PREDICTING THE TIMING AND CHARACTERISTICS OF PETROLEUM FORMATION USING TAR MATS AND PETROLEUM ASPHALTENES: A CASE STUDY FROM THE NORTHERN NORTH SEA

The Northern Viking Graben area in the Norwegian North Sea was studied in order to investigate the petroleum formation characteristics of the Upper Jurassic Draupne Formation. In this area, the organofacies of the Draupne Formation, and consequently its petroleum generation characteristics, show significant variations. These variations represent a major risk, particularly in the context of basin modelling studies. Therefore, tar‐mat asphaltenes, oil asphaltenes and source‐rock samples from this area were studied in order to evaluate the use of migrated asphaltenes from petroleum reservoirs and tar mats in basin modelling. The samples were studied using bulk kinetic analysis, open‐system pyrolysis‐gas chromatography and elemental analyses, and the results were integrated into a basin modelling study. The results from these different sample materials were compared both to each other and to natural petroleum, in order to assess their significance for future petroleum exploration activities. We show that in cumulative petroleum systems, the transformation characteristics of the asphaltenes incorporate those of the individual source rock intervals which have contributed to the relevant reservoir system. Thus, the petroleum formation window predicted by the use of asphaltene kinetics is broad, and covers the majority of the formation windows predicted from the individual source rock samples. In addition, the molecular characteristics of asphaltene‐derived hydrocarbons show that compositional characteristics, such as aromaticity, correspond more closely to natural oils than to the respective source‐rock products. Our results confirm that the heterogeneous nature of the Draupne Formation results in a significantly broader petroleum formation window than is conventionally assumed. We propose that oil and tar‐mat asphaltenes from related reservoirs represent macromolecules which account for this heterogeneity in the source rock, since they represent mixtures of charges from the different organofacies. One conclusion is that the use of oil and tar‐mat asphaltenes in kinetic studies and compositional predictions may significantly improve definitions of petroleum formation characteristics in basin modelling.     

非均相成核中间相炭微球的形成过程及其结构演变

以含有喹啉不溶物的煤焦油沥青为原料，在410℃、不同反应时间下获得一系列中间相炭微球(MCMB)和小于0．5μm的碳质颗粒(SCP)。通过对中间相沥青的软化点、族组成和MCMB、SCP的形貌及MCMB断面结构的分析，认为非均相成核MCMB的形成和生长过程不同于均相成核的融并生长过程，而是SCP碳质颗粒的构筑过程，我们称之为“球形基本单元构筑”过程。在MCMB生长过程中，体系的黏度对SCP的形成和MCMB的生长起着重要的作用。非均相成核MCMB的内部结构不是三种模型结构(“地球仪”型、“洋葱”型和“同心圆”型)中的任一种，而是炭层具有收缩点的复杂结构，并且球体的结构不具有“继承性”，即随着反应时间的延长而不断发生变化和调整。MCMB内部分子在球体生长过程中的主要变化趋势是分子的不断缩合长大，而不是分子片层的平行趋向。     

Selective preparation of light aromatic hydrocarbons from catalytic fast pyrolysis vapors of coal tar asphaltene over transition metal ion modified zeolites

The catalytic cracking of coal tar asphaltene (CTA) pyrolysis vapors was carried out over transition met-alion modified zeolites to promote the generation of light aromatic hydrocarbons (L-ArHs) in a pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) micro-reactor system.The effects of ultra stable Y(USY),Co/USY and Mo/USY on the selectivity and yield of L-ArHs products and the extent of deoxygena-tion (Edeoxygenation),lightweight (Elightweight) from CTA pyrolysis volatiles were investigated.Results showed that the yields of L-ArHs are mainly controlled by the acid sites and specific surface area of the catalysts,while the deoxygenation effect is determined by theirs pore size.The Elightweight of CTA pyrolysis volatiles over USY is 9.65％,while the Edeoxygenation of CTA pyrolysis volatiles over Mo/USY reaches 20.85％.Additionally,the modified zeolites (Mo/USY and Co/USY) exhibit better performance than USY on L-ArHs production,owing to the synergistic effect of metal ions (Mo,Co) and acid sites of USY.Compared with the non-catalytic fast pyrolysis of CTA,the total yield of L-ArHs obtained over USY (4032 mg·kg-1),Co/USY (4363 mg·kg-1) and Mo/USY (4953 mg·kg-1) were increased by 27.03％,38.19％ and 54.78％,respectively.Furthermore,the possible catalytic conversion mechanism of transition metal ion (Co and Mo) modified zeolites was proposed based on the distribution of products and the characterizations of catalysts.     

Ni/W比对NiWCx催化剂加氢性能的影响

过渡金属碳化物具有类似贵金属的电子结构和加氢性能。采用等体积浸渍法制备了不同Ni/W比的NiW/γ-Al₂O₃催化剂,以程序升温碳化法转化为NiW碳化物后对芳烃模型化合物和低温煤焦油中分离所得芳烃组分进行加氢处理。催化剂的N₂吸附、XRD、H₂-TPR和SEM表征表明,Ni的添加促进了载体表面WO₃物种的分散和还原,抑制了WO₃晶体的团聚和大晶粒的生成。萘的加氢实验表明,Ni/W原子比为0.6时催化剂的活性最佳,而添加苯酚和吡啶后的模型油加氢过程中萘的转化率和十氢萘的产率均明显下降,Ni/W原子比为0.47和0.6的催化剂性能相近,煤焦油中芳烃组分加氢后Ni/W原子比为0.47的催化剂性能更优。结果表明,Ni和W均具有良好的加氢活性,但Ni耐杂原子性能较差,二者存在一个最佳的配比以使加氢性能更优。有杂原子化合物存在时,如煤基芳烃组分的加氢,Ni/W原子比为0.47的NiW碳化物催化剂具有更好的加氢性能。     

煤焦油加工技术的探讨

煤焦油曾为近代有机化工作出了历史性贡献。我国煤焦油资源丰富,但尚未得到有效和合理利用。根据高温煤焦油的组成特点,对煤焦油的初馏、沥青加工利用和煤焦油产品的深加工技术进行了探讨,提出一些建议。此外还讨论了煤焦油加工企业的发展模式。     

煤焦油改性酚醛树脂研究

引入含有多环芳烃煤焦油组分来改性酚醛树脂,在反应釜中按一定比例加入苯酚、甲醛、氢氧化钠和煤焦油.在碱性催化剂作用下反应4～7 h,真空脱水,得到了煤焦油改性热固性酚醛树脂.对改性后树脂的固含量、残炭值测定和热失重-差热分析,结果表明煤焦油加入量为苯酚质量的15%时改性树脂具有较大的固含量和残炭值,耐热性也得到了显著提高.     

两种聚氨酯防水涂料的比较

对焦油型和非焦油水固化型聚氨酯防水涂料B组分的生产工艺、配方特点，施工操作工艺、固化时间、涂膜性能等方面进行了比较，指出新开发的非焦油型聚氨酯涂料生产周期短、能耗少、气味小，是环保型聚氨酯防水涂料。     

絮凝剂和溶剂对煤焦油净化效果的影响

研究煤焦油净化处理过程中絮凝剂和溶剂对净化效果的影响，确定一种无机絮凝剂为煤焦油净化处理最佳絮凝剂，其最佳用量为8％（絮凝剂／煤焦油），芳香族溶剂洗油的最佳用量为混合液的35wt％～45wt％，脂肪族溶剂煤油的最佳用量为混合液的20wt％～25wt％，净化澄清液QI含量在0．5％左右。     

生物质焦油裂解催化剂制备及其催化裂解性能

以萘为生物质焦油模型化合物 ,在以白云石为载体制备的 Ni基催化剂上进行了催化裂解实验研究 ,对催化剂的制备技术、活性、积炭失活性能和再生方式进行了实验分析。结果表明 :在 70 0℃的裂解温度、重量空速 0 .8L· h-1的反应条件下 ,萘的单程转化率可达 95 %,以饱和湿空气为再生气流 ,在程序升温的条件下烧碳 ,催化剂再生时间短 (<0 .5 h) ,与同温度的热裂解相比催化裂解更有利于萘的深度裂解 .     

循环灰条件下1-甲基萘催化裂解的实验研究

热解气化过程中 ,促进焦油的裂解使之转化为高热值煤气 ,对高挥发分劣质煤和生物质燃料的清洁高效利用具有重要的意义 .在固定床反应器上 ,以石英砂和两种烟煤在循环流化床锅炉上燃烧形成的循环灰为床料 ,实验研究了焦油中含量较高的 1 -甲基萘的裂解反应 ,测定了反应动力学参数 .结果表明 ,与石英砂条件下相比 ,循环灰促进了 1 -甲基萘的裂解 ,反应活化能降低 ,裂解气体的总产率提高