轻质烷烃异构化进展述评

轻质正构烷烃异构化是油田液态烃加工利用的重要手段，也是炼厂提高汽油轻质馏分辛烷值的重要方法。由于绿色化工和清洁燃料的要求，异构化工艺将发挥越来越重要的作用，因此受到人们的普遍重视，有关技术问题逐渐成为炼油和化工界研究的热点。从工艺和催化剂两方面，回顾了异构化技术的发展历程，综述了近年来研究工作的进展，分析了异构化技术未来的发展趋向。     

C5/C6烷烃异构化催化剂制备及性能研究

以工业丝光沸石为载体,采用等体积浸渍法制备了C5/C6正构烷烃中温异构化催化剂.采用微型固定床反应器,以正戊烷、正己烷为模型化合物,考察反应温度、反应压力、液时体积空速和氢油比对催化剂异构化性能的影响.结果表明,正构C5、C6烷烃异构化的适宜反应条件为:反应温度280℃、反应压力2 MPa、体积空速1.0 h-1、氢油...     

预处理温度对SAPO-11催化丁烯骨架异构化性能的影响

采用水热合成法合成的SAPO-11分子筛，经酸洗、干燥和焙烧处理得H-SAPO-11分子筛，考察了预处理温度对催化剂物化性能的影响，采用XRD、XRF、IR和NH₃-TPD等手段对催化剂进行表征。实验证明，500 ℃预处理后H-SAPO-11分子筛的结构缺陷较少，B酸位较多，骨架更完美；将其成型制成催化剂，对丁烯骨架异构化反应显示更优良的催化活性、选择性和稳定性。     

New approaches to measuring biochar density and porosity

It is clear that the density and porosity of biochar will impact its mobility in the environment, its interaction with the soil hydrologic cycle, and its suitability as an ecological niche for soil microorganisms. However, the wide range of biochar pore sizes complicates biochar porosity characterization, making it challenging to find methods appropriate to connect the fundamental physical properties of density and porosity to environmental outcomes. Here, we report the use of two fast, simple density measurement techniques to characterize biochar density and porosity. We measured biochar skeletal density by helium pycnometry and envelope density by displacement of a dry granular suspension. We found that biochar skeletal density ranged from 1.34 g cm⁻³ to 1.96 g cm⁻³, and increased with pyrolysis temperature. Biochar envelope density ranged from 0.25 g cm⁻³ to 0.60 g cm⁻³, and was higher for wood biochars than grass biochars—a difference we attribute to plant cell structures preserved during pyrolysis. We compared the pore volumes measured by pycnometry with those measured by nitrogen gas sorption and mercury porosimetry. We show that biochar pore volumes measured by pycnometry are comparable to the values obtained by mercury porosimetry, the current benchmark method. We also show that the majority of biochar pore volume is in macropores, and thus, is not measured by gas sorption analysis. These fast, simple techniques can now be used to study the relationship between biochar's physical properties and its environmental behaviors.     

Palladium‐Catalyzed Direct Arylations of 1,2‐Azolo[1,5‐a]pyridines using Copper(I) Chloride as a Lewis Acid Activator and the Synthesis of 2,6‐Disubstituted Pyridines

A direct method for the arylation of 1,2‐azolo[1,5‐a]pyridines has been developed. In the process, the fused pyridines react with aryl halides in the presence of the palladium complex Pd(OAc)₂(Phen) as a catalyst and copper(I) chloride (CuCl) as a Lewis acid to form arylated derivatives. While pyrazolo[1,5‐a]pyridines and [1,2,4]triazolo[1,5‐a]pyridines are arylated at ortho‐positions of their pyridine rings using this method, in situ ring‐opening of the formed C‐7 arylated [1,5‐a]pyridine takes place to generate the 2,6‐disubstituted pyridine. Also, upon treatment with lithium diisopropylamide (LDA), C‐7 arylated pyrazolo[1,5‐a]pyridine‐3‐carboxylates react to produce diversely substituted 2,6‐disubstituted pyridines. Finally, a sequential C‐3 arylation was accomplished through a two‐step sequence involving hydrolysis of pyrazolo[1,5‐a]pyridine‐3‐carboxylates followed by the bimetallic Pd/Cu‐catalyzed decarboxylative coupling reaction with aryl bromide.

     

酸性离子液体催化甲基环戊烷异构化反应

以三级胺、盐酸和AlCl_3为主要原料制备了氯铝酸盐型酸性离子液体催化剂,并优化了催化剂的配比。考察了催化剂用量、反应温度、反应时间以及原料杂质等对甲基环戊烷异构反应的影响。结果表明,提高催化剂用量和反应温度可加快反应速率,在反应温度70℃,油剂比3.0,反应4 h后,环己烷的产率达到70%以上,微量杂质(正己烷和苯)几乎不影响甲基环戊烷的异构化反应。离子液体催化剂在补充活性组分AlCl_3的情况下可以实现循环使用。     

轻质烷烃异构化催化剂研究进展

轻质烷烃异构化技术是提高汽油辛烷值的重要手段,是实现汽油清洁化生产的理想选择。异构化反应是微放热反应,低温更有利于异构化反应的进行,而轻质烷烃异构化技术应用生产的前提是获得高效、稳定的催化剂。综述当前工业应用的低温型异构化催化剂、中温型异构化催化剂和固体超强酸催化剂的发展现状,指出异构化催化剂今后的研究方向。低温型催化剂为贵金属卤化物无定型催化剂,具有温度低和活性高的特点,但腐蚀性强,其应用受到限制。中温型异构化催化剂多为贵金属负载分子筛型双功能催化剂,稳定性高,但反应温度高,单程异构转化率低。固体超强酸催化剂多为将贵金属负载到固体超强酸上制备得到,活性高,反应温度低,环境友好,具有较好的发展前景。     

An Organogermanium Compound Enhances the Initial Reaction Rate of Alkaline Isomerization of an Aldose into a Ketose through Enediol Complex Formation

We previously demonstrated that the organogermanium compound 3-(trihydroxygermyl)propanoic acid (THGP) enhances the enzymatic and alkaline isomerization of an aldose to a ketose through cis-diol complex formation by multiple mechanisms. Its higher affinity for the ketose than the aldose protects the ketose complex from alkaline decomposition. Furthermore, it has been reported that the aldose-ketose alkaline isomerization pathway includes 1,2-enediol. Therefore, we speculated that the complex-forming ability of THGP could also be applied to enediol, a transient intermediate of alkaline isomerization. To test this prediction, we analyzed the initial rates of glucose or lactose isomerization in a region where there was no substantial difference in pH with and without THGP addition. The results showed that THGP enhanced the rate of fructose or lactulose formation per unit time by approximately 2-fold compared to the control. This finding indicated that THGP could form a complex with the transition state of aldose-ketose alkaline isomerization.     

SKI-210催化二甲苯异构化反应的动力学研究

利用固定床反应装置,研究了SKI-210催化二甲苯异构化反应动力学。反应网络包括3种二甲苯异构体之间的连串主反应和二甲苯的歧化副反应。选择基于Langmuir吸附的一级反应动力学模型,采用初始速率法拟合得到反应速率常数和吸附平衡常数。模型计算得到的反应转化率与试验值吻合较好。利用该模型进行模拟分析,能较准确地描述反应条件对对二甲苯收率的影响。     

正丁烷异构化制异丁烷反应热力学分析及试验研究

在分析正丁烷异构化制异丁烷反应特点的基础上,通过系统的热力学计算,获得了不同反应温度下目标反应的标准摩尔焓变、标准摩尔吉布斯自由能变、标准平衡常数及正丁烷平衡转化率,并以Pt/Al₂O₃-Cl为催化剂进行了正丁烷异构化反应试验研究。结果表明,正丁烷异构化属微放热反应,降低反应温度可提高正丁烷的平衡转化率;对于Pt/Al₂O₃-Cl催化正丁烷异构化反应,反应温度、反应压力、正丁烷进料空速和氢/烃摩尔比均对正丁烷转化率有较明显的影响,选择合适的反应温度和压力,并适当降低进料空速和氢/烃摩尔比,有利于提高正丁烷转化率;在优化的反应条件下,正丁烷的试验转化率与热力学平衡转化率基本吻合,验证了热力学分析结果的可靠性。