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。     

煤沥青基中间相沥青的制备研究

以纯化的煤焦油沥青为原料,考察了热聚合温度和恒温时间对中间相沥青的收率、光学显微形态、软化点和族组成的影响.结果表明:反应温度在420℃,恒温5 h时得到了软化点为312℃的流线体型中间相沥青,其收率为79.1%;热聚合反应在相对较低的温度400℃,反应时间为10 h时形成了软化点为305℃、收率为81.4%的优质广域型可纺性中间相沥青.对该原料煤沥青而言,通过控制热聚合反应温度和恒温时间可以达到制备优质中间相的目的.     

2种煤沥青的中间相热聚合行为研究

以中温煤沥青(MTCP)和改质煤沥青(MCP)为原料，采用热聚合反应方法，在相同的反应时间下，研究不同反应温度下2种煤沥青的中间相热聚合行为。采用软化点仪、偏光显微镜、X射线粉末衍射仪(XRD)以及激光共焦拉曼光谱仪(Raman)对中间相沥青表征和分析。结果表明，2种煤沥青在相同工艺条件下呈现出相似的中间相聚合行为。偏光显微镜照片说明2种煤沥青聚合所得到的中间相类型均为镶嵌结构。XRD与Raman分析表明随着聚合温度的升高，中间相沥青内部芳香片层分子的取向性更好，排列更为规整。MTCP经过430℃、8 h聚合，可制备软化点为319℃的中间相含量高于80%的中间相沥青；MCP经过420℃、8 h聚合，可制备软化点316℃,中间相含量高于80%的中间相沥青。     

煤焦油基沥青的热缩合聚合反应研究

本文以改质沥青为原料,采用直接热缩合聚合和催化热缩合聚合反应的方法,在高压反应釜中,氮气气氛保护进行热缩合聚合反应,合成出沥青中间相。考查了不同热缩合温度和不同恒温时间对合成煤沥青中间相的影响,用软化点测定仪对煤沥青的软化点进行了测定,并利用偏光显微镜对中间相的光学结构进行了观察。研究结果表明:采用直接热缩合聚合反应,在热缩合温度400℃下,恒温时间为5h,得到软化点为250℃的光学各向异性含量较高的优质中间相。催化热缩合可以降低煤沥青热缩合聚合反应的温度,控制反应温度为330℃,反应时间7h时,得到软化点263℃的光学各向异性含量较高的优质中间相。     

热缩聚条件对均四甲苯基中间相沥青形态和性能的影响

主要研究了热缩聚工艺参数──温度和停留时间对均四甲苯亚甲基齐聚物衍生中间相沥青形态和性能的影响,结果发现：随着温度的升高、齐聚物的热反应性增强,所得中间相沥青的光学各向异性会逐渐提高,软化点升高,收率降低;停留时间的延长利于中间相的生成和融并。该齐聚物在较低的温度（360℃）下停留17h就可完全转化为光学各向异性发达（100％）,软化点低（260℃）,溶解性能好（PS％＝48．5％）,H／C（0．86）高且可纺性优异的中间相体。     

催化剂用量对均四甲苯亚甲基齐聚物的组成结构及其衍生中间相沥青性能的影响

以均四甲苯为原料，通过三聚甲醛／对甲基苯磺酸交联合成以亚甲基桥连接的芳烃齐聚物，进一步热处理制取优质可纺性中间相沥青。详细考察了催化剂对甲基苯磺酸用量对均四甲苯亚甲基齐聚物的组成结构及其衍生中间相沥青性能的影响，结果表明：催化剂用量的增加使均四甲苯亚甲基齐聚物收率提高，软化点上升，平均聚合度提高，体系的副反应减少，易于得到光学各向异性发达的软化点较低的可纺性中间相沥青。     

催化剂用量对均四甲苯亚甲基齐聚物的组成结构及其衍生中间相沥青性能的

以均四甲苯为原料，通过三聚甲醛／对甲基苯磺酸交联合成以亚甲基桥连接的芳烃齐聚物，进一步热处理制取优质可纺性中间相沥青，详细考察了催化剂对甲基苯磺酸用量对均四甲苯亚甲基齐聚物的组成结构及其衍生中间相沥青性能的影响，结果表明：催化剂用量的增加使均四甲苯亚甲基齐聚物收率提高，软化点上升，平均聚合度提高，体系的副反应减少，易于得到光学各向异性发达的软化点较低的可纺性中间相沥青。     

采用加压-真空两段热缩聚法制备中间相沥青炭纤维的原料

以深度裂解石油渣油为原料，采用两段热缩聚法可制得软化点为268℃，可编性良好的中间相沥青。本文详细考察了温度，时间对中间相沥青软化点，可编性，中间相沥青形态及碳化收率的影响，并初步探讨了两段热缩聚反应的机理。研究结果表明反应温度，时间对中间相沥青的结构和性能影响较大，选择适宜石油渣油，采用加压－真空两段热缩聚法，调整反应条件，可制得可纺性良好的中间相沥青。     

煤基沥青中间相研究现状

论述了煤沥青中间相的三种形成机理及其缺陷,阐述了煤沥青转化过程的化学反应和中间相的形成条件,探讨了煤沥青组分中QI、B树脂,反应温度和热聚合时间,反应压力,反应气氛,改性添加剂对中间相形成和结构的影响。     

煤系中间相沥青的制备与分离研究

以精制煤焦油沥青为原料,采用常压热聚合法进行中间相转化。根据产物中中间相沥青与母体沥青之间的密度差,将中间相沥青分离出来。系统考察了热聚合温度和恒温停留时间对中间相沥青的收率、软化点、族组成和光学显微形态的影响,采用FT-IR分析技术分析了中间相沥青的官能团结构。实验结果表明:聚合温度430℃,聚合时间4 h,中间相沥青的软化点为316℃,w(QI)为74.62%,w(TI)为73.81%,收率为12.5%。     

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℃.     

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。     

Mesophase pitches for 3D-carbon fibre preform densification: rheology and processability

Synthetic mesophase pitches, produced from naphthalene (ARA24, ARA24r), were examined in terms of fluidity and thermal stability in comparison with other mesophase, isotropic pitches, or mesophase pitch/softening molecules blends. Their interest for carbon/carbon (C/C) composites processing by liquid impregnation or vacuum transfer inside three-dimensional carbon preform is discussed. Viscosity versus reduced temperature plots is reported on the same graph to compare the studied pitches and to define a suitable C/C processing window. Methylnaphthalene-based pitch is a good candidate with viscosity and stability adapted to the processing temperature and high carbon yield.     

Preparation of mesophase-pitch-based carbon foams at low pressures

A simple method for preparing the mesophase-pitch-based carbon foams at low pressures through prolonging the soaking time in the preparation process of the mesophase pitch was disclosed. The physical properties, morphologies and the crystal structure of the as-obtained foams were investigated. Bulk density of the resultant carbon foams cover a range 0.514-0.624 g/cm³, under the preparation pressure range 0.5-2 MPa. The SEM micrographs revealed that the thermal shrinkage of the graphitized foams derived from the higher softening point mesophase pitch was less than that of the foam from the lower softening point; Optical micrographs showed that higher softening point mesophase pitch derived carbon foams exhibited better orientation and less microcracks in both junctions and ligaments; The XRD results revealed that higher softening point pitch derived graphitized foams exhibited smaller interlayer spacing and larger crystallite size. The properties of the carbon foam can be severely affected by the properties of the precursor, so it is critical to tailor the properties of the pitch precursor so as to obtain high performance and low cost products.     

Structure and carbonization properties of pitches produced catalytically from aromatic hydrocarbons with

Carbonization properties of pitches synthesized from some aromatic hydrocarbons by the aid of were studied under atmospheric 1.1 and 3.1 MPa pressures. The highest coke yields obtained under atmospheric pressure and 3.1 MPa were 64% and 85%, respectively, both of which were observed with anthracene pitch. Pyrene pitch exhibited a low coke yield of 37% under atmospheric pressure, but as high as 85% under 3.1 MPa.The pitches were revealed with ¹H-NMR and FD-MS to consist essentially of oligomers of starting aromatic rings such as dimers, trimers, and tetramers. The oligomers carried significant amounts of naphthenic hydrogens, which provide their low softening point and enable the development of an anisotropic flow texture when the pitch was carbonized. The carbonization scheme is discussed in relation to the coke yield.     

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.     

Rheological characteristics of coal tar and petroleum pitches with and without additives

An extensive study of rheological characteristics of coal tar and petroleum pitches with and without additives, namely, petroleum coke, natural graphite and carbon black has been made. It is found that all pitches, pure or mixed with a carbon additive are not Newtonian as reported in the literature, but behave Theologically as Bingham plastics with certain yield stress and plastic viscosity at all temperatures of measurement between 85–180°C. The yield stress and plastic viscosity both decrease with increase in temperature of the pitch. A pure petroleum pitch having the same softening point as that of a coal tar pitch is found to have a lower viscosity compared to that of the latter at all temperatures of measurement. This suggests that the criterion of softening point as a measure of suitability of a coal tar pitch binder in the manufacture of artificial carbon is not sufficient for petroleum pitches. Addition of ten parts of carbon black by weight of pitch results in a considerable decrease in viscosity change with temperature of the coal tar pitch compared to almost insignificant change in the case of the petroleum pitch of the same softening point. However, the addition of petroleum coke or natural graphite makes the pitch more viscous but does not change the temperature dependence of viscosity of either of the two types of pitches. The implications are discussed.     

催化裂化油浆组成分布对中间相沥青光学织构的影响

以SLO-LH、SLO-SH和SLO-YN催化裂化油浆为原料,利用热缩聚法制备中间相沥青,系统分析了油浆的烃组成分布、沸点分布以及核磁结构特征,关联了中间相沥青光学织构与原料性质组成关系。结果表明,SLO-SH和SLO-YN油浆中的分子量和组成分布较窄,在给定反应条件(430℃、0.7 MPa)下制备中间相沥青的光学织构指数(OTI)值分别为45和50,中间相织构主要由大面积的域及流域组成,镶嵌结构较少。相对于SLO-SH与SLO-YN,SLO-LH样品的烃组成与沸点分布明显疏散,得到的中间相主要由镶嵌组织与小域构成。结果表明集中分布且芳烃含量高有利于得到高收率与高OTI值的优质中间相沥青,对油浆组分进行分离是制备高品质中间相沥青和针状焦的必要途径。     

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.