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。     

流化催化裂化重芳烃试制沥青碳纤维

探索了流化催化裂化 (F CC)重芳烃试制沥青基碳纤维的可行性 ,初步实验表明 ,FCC重芳烃中芳烃含量高 ,相对分子质量分布和环结构较均匀 ,是制备中间相沥青碳纤维的优良原料 ,并能制备出接近中强水平 (抗拉模量在 80～ 10 0 GPa)的中间相沥青碳纤维。降低中间相沥青的杂质含量 ,可大幅度提高沥青碳纤维的力学性能     

中间相沥青中试的研究

中间相沥青是一种各向异性的沥青产品,是制备高性能炭材料必需的原料,本文介绍了中间相沥青的研究现状和中试研发内容及意义.通过以萘为原料,采用催化法,以反应-传质强化技术调整中间相沥青合成过程中的各个阶段,制备出广域流线型体中间相沥青,摸索出中间相沥青的工业化工艺技术,以期在时机成熟时投入工业化生产,满足国家对高端炭材料制...     

中间相沥青调制—热解

文章采用以萘和三氟化硼与氟化氢为原料制备的齐聚物沥青,研究齐聚物沥青在中温条件下通过热缩聚制备出的低软化点,中间相含量高,纺丝性能良好的中间相沥青,探讨齐聚物沥青调制的时间,热缩聚反应的时间以及热缩聚反应的温度对于中间相沥青的影响。     

煤焦油沥青改性乙烯焦油制备中间相沥青的研究

以煤焦油沥青为改性剂改性的乙烯焦油在温度420℃、常压及惰性气体(N_2)保护下进行炭化,制备出广域融并体各向异性中间相沥青。对生成的中间相沥青进行X射线衍射分析、元素和组分分析、偏光显微观察及高温条件下的粘度测定,讨论了改性乙烯焦油的炭化行为。结果表明,由煤焦油沥青改性乙烯焦油制备的中间相沥青(ET-CTP-MP)与没有经过改性的乙烯焦油制备的中间相沥青(ET-MP)相比,有序度高、流变性好、β树脂含量高,是优质的中间相沥青。     

探究煤沥青中间相的研究进展

在炭化的过程中,煤沥青会发生各向异性的中间相,文章主要针对国内外关于煤沥青中间相研究的现状以及相关进展,对煤沥青中间相的形成条件以及形成机理进行研究,对煤沥青中间相转化的动力学和热力学的发展动态进行深层次的阐述,总结出了中间相的表征与分离技术,同时探讨了煤沥青的热条件处理和添加剂对煤沥青中间相结构和形成的影响以及化学组成,并提出了未来的发展方向。     

中间相沥青的调制及其性能研究

以沥青为原料,采用热缩聚法合成了一系列不同各向异性组分含量的中间相沥青(MP)。以不同各向异性组分含量的中间相沥青为原料,采用KOH活化法制备了中间相沥青基活性炭(MP-AC)。使用透反射偏振光显微镜对中间相沥青的显微结构进行静态观察,考察了不同恒温时间中间相沥青的收率和光学显微形态的变化,使用物理吸附仪对MP-AC的比表面积进行了考察。结果表明:反应温度在410℃,恒温6.5 h时可以得到各向异性组分含量约为100%的优质广域型中间相沥青;MP中各向异性组分含量的不同对MP-AC的比表面积影响不大。     

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。     

萘沥青的合成条件与其中间相热转化行为的关系研究

以萘为原料,采用AlCl3催化合成和热转化处理二步法制备了高软化点、低QI含量的优质萘系中间相沥青。通过分析表征不同条件下合成的萘沥青经热转化后所得中间相沥青的性质和中间相织构形态,重点研究了萘沥青的合成条件与其中间相热转化行为间的内在关系,以确定合成萘沥青的最佳工艺参数。结果表明,在合成温度240℃、合成时间6 h、催化剂用量10%的条件下合成的萘沥青在390℃恒温8 h后能得到100%的广域流线型的体中间相沥青,其软化点为244.6℃,QI含量仅为10.32%。     

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。     

Determining the anisotropic content in a petroleum pitch - Comparison of centrifugation and optical microscopy techniques

The anisotropic content of a pitch is one of the most important parameters for characterizing such materials. Polarized light optical microscopy is the technique most commonly employed (ASTM D 4616 standard procedure) to measure this pitch parameter. However, this standard procedure is limited to pitches with mesophase contents only up to 20%. An alternative technique for determining the anisotropic content of a pitch is high-temperature centrifugation, which can be used without limitation for pitches with up to 100% anisotropic content. In this work, the two techniques have been compared; samples of four pitches with mesophase contents lower than 20% have been analyzed by both techniques and the results have been compared. The high-temperature centrifugation technique showed good repeatability, and the results that it yielded matched those obtained from optical microscopy when the anisotropic content of the pitch was higher than around 5%. The centrifugation technique is always faster, simpler, and possibly more accurate than optical microscopy for pitches with mesophase contents higher than 20%.     

Quantitative determination of anisotropic domain size in mesophase pitch

The optical texture of the carbonaceous mesophase is related to the nature of the pitch precursor, the mesophase viscosity and mode of preparation. The anisotropic domain size, represented by the distance between extinction lines, has been a useful parameter for characterizing mesophase pitches. A procedure for quantitative determination of mesophase domain size, utilizing annealing techniques and image analysis, is described and applied to several different mesophase pitch systems.     

A novel method to obtain a petroleum-derived mesophase pitch suitable as carbon fibre precursor

This paper studies a novel method for the preparation of mesophase pitches suitable as carbon fibre precursors. A series of thermally treated petroleum pitches with mesophase contents ranging from 10.8 to 52.2 vol.% was obtained from pitch A-240. Separation of the phases was initially attempted by hot filtration, a suitable method for separating the phases in thermally treated coal-tar pitches. Although filtration failed for the petroleum samples, the behaviour observed led to the development of a new separation method that consists in the sedimentation of the mesophase. This method, after optimisation, yielded pitches with mesophase contents up to 97 vol.%, which were easily spun into carbon fibres of reasonable mechanical properties.     

Rheological characteristics of mesophase pitch

Rheological characteristics of two pretreated petroleum pitches, during their transformation to mesophase, have been studied by using rotalional viscometer. Simultaneously, the formation, growth, coalescence of mesuphase spheres, and the alignment of coalesced mesophase were observed by Hot-Stage-Cinema-Microscope, discussed with the results of viscosity change and the Q.I. content. It is found that both pretreated pitches were Newtonian fluids at low temperature, but behaved pseudoplastics as increase of mesophase content above 390C. Shear thinning behaviour was also apparent in the shear rate range of 1.9–20 sec⁻¹ at temperature above 390C. The apparent viscosity-temperature curves of this pyrolysed pitches were much affected by the pretreatment conditions.     

Modified characteristics of mesophase pitch prepared from coal tar pitch by adding waste polystyrene

The toluene soluble of coal tar pitch was carbonized with waste polystyrene. The properties of mesophase pitches were characterized using polarized light optical microscope, apparent viscometer, FT-IR, ¹H NMR and X-ray diffractometer. After adding the waste polystyrene into the toluene soluble of coal tar pitch, the soluble mesophase were was increased from about 9% to 52% and the mesophase pitches were changed from 74% with coarse mosaic texture to 100% with flow domain texture. The mesophase pitches were transformed from thixotropy to unthixotropy. By waste polystyrene added into the toluene soluble of coal tar pitch, the methylene group was increased a lot. The presence of more alkyl groups modified the characteristics of mesophase pitches and improved the assembly of mesophase pitch molecules.     

Rheological investigation of coal-tar pitch during its transformation to mesophase

Rheological characteristics of two coal-tar pitches, during their transformation to mesophase, have been followed by rotational viscometry. In certain instances samples were also taken, enabling the mesophase microstructure to be correlated with the flow behaviour. Flow curves established that the pitches are Newtonian liquids at low temperatures, but non-Newtonian character appears at temperatures above 380 °C. Scanning the viscosity-temperature curve of a binder pitch showed that the viscosity began to change, as a result of polymerization processes, at about 240 °C. In both pitches the apparent viscosity, at all rates of shear, increased very rapidly at temperatures above 420 °C when the mesophase content was in excess of 25%. Shear-thinning behaviour was apparent and a peak in the apparent viscosity-temperature curves appeared at all the rates of shear investigated. It is suggested that the systems can be regarded as emulsions. Initially an emulsion of mesophase in isotropic liquid exists but this transforms, at higher temperatures, to one of isotropic liquid in mesophase. The maximum in the apparent viscosity appears to correspond to the phase inversion point.     

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。     

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。     

Effects of borane-pyridine complex on the mesophase pitch formation from decant oil

Mesophase pitches were prepared by adding 0.5 to 2 wt.% of a borane-pyridine complex to a decant oil in a tubing bomb reactor and heating in a fluidized-sand bath held at 500 °C for 30, 45, and 60 min, respectively. The mesophase pitches were analyzed using thermal gravimetric analysis, X-ray diffraction and polarized-light microscopy. Growth and coalescence of mesophase spheres were hindered, while the crystallinity of mesophase pitches was increased when the materials were heat treated with the boron compound. The addition of the borane-pyridine complex also accelerated the coke formation.