碘掺杂聚苯胺催化剂催化合成环己酮乙二醇缩酮

以自制的单质碘掺杂聚苯胺(I2/PAn)为催化剂,环己酮和乙二醇为原料,合成了环己酮乙二醇缩酮。探讨了碘掺杂聚苯胺催化剂对缩酮反应的催化活性,较系统地研究了原料摩尔比、催化剂用量、反应时间等因素对产物收率的影响。实验表明:碘掺杂聚苯胺是合成环己酮乙二醇缩酮的良好催化剂,在酮醇摩尔比1:1.6,催化剂用量为反应物料总质量的0.2%,环己烷为带水剂,反应时间1.0 h的优化条件下,环已酮乙二醇缩酮的收率可达90.1%。     

邻苯基苯酚的合成研究

以环己酮为原料,酸性树脂为催化剂,在减压下进行缩合反应,得到中间体2-(1-环己烯基)环己酮。然后,在贵金属催化剂存在下,进行气相脱氢反应,合成邻苯基苯酚。考察了反应温度、2-(1-环己烯基)环己酮的进料流量、氢气的进料流量以及贵金属催化剂的预处理对邻苯基苯酚收率的影响。从而确定了合成工艺条件为:反应温度375℃;2-(1-环己烯基)环己酮的进料流量4mL/h;氢气的进料流量60mL/min;用去离子水洗涤处理贵金属催化剂。在此条件下,邻苯基苯酚的收率达94%以上。     

环己酮和环己酮肟在甲苯-磷酸缓冲溶液中的液液平衡

以肟化塔的优化操作为背景,测定了环己酮肟和环己酮在甲苯和磷酸缓冲溶液中的分配系数,考察了pH值和磷酸根浓度等因素对其平衡关系的影响。并在此基础上总结了半经验公式,可用于肟化塔的设计和操作分析。利用Margules方程对环己酮的平衡数据进行了关联,求出了相应的模型参数,并结合实际,就有关实验结果进行了分析和讨论。     

Solvent-free partial oxidation of cyclohexane to KA oil over hydrotalcite-derived Cu-MgAlO mixed metal oxides

A highly efficient and stable hydrotalcite-derived Cu-MgAlO catalyst was developed for the partial oxidation of cyclohexane with molecular oxygen. The physical-chemical properties of Cu-MgAlO catalysts were studied, and the results indicated that the copper component had been successfully introduced into the hydrotalcite unit layer structure. The catalytic reaction results showed that copper as the active species could activate C-H bond and effectively promote the decomposition of cyclohexyl hydroperoxide (CHHP) to the mixture of cyclohexanol and cyclohexanone (KA oil). 8.3% of cyclohexane conversion and 82.9% of selectivity for KA oil were obtained over 9%Cu-MgAlO catalyst at 150℃ with 0.6 MPa of oxygen pressure for 2 h. Especially, its catalytic performance was still stable after five runs.     

ZnMgAl三元类水滑石催化合成ε-己内酯

通过共沉淀法制备了ZnMgAl三元类水滑石,利用X射线衍射(XRD)对其结构进行了表征,研究了其对双氧水氧化环己酮成ε-己内酯的催化性能.比较了不同催化剂的反应性能,考察了反应温度、反应时间、双氧水用量等工艺条件对反应性能的影响.结果表明,ZnMgA1三元类水滑石对ε-己内酯的合成具有较好的催化活性.当催化剂用量0.375 9、环己酮18.5 mmol、30％ H2O2 245 mmol、乙腈15 mL、反应温度80℃、反应4h时,环己酮转化率为74.1％,ε-己内酯选择性达95.0％.     

Effect of sodium ions in synthesis of titanium silicalite-1 on its catalytic performance for cyclohexanone ammoximation

Titanium silicalite-1 (TS-1) has been hydrothermally synthesized with tetrapropylammonium hydroxide (TPAOH) as the template in the presence of various amounts of Na⁺, characterized by inductively coupled plasma, X-ray diffraction, scanning electron microscope, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and ultro-violet-visible spectroscopy and studied in cyclohexanone ammoximation. The characterization results show that with the increase of Na⁺ concentration in the synthesis, both the crystal sizes of TS-1and extra framework Ti increase but framework Ti decreases. The addition of Na⁺ below 3 mol-% of TPAOH in the synthesis does not influence the catalytic properties with above 98% conversion of cyclohexanone and 99.5% selectivity to cyclohexanone oxime. However, at the concentrations of Na⁺≥3 mol-% of TPAOH in the synthesis, the catalysts are deactivated faster with the increase of Na⁺ addition, which can be attributed to more high molecular weight byproducts deposited in the large TS-1 particles and the loss of the frame-work titanium. The results of this work are of great importance for the industry.     

用醇酮废水生产C_(4～6)混合二羧酸的影响因素分析

以醇酮废水(环己烷空气氧化法生产环己醇/环己酮装置水洗塔酸性洗涤水)为原料生产C4～6混合二羧酸,考察了产品纯度(产品中C4～6二羧酸的质量分数)的影响因素.结果表明,在分解液密度为1.072～1.092 g/cm3,m(硝酸)/m(分解液)为0.8～1.2,氧化温度为35～78℃,氧化时间为4～6 h,蒸发终点温度为150～155℃的最佳工艺条件下,可获得纯度大于94%的混合二羧酸产品.     

杂多酸(盐)催化环己酮氨肟化反应

 制备了4种杂多酸并用红外光谱对其进行了表征,研究了它们及其负载型催化剂对环己酮氨肟化反应的催化性能,并以磷钨酸为催化剂,考察了催化剂用量、反应温度、反应时间、H2O2用量、氨水用量和溶剂种类对环己酮氨肟化反应转化率和环己酮肟选择性的影响。结果表明,所制备的4种杂多酸均具有Keggin型结构。以水为溶剂时,4种杂多酸对环己酮氨肟化反应均具有催化活性,其中磷钨酸的催化活性最高。在m(H3PW12O40)/m(C6H10O)为0.3、n(H2O2)/n(C6H10O)为1.6、n(NH3)/n(C6H10O)为3.0、20℃下反应5h的条件下,环己酮氨肟化反应的转化率为90.88%,环己酮肟选择性达98.38%。在相同的反应条件下,负载型磷钨酸催化剂中,以活性Al2O3为载体的磷钨酸催化剂环己酮氨肟化反应的催化活性最高,环己酮转化率为87.60%,环己酮肟选择性达到97.45%。     

焙烧温度对Silicalite-1催化环己酮肟气相Beckmann重排反应的影响

采用水热方法合成Silicalite-1分子筛,考察不同焙烧温度处理后用于催化环己酮肟气相Beckmann重排反应的催化性能。利用XRD,IR,BET和热分析方法对催化剂进行表征。结果表明,焙烧温度对环己酮肟的转化率和催化剂稳定性的影响较大,而对己内酰胺的选择性影响不明显。随着焙烧温度的升高,分子筛的比表面积变化不明显,而外表面积先增大后减小,微孔体积积占总孔体积积的比例呈下降趋势。最佳的焙烧温度为400 °C,在该焙烧温度下的分子筛用于气相Beckmann重排反应中的活性和稳定性最佳。     

苯酚催化氢转移制环己酮的新工艺

以3-(三苯基膦)二氯化钌[RuCl2(PPh3)3]作催化剂,甲酸钠为氢供体,研究了氢转移催化苯酚加氢制环己酮的新工艺。确定了氢转移加氢过程的适宜反应条件为：甲酸钠和苯酚用量摩尔比为4∶1,反应温度为70 ℃,反应时间为3.0 h,RuCl2(PPh3)3和苯酚用量质量比为5∶100。苯酚的转化率为100%,环己酮产率为95.1%。探讨了以甲酸钠为氢供体的反应过程,发现RuCl2(PPh3)3对苯酚氢转移加氢制环己酮具有优异的催化活性。