反应温度和压力对制备中间相沥青的影响

以中温煤沥青为原料,于高压反应釜中进行热转化,在不同的反应温度和压力条件下制备中间相沥青。采用偏光显微镜、红外光谱仪、x射线衍射仪等测试仪器对所得中间相沥青进行分析和表征。结果表明,温度对中间相沥青的产率、形貌和结构影响显著,随着温度升高,中间相含量增加;中间相小球体的尺寸增大,逐渐出现融并现象,最终形成流域型体中间相。压力对中间相的含量和结构也有一定影响,实验结果显示施加3MPa压力,有利于中间相的形成和其含量的提高。420℃、3MPa条件下形成的中间相含量高达81．0％,并形成流线域状体中间相。     

热聚合温度对煤液化沥青制备中间相沥青的影响

为制备优质的中间相沥青,以煤液化沥青为原料,在不同热聚合温度下制备中间相沥青,采用偏光显微镜、红外光谱仪、XRD、热分析等测试仪器对所得中间相沥青进行分析和表征。结果表明,温度对中间相沥青的收率、形貌和结构影响显著。随着温度升高,中间相沥青的收率降至86.2%,H含量降至3.96%,S含量有所下降,残炭率增大;中间相小球体的尺寸增大,逐渐出现融并现象,最终形成广域型中间相;煤液化沥青中的稠环芳烃、芳香烃的含量明显增加,烷烃成分则明显减少;煤液化沥青中的无定型区含量减少,分子的排列与取向性变好。选择低的热缩聚温度(410~420℃),适当延长反应时间有利于反应方向的控制,从而达到制备优质中间相的目的。     

两种煤焦油沥青恒温热转化过程研究

通过对两种煤焦油沥青恒温热转化过程的研究,得出了中间相转化的特征时间和动力学参数,试验表明,在中间相产率约１５％之前,主要产生中间相小球体的生成反应,活化能较高,而后期反应活化能较低。     

针状焦制法原理

针状焦是生产UHP电极的重要原料,针状焦的生成机理是沥青经逐渐加温生成不稳定中间相小球体,再经堆积中间相转变为针状焦,工业生产针状焦的原则是选择适应的原料,控制堆积中间相组织结构、调整温度 ,压力,速度,时间,共存物质等。     

影响炭质中间相形成和发展的因素——Ⅱ.添加剂和外加场

在制备炭质中间相的过程中,为了调整中间相形成的速度、获得特种中间相产品或研究中间相的形成机理,研究者们往往向制备中间相的原料中添加某些添加剂,这些添加剂的存在对中间相的形成过程和生成方式产生了影响。另外,在外加场(如力场、磁场、电场)的作用下,中间相分子的取向发展也会受到一定的影响。本文主要讨论添加剂(包括物理添加剂和化学添加剂)存在下中间相形成的特征以及外加场(力场、磁场和电场)对中间相形成和发展的影响,并利用“粒状基本单元构筑”中间相形成理论对这些影响因素的作用机理给予了合理的解释。     

煤沥青中间相热聚合行为研究

以煤沥青为原料,采用程序升温、多管井式坩埚炉进行热转化反应,研究不同结构反应器中中间相的热聚合行为。试验显示:煤沥青中间相的光学结构与均相成核的中间相沥青相似;另一方面,热转化过程中不同结构反应器内样品的中间相生长存在差异。随着反应时间的延长,样品收率、挥发份产率不断降低,而软化点和甲苯不溶物含量则不断升高。对于不同结构的反应器,等径管内热反应样品的收率、挥发份产率比变径管内样品的偏低,甲苯不溶物含量和软化点则偏高;同时光学结构显示,等径管内中间相球体生成、长大、融并到变形的速率比变径管内样品快。分析认为:由于变径管中段直径的改变,对底端样品中的轻组分产生了中段截流作用,致使热聚合反应程度不同。     

中间相沥青的纺丝——中间相沥青的流变性和可纺性

为了调制出适宜于纺丝的中间相沥青,考察中间相沥青的流变行为和可纺性是必不可少的。本工作从几种不同原料热处理而得的中间相沥青的流变行为着手,比较了同种原料中间相沥青的粘度—温度曲线与软化点、中间相含量及中间相沥青可纺性之间的关系。不同原料中间相沥青,由于中间相分子大小和性质的不同,流变行为和可纺性能并不遵循同种原料中间相沥青的规律。这对进一步改进中间相沥青的调制工艺及进一步优化熔融纺丝工艺具有一定的指导意义。     

改性煤沥青中间相的微观结构研究

以对甲基苯甲醛(4-MB)为改性剂,在对甲苯磺酸(PTS)的催化作用下对煤沥青(CTP)进行改性制取沥青中间相。采用偏光显微镜研究改性煤沥青的光学组织结构;采用扫描电镜(SEM)观察改性煤沥青的形貌。结果表明:随对甲基苯甲醛的用量、温度及热处理时间的不同,改性煤沥青可得到超镶嵌(SM)、小域(SD)和广域(D)3种光学组织结构;在一定的工艺条件下,改性煤沥青的光学组织结构显著改善,出现了大量的中间相小球体;改性后煤沥青出现较好的纤维状结构。因此,改性后的煤沥青有望成为优质的沥青中间相。     

中间相的分子结构

本文用乙二胺—锂还原法将由大庆澄清油芳烃馏份经压力下热解所得的中间相(吡啶不溶物)进行加氢还原。用核磁共振氢谱法对中间相还原产物的正己烷可溶组份及甲苯可溶组份的结构进行了解析,从此结果推测了原中间相中各种组份的平均分子结构特征及中间相小球体的形成机理。     

影响炭质中间相形成和发展的因素——Ⅰ.原料和热缩聚条件

炭质中间相是制备炭材料,尤其是高附加值炭材料的优质前驱体。它在高性能炭纤维、超高功率电极用针状焦、锂离子二次电池负极、超高比表面积活性炭及催化剂载体、泡沫炭等领域得到了较好的应用。综述了原料和热缩聚条件对炭质中间相形成和发展的影响,这些影响因素包括原料的种类、热缩聚温度、反应压力和保温时间等。通过讨论指出,由于炭质中间相涉及的原料种类多样,热缩聚制备过程中涉及的反应、物相复杂,因此,在制备特定性能的产品时,应针对产品的特定性能要求来选择原料、设定热缩聚条件,以制得具有最佳结构和性能的产品。     

Mesophase formation in coal liquid solvent fractions

The single greatest influence on the mesophase microstructure is the chemical composition of the organic precursor. The effects of oxygen content and structural parameters of precursors from solvent fractions of coal liquefaction products on the microstructure and pyrolysis yields were determined. The fractions were analysed using the Brown-Ladner method to obtain average molecular structural parameters. It was found that pyrolysis yield increases with increased aromaticity and oxygen content and that mesophase microstructure is determined primarily by the oxygen content of the precursors.     

Biomedical implications of altered product composition in advanced coal liquefaction processes

Chemical and toxicologic characteristics of direct coal liquefaction materials are highly dependent upon the specific process operations by which the coal liquids were produced, including, in particular, those that affect boiling point range and degree of hydrogen incorporation. Recent advances in direct coal liquefaction technology, such as the use of catalytic hydrogenation, reduced liquefaction severity and lowering the upper temperature cut point for the distillation of fuels, have resulted in products with higher hydrogen-to-carbon ratios and lower heteroatom content. These higher-quality fuels tend to be less mutagenic and carcinogenic in laboratory assays than earlier coal liquefaction products. It is likely that application of postproduction hydrotreatment, as well as restriction of upper distillation temperature, for coal-based fuel products could result in materials that exhibit mutagenic or carcinogenic activity which is no greater than that of their petroleum-derived counterparts.     

煤直接液化残渣热解特性研究

介绍了煤直接液化残渣热解特性的基础实验研究,主要为温度对液化残渣干馏产物产率及性质的影响,给出了部分煤直接液化残渣热解特性基础数据,可为液化厂液化残渣的回收利用提供参考。     

Effects of ion-exchanged calcium, barium and magnesium on cross-linking reactions during direct liquefaction of oxidized lignite

In this work the influences of alkaline earth metals on cross-linking reactions (CLRs) during direct liquefaction of lignite were investigated. The oxidized lignite, which has been proved to be appropriate for quantitatively examine the extent of CLR during direct liquefaction, was used as a model coal to study the effects of ion-exchanged calcium, barium and magnesium on CLR during direct liquefaction of the oxidized lignite. The amounts of tetrahydrofuran (THF) insoluble solid products after liquefaction were used to quantitatively evaluate the CLR during liquefaction of the ion-exchanged coal. The results show that the oxidized coal is appropriate to quantitatively examine the extent of CLR and the targeted ions are exchanged to the oxidized coal in the form of highly-dispersed ion. The ion-exchanged Mg^2 + suppresses the CLR during direct liquefaction of coal at both low and high temperature. However, the exchanged Ca^2 + always promotes the CLR at the selected temperatures. While the exchanged Ba^2 + promotes the CLR at low temperature, but suppresses it at high temperature.     

三种不同原料中间相沥青的性质表征

为更深入地理解不同原料制备的中间相沥青的性质差别,从挥发分、饱和度、分子量分布、有序度的角度研究了以萘、煤沥青、精制煤液化沥青（DCLR）为原料的3种中间相沥青,分析手段包括偏光显微镜、元素分析、TGA、红外光谱（FTIR）、MALDI-TOF MS、XRD、拉曼。结果表明：萘系中间相沥青分子量最高且分布窄,挥发分低,饱和基团含量高,分子柔性大,平面性和规整性较差,分子堆砌紧密度较低,有序度较差,因此具有较低的软化点和广域流线型光学组织结构;煤系中间相沥青分子量较高,分布最宽,挥发分高,饱和度低,烷基侧链少,分子刚性和平面性较大,易堆积成紧密结构,因此具有较高的软化点,流动性差,较难形成流线型光学组织结构;DCLR系中间相沥青分子量低且分布窄,挥发分较高,含有一定量的饱和基团,分子具有一定的韧性,分子刚性和规整性较好,有序度高,因此流动性较差,软化点较高。     

煤炭直接液化过程的元素平衡分析

对煤直接液化过程的原料和产物进行了元素平衡研究，并对C，H，N，S，O各元素在产品中的分布进行了分析。对煤直接液化反应的深入解析和过程优化具有一定的指导作用。     

溶剂对依兰煤液化反应特性的影响

不同的溶剂对煤直接液化过程产生不同的影响，其组成和性质决定了反应进行的途径。本文介绍了进行该项研究的试验装置和工艺过程，从试验结果得出了三种不同溶剂即ＨＡＯ，ＤＡＯ和循环溶剂对煤液化产物及各项收率的影响。     

Characteristics of residues from thermal and catalytic coal hydroliquefaction

The properties of residues from thermal or catalytic coal hydroliquefaction experiments were characterised by the ultimate, proximate analyses. The relations between the properties of the residues and the liquefaction reaction conditions, such as temperature, time, catalyst, H-donor solvent and atmosphere were investigated. Variations in H/C ratio and organic volatile matter (OVM) content of the residues with liquefaction conditions and coal conversion were studied. Results show that liquefaction temperature and time are main factors that control the organic properties of the residues. The roles of the Fe-S catalyst and H-donor solvent are to reduce the proportion of condensation products in the residue rather than increase the extent of polymerisation. Consequently, coal liquefaction conversion is improved by 100% by the catalyst, but H/C ratio and OVM content of the residues are not significantly decreased.