In situ13C NMR study of tert-butanol interaction with moderately concentrated sulfuric acid

An in situ NMR study of tert-butanol dehydration in 95 and 85% sulfuric acid did not indicate the formation of tert-butyl cations as active reaction intermediates. Instead, only NMR lines from oxonium ions under the condition of fast exchange with water and the acid were observed. It is most likely that, in the concentrated acid, the active intermediates of this reaction are represented by tert-butyl sulfuric ester which probably is a precursor of invisible tert-butyl carbenium ions representing short-lived excited or transition states.     

加碱萃取精馏制取无水叔丁醇

以乙二醇与KOH的混合物作萃取剂,采用加碱萃取精馏对85%叔丁醇进行分离,得到了纯度为99.5%的叔丁醇产品。设计了工艺流程,确定了操作条件,萃取剂可用减压精馏的方法回收,回收的萃取剂循环使用不影响分离性能。实验结果表明:加碱萃取精馏也是分离叔丁醇-水恒沸体系的有效方法。     

Butanol isomer separation using polyamide-imide/CD mixed matrix membranes via pervaporation

Mixed matrix membranes (MMMs) comprising polyamide-imide (PAI) and α-, β- or γ-cyclodextrin (CD) have been investigated experimentally and computationally for isomeric n-butanol/tert-butanol (n-BuOH/t-BuOH) separation via pervaporation. Consistent with molecular simulation, experimental results show that the CD inclusion ability and butanol discrimination ability are dependent on both CD cavity size and butanol molecular size. The PAI membrane incorporated with α-CD has the smallest cavity and has the highest discrimination ability for the n-BuOH/t-BuOH pair but with a low butanol flux. The mixed matrix membrane embedded with γ-CD has the lowest selectivity and the highest flux. The PAI/β-CD membrane has a comparable selectivity and flux, and exhibits preferential sorption and diffusion selectivity toward n-BuOH. A maximum separation factor of 1.53 with a corresponding flux of 4.4 g/m² h are obtained at an optimal β-CD loading of 15 wt%. Further increments in the CD content eventually lead to a decrease in separation performance because of CD agglomeration and severe phase separation. To better understand the influence of CD on the separation performance of mixed matrix membranes, SEM, FTIR and XRD have been employed for membrane characterizations. The effect of n-butanol/t-butanol ratio in the feed composition has also been studied. It is found that both flux and separation factor decrease with increasing n-butanol content in the feed. The decline is attributed to the change in total vapor pressure at the upstream and the mutual drag effect of isomeric butanol molecules.     

分隔壁共沸精馏塔分离叔丁醇水混合物的模拟研究

提出了一种单塔共沸精馏分离叔丁醇水混合物的新工艺,新工艺采用分隔壁共沸精馏塔(DWC-A)替代常规共沸精馏流程的共沸精馏塔及回收塔,不仅节省了设备投资,而且降低了总能耗。利用ASPENPLUS模拟软件,对分隔壁共沸精馏塔及常规萃取流程进行了模拟。分隔壁共沸精馏塔的操作条件为:主塔理论板数为25块,副塔理论板数为10块,环已烷为共沸剂,在此条件下,比较了常规萃取精馏流程与分隔壁精馏塔内温度、液相组成及汽液相流量的变化。结果表明,分隔壁共沸精馏塔比常规的两塔萃取精馏流程节能17.8%。     

蒽氧化合成蒽醌研究进展

对国内外目前蒽氧化生产蒽醌相关研究进展进行了综述,对蒽醌生产的方法及应用进行了分析,得出目前蒽气相氧化法制备蒽醌具有原材料充足、成本相对低廉、环境友好等优势,是目前较为理想的蒽醌生产方法。并对使用过氧化叔丁醇、双氧水和氧气3种不同氧化剂制备蒽醌的方法进行了分类综述,详细的介绍了这3种氧化剂制备蒽醌的研究现状。     

汽油抗爆剂甲基叔丁基醚合成研究进展

根据原料的不同,对汽油抗爆剂甲基叔丁基醚的合成方法进行了综述。威廉逊合成法因为原料昂贵只适用于少量合成;甲醇和叔丁醇脱水醚化合成甲基叔丁基醚由于原料相对便宜,既可以用于实验室合成,也可以推广至工业化生产;甲醇和异丁烯反应生产甲基叔丁基醚是目前最主要的工业化生产方法。由于异丁烯来源受限,利用廉价原料生产异丁烯成为甲基叔丁基醚合成中的重要研究方向,也有以非异丁烯为原料的甲基叔丁基醚合成路线研究。     

Al-MSU-S(Y)催化剂上对苯二酚与叔丁醇的烷基化反应

合成了不同Al含量的介孔分子筛MSU-S(Y)(Al-MSU-S(Y))催化剂,并利用X射线衍射、N2吸附-脱附和NH3程序升温脱附(NH3-TPD)方法对它们的结构和表面酸量进行了表征;考察了Al-MSU-S(Y)催化剂在对苯二酚与叔丁醇烷基化反应中的催化活性。实验结果表明,随Al含量的增加,Al-MSU-S(Y)催化剂的介孔结构变得无序,而且Al-MSU-S(Y)催化剂的活性与其表面强酸位的酸量有关。Al质量分数5%的Al-MSU-S(Y)催化剂具有规整的介孔结构,其表面强酸位的酸量最多,表现出良好的催化活性,在140℃时对苯二酚的转化率和2-叔丁基对苯二酚(2-TBHQ)的收率分别为62.2%和44.7%,催化剂重复使用3次后,2-TBHQ的收率仅降至41.5%。该催化剂不仅性能稳定而且可重复使用。     

离子液体催化邻苯二酚与叔丁醇烷基化反应

 以廉价的烷基胺为原料合成了SO3H-功能化的离子液体（IL）。采用NMR、ESI-MS、TG-DTG等手段对其结构及物性进行了表征。将该离子液体作为催化剂,考察反应条件对离子液体催化邻苯二酚叔丁醇(TBA)烷基化反应性能的差别。结果表明,在反应温度150 ℃、反应时间3 h、n(邻苯二酚):n(TBA):n(IL)为2:1:0.1的优化条件下,邻苯二酚的转化率、4-叔丁基邻苯二酚(4-TBC)的选择性分别可达41.5%和97.1%。与液体酸的催化效果接近。根据实验结果和模拟计算推测了可能的反应机理。     

叔丁醇钠合成新工艺

简要介绍了叔丁醇钠的性质、用途和合成方法,重点对叔丁醇与氨基钠合成叔丁醇钠新工艺进行了实验研究。实验结果表明:新工艺与老工艺(金属钠与叔丁醇反应合成叔丁醇钠)相比,在缩短反应产物干燥时间(由原来的15 h以上降低到2 h以下)、提高产品产量和质量(含量在99%以上)、安全操作等方面具有明显的工艺优势。