension (D_s) of coal/char particles was calculated. The D_s change trend of three Chinese coals is similar to their S_BET development. It means the D_s can quantitatively describe the inner pore structure character of coal/char particles.     

Comparison of fractal properties of porous structures during coal devolatilization

This paper investigates fractal property changes of pore structures during coal devolatilization. Similar to char pores, coal pores can also be classified as micro pores and macro pores based on their fractal dimensions. The specific surface area and fractal dimension of micro pores in coal particles are basically unchanged after devolatilization. However, the specific surface area and fractal dimension of macro pores, which are key factors in char combustion, are increased after devolatilization. In fact, the fractal dimensions are basically doubled. These parameters will affect another fractal geometrical factor β in char pores that is correlated to char combustion rate. Since the rate of char combustion can be predicted from their fractal pore properties, it may be possible to predict char combustion directly from the properties of their parent coal pores in the future. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

包含反应阶数变化的分形煤焦颗粒燃烧模型的建立与实验验证

为了深入研究煤焦燃烧的机理并提高对煤焦燃烧过程的预测精度,建立了一个综合的煤焦燃烧模型。该模型考虑了煤焦颗粒孔隙内二次反应与扩散的耦合作用、煤焦燃烧反应阶数的变化和反应过程中CO/CO₂比例等问题。使用热天平(TGA)对11种煤焦的燃烧特性进行分析,测得各种煤焦的表观活化能与指前因子,以确定模型中的待定参数。在沉降炉(DTF)中对这11种煤焦做燃烧实验,用TGA基于灰分守恒测得DTF炉管出口处的煤焦样品的转化率。运用建立的模型模拟这些煤焦的燃烧过程,预测的转化率与实验结果有较好的吻合度,相比传统的本征动力学模型,该模型预测的精度有了较大提高,证明了该模型能适用于从褐煤到无烟煤的较广煤焦范围。研究还发现,煤焦燃烧的表观反应阶数在燃烧过程中不断减小并最终趋于稳定。     

Evolution of porous fractal properties during coal devolatilization

The evolution of pore structures during coal devolatilization was studied using the mercury porosimetry to classify pore structures as micro pores or macro pores based on fractal theory. Pyrolysis caused few changes in the total specific surface areas and micro pore surface areas of most samples. However, the specific macro pore surface areas and the ratio of the specific macro pore surface areas to the total specific surface areas were significantly increased, mostly a result of the shapes of some micro pores becoming less complex after pyrolysis. After devolatilization, the fractal dimensions of the macro pores, which reflect the complexity of the geometrical shapes and hence, the resistances to gas diffusion increased. The fractal geometric factor β, which combines the effects of the ratio of the macro pore surface area to the total surface areas and the fractal dimension of the macro pores after char combustion presented in the previous study is also increased. The volatile content in the parent coal affects the changes of the pore structures.     

The use of fractal analysis in the textural characterization of coals

The materials studied were four bituminous coals as well as the corresponding coal samples oxidized in air at 543 K for different periods of time. The method proposed by Friesen and Mikula, the procedure of Neimark and the methodology of Zhang and Li were successfully employed to analyze mercury porosimetry data from a fractal perspective. Fractal dimensions as well as fractal profiles are sensitive to oxidation treatment, being useful to follow the changes undergone by the coal samples. The evolution of the fractal dimension of coals with oxidation is determined by a balance between two main mechanisms of pore development: the oxidation of the pore surface itself that tends to lower the fractal dimension and the access of mercury to previously non-accessible regions that tends to increase this dimension.     

Identification of the mechanism of coal char particle combustion by porous structure characterization

Two limiting models—the shell progressive mechanism and the homogeneous mechanism—can describe combustion of a single coal particle. Some information about the real mechanism can be obtained from investigation of the porous structure development during combustion. Using the principles of gas adsorption and mercury penetration, the porous structure of a partially combusted particle was estimated. Experiments were carried out in an equipment by applying the thermogravimetric method and using a single devolatilized coal particle. The inlet concentration of oxygen was 5 and 15 mol%. The initial temperature of combustion was in a range from 450 to 800 °C. The mechanism of coal char particle combustion depends on the initial temperature and the inlet concentration of oxygen. At low temperature and low inlet concentration of oxygen, the rate of principal chemical reactions is comparable with the rate of diffusional transport of oxygen inside the particle. Combustion is governed by the diffusion mechanism. This is evident from the values of the specific surface area of pores and proportional representation of individual pore types. At higher temperatures and low inlet concentrations of oxygen, combustion proceeds by the shell progressive mechanism. The specific surface area is lower in comparison with the previous case. There is a sharp interface between the particle core and the ash shell. The core exhibits a higher value of specific surface area than in the case of a non-combusted coal char particle. This fact can be explained by the consecutive reaction of carbon dioxide with carbon in the core of the particle. The rate of this reaction is sufficiently high at temperatures above 800 °C.     

碱矿渣水泥硬化体孔结构的分数维特征

将分形和分数维概念用于碱矿渣水泥硬化体中微孔结构的研究,并通过对压汞仪测定孔结构(mercury intrusion porosimetry)测试数据的分析证明:碱矿渣水泥硬化体中微孔结构具有分形特征,其容积分数维越大,微孔占有空间的结构越复杂.因此,该方法为水泥硬化体中微孔结构的研究提供了一种新方法.