韩国70道路沥青老化特性分析（Ⅱ）管能团与分子结构变化

利用现代分析方法（IR光谱，SEC，XPS）考察了进口韩国70道路沥青在0－250h和60℃－130℃薄膜老化过程中特征官能团与分子结构变化。试验发现，沥青经薄膜热老化时分子中羰基官能团的吸收峰面积随老化时间逐渐增加，老化温度愈高变化愈明显，亚砜官能团的吸收峰面积有变化但不显著，老化后沥青分子中高分子量组分的含量增加，分散度变大，特征官能团与分子量分布的变化说明沥青分子间存在极性官能团之间的缔合作用，沥青分子中O，S原子的存在形态比较复杂，主要以亚砜，羰基官能团以及硫醚，硫醇的形式存在，沥青的老化是一个缓慢的自氧化过程，氧化反应符合自由基醚反应历程。     

韩国70道路沥青老化特性分析（Ⅰ）族组成与性质变化

采用薄膜热老化方法考察了进口韩国70道路沥青在0－250h和60℃－130℃范围内族组成与性质的变化。老化试验结果表明：芳香分与胶质含量减少,沥青质含量增加;针入度与延度下降,软化点与粘度升高。沥青质含量随老化时间的变化符合一级反应动力学规律,粘度随温度的变化符合双对数经验模型。     

韩国70道路沥青老化特性分析(Ⅱ)官能团与分子结构变化

利用现代分析方法（ＩＲ光谱，ＳＥＣ．ＸＰＳ）考察了进口韩国 ７０道路沥青在 ０～２５０ ｈ和６０℃～１３０℃薄膜热老化过程中特征官能团与分子结构变化。试验发现：沥青经薄膜热老化时分子中连基官能团的吸收峰面积随老化时间逐渐增加，老化温度愈高变化愈明显。亚砜官能团的吸收峰面积有变化但不显著。老化后沥青分子中高分子量组分的含量增加，分散度变大。特征官能团与分子量分布的变化说明沥青分子间存在极性官能团之间的缔合作用。沥青分子中Ｏ，Ｓ原子的存在形态比较复杂．主要以亚砜、羰基官能团以及硫醚、硫醇的形式存在。沥青的老化是一个缓慢的自氧化过程．氧化反应符合自由基链反应历程。     

沥青催化氧化研究

沥青是一种热塑性材料，需要在炭化前进行不熔化处理以便得到性能优异的炭材料前驱体．在300℃条件下分别选择不同的催化剂(硝酸钾、三氯化铝以及对甲苯磺酸)考察了沥青空气催化氧化过程中性质、组成与分子结构的变化．结果表明：沥青空气氧化时其软化点逐渐增加，添加不同催化剂时对氧化沥青软化点的影响不同，且符合一元二次数学模型，即SP=A0 A1θ A2θ^2。沥青空气催化氧化的结果使其甲苯不溶物的含量明显增加，由此认为氧化的结果增加了沥青中高分子量组分的含量．元素分析表明沥青经空气氧化时H／C原子比逐渐减小，氧元素含量逐渐增加，反应的后期变化趋于稳定．IR光谱分析同样反映出沥青经催化氧化后分子结构中侧链减少，芳环上的氢减少，整个芳环的缩合程度增加．因此沥青催化氧化的结果是促进了氧分子在沥青中的传递，并参与分子间的交联反应．     

反应温度对煤焦油沥青质组成与结构的影响

以中低温煤焦油为原料,在高压釜反应器内进行加氢实验,研究反应温度对加氢油品中沥青质组成与结构的影响。结果表明:在实验研究加氢工艺条件下,沥青质转化率随反应温度的升高而增加;与原料沥青质相比,在350—410℃不同温度下加氢后的沥青质中硫、氮、氧杂原子含量均降低,但脱除规律不一致,杂原子硫和氧含量随温度的升高而降低,但氮原子含量随温度的升高呈先增加后降低的趋势,说明各杂原子脱除规律与其赋存形态有关;另外,不同反应温度下沥青质平均分子结构参数相差很大,反应温度越高,沥青质缩合度越大。加氢反应压力为7 MPa时,反应温度不宜高于380℃。     

道路沥青的硫化反应

用化学分析与仪器分析（^1H-NMR,XPS与凝胶色谱）相结合的方法探讨了道路沥青与元素硫之间的反应行为以及改质后沥青中硫的存在形式。结果显示硫与沥青的反应一是硫与沥青分子交联,生成分子量大的含硫基团组分,并显著改善沥青的塑性、延展性以及亲水性;二是硫与沥青的反应主要发生在侧链α碳原子位置上,随反应温度的升高也夺取β,γ侧链碳原子上的氢。硫与沥青反应使沥青中胶质含量下降,沥青质增加,重均与数均分子量增加。XPS测定发现沥青原料中的S原子以噻吩与亚砜结构形态存在,硫化反应后S主要以元素硫和结合硫形态存在。     

PE废塑料溶剂裂解制备聚乙烯蜡

本文以废旧聚乙烯为原料,在溶剂水的作用下进行裂解制备聚乙烯蜡。实验过程中考察了温度、时间及溶剂加入量对产品性能的影响。结果表明:随裂解温度的升高和反应时间的延长都使得反应体系获得了更高的能量,容易使PE大分子发生断链从而得到低分子量PE,从而使产物收率逐渐降低,粘均分子量减少,熔程也随之下降。溶剂加入量对产品性质也有一定影响。当裂解温度为370℃,反应时间60min,溶剂加入量占原料总质量50%时,得到灰白色的聚乙烯蜡,其熔程在104~110℃之间,酸值为0.0143mg·g-1,粘均分子量为3426.4,且具有较高的热稳定性。通过溶剂裂解制得的聚乙烯蜡具有一定的工业应用前景。     

重油和煤沥青制备煤沥青油浆的过程研究

将自制的煤沥青粉添加到重油中制得浆体燃料煤沥青油浆,对成浆性和流变性的影响规律进行了研究.结果表明,在相同温度下,煤沥青油浆的表观黏度随煤沥青粉添加量的增加而增大,剪切速率相同时黏度随温度的升高而减小.添加不同质量分数制得的煤沥青油浆在同一剪切速率下的黏度随温度的升高而减小,且随温度的升高黏度减小趋势逐渐变小,当煤沥青粉添加量≤12%时,煤沥青粉添加量对煤沥青油浆的流变性影响较小.随着煤沥青粉添加量的增加,煤沥青油浆的低位发热量稍有下降,但降低幅度较小.     

中低温煤焦油加氢过程中沥青质组成与性质

以中低温煤焦油为原料,采用小型固定床连续加氢反应装置进行2 500 h全馏分加氢实验,研究煤焦油加氢沥青质组成与性质随加氢反应器运行时间延长的变化规律。结果表明:随反应时间的延长,催化剂活性逐渐降低,煤焦油沥青质脱除率降低,加氢沥青质S和N杂原子含量以及Fe和Ca金属含量均增加,脱除率均降低,在一定温度范围内,提高反应温度可以提高煤焦油沥青质加氢转化性能,但也促进大分子量的沥青质生成;此外,随反应时间的延长,加氢沥青质芳香度(f_A)增大,H和C原子比降低,说明加氢沥青质缩合度提高,另外,加氢沥青质分子量逐渐增大,甚至超过原生沥青质,说明部分沥青质发生缩聚反应;反应后期,沥青质缩聚反应加剧,金属Fe和Ca易沉积在催化剂上,催化剂失活严重。     

醋酸乙烯乳液聚合条件对聚乙烯醇水溶液粘度变化和凝胶行为的影响

将VAc分别在40、50、60℃下进行乳液聚合来制备PVA，这些不同分子参数的PVA以3％．5％．7％（g/L)的浓度溶解在水中，并在30℃和60℃下老化。研究分子量和聚合温度对PVA水溶液的粘度变化和凝胶行为的影响。当其他条件不变时，粘度随着分子量的增加而增加。由VAc在较低温度下聚合制得的PVA具有很好的分子规整性且其粘度相应更高。PVA的粘度及其变化随聚合温度、水溶液浓度和老化时间的变化而变化。在40℃下由VAc聚合制备的PVA其平均聚合度为2800，这种PVA7％的水溶液在老化处理500分钟后其粘度急剧增加。     

Coprocessing of a Turkish lignite with a cellulosic waste material: 2. The effect of coprocessing on liquefaction yields at different reaction pressures and sawdust/lignite ratios

Most of the research works done for alternative energy sources have shown that, in general, coprocessing of coal with biomass-type wastes has a positive effect on the liquefaction yields and these materials are increasingly studied as coliquefaction agents for the conversion of coal to liquid fuels. Addition of biomass waste materials to coal is known to be synergetic in that it improves the yields and quality of liquid products produced from coal under relatively mild conditions of temperature and pressure. This paper reports the coprocessing of a Turkish lignite with sawdust in the category of biomass-type waste material. The experiments have been conducted in a stainless-steel reactor, and temperature and tetralin/(lignite+sawdust) ratio were kept constant at 350 °C and 3:1 (vol/wt), respectively. This is the first time that the influence of reaction pressures on coliquefaction yields was investigated. In addition, the influence of the sawdust/lignite ratios on coprocessing conversion and product distribution was also investigated under the same reaction conditions. The runs were carried out at 10, 25, 40, 55, and 70 atm initial cold hydrogen pressure values and at 0.5:1, 0.75:1, 1:1, 1.25:1, and 1.5:1 sawdust/lignite (wt/wt) ratio values.     

Effects of coal rank and reaction conditions upon coprocessing coal with waste tyre

It is well known that the amount of waste tyre increases every year, and a numerous amount of waste tyre is landfilled or dumped all over the world, which causes environmental problems, such as destruction of natural places and the risk of fires. Coprocessing waste tyre and coal is considered as one of the effective processing methods of both materials. Upon coprocessing lower rank coal (Wyoming, C; 68%) with waste tyre, the synergistic effects to upgrading, such as the increase of oil yield and the decrease of residue yield, were appeared. However, the synergistic effects were not observed on coprocessing two kinds of higher rank coals with waste tyre. The reactions of coal with benzophenone were carried out to discuss the hydrogen donatability of coal. Conversion of benzophenone to diphenylmethane on the reaction with Wyoming coal was higher than those of higher rank coals. Accordingly, it was considered that the synergistic effects to upgrading upon coprocessing Wyoming coal with waste tyre were obtained owing to the enhancement of stabilization of radicals from tyre and Wyoming coal through the hydrogen donation from both tyre and Wyoming coal. The effects of reaction temperature and the amount of solvent upon coprocessing Wyoming coal with waste tyre were also discussed in this study.     

平朔煤显微组分与低温煤焦油及石油渣油共处理的研究

采用高压微型反应釜，将平朔煤的洗精煤以及分离出的显微组分与低温煤焦油、石油渣油在不同反应温度和初始氢压下分别进行共处理，考察了各显微组分的共处理活性，比较了低温煤焦油与石油渣油在共处理过程中的效果，并分析了煤油共处理过程中可能发生的反应。     

中低温煤焦油沥青催化聚合制备改质沥青

以中低温煤焦油沥青为原料,采用催化聚合法制备改质沥青,并在中低温煤焦油沥青中加入乙烯焦油和蒽油进行调和来提高改质沥青的流变性能,分别考察反应时间、反应温度及催化剂和交联剂的加入量对改质沥青的软化点、结焦值、甲苯不溶物含量和喹啉不溶物含量的影响。结果表明:加入乙烯焦油和蒽油调和可以有效提高改质沥青的流变性能,催化剂和交联剂按照1∶1的质量比加入,可以有效降低改质沥青的软化点,这是因为酸性催化剂和交联剂之间形成相对均相的反应体系,解决了改质沥青软化点高的问题。采用调和中低温煤焦油沥青制备改质沥青,筛选出的最佳工艺条件为:反应温度370℃,反应时间7h,催化剂和交联剂的加入量2.5%,该条件下制备的改质沥青的性质符合工业标准YB/T 5194-2015的要求,改质沥青的软化点为120℃,结焦值为56.28%,甲苯不溶物含量为30.52%,喹啉不溶物含量为8.21%,β树脂含量为22.31%。采用傅立叶变换红外光谱仪和偏光显微镜对制备出的改质沥青和中低温煤焦油沥青进行分析,初步推断出改质沥青中化合物芳环上的取代基明显增加且烷基取代的化合物大多数为芳烃分子,且在偏光显微镜下改质沥青中出现小球体,表明中低温煤焦油沥青在制备成改质沥青的这一过程中其相对分子质量变大,稠环芳烃含量增多。     

Modification of FCC slurry oil and deoiled asphalt for making high-grade paving asphalt

With the rapid development of modern industry, high-grade paving asphalt is massively required to meet the demands for modern transportation. As one of additives, natural asphalt is indispensable since it can improve the performance of paving asphalt in all aspects. However, the application of non-renewable natural asphalt is increasingly restricted by its limited reserves. It is imperative to find alternative approaches to produce high-grade paving asphalt. Fluid catalytic cracking (FCC) slurry oil is an ideal soft component for producing paving asphalt due to its high content of aromatics and resins. However, its bad ageing resistance limits its application to only low-grade paving asphalt. In the present work, a novel approach for producing high-grade paving asphalt was investigated using chemically modified FCC slurry oil and deoiled asphalt (DOA). The FT-IR and NMR results showed that dehydrogenation and condensation reaction occurred during the ageing process. From a series of aliphatic alcohols and aldehydes, propanal was selected as a proper modifier to improve the ageing resistance of FCC slurry oil. The propanal-modified slurry oil possessed more substituted aromatic units and less aromatic hydrogen atoms than other modified slurry oils, thus showing better ageing resistance. With the increase of length of aliphatic chains in modifier, the modified slurry oil contained more and longer alkyl substituent group on aromatics. Compared with the cross-linked oil (slurry oil modified by cross-linking agent), modified slurry oil possessed similar ageing resistance but higher flowing ability. Also, the effect of operation conditions on the kinematic viscosity of modified slurry oil were investigated. Blended with modified slurry oil, the penetration ratio of asphalt product increased from 53.7 to 66.2, which met the standard of 70# paving asphalt. Both the microscopic observations and FT-IR results indicated that modification process effectively reduced the oxidation degree of asphalt product, thus increasing the ageing resistance. Consequently, with aid of this process, high-grade paving asphalt was readily produced from low value oil from downstream products of refinery, instead of the depleting natural asphalt.     

高挥发烟煤和富氢固态废弃物共液化的研究

在50mL的小型反应器内，考察了煤和废塑料共处理的反应规律及工艺条件。结果表明，在煤和废塑料共处理过程中，废塑料在一定的条件下，可有效促进煤的转化，提高油收率，降低氢耗量，减缓反应条件的苛刻度。     

煤沥青与石油沥青共混作筑路材料

介绍了国外煤沥青与石油沥青共混作筑路材料的发展概况、混合沥青胶体结构模型以及国产煤沥青共混初步试验结果。对两个国产石油沥青样品与一个煤沥青样品共混得到的混合沥青性质的初步试验表明,混合沥青对碎石特别是酸性碎石的粘附力高于原石油沥青。与石油沥青相比,混合沥青的抗高温变形能力强,并可降低生产沥青碎石混合料的操作温度。所得混合沥青样品多项指标接近德国和波兰同类产品的水平。     

煤油共处理过程中的反应机理

主要从煤中键的裂解、氢转移机理以及逆反应等方面论述了近年来在煤液化过程特别是煤油共处理过程反应机理研究的新进展, 着重介绍了溶剂、催化剂对氢转移机理的影响, 指出今后应加强对煤油共处理反应机理的研究, 用于指导将来可能的工业实践．     

煤沥青作为筑路材料的研究进展

简述了煤沥青的组成和性质,综述了煤沥青改性后用作筑路材料、煤沥青和石油沥青混合料用作筑路材料的研究进展及其毒性防治,展望了筑路用煤沥青材料的研究新方向及应用前景。     

煤炭直接液化先进工艺的经济性

煤直接液化可以生产液体燃料油。比较了碳氢化合物研究公司（ＨＲＩ）的两段催化液化（ＣＴＳＬ）、煤油共炼和氢─—煤工艺的经济性。煤油共炼可以看作是重质渣油提质和煤液化之间的过渡技术。作出在中国建设煤油共炼示范工厂的经济分析和评价。