停留时间对褐煤半焦孔隙特征及水分复吸的影响

利用螺旋热解装置在不同热解停留时间下制备半焦产品,研究了停留时间等对半焦孔隙结构和水分复吸的影响;结果表明,随着热解停留时间的增加,褐煤热解半焦比表面积和孔体积增大,平均孔径减小;饱和含水质量分数随着半焦比表面积的增大而增大,且维持在8.9%～12.5%。     

大同煤不同显微组分富集物焦与CO2反应性研究

用热重分析仪考察了大同煤惰质组和镜质组富集物焦与 CO2 的气化反应活性 .发现在 95℃～ 1 1 0 0℃范围内 ,大同煤不同显微组分富集物焦与 CO2 的气化反应活性次序为惰质组 >镜质组 ,特别是当气化温度在 1 0 5 0℃～ 1 1 0 0℃时 ,二者之间差异更显著 .分析认为 ,单纯从活化能不能正确描述煤岩显微组分富集物的气化行为 ,必须考虑热解和气化过程中孔结构及比表面的变化 ;不同显微组分富集物焦与 CO2 的反应性和煤的黏结性有关     

煤岩显微组分分离富集物热化学反应特性

依据煤中不同类型有机质性质差异对其进行分离，进而分质利用是实现煤炭清洁高效利用的有效手段。论文利用重选法将一种低变质烟煤分质得到镜质组较原煤48.25%增加至76.02%的富镜样，惰质组较原煤43.96%增加至63.98%的富惰样，以及矿物质含量高于61.99%的富矿样。利用热重-质谱分析仪，考察了分离富集物的热解反应特性及气体逸出规律，及其燃烧和气化反应特性。结果表明，分离所得富镜样热解反应失重量及热解过程中逸出的小分子挥发分的量及组成与富惰样和富矿样均有明显差异，表明分质实现了煤中不同类型官能团的分离富集。而由分离所得富镜样、富惰样和原煤热解失重峰温基本一致则表明分质所得煤的主体官能团结构仍较为接近，但含量有明显差距。富镜、富惰与原煤的燃烧曲线整体趋势较为类似，燃烧活性差别不大。以气化反应峰值温度高低判断，富镜样气化反应活性最低，富惰样与原煤气化反应活性较为接近，富矿样气化反应活性最高。将原煤在对应热反应时的理论反应曲线与实验曲线进行对比，发现煤分质过程及煤中镜质组、惰质组和矿物质的分离与否对热解过程挥发分的逸出影响较小，但导致了其燃烧和气化反应活性有所降低。     

年青煤热解半焦比电阻的研究

本文较系统地研究了影响年青煤热解半焦比电阻的因素和比电阻的变化规律。主要考查了半焦的常温粉末比电阻、煅烧比电阻和高温比电阻。结果表明:半焦的常温粉末比电阻主要受热解温度所控制,随热解温度的提高呈阶段性下降,热解温度在600～700℃范围内,半焦常温粉末比电阻的下降速度较快。半焦高温煅烧比电阻与原煤性质有关,与半焦的热解温度关系不明显。直接测定的半焦比电阻随测量温度的提高亦呈阶段性下降。半焦的高温比电阻和高温煅烧比电阻均是半焦在高温下内部炭结构变化的函数,二者都可以作为考查半焦在高温下比电阻特性的指标。     

山西地区1/3焦煤显微组分的热解特性研究

利用密度梯度离心法对山西3种1/3焦煤显微组分进行分离富集,同时研究其各显微组分热解特征。结果表明：随着热解温度的升高,显微组分在350～600℃均出现明显的失重现象。热重（TG）和微商热重（DTG）曲线表明,惰质组与镜质组相比,有较高的剧烈热解开始温度、最大热解速率峰温和最大热解速率,原煤的热解参数介于镜质组与惰质组之间。热解过程中镜质组的质量损失最大,其次是原煤,惰质组的质量损失最小。     

热解温度和脱灰处理对褐煤半焦孔结构的影响及分形分析

采用低温氮气吸附法分析了胜利褐煤在低温(350℃~600℃)热解过程中孔结构的变化,研究了热解温度及脱灰处理对半焦的平均孔径、比表面积和孔径分布等孔结构参数的影响,并利用FHH(Frenkel-Halsey-Hill)模型,分别在相对压力为0~0.50和0.50~0.95内计算了不同的分形维数D_1和D_2,用以表征煤样的分形特征.结果表明:在热解过程中,半焦的比表面积与孔容积具有相同的变化趋势,与平均孔径呈相反的变化趋势;当热解温度高于500℃时,脱灰褐煤转化为半焦的过程中孔结构变得更为发达,比表面积和微孔孔容明显增大,孔径区间在0.45nm~1.58nm及2.65nm~10.00nm内的孔数量明显增加;FHH模型分析表明,半焦内存在两种变化趋势相反的分形维数D_1和D_2.D_1可以描述450℃之前脱灰褐煤半焦微孔表面的粗糙程度,D2可以反映出整个热解过程中脱灰褐煤的中孔孔容粗糙程度.     

半焦催化裂解煤焦油试验研究

为了提高褐煤热解制得半焦对焦油的催化裂解效果,采用煤热解制备的半焦催化裂解煤热解过程中产生的煤焦油。采用两段式固定床反应器,在反应器上段放置煤样热解,下段放置半焦催化剂催化裂解上段产生的焦油。研究了制焦温度、半焦用量、经O_2活化后半焦对焦油催化裂解效果的影响。结果表明,增加褐煤的制焦温度,焦油产率明显下降,褐煤900℃制备的活化半焦1 g时的焦油产率仅6.3%,提高半焦制焦温度有利于焦油中的大分子芳香类物质催化裂解成少环物质和小分子气体组分;增加半焦用量对焦油脱除效果作用不明显,焦油产率缓慢减少。与未活化半焦相比,O_2活化后的半焦对焦油的脱除效果更好。半焦的比表面积及孔隙分析(BET)表明,活化后半焦的比表面积更大,且孔隙更丰富;能谱分析(EDS)发现,活化后半焦表面金属元素总量高于未活化半焦。     

煤热解半焦特性及其钝化工艺初步设想

由于热解半焦在生产、储运及应用过程中,存在自燃等安全隐患,从热解半焦的自燃机理出发,分析了热解半焦的组成特性、官能团种类、比表面积以及孔道特性对其自燃倾向性的影响,提出将热解半焦冷却、钝化和余热回收高度集成耦合的新型半焦钝化工艺,即利用N2惰性气体作为冷却介质,回收利用高温半焦携带显热;通过水蒸气与半焦活性基团反应,适当减少含氧官能团数量;通过钝化剂前驱体Ca(OH)2和CO2在半焦颗粒表面的分步反应包覆,适当减少活性焦比表面积;通过适当增加半焦含水量,有效防止半焦存放时水分复吸,从而实现半焦钝化和余热回收的双重目的。     

碱熔融法对褐煤半焦脱灰的研究

半焦是煤在较低温度(低于700℃)下热解的产物,具有相对发达的孔结构,有一定的吸附性能力,但未经改性半焦的吸附能力不及普通活性炭,且灰分含量较高,需要对其进行脱灰处理以提高其性能。本文选用白音华褐煤,在500℃制备半焦,利用碱熔融法对半焦进行脱灰实验。其中着重考察了粒度、碱焦比、反应温度、反应时间以及酸浸条件对脱灰的影响。     

煤拔头中低温快速热解烟煤半焦的孔隙结构

利用喷动载流床模拟煤拔头工艺,在550, 650, 750和850℃热解温度下对大同烟煤进行热解得到拔头半焦. 采用氮吸附法对该烟煤及其半焦的孔隙结构进行了研究. 结果表明,拔头半焦的孔隙发达度都弱于原煤;由低到高4个热解温度下挥发分析出率(Y)依次为7.89%, 21.79%, 22.12%, 39.33%,中孔尺寸随Y增加而减小,微孔和大孔尺寸及总孔体积和总孔比表面积基本随Y增加而增加;550℃时挥发分的析出对孔隙结构的发展无明显有利影响. 从原煤到半焦(热解温度由低到高),样品满足BET吸附等温式的相对压力范围依次为0.101~0.351, 0.093~0.201, 0.072~0.152, 0.032~0.053, 0.058~0.108,BET比表面积与NLDFT总孔比表面积变化趋势一致.     

Pyrolysis behavior of vitrinite and inertinite from Chinese Pingshuo coal by TG-MS and in a fixed bed reactor

The pyrolysis behaviors of vitrinite and inertinite from Chinese Pingshuo coal were investigated by using the thermogravimetry coupled with mass spectrometry (TG-MS) and in a fixed bed reactor, respectively. The results showed that inertinite has lower pyrolysis reactivity, lower tar and gas yields, but higher water yield than vitrinite. At 650 °C, the tar and gas yield of vitrinite is 22.4% and 14.4%, respectively, obviously higher than 13.4% and 10.2% of inertinite. The TG-MS analysis also showed much difference of vitrinite and inertinite in gas evolution profile. The ultimate and XRD analyses of chars indicated that the difference in element composition of vitrinite char and inertinite char decreases with the increase of temperature, and have similar element composition and structure characteristic at 650 °C. The total sulfur removal of both vitrinite and inertinite increases with the pyrolysis temperature, and reaches to 60% at 650 °C, but the organic sulfur in inertinite seems more stable than that in vitrinite.     

淖毛湖煤慢速热解过程官能团相互作用

采用滴管炉,在短停留时间下,制备具有一定低温反应活性而消除主要低温交联位点的淖毛湖煤（NMHcoal）快速热解半焦（NRPchar）,再将NMHcoal和NRPchar混合进行慢速热解,研究官能团间的相互作用。热重分析结果表明,NMHcoal/NRPchar混合比为5∶5,温度为500℃热解时具有较强的负协同作用。固定床热解结果表明,NMHcoal热解生成的挥发物部分扩散至NRPchar中,?CH₃与芳碳自由基以及?O有更多的结合概率与时间,使焦油中含甲基的萘、酚类增多,半焦中烷基化邻氧芳碳结构与醚类结构增加。析出的酚类增多,使半焦中连氧芳碳结构减少。NRPchar中生成较多的多环芳烃前体,它们与酚类物质发生反应生成多环芳烃和CO,使共热解焦油中5、6环化合物含量增加,而另一部分滞留在半焦中使其比表面积降低。     

The estimation of char reactivity from coal reflectogram

Measurements of the intrinsic reactivity of chars to oxygen are increasingly being sought as an indicator of the combustion potential of fuels. The coal reflectogram has been used to characterize the chemical properties of coal and its resultant char structure. In this study, six Australian coals varying in rank were separated using density separation technique to obtain vitrinite and inertinite rich fractions. Chars were obtained from these density fraction samples in a Drop Tube Furnace (DTF) at 1673 K. The reactivity of the chars was measured non-isothermally in a Thermal Gravimetric Analysis (TGA) in the temperature range of 573–1073 K. The results suggested that with the increase in the coal rank, the maximum reactivity of chars derived from vitrinite rich fractions decreases, while the reactivity of chars derived from inertinite rich fractions decreases with the increase in the inertinite content in samples and has no obvious relationship with rank. The kinetic parameters were derived using data from non-isothermal TGA after accounting for changing in surface area with conversion. The frequency factor is found to decrease with increasing coal FMR, defined as the summation of each reflectance value multiplied by its frequency, for a constant activation energy (E=146 kJ/mol). This suggests that the behavior of a maceral is characterized primarily by its reflectance distribution instead of the type of its parent coal.     

The CO2-gasification and kinetics of Shenmu maceral chars with and without catalyst

The CO₂ gasification of maceral chars was performed using CAHN TG-151 pressurized thermobalance under different conditions. The effect of mineral in macerals and catalyst on the gasification reactivity of maceral chars and the gasification kinetics were systematically investigated. The results showed that the apparent gasification rate of maceral chars depends on the temperature, pressure, BET surface area of chars and the gasification extent. With increasing temperature and pressure, the gasification rate of maceral chars all increase. After demineralization, the gasification reactivity of maceral chars all decrease. The gasification reactivity of maceral chars greatly increases with loading catalyst. And the loading method of catalyst has great effect on the gasification reactivity. The maceral chars loaded with catalyst by ultrasonic treatment have higher gasification reactivity than that by impregnation. The comparison of gasification reactivity of maceral charas demineralized maceral chars and maceral chars with and without catalyst showed that vitrinite chars always have higher gasification reactivity than inertinite chars. The kinetic results by distributed activation energy model showed that inertinite char has higher activation energy than vitrinite char, and the addition of catalyst greatly minimizes the activation energy and enhances the gasification rate.     

Hydrogen production from CO2 reforming of methane over high pressure H2O2 modified different semi-cokes

H₂O₂ was used under different temperatures and pressures to activate three kinds of different semi-cokes. FTIR, BET, SEM and Boehm titration were used to analyze properties of the semi-cokes surfaces, finding that catalytic activities of these semi-cokes after modification by high temperature and high pressure H₂O₂ were improved. FTIR shows that the characteristic infrared absorption peak of functional groups on the semi-cokes surface does not change, but the absorption peak intensity of some functional groups is increased. The strength of OH absorption peak of Hongce lignite (HCL) semi-coke at 3444 cm⁻¹, carboxyl CO at 1598 cm⁻¹, aliphatic ether, cyclic ether and other organic functional groups at 1023 cm⁻¹ in the modified Shenmu bituminous(SMB) semi-coke and Jincheng anthracite (JCA) semi-coke are increased significantly. BET finds that the specific surface area and pore volume of three semi-cokes are increased after modification. Boehm titration shows that the basic functional group content in semi-coke is increased after modification, and the net alkali content is increased significantly. Compared with the raw semi-coke, SEM shows that the surface of semi-coke modified with H₂O₂ becomes rough. Modified JCA semi-coke surface pitted with holes, modified HCL and SMB semi-coke surface present porous.     

温度和催化剂对木屑炭二氧化碳气化的影响（英文）

通过热重分析仪和管式反应炉研究了温度和催化剂对木屑炭二氧化碳气化的影响。结果表明,提高反应温度有利于加快气化反应速率,增加CO产率及产气热值,同时有助于降低CO2及固体剩余物的含量,温度从850℃升至1 000℃,燃气中CO含量从28.86%增加到54.45%,热值从4.50 MJ/m3增加到7.95 MJ/m3,而CO2含量从64.34%减少到36.54%;2 g木屑炭气化后,固体产物从1.32 g减少到0.79 g。研究发现,催化剂CaCO3和K2CO3对木屑炭二氧化碳气化有促进作用,其作用效果与升温相同,K2CO3对气化反应的促进作用明显强于CaCO3。利用混合反应模型对添加催化剂前后的木屑炭二氧化碳气化动力学进行了研究,发现该模型适用于木屑炭二氧化碳气化反应,而且催化剂的添加有利于降低反应活化能和指前因子,木屑炭、添加CaCO3的木屑炭和添加K2CO3的木屑炭的活化能分别是94.509、81.740和50.271 kJ/mol;指前因子分别是1 208.428、428.825和19.965 min-1。     

陕北低阶烟煤显微组分结构特征及分子结构模型

为了更好地利用我国丰富的低阶煤资源,以变质程度较低的陕北低阶烟煤镜质组、惰质组富集物作为研究对象,采用常规的煤质分析、傅立叶变换红外光谱、高分辨固体13C核磁共振、X射线衍射等分析表征手段,对样品结构进行全面分析,得到了陕北低阶烟煤显微组分分子结构特征及结构参数,建立了镜质组和惰质组的部分分子结构模型。结果表明,陕北低阶烟煤镜质组和惰质组氧含量均较高,硫含量很低,所选镜质组的芳碳率为0.634,平均缩合环数约为2.98个;惰质组的芳碳率为0.734,平均缩合环数约为3.15个;相对于镜质组,惰质组的缩合程度更高,芳核尺寸更大,排列也更加规则有序。今后低阶烟煤加工转化工艺的研究应从分子层面揭示其不同显微组分结构特征的差异性,为低阶烟煤清洁高效利用新工艺的开发奠定基础。     

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。     

Study on the structure and pyrolysis characteristics of Chinese western coals

The structure and pyrolysis characteristics of three inertinite-rich Chinese western coals were researched and compared with one relative vitrinite-rich Chinese middle coal by means of XRD, TG-DTG and fixed-bed reactor. The results show that the atomic ratio O/C, aromaticity factor, even ring condensation number and ring condensation index increase and atomic ratio H/C decreases with increasing inertinite content in coal; inertinite contains more aromatic ring structure than that of vitrinite; the crystallite structure order of coal char increases slightly with increasing heat treatment temperature. The higher inertinite content in coal is, the lower pyrolysis reactivity of coal is at lower temperature, and yet they have obvious second pyrolysis reactivity in higher temperature. The pyrolysis reaction in primarily devolatilisation phase that comes mainly from the decomposition of containing hydrogen function groups and the secondary devolatilisation at high temperature is mainly the decomposition of stable containing oxygen function groups in coal matrix with higher inertinite.     

高温干燥对褐煤孔隙结构及水分复吸的影响

利用卧式固定床实验炉制得不同温度下干燥处理的煤样,采用低温氮吸附法测试煤样的比表面积、孔体积和孔径分布等孔隙特征参数,使用复吸实验装置测定不同干燥程度褐煤煤样的平衡含水量,探索了高温干燥处理后褐煤孔隙结构的演变与其复吸特性之间的关联规律。结果表明：褐煤原煤及不同干燥温度(600~800℃)下半焦的等温吸附曲线均属于第Ⅱ类吸附等温线,褐煤原煤、600℃和700℃干燥半焦的吸附回线均属于L1型,800℃干燥半焦的吸附回线有从L1型转变为L2型的趋势;随着干燥温度的增加,干燥半焦的比表面积先增大后减小,介孔峰值的孔径微分同样先增大后减小,而大孔孔径微分基本保持不变;分形维数D₁和D₂呈相反的变化趋势,且D₂>D₁;不同干燥程度半焦的复吸曲线变化趋势相同,且平衡含水量随着干燥温度的升高而减小;半焦复吸特性与孔隙结构有关,平衡含水率与其孔容积之间呈较好的线性关系。