高性能炭材料生产用煤沥青的研究

研究了软化点在评价煤沥青聚合程度中的作用；描述了热聚合改质过程中煤沥青热解缩聚行为，分析了中温煤沥青热聚合改质过程中各种沥青组分随热聚合温度和热聚合时间的转变规律，探讨了QI组分影响煤沥青热聚合改质的机理，认为原料煤沥青所含原生QI炭微粒促进了热聚合改质过程中煤沥青芳烃分子的聚合；描述了煤沥青的流变性能及其在炭材料实际生产中的意义，研究了中温沥青和改质沥青高温流变性能的差异，探讨了硬脂酸和油酸对煤沥青的改性作用；分析了煤沥青的热解缩聚特征，研究了升温速率对煤沥青热解缩聚的影响。     

反应温度对苯甲醛齐聚物及其中间相沥青性能的影响

以中温煤沥青为原料,通过苯甲醛/对甲苯磺酸交联合成出以次甲基相连接的齐聚物,进一步热解制备了中间相沥青,考察了反应温度对齐聚物及其中间相沥青性能的影响。结果表明,随着反应温度的提高,改性煤沥青的收率、软化点、残炭率和密度都呈现上升的趋势;反应温度适当,易于得到光学各向异性发达、软化点较低的优质中间相沥青。     

多聚磷酸改性基质沥青温度对SBS改性沥青性能的影响研究

在不同温度条件下,用多聚磷酸改性基质沥青,研究了SBS改性沥青的各项性能变化趋势;探讨了多聚磷酸改性基质沥青的合理温度。结果表明,随多聚磷酸改性基质沥青温度的提高,改性沥青的软化点、5℃延度均降低,135℃运动粘度有所升高;离析软化点差减小;其他指标如针入度、车辙因子、针入度指数、针入度比等技术指标呈不规律变化。     

调制煤沥青对复合改性乳化沥青性能的影响

为提高复合改性乳化沥青的使用性能,采用加入调制煤沥青的方式和用SBS改性制备复合改性乳化沥青。结果表明,随着调制煤沥青添加量的增加,复合改性乳化沥青的延度和软化点得到改善。当添加20%调制煤沥青后,延度提高至30cm,软化点升到70℃,复合改性乳化沥青已具有良好的高低温性能。荧光显微图像和红外光谱分析表明,在改性过程中SBS与沥青材料之间除物理改性外,还发生了某种化学接枝反应形成网络构架,从而提高了SBS与沥青材料的结合强度,使得沥青体系更加稳定。     

炭素材料用煤沥青流变性能表征指标的研究

用美国产的BROOKFIELD转子流变仪测定了5种铝工业常用的不同种类的煤沥青在不同温度下的粘度值,并进行了回归计算,结果表明,沥青的表观粘度对温度具有良好的指数方程规律。分析了回归方程的两个系数α和β的物理意义,认为α是沥青在软化点时的粘度,称为软化粘度,受喹啉不溶物含量的影响;β可以用来表示粘度随温度变化的速率,称为温度敏感指数,并给出了粘度变化速率的计算公式。软化粘度和温度敏感指数是依据沥青种类不同而固有的常数,可以用来表征沥青流变性的指标,用于评价沥青流变性能。利用这些指标,可以通过较为简单的测试数据得到沥青的粘度-温度方程,为炭素工业提供一套有实用价值的沥青流变性指标的表征方法。     

层剥离高岭土改性煤沥青的结构与热稳定性

在超声波作用下,以二甲基亚砜(DMSO)插层处理高岭土,通过熔融复合法改性煤沥青。采用XRD、FTIR、SEM、TEM、TG、DSC表征测试了插层高岭土的层间距、层间相互作用、层分散形态,以及改性煤沥青的热稳定性。结果表明,DMSO削弱了层间铝羟基与硅氧键间的氢键作用,插层高岭土的层间距由0.716 nm增加至1.124nm,插层率达到98.57%;熔融复合后,高岭土发生层剥离,(001)衍射峰消失,以薄片形态分散于煤沥青中。薄片形态的高岭土通过延缓空气传输速率的方式改善了煤沥青的热稳定性,当插层高岭土掺杂质量分数为6%时,插层高岭土改性煤沥青的最大失重速率所对应温度为650℃,对应的失重为78.04%,而最大失重速率处原煤沥青失重85.41%。原煤沥青失重50%时的温度为490℃,而改性煤沥青达到550℃。未掺杂高岭土时,煤沥青软化点为42.3℃,改性煤沥青软化点增加到45.4℃,继续增加高岭土质量分数,软化点上升幅度减小。     

硅油改性沥青的制备与性能研究

使用硅油接枝法改性AH-70号石油沥青,通过沥青的135℃黏度、离析实验以及针入度、软化点和延度来研究硅油接枝后对沥青的性能影响。结果表明:使用乙烯基硅油改性沥青的综合性能最佳,在改性温度为120℃和硅油平均分子量为104时,得到改性沥青的软化点、针入度和延度三大指标均能满足国标I-D的要求,具有实际应用意义。     

煤沥青改性石油沥青热老化流变性能

为了研究煤沥青复配石油沥青热老化后流变性能,采用中温煤沥青和70#石油沥青制备混合沥青,模拟施工过程中的老化,通过三大指标和动态剪切流变仪对老化后混合沥青的宏观性能和流变性能进行评价。结果表明,随着煤沥青掺加比率增加,混合沥青软化点增加,针入度和延度降低;储能模量、损耗模量、车辙因子和当量粘度都随煤沥青掺比增加而增加。因此,混合沥青老化后具有更好的高温流变性能。     

二乙烯基苯改性煤沥青的工艺及性能研究

以二乙烯基苯为交联剂,在酸性催化剂的作用下对煤沥青进行了改性,并对其工艺及性能进行了研究.采用不同溶剂对改性前后煤沥青的组分进行分析,并测定不同工艺改性沥青的软化点、残炭率及密度等性能;采用扫描电镜对改性煤沥青炭化产物的形貌进行观察.研究表明,改性工艺对改性煤沥青的组成和性能影响很大.     

烷基酚醛缩合物对松香改性树脂性能的影响

通过对松香改性酚醛树脂的粘度、软化点、正庚烷容纳度等性能的分析,考察了酚醛树脂制备过程中不同烷基酚单体和缩合温度对松香改性树脂性能的影响。结果表明:随着烷基酚取代基碳链的加长,松香改性树脂分子链柔顺性增加,提高了树脂在正庚烷中的溶解性能,同时由于空间位阻增大,烷基酚与松香加成反应活性降低,产物的分子质量变小,粘度和软化点降低。随着缩合温度的升高,酚醛树脂缩合度逐渐增加,羟甲基含量减少,与松香反应后改性树脂的分子质量增大,正庚烷溶解性增加,软化点降低。     

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.     

煤沥青改性后流变性能的变化分析

为了探讨对苯二甲醛(TPA)对煤沥青改性后流变性能的变化,采用旋转黏度计测定了煤沥青及TPA改性的煤沥青的表观黏度,研究了表观黏度与温度的关系;采用示差扫描量热法研究了煤沥青和TPA改性的煤沥青的热行为。结果表明,TPA改性的煤沥青的黏度与温度的关系曲线呈现W型,在200℃～225℃处于低黏流区,表观黏度值200mPa.s～400mPa.s,可以作为浸渍剂煤沥青使用;TPA改性的煤沥青在高于225℃时,表观黏度值迅速上升;TPA改性的煤沥青在低黏度区域具有较低的活化能,这对煤沥青的浸渍工艺有益。     

Carbon foams prepared from coal tar pitch for building thermal insulation material with low cost

A new approach is provided to resolve the large-scale applications of coal tar pitch. Carbon foams with uniform pore size are prepared at the foaming pressure of normal pressure using coal tar pitch as raw materials. The physical and chemical performance of high softening point pitch(HSPP) can be regulated by vacuumizing owing to the cooperation of vacuumizing and polycondensation. Results indicate that the optimum softening point and weight ratio of quinoline insoluble are about 292℃ and 65.7%, respectively. And the optimum viscosity of HSPP during the foaming process is distributed in the range of 1000-10000 Pa·s. The resultant carbon foam exhibits excellent performance, such as uniform pore structure, high compressive strength(4.7 MPa), low thermal conductivity(0.07 W·m~(-1) ·K~(-1)), specially, it cannot be fired under the high temperature of 1200 ℃.Thus, this kind of carbon foam is a potential candidate for thermal insulation material applied in energy saving building.     

两种煤沥青的浸渍性能分析

采用热重／差热分析、核磁共振、热台显微镜在位观察等方法,对太钢改质沥青和北京焦化厂中温煤沥青的软化点、元素组成、结构、组成、粘度进行了分析,以评价其作为浸渍沥青的性能。结果表明：太钢改质沥青比北京焦化厂中温煤沥青的吡啶不溶物含量高,芳香度低,高温流动性略好,产碳率也高。     

SBS改性煤基沥青结构的研究

以SBS为改性剂,无水三氯化铝为引发剂改性煤基沥青为路用沥青。经测定,改性后沥青的软化点增加,针入度减小。SEM表明,改性沥青比原料沥青结构均匀。IR表明,沥青与SBS发生了化学反应。     

Effect of different oxidation treatments on the chemical structure and properties of commercial coal tar pitch

Different oxidation treatment was used for the increase of the softening point of a commercial coal tar pitch. H₂SO₄, HNO₃, H₂O₂ and air are selected as treatment reagents. These preliminary investigations show that the oxidation treatment of commercial coal tar pitch with different reagents at 160 °C and heat treatment to 250 °C causes considerable changes in the chemical composition of obtained pitches. This leads to increase of TI and QI fraction, and results in considerable increase in the softening point of the pitches. The yield of modified pitches is considerable in the case of treatment with H₂SO₄, H₂O₂, and HNO₃ and lesser in the case of air blowing. The data obtained also indicate some differences in the composition and softening point of pitches obtained after modification with different reagents. These differences could influence the applicability of the obtained pitches in the various areas of carbon material production.     

热聚合-氧化法制备高β树脂改性沥青

以中温沥青为原料,通过溶剂萃取沉降分离获得低喹啉不溶物含量(QI<0.1%)的精制沥青。对精制沥青进行热聚合-空气氧化改性处理,得到高β树脂含量的改性沥青。经特定热聚合条件处理后,研究了空气氧化阶段的反应温度、氧化时间和空气流量对沥青改性的影响。实验结果表明,在空气氧化阶段,当氧化温度为280℃,氧化时间为2h,空气流量为0.04m³/h时,可以获得软化点为220℃、甲苯不溶物为61.59% 、喹啉不溶物为4.35%、结焦值为78.44%,β树脂含量为57.24%的优质改性沥青。     

Preparation,modification, and characterization of pitches from apricot stones

Apricot stones steam pyrolysis tar and mixtures with petroleum pitch were modified by sulfuric acid and heat treatment at various temperatures for the purpose of obtaining a raw material for the production of carbon-related materials. The products obtained were characterized by elemental analysis, total carbon contents, FTIR spectroscopic analysis, ¹H and ¹³C NMR spectroscopic analyses, softening point measurement, and oxygen functional group content. During the acid and heat treatment, the reactions of polycondensation and polymerization occur. The heat-treatment modification of the pitches decreases the oxygen-containing groups and sulfur content and increases the content of aromatic structures. Chemical transformations and the removal of light components increase the softening point of the pitches. The results show that apricot stones tar with some additional modifications can be used as a raw material for the production of advanced carbon materials.     

碳纤维用基体前驱体煤沥青的改性研究

煤沥青经喹啉萃取后,以三氟化硼乙醚和硝基苯作为催化剂,在氮气氛下热缩聚制得改性沥青,并对改性沥青的工艺进行初步研究;利用FT-IR、热分析仪对改性沥青的结构和热稳定性进行了分析。结果表明改性后沥青脂肪族侧链明显减少,芳构化程度增加,热失重率减小,适合用于制备碳纤维。