摘要
本课题是以废聚苯乙烯（WPS）为添加剂，分别与煤焦油沥青和乙烯焦油共炭化制备改性中间相沥青，进而制备针状焦，以达到资源的充分利用。在此基础上研究中间相沥青的改性机理和共熔效应对中间相性能以及后续产品针状焦的影响，为中间相沥青的改性和针状焦的生产打下理论基础。
分别以煤焦油沥青的喹啉可溶物和乙烯焦油与WPS共炭化，以红外（FTIR）、核磁共振（~1HNMR）、X射线衍射（XRD）、热分析（TG/DSC）、扫描电镜（SEM）、高温粘度仪和热膨胀系数（CTE）等现代物理分析作为表征手段，对中间相沥青及针状焦性能进行研究。
在添加聚苯乙烯（WPS）共炭化反应过程中，由于共熔效应，生成的中间相沥青性能得到很大改善。在与煤焦油沥青的共炭化过程中，可溶性中间相的含量从10%提高到52%，光学结构从中间相含量为65%的粗镶嵌结构改善为中间相含量为100%的广域融并体；在与乙烯焦油的共炭化过程中，可溶性中间相的含量从5%提高到46%，中间相的光学结构从中间相含量为32%的未完全融并结构变为广域融并体结构。添加WPS和二者的共炭化反应中，中间相沥青从触变性变为非触变性，芳香平面分子取向排列变好。共炭化过程中发生交联反应，生成了较多的1-亚甲基结构和环烷结构。烷基结构的增多是共熔效应发生的主要原因。
在共炭化过程中，WPS和沥青分子热裂解产生的自由基发生交联反应，生成了较多的环烷结构和1-亚甲基结构。环烷结构一方面起到增大可溶性中间相含量的作用，另外一方面在不破坏芳香层面分子堆积排列的情况下有利于分子间的滑动和运动，起到增加流动性的作用。除环烷外的1-亚甲基结构虽然一定程度上破坏中间相沥青分子的排列，但是能起到增大溶解性和流动性的作用，其作用整体表现为中间相性能的改善。共熔效应发生的原因来自于两个方面，一是分子之间在共炭化过程中发生的烷基交换和氢转移反应；二是分子在共存体系中的互溶作用。在添加WPS共炭化过程中，WPS在起始阶段起到引发分子之间交联和促进中间相生成、长大和融并的作用；在中后期阶段，由于氢转移反应缓解了炭化反应的剧烈程度，使体系长时间保持较低的粘度。
共炭化中间相的改性可以用引入的新溶液理论模型来解释。中间相形成有两个基本的推动力，一是分子量大的分子在小分子溶液中弱的溶解能力促进中间相的形成，二是通过圆盘状分子的定向排列降低其自由能，定向差的小分子进入各向同性相。中间相的性质与中间相分子的缩合程度和烷基结构有关，共炭化过程中，WPS能够在不同的炭化阶段调节体系的分子量分布和结构，引起分子体积的增大和结构的不规则性。根据溶液理论模型分子缩合程度低、烷基结构多能有效降低中间相的化学势，有利于中间相的形成、发展和运动，进而改善中间相性能。
煤焦油沥青和废聚苯乙烯共炭化制备的针状焦，光学结构单元中平行于热膨胀系数方向的轴向分矢量平均长度和矢量平均长度的值，分别从20.8μm增加到28.4μm和23.4μm增加到28.8μm，热膨胀系数从0.8×10~(-6) /℃降低到0.1×10~(-6) /℃。乙烯焦油和废聚苯乙烯共炭化制备的针状焦，光学结构单元中平行于热膨胀系数方向的轴向分矢量平均长度和矢量平均长度的值分别为10.8μm增加到28.4μm和12.6μm增加到28.8μm，热膨胀系数从接近普通石油焦的3.2×10~(-6) /℃降低到优质商品焦的0.3×10~-6) /℃。在上述二者添加WPS共炭化可以制备出热膨胀系数更低、光学各向异性排列更好的针状焦。中间相沥青中烷基结构的增加降低了体系粘度，有利于中间相的融并，同时在固化阶段产生足量的气体，使中间相的芳香平面分子沿轴向排列更为规整。中间相沥青从触变性变为非触变性。中间相沥青中生成了较多的烷基结构。
单独炭化时，炭化行为差别很大的煤焦油沥青和乙烯焦油制备的中间相沥青和针状焦的性能差别很大，但是在添加WPS共炭化后所得到中间相沥青和针状焦的性能都得到较大提高，并且其性能比较接近，说明WPS是一种优异的共炭化改性剂。
The purpose of this research was to manufacture the modified mesophase pitch, as well as needle coke, by co-carbonization of toluene soluble of coal tar pitch (TS) and waste polystyrene (WPS), ethylene tar pitch (ETP) and WPS, respectively. The mechanism of co-carbonization and modification were investigated. The eutectic effect and its influence on the resultant product were also discussed.
The properties of mesophase pitches were characterized using polarized light optical microscope, apparent viscometer, FT-IR, ~1H NMR and X-ray diffractometer. And the characteristics of needle cokes derived from co-carbonization were examined using polarized light optical microscope, FT-IR, X-ray diffractometer, co-efficient of thermal expansion (CTE), scanning electron microscope.
The toluene soluble of coal tar pitch (TS) was co-carbonized with waste polystyrene (WPS). The contents of soluble mesophase were increased from 10% to 52% and the anisotropic contents of mesophase pitches were developed from 65% with coarse mosaic texture to 100% with flow domain texture by TS added with WPS. During the co-carbonization of ethylene tar pitch and waste polystyrene, the content of soluble mesophase was increased from 5% to 56%, the mesophase content was increased from 32% to 100% and the optical texture was developed from incomplete coalescence to flow domain after adding waste polystyrene into ethylene tar pitch. During the co-carbonization of WPS with TS and ETP, the mesophase pitch was changed from thixotropy to unthixotropy, suggesting a better rheological behavior. The increased alkyl groups, which were mainlyαmethylene, improved the molecule assembly of mesophase pitch and resulted in the eutectic effect. The properties of the mesophse pitch were greatly improved due to eutectic effect.
During co-carbonization, crosslinking of radicals derived from WPS and the pitches brought someαmethylene group and naphthenic structure to polymerized aromatic hydrocarbons (PAH). The fluidity and solubility of the mesophase pitches were improved by increasing alkyl groups in the pitch molecule. The naphthenic structure availed the slipping of aromatic planar molecule without destroying the stacking of the crystal. Although the arrangement of the crystal was disturbed a little, the other alkyl groups were able to improve the fluidity and solubility of the mesophase pitch. As a whole these alkyl in the mesophase showed positive effect in mesophase formation. The eutectic effect consisted in two aspects: one was intermolecule hydrogen transfer and alkyl transfer, the other was interaction of intramolecule and intermolecule in the pitch matrix. The former was the inherent reason and the latter was extrinsic one. During the early stage of co-carbonization, WPS availed the crosslink of pitch molecule and the earlier formation of mesophase. In the middle and latter stage, methylene groups improved the coalescence of the mesophase and kept a lower viscosity for a longer time. The rigorous reaction was inhibited during the middle and latter co-carbonization stage due to hydrogen transfer.
The mechanism of modification of the mesophase pitch derived from co-carbonization was able to be interpreted by a newly introduced solutions theory. The formation of mesophase was in response to two primary driving forces: one was poor solubility of high molecular weigh aromatic molecules in the lower molecular weight fractions, promoting liquid/liquid phase separation, the other was lowering of the system free energy by molecular orientation of the large, disc-like molecules and expulsion of some of the smaller, less orientated molecules to a separate (isotropic) phase. The characteristics of mesophase pitch were able to correlate with the degree of condensed structure and alkyl content of the mesophase pitch. The molecule weight distribution and structure were improved by co-carbonization during different stage of carbonization, leading to increasing molecule volume and irregular structure of molecule. Based on the model of solutions theory, the chemical potential of mesophase was depressed by the alkyl structure, availing the development of mesophase.
Co-carbonization properties of toluene soluble of coal tar pitch and waste polystyrene were studied in a tube bomb to correlate the content of alkyl groups in the mesophase pitches with CTE and anisotropic orientation. The more alkyl contents improved the properties of resultant needle coke in terms of optical texture and CTE value. The anisotropic indices of average length of vectors parallel to the CTE axis and average length of anisotropic unit vectors increased from 20.8μm to 28.4μm and 23.4μm to 28.8μm, respectively, and CTE value decreased from 0.8×10~(-6) /℃to 0.1×10~(-6) /℃. Ethylene tar pitch was co-carbonized with waste polystyrene to prepare needle coke. The anisotropic indices (average length of vectors parallel to the CTE axis and average length of anisotropic unit vectors) increased from 10.8μm to 28.4μm and 12.6μm to 28.8μm, respectively. The anisotropic indices of average length of vectors parallel to the CTE axis and average length of anisotropic unit vectors increased from 20.8μm to 28.4μm and 23.4μm to 28.8μm, respectively. The CTE value was decreased from 3.2×10~(-6) /℃to 0.3×10~(-6) /℃and the optical texture of the coke was changed from coarse mosaic of incompleteness coalescence to flow domain with high uniaxial orientation after adding WPS into ETP. Due to the increasing alkyl groups, the lower viscosity of the carbonization system favored the development of flow texture and uniaxial orientation. And the sufficient gas evolution of good timing in co-carbonization forced the uniaxial arrangement of bulk mesophase molecules at the solidification stage.
The enormous difference of carbonization behavior of CTP and ETP, when carbonized singly, was vanished when mesophase pitch and needle coke were manufactured through co-carbonizing. And the characteristics of the mesophase pitch and needle coke were greatly improved, suggesting WPS being an excellent additive of co-carbonization.
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