催化剂级配在加氢裂化装置中的应用

采用催化剂级配技术,对中国石油四川石化有限责任公司2.7 Mt/a加氢裂化装置的两个反应器进行改造;并对调整原料性质及操作条件(尽量接近于第一周期标定工况数据)后的第二周期应用情况进行了催化剂活性、产品分布、产品质量、操作安全性等对比分析。实验结果表明,通过催化剂活性级配和加氢选择性级配,实现了多环芳烃的进一步转化,最大程度保留链烷烃在尾油组分中,与第一周期相比,喷气燃料烟点提高3.0 mm,尾油芳烃指数降低6.5个单位;第二周期转化率(282℃)控制在79%、尾油切割点为252℃工况下,重石脑油与喷气燃料总收率可达60.9%,实现多产重石脑油与喷气燃料的目标;降低了反应器压降和循环氢压缩机的能耗,节约了投资成本。     

Effect of oil-solubility catalysts on the low-temperature oxidation of heavy crude oil

Due to low oil recovery factor in heavy oil reservoir, air injection with catalyst becomes a competitive technology to effectively reduce viscosity of crude oil as a result of the low cost and small environment pollution. This paper determined the feasibility of air injection with catalyst in a heavy oil reservoir through static and dynamic experiments. The results indicated that under the effect of catalyst, oxidation between heavy oil and air could significantly reduce the viscosity of crude oil. The optimal catalyst contained 0.7?wt. % oil-solubility organic acid copper and 0.5?wt. % sodium hydroxide. With the oxidation time increasing, viscosity of crude oil decreased and oil recovery factor increased. With temperature increasing, viscosity of crude oil decreased sharply and oil recovery factor increased. The oil recovery factor of air huff-n-puff process was 30.2%. Air injection with catalyst in the reservoir is a promising technology.     

Ni/Mo/MgAl(O)催化甲烷干重整制合成气的研究

通过焙烧由共沉淀法制备的NiMgAl-Mo₇O₂₄^6-类水滑石,制备了一系列不同MoO₃质量分数(0、10%、15%、20%、25%和30%)的Ni/Mo/MgAl(O)复合氧化物催化剂。将该催化剂用于甲烷干重整(DRM)反应中,并研究了MoO₃的含量对催化剂性能的影响。借助XRD、BET、H₂-TPR、CO化学吸附、CO₂-TPD以及O₂-TPO等表征手段研究了催化剂结构和性能之间的关系。结果表明,催化剂的催化活性和抗积炭性能与MoO₃含量有关,当MoO₃的负载量为15%时,催化剂的催化活性和稳定性最佳,其在GHSV=60000 mL/(g·h),800℃反应57 h后,甲烷转化率仍维持在66%以上。较大的比表面积、强的金属与载体作用力、较高的金属分散度、适量的酸性和碱性位点数以及Ni-Mo双金属合金的协同作用,使得催化剂具有较好的催化活性和较强的抗积炭能力。     

负载型中孔分子筛催化剂的研究进展

本文对M41S中孔分子筛作载体的负载试剂的研究进展进行了综述，主要介绍了负载酸型、负载碱型和负载氧化型催化剂的研究现状，以及对其应用和发展前景作了总结和评述。     

二茂铁衍生物的化学结构对高氯酸铵燃速的影响

本文研究了几种不同化学结构的二茂铁衍生物对高氯酸铵燃烧的催化作用,探讨了它们的化学结构与催化效应之间的关系,给出了燃速压力曲线和热分解温度。得出结论:二茂铁衍生物催化剂分子的空间结构的对称性和取代基的电子效应是影响其催化效率的主要因素。     

Fabrication of Fischer–Tropsch Catalysts by Deposition of Iron Nanocrystals on Carbon Nanotubes

The fabrication of supported catalysts consisting of colloidal iron oxide nanocrystals with tunable size, geometry, and loading—homogeneously dispersed on carbon nanotube (CNT) supports—is described herein. The catalyst synthesis is performed in a two‐step approach. First, colloidal iron and iron oxide nanocrystals with a narrow size distribution are produced. Second, the nanocrystals are attached to CNT grains serving as support structure. Important features, like iron loading and nanocrystal density on the CNT support, are controlled by changing the nanocrystal concentration and ligand concentration, respectively. The Fischer–Tropsch performance reveals these new materials to be active, selective toward lower olefins (60% C of hydrocarbons produced in the absence of promoters), and remarkably stable against particle growth.     

ZSM-5催化剂在多周期MTP反应中的性质变化及反应行为

通过XRD、N2物理吸附 脱附、NH3 TPD、TG、二氯甲烷萃取及GC MS分析等手段研究了ZSM 5催化剂在多周期甲醇制丙烯(MTP)反应中的性质变化和内、外表面可溶积炭的组成。在反应压力01 MPa、温度480 ℃、甲醇质量空速1 h-1（甲醇分压为125 kPa）的条件下,考察了不同反应周期ZSM 5催化剂的MTP催化活性。结果表明,在多个反应 再生过程中,ZSM 5催化剂的骨架结构受到各周期积炭、水热脱铝及床层局部高温的影响,使其在脱铝过程中晶体结构遭受破坏,进而影响其孔道结构和酸性质;工业失活ZSM 5催化剂的结焦物主要是不可溶积炭,随着反应 再生周期的增加,积炭物种会不断的发生脱氢、环化等反应,最后生成重质稠环芳烃,甚至石墨化的碳,致使不可溶积炭量逐渐增加。     

酸催化二甘醇脱水环化反应研究

以硫酸、磷钨酸、ZRP-5分子筛为催化剂,研究了二甘醇(DEG)脱水环化的反应规律。结果表明,DEG发生分子内脱水环化反应,生成1,4-二氧六环(DOX),DEG分子间脱水不仅可以生成四甘醇、六甘醇等,同时可生成三甘醇、五甘醇等一系列的多甘醇(PEG)。不仅DEG可以脱水环化生成DOX,在反应中生成的PEG也同样可以进行生成DOX的反应。对于二甘醇(DEG)脱水环化反应,硫酸是性能优良的催化剂,反应可以在较低的温度下进行,馏出产物中DOX选择性大于95％。     

固体酸催化合成2-乙酰噻吩

采用固体酸催化剂,以乙酸酐和精制焦化苯工艺过程中得到的浓缩噻吩为原料合成了2-乙酰噻吩。考察了固体酸催化剂用量、反应时间对噻吩转化率的影响,结果表明,含B酸和L酸中心的固体酸催化剂均能催化噻吩与乙酸酐合成2-乙酰噻吩的反应,其中CT-175树脂催化剂在常压、80℃、n(乙酸酐):n(噻吩)= 3:1的条件下,噻吩转化率达到100％。通过对固体酸催化剂HY、CT-175、MCM-41、HZSM-5、Hβ的BET、TPD表征,结果表明,酸性及孔径大小是影响噻吩乙酰化反应活性的主要因素。     

Pre-Activation of CO2 at Cobalt Phthalocyanine-Mg(OH)2 Interface for Enhanced Turnover Rate

Cobalt phthalocyanine (CoPc) anchored on heterogeneous scaffold has drawn great attention as promising electrocatalyst for carbon dioxide reduction reaction (CO₂RR), but the molecule/substrate interaction is still pending for clarification and optimization to maximize the reaction kinetics. Herein, a CO₂RR catalyst is fabricated by affixing CoPc onto the Mg(OH)₂ substrate primed with conductive carbon, demonstrating an ultra-low overpotential of 0.31 ± 0.03 V at 100 mA cm⁻² and high faradaic efficiency of >95% at a wide current density range for CO production, as well as a heavy-duty operation at 100 mA cm⁻² for more than 50 h in a membrane electrode assembly. Mechanistic investigations employing in situ Raman and attenuated total reflection surface-enhanced infrared absorption spectroscopy unravel that Mg(OH)₂ plays a pivotal role to enhance the CO₂RR kinetics by facilitating the first-step electron transfer to form anionic *CO₂⁻ intermediates. DFT calculations further elucidate that introducing Lewis acid sites help to polarize CO₂ molecules absorbed at the metal centers of CoPc and consequently lower the activation barrier. This work signifies the tailoring of catalyst-support interface at molecular level for enhancing the turnover rate of CO₂RR.