煤热解动力学模型的建立

通过对煤热解反应动力学分析,基于分布活化能模型DAEM,建立了集总反应动力学模型表示煤炭热解过程。确定了可以预测热解产物组成、分布与热解终温和升温速率关系的动力学方程。结果表明：随热解温度升高,各种挥发分产物析出率越来越接近最大产率;半焦C含量增加,但产率下降,H,O,N和S等元素降低。升温有利于提高半焦脱硫率、脱氮率。温度为600℃左右时,除H2外的大部分挥发分基本析出,半焦元素变化幅度减小。热解终温较低且一定时,较慢的升温速率有利于各热解挥发分最大限度析出。秦丽娜     

神木煤热解的挥发分收率与岩相组成的关系

引　言从构成煤的微观层次的显微组分入手研究煤的组成、结构和性质已成为煤化学研究的一个重要方面 ,在这方面一些研究者已做过许多有意义的尝试 ,主要集中在有关配煤制优质焦炭等方面[1] ,对于煤的热解挥发分收率与岩相组成相关联的研究也有零星报道 .Ｄｕｘｂｕｒｙ[2 ] 对一系列煤及其显微组分的热解研究结果表明 :不同煤的镜质组和惰质组的热解挥发分产率相差不大 ,相同量的不同煤种挥发分量的不同是由壳质组引起的 .其他研究者因不能得到纯度较高的显微组分而仅对热解过程中镜质组和惰质组的相互影响做过推测 .对于煤的挥发分收率与岩…     

基于显微组分化学键特征的宁夏庆华煤热解特性及动力学分析

通过X射线光电子能谱和傅里叶红外光谱表征宁夏宁东庆华煤不同显微组分的官能团种类、表面结构元素价态分布及化学键赋存特征。采用热重-质谱联用考察庆华煤镜质组和惰质组在不同热解温度下的失重行为和关键气体组分变化。进一步基于Coats-Redfern模型从化学键断裂特征和反应动力学角度探讨煤镜质组和惰质组的热解行为差异。结果表明,庆华煤显微组分的热解失重峰与相应化学键断裂信息能够很好地吻合。不同显微组分的热重曲线变化趋同,但相同热解温度下镜质组的失重率始终高于惰质组。快速热解阶段镜质组较惰质组表现出更大的失重率和最大失重速率。其主要原因在于镜质组的脂肪族官能团相对含量更高,快速热解阶段会发生更多的C_al—C_al断裂。不同热解温度下庆华煤显微组分三个主要热解阶段的活化能和频率因子大小次序为：快速热解阶段>快速缩合阶段>缓慢热解阶段。在快速热解阶段,镜质组和惰质组的平均活化能均约为75 kJ/mol,但镜质组的频率因子更高。     

果壳生物质热解特性与动力学

采用热重分析仪对林产果壳生物质（澳洲坚果壳、油茶壳、核桃壳）热解特性进行了研究,利用分布活化能模型（DAEM）分析了热解动力学。热解特性研究表明：油茶壳最大失重速率最小,热解起始温度、结束温度、最大失重速率温度均低于澳洲坚果壳和核桃壳;澳洲坚果壳和核桃壳热解特征值近似;3种果壳生物质随升温速率的增加,热解过程向高温区转移。DAEM研究表明：DAEM适用于3种果壳生物质的热解动力学研究,相关系数R²在0.914~0.999之间;澳洲坚果壳热解活化能83.91~211.86 kJ/mol,油茶壳热解活化能68.64~244.49 kJ/mol,核桃壳热解活化能98.69~267.75 kJ/mol;随转化率的增加,3种果壳生物质活化能呈现相同的变化趋势,但变化幅度不同。     

三种常见生物质热解动力学特性的研究

采用热重法对三种常见生物质热解特性及反应动力学进行研究。考察了粒径和升温速率对生物质热解特性的影响。粒径减小时,稻草开始热解的温度和热解结束的温度都降低,最大失重变化率对应的温度也降低;升温速率增加时,热解挥发分起始析出温度和DTG曲线峰值温度均相应增加。采用Coats-Redfern法对生物质热解过程进行处理,并求出了生物质热解的动力学参数,求出的表观活化能变化范围在30～70kJ/mol。     

松木屑加压CaO催化热解动力学研究

研究了不同压力、升温速率以及添加CaO催化剂对松木屑热解过程的影响并进行了动力学分析。研究结果表明：1）增加系统的反应压力会降低热解过程的最终失重率,最终的剩余物质增加,并且提高反应压力,不利于挥发分析出。但是通过动力学分析发现,一定范围内增加压力能够降低热解过程中的活化能,从而有利于热解反应的发生,但是压力超过0.7 MPa以后,活化能开始增加。2）增加升温速率,挥发分释放的越强烈,有利于热解反应的进行,但挥发分大量析出的温度范围并没有很明显的浮动。通过动力学分析发现,随着升温速率增加,反应的活化能出现减少趋势,这说明随着升温速率增加,松木屑热解反应更加激烈。3）在松木屑热解反应中添加CaO对反应过程有较大的影响。随着CaO催化剂添加量增加,松木屑最终失重率逐渐减少,从72.81 %减少到59.61 %,降幅达到18.13 %。DTG曲线显示失重峰增加到4个,另外两个为Ca（OH）₂和CaCO₃分解所引起的失重峰。随着CaO添加量的增加,第1个失重峰的峰值和第2个失重峰的峰值逐渐减小,最大峰值对应的温度点变化不明显;第3、第4个失重峰的峰值逐渐增加,最大峰值对应的温度出现明显增加趋势。     

型煤热解的热传递数学模型研究

以热解能量方程和热解分布活化能模型(DAEM)的理论分析为研究重点,对型煤热解中的热传递进行了系统的研究,建立了型煤热传递过程的数学模型。通过热解能量方程的计算,得出型煤热解过程中的热传递速率与煤质和型煤内部的挥发分传递速率有关。通过DAEM模型进一步分析,得出影响型煤热解热传递速率的因素是煤质和型煤内部的活化能分布。     

显微组分在热解过程中的相互作用

在镜质组中加入5%等不同含量的稳定组或丝质组配制了两组分试样;以正交试验原理配制了九种三组分模拟煤样;用PRT-1型热天平在常压、线性升温,N_2流动气氛条件下考察了各试样的热解特性。研究表明:各显微组分在热解过程中的相互作用可用热解游离基“大碎片”和带游离基的小基团之间的三类不同反应来解释;三组分模拟煤样在温度T时的累计失重率X_N(%)可用X_N=X_ih_if_i求取其中相互作用系数f_i的数值分布与y=c·exp(b/x)相似。     

混煤的流化床热解动力学研究

采用微型流化床热分析仪(MFBRA),探讨了不同煤种及其混煤在相同的热解条件下甲烷的析出特征及其生成动力学.结果表明,在相同的热解条件下,煤热解过程中甲烷的开始析出温度随煤中挥发分的升高而降低,甲烷的最大析出速率及甲烷的生成总量都随煤中挥发分的升高而增加;煤热解反应的活化能(E)随煤中挥发分的升高而降低,表示煤的挥发分愈高,煤的热解愈容易进行;配煤改变了单种煤的煤质特征,其水分、挥发分和灰分等煤质指标等于单种煤相应煤质指标的加权平均值,但混煤热解的活化能(E)并不等于配合单种煤活化能(E)的加权平均值.     

非等温热重分析长焰煤热解过程与动力学特征

为提高煤热解过程中焦油的产率,用非等温热重分析方法研究了不同粒径、热解终温和升温速率条件下长焰煤的热解过程和机理,分析了20和100℃/min升温速率下长焰煤热解过程特征,并求解了热解动力学参数。结果表明,煤颗粒在2.8mm以下时,粒径对热解过程影响较小;热解终温越高,热解最终固体产物中挥发分产率越低;升温速率越快,挥发分的析出速率越快。在同一升温速率下,不同热解温度段得到的活化能呈现两头大中间小的特征,且指前因子随活化能的增大而增大。     

The variation of structural characteristics of macerals during pyrolysis

Vitrinite and inertinite were separated by DGC from Chinese Shenmu bituminous coal and the structural characteristics of the macerals, before and after pyrolysis, were analyzed by ultimate analysis, FTIR and ¹³C NMR. The results showed that vitrinite chars always had higher H and lower C content than inertinite char at the same pyrolysis temperature. The FTIR and ¹³C NMR indicated that vitrinite had more aliphatic C-H, hydrogen bonding and lower aromaticity. With increasing temperature, the aliphatic C-H decreased, aromatic C-H, aromaticity and H_ar/H_al ratio increased. At the same temperature, inertinite always had higher H_ar/H_al ratio than vitrinite, which is consistent with that inertinite had higher aromaticity than vitrinite. And the H_ar/H_al ratio was also related to the remainder volatile matter. With increasing H_ar/H_al ratio, the remainder volatile matter in vitrinite and inertinite decreased. The higher aromaticity and H_ar/H_al ratio and lower H content of the inertinite in all temperature range were correlated with its higher thermal stability and lower volatile yield than vitrinite.     

Chemical structure of coal macerals in Balmer 10 coal and fusinite from Illinois coal as indicated by reductive alkylation

A Canadian Cretaceous coking coal from the Balmer 10 seam, Fernie, British Columbia, was separated by sink-and-float methods into vitrinite and a semifusinite-rich fraction. A portion of the vitrinite fraction was oxidized in air at 100 °C for 72 h to destroy the coking properties. The fresh vitrinite, oxidized vitrinite, and semifusinite of the Balmer coal, and the fusinite from Illinois coal, were each subjected to the reductive alkylation procedure of Sternberg, to cleave the ether linkages and octylate the products. The oxygen functional groups before and after ether cleavage were determined, as were the extractabilities by benzene of the octylated products. Thus the molecular weights of the benzenesoluble fractions of the octylated cleavage products were: fresh vitrinite 1930, oxidized vitrinite 1830, and fusinite 1490. The molecular-weight distribution of the octylated cleavage products was estimated by volatility analysis, which demonstrated the presence of much lower-molecular-weight material. Dilatation analysis of fresh and oxidized vitrinite showed that after cleavage of the ether linkages with potassium in tetrahydrofuran, the two could be brought to the same state. The dilatation behaviour of semifusinite after cleavage of the ether links and octylation showed only contraction, whereas the oxidized vitrinite treated in a similar manner exhibited a large dilatation.     

Microscopic changes in the coal-based catalysts used in the hydrocracking of Athabasca bitumens

Conventional catalysts are rapidly fouled with coke and metal deposits when used to hydrocrack residual oils. This work is part of a study in which a slurry of coal particles coated with catalyst was used in the hydrocracking of Athabasca bitumen in a continuous-flow pilot plant operated on the scale of one barrel (159 litres) per day. The fusinite and semi-fusinite macerals were unreacted after passing through the reactor and served as sites for coke and mineral-matter deposition. Unoxidized vitrinite macerals were converted to gas and oil and gradually disappeared, but oxidized vitrinite remained visible. This oxidized vitrinite, which had an oxidation rim around the periphery of the maceral, was coked in the interior. It is presumed that the gases and liquids evolved passed through fractures in the oxidation rim. The semi-coke-like structure resulting from partially oxidized vitrinite then behaved like the other coal inerts and served as a site for deposition of coke and mineral matter from the bitumen.     

Redox conditions and the transformation of organic matter in coal

The reduction and oxidation of organic matter play a key role in the petrography of coal—in particular, by determining the relative content of vitrinite and fusinite microcomponents. These, in turn, determine the quality and thereby influence the technological characteristics of the coal [1–4]. However, in the petrography of coal, the physicochemical character of oxidation and reduction is not always sufficiently emphasized. In the present work, we briefly consider some aspects of these very complex processes.     

Studies of elemental distributions within discrete coal macerals: Use of secondary ion mass spectrometry and X-ray photoelectron spectroscopy

Secondary ion mass spectrometry has been used to measure qualitatively the distributions of many trace and minor elements within some well-characterized coal macerals: vitrinite, fusinite and exinite. Complementary information was obtained by using X-ray photoelectron spectroscopy. Within the vitrinite specimens studied, a widely-dispersed largely inorganic aluminosilicate phase was identified, which contained a number of other trace elements. By contrast, within the organic-rich phase of this macerai, titanium was detected in a very even distribution; this suggests that some titanium may be bonded in an organic complex. The fusinite was shown to contain elevated concentrations of calcium, magnesium and fluorine, dispersed over a large portion of the maceral. The high fluorine content could be identified as an organo-fluoro compound using XPS. Exinite was found to contain lower concentrations of most elements, compared to other macerals. The organic composition of this maceral was significantly different from that of surrounding macerals; this could be seen from the enhanced emission of the C₂H₂-secondary ion and images of this ion thus clearly outlined the position of such macerals.     

13C1H Cross-polarization nuclear magnetic resonance spectra of macerals from coal

The carbon aromaticities (f_a) of vitrinite, exinite, micrinite and fusinite from a high-volatile A bituminous coal have been determined by ¹³C¹H cross-polarization nuclear magnetic resonance spectrometry. Values of f_a for the four macerals were found to decrease in the order: fusinite > micrinite ≈ vitrinite > exinite. Estimates of the average ring size using the f_a value and the elemental composition of each macerai indicated that the fusinite contained the largest polynuclear condensed aromatic ring system (> 5 rings) whereas the mean structural unit of the vitrinite contains 3–4 condensed rings.     

Pyrolysis and hydropyrolysis of Louisiana lignite

Pyrolysis and hydropyrolysis kinetics of five samples of Louisiana lignite have been studied in an atmospheric pressure TG system as a function of heating rate and atmosphere. Final pyrolysis temperature was always 800 °C. The total volatile yield (dry basis) was 33.5–43.8wt%. For all lignites the volatile yield in hydrogen was greater than that obtained in nitrogen at similar conditions. However, variation in heating rate produced an opposite result in the two atmospheres with volatile yield increasing with heating rate in nitrogen but decreasing in hydrogen. Results have been analysed using the distributed activation energy pyrolysis model and parameters compared to similar studies using North Dakota and Montana lignites.     

Maceral and pyrite partitioning through high-gradient magnetic separation of selected western kentucky coals

The ?0.5 inch (?1.27 cm) and ?28 mesh (?600 μm) fractions of the run-of-mine coals from seven western Kentucky preparation plants were crushed to 90 percent passing 200 mesh (75 μm) and processed through high-gradient magnetic separation (HGMS). Petrographic analysis of the clean and refuse fractions indicated that the refuse contained nearly the same amount of vitrinite as the associated clean coal. This contrasts with the findings for other fine coals from the same plants where fine refuse had consistently less vitrinite and more fusinite and semifusinite than fine clean coals. Pyrite remaining in HGMS clean coals was significantly finer than pyrite in the refuse. Most of the pyrite in the clean was less than 5 μm in diameter, and, in all but one case, greater than 98 percent of the “clean” pyrite was less than 10 μm.     

Nickel-catalysed gasification of brown coal in a fluidized bed reactor at atmospheric pressure

Pyrolysis and steam gasification of nickel-loaded Yallourn coal were carried out in a fluidized bed reactor at ambient pressure. The pyrolysis mode was influenced by the addition of nickel catalyst. The yield of total volatile matter decreased whereas the gas yield markedly increased, when compared with uncatalysed pyrolysis. This is considered to result from tar decomposing on the catalyst and being converted to gases and deposited carbon. For the catalysed steam gasification, ≈ 80 wt% of coal conversion was achieved at 873 K and the gas yield was twelve times as much as that for the uncatalysed reaction. The homogeneous equilibrium in the gas phase controlled the composition of the product gas. The product gas contained little tarry material and a negligible amount of hydrogen sulphide. Nickel was efficiently recovered from the residue by an ammonia-leaching method.