改性煤沥青热转化中间相结构性质与表征

采用实验室自制石英管式炉,以中温煤焦油沥青（CTP01）、改性沥青（CTP02）进行热缩聚反应。通过红外光谱（FT-IR）、拉曼（Raman）、X射线衍射法（XRD）、热重（TG/DTG）以及偏光显微镜对CTP01和CTP02在热转化过程中生成的中间相沥青进行了表征分析。结果表明：在反应温度430℃、恒温时间7 h制得中间相沥青,CTP02内部具有排列规整、取向性更好的芳香片层分子,热聚合后明显相对分子质量变大,芳环上的取代基明显增强,稠环芳烃含量增加;CTP01制得中间相沥青光学各向异性含量较低,很难形成稳定的区域型结构,主要以中小区域镶嵌型为主,而CTP02制得中间相沥青光学各向异性含量较高,易形成广域型结构。     

原料及缩聚条件对中间相沥青性质的影响

本研究用刮膜蒸发器对制备中间相沥青的原料（软化点为６０℃的石油沥青）进行了分离，并分别以未分离的沥青及分离出的重质沥青为原料在不同的条件下调制成中间相沥青。探讨了原料分子量分布及缩聚过程中温度、Ｎ２流量、缩聚时间对中间相沥青族组成分布、软化点和可纺性等性质的影响。     

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。     

煤直接液化沥青制备中间相沥青炭纤维的研究北大核心

中间相沥青基炭纤维的性能直接取决于纺丝用中间相沥青,煤直接液化沥青因其饱和烃含量高,氢碳比高,高温融变性好,硫含量低等优点成为制备纺丝用中间相沥青的优良前驱体。本文以煤直接液化沥青为原料,研究不同热缩聚工艺对中间相沥青组成和结构的影响,通过考察其偏光织构、软化点、喹啉不溶物含量、黏温曲线和纺丝时长等指标综合评价可纺性。采用高低温结合多段聚合工艺制得具有大融并体结构、可纺性优良的中间相沥青,并进一步制得具有理想微观形貌的纤维,其拉伸强度为2.03 GPa,拉伸模量达到581 GPa。     

原生喹啉不溶物对沥青中间相转化及动力学影响

本文研究了煤焦油沥青中间相转化及动力学,测定了中间相转化动力学参数.结果表明,煤焦油沥青中间相转化属于一级动力学反应,在420～450℃之间其表观活化能在124.54～187.8KJ/mol范围.原生QI降低了中间相转化活化能,促进了中间相的成核,缩短了中间相转化特征时间区间.     

合成中间相沥青

本文综述了用于制备高性能炭纤维的中间相沥青的合成方法，阐明了合成机理并介绍了我们这方面开展的一些工作。     

热缩聚工艺条件对中间相碳微球形成的影响

以中温煤沥青为原料采用常压热缩聚工艺制备中间相炭微球。考究了不同聚合条件对中间相碳微球收率及形态的影响,从而找出制备中间相碳微的最佳工艺中每。     

精制沥青中间相热转化的研究

以2种精制沥青(LSP和HSP)为原料,通过常压热转化反应,研究了热转化过程中产物的QI和TI随反应时间的变化规律.分析表明,随着反应温度的升高和反应时间的延长,沥青的各向异性组分不断增加.其中LSP沥青生成的中间相小球大于HSP沥青生成的中间相小球.400℃恒温9h,LSP沥青的软化点达到242℃,HSP沥青的软化点达到220℃.     

Carbonization behaviour of modified synthetic mesophase pitches

Stabilization of naphthalene-derived synthetic mesophase pitch was achieved by controlled oxidation or reaction with phenanthrenequinone (PHQ) in order to suppress the swelling during high-temperature treatments. The modified pitches were characterized and their carbonization behaviour was studied by thermogravimetry-mass spectrometry. The results show that naphthenic groups are involved in the stabilization process. PHQ reacts via cycloaddition reactions, yielding oxygen-containing non-planar structures, a feature that accounts for the loss of anisotropic properties of the final material.     

In situ ESR measurement of mesophase formation during the heat treatment and cooling processes of pitches

Both heating and cooling processes for mesophase formation from various pitches have been followed by in situ ESR measurements. In addition to signal intensity and linewidth, the saturation phenomenon of the signal intensity with changing microwave power was measured during heat treatment and cooling processes. As a convenient measure of the saturation factor, l/P_max(P_max is the microwave power at which the signal shows maximum intensity) was employed. In general, 1/P_max decreased with an increase in heat-treatment temperature; this change seems to correspond to a decrease in the viscosity of pitch. When pitches were heat treated at 500°C for 2 h, the carbonization reactions and the rearrangement of molecules may occur, which irreversibly changes 1/P_max. Pronounced differences in the behavior of 1/P_max measured during cooling of the heat-treated pitches were found to depend upon pitch optical texture (isotropic, flow and mosaic).     

Carbon-boron-nitrogen alloys from borazarene-derived mesophase pitches

Synthetic routes to new C-B-N-containing mesophase materials from borazarene-type precursors have been explored. Such mesophases have the potential for forming C/BN alloys which could be processed in analogous ways to carbonaceous mesophases, e.g. into cokes, fibres and composites. Carbon-boron-nitrogen-based mesophase pitches have been generated at ambient pressure by pyrolysis of borazarenes in the presence of AlCl₃. The AlCl₃ is essential for mesophase formation in these systems. Pyrolyses of 10-chloro-9-aza-10-boraphenanthrene and 2,2′-bis(dichloroborylamino)biphenyl have both yielded black, optically anisotropic pitches. These precursors form C/BN ceramic alloys which are turbostratic following heat treatment to 1000 °C. The alloys show a clear advantage in terms of their oxidation resistance, compared with that of carbon derived from naphthalene mesophase pitch, despite contamination with AlCl₃, which probably catalyses their oxidation.     

Influence of heat and pressure treatment on the rheological behavior of petroleum pitches

Pitch rheological properties are extremely important during the manufacturing process of carbon materials, in mesophase formation, and with regard to the final properties of the carbon products. In this work, pitch samples have been prepared from three different FCC decant oils by heat-treatment, under 0.9 MPa pressure, in a reactor at 390 °C, 410 °C, and 430 °C. These samples were analyzed in a rotational rheometer using a parallel-plate sensor. The rheometric softening points matched the results obtained using conventional equipment and exponential relationships were found to exist between these softening points and the pitch cosity when the former approached 180 °C. The quinoline-insoluble content (QI) has been shown to be more important in increasing the pitch viscosity than the toluene-insoluble content (TI). Oscillatory rheometry analysis has shown that an elastic response is not always found in creep and recovery tests, even when the elastic modulus G′ is dominant over the viscous modulus G′′. Pitch elasticity was found to be independent of the mesophase, and this pitch property was either only observed when the cross-over point occurred at very high frequencies or did not occur at all within the frequency range studied.     

A two-stage preparation of mesophase pitch from the vacuum residue of FCC decant oil

The preparation of mesophase pitch as a precursor for the high-performance carbon fiber from a vacuum residue of FCC-decant oil (FCC-DOVR) was studied, applying a two-stage heat treatment to improve the pitch yield as well as its liquid crystal properties. The present two-stage preparation consisted of the pressurized heat treatment (1–5 MP) of the first stage at 430–480°C and the successive heat treatment under 13–260 Pa at 430°C. Such a two-stage preparation increased the yield of the spinnable mesophase pitch of 100% domain texture with lower softening point to 45% from 22% by the single-stage one from the same feedstock. Spinning properties of the mesophase pitch were excellent to allow smooth spinning for longer than 15 min and random orientation of mesogen molecules in the tranverse section of the fiber perpendicular to the fiber axis. The chemistry of the two-stage preparation for the higher yield and better properties as the fiber precursor is briefly discussed.     

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。     

Rheostructural studies on a synthetic mesophase pitch during transient shear flow

The steady, shear viscosities of a synthetic mesophase pitch (Mitsubishi AR-HP) obtained from rate-sweep experiments at 0.1-10 s⁻¹ exhibited shear-thinning (region I) and plateau responses (region II), but displayed a hysteresis during the decreasing rate sweep. Transient tests revealed that the shear stress (and consequently the shear viscosity) displayed a local maximum and a minimum before approaching a steady state. Following steady flow at 1 s⁻¹, a reversal of flow direction or a very short interruption in flow did not lead to the maxima or minima in the transient shear stress, but the maxima and the minima reappeared in the transient stress after a rest time of ∼1000 s. An experimental protocol was developed to preserve the rheological samples, and their microstructure was characterized in three orthogonal planes for the initial and final states. The initial microstructure was found to have a weak, but preferred, orientation of mesophase layers in the radial direction of the rheometer cone-plate (due to the initial squeezing flow). The initial microstructure changed to a flow-aligned fibrous structure after shearing in the viscometric flow.