丙烷均相氧化脱氢及其应用

丙烷在８００～８４０Ｋ、Ｏ２／Ｃ０３比０．４４～１．６５、停留时间６．０～１３．５ｓ的条件下进行均相氧化脱氢。在丙烷转化率为４０％时，丙烯选择性为４２．５％，产率为１７．０％。用自丙烯生产丙烯醛的Ｍｏ－Ｃｏ－Ｒｅ－Ｂｉ－Ｏ催化剂，将上述反应产物在５９０～６１５Ｋ、Ｏ２／Ｃ０３综合比０．６５～１．１３、停留时间２．４～４．２ｓ的条件下氧化，得到丙烯醛按丙烷衡算的选择性＞３３．５％，产率＞１３．５％。这些结果可与用丙烷直接催化合成丙烯醛的文献数据相比拟。

丙烷均相氧化脱氢及反应动力学模拟

在不锈钢连续流动反应器内进行丙烷均相氧化脱氢的小型试验。丙烷转化率５５％～７５％时，主要产物Ｃ３Ｈ６、Ｃ２Ｈ４、ＣＨ４及ＣＯｘ（ＣＯ＋ＣＯ２）收率（按丙烷）分别为１７％～１９％、１９％～２８％、８％～１４％及１０％～１４％及约２．５％的乙烷。得出了符合本试验条件的以自由基反应机理为基础的动力学模型。用模型计算得的产物收率与试验结果吻合甚好。以丙烯收率为目标函数，对反应条件做了优化，得丙烯最高收率及相应的乙烯收率分别为２２％及３６％，丙烷转化率为８８．５％。反应条件为：温度８７０Ｋ（恒温），Ｏ２／Ｃ０３值０．４４，停留时间１．７ｓ。

丙烷均相氧化脱氢及丙烯氧化制取丙烯酸的方法及其装置

一种由丙烷直接均相氧化脱氢及丙烯氧化制取丙烯酸的方法及联合装置，其中包括脱氢管式反应炉、丙烯氧化反应器及丙烯醛氧化器等装置，脱氢后的反应混合物不经分离直接进入丙烯反应器，该方法减少工艺步骤，降低成本，可大幅度地增加丙烯、丙烯醛、丙烯酸的产率，在工业上很有利用价值。

Cu-catalyzed deoxygenative gem-hydroborylation of aromatic aldehydes and ketones to access benzylboronic esters

Organoboron compounds are widely used in synthetic chemistry,pharmaceutical chemistry and material chemistry.Among various organoboron compounds,benzylboronic esters are unique and highly reactive,making them suitable benzylation reagents.At present,the synthetic methods for the syntheses of benzylboronic esters are still insufficient to meet their demands.It is necessary to develop novel and practical methods for their preparation.In this work,a novel copper‐catalyzed deoxygenative gem‐hydroborylation of aromatic aldehydes and ketones has been developed.This direct and operationally simple protocol provides an effective approach for the synthesis of a variety of primary and secondary benzylboronates,in which broad functional group tolerance was presented.Widely available B2pin2(pin=pinacol)was used as the boron source and alcoholic proton was applied as the hydride source.