金属酸盐催化剂对苯酚羟基化反应的活性考察

苯酚羟基化联产邻苯二酚和对苯二酚是一条典型的绿色工艺路线.通过对多种金属酸铁酸盐进行筛选,得出以Fe(NO3)3.9H2O为铁源、Cu(CH3COO)2.H2O为铜源,以氨水为沉淀剂,采用共沉淀法制备的Fe-Cu复合金属酸盐催化剂具有最好的催化活性.结果表明,在水作溶剂,催化剂与苯酚的质量比为1∶100,苯酚初始浓度25%,反应温度65℃,苯酚与双氧水的摩尔比为2的条件下,采用Fe-Cu催化剂,苯酚单程转化率可达25%,苯二酚总选择性在90%左右.通过对铁酸盐催化剂的XRD、IR表征,可以看出,Fe-Cu催化剂具有独特的CuFe2O4尖晶石结构,因而具有不同于其它铁酸盐的衍射峰和吸收峰.另外,Fe-Cu催化剂制备简便、原料廉价易得,因此具有良好的工业应用前景.     

邻对苯二酚的合成方法

用自制的钛硅沸石ＴＳ－１为催化剂，对Ｈ２Ｏ２存在下苯酚直接羟基化合成邻、对苯二酚的反应条件，主要影响因素及机理进行了探讨，发现该民传统的合成方法相比，反应的选择性及转化率较高，工艺简单，成本低和污染少。     

在La-TiO2催化剂上由苯酚直接氧化制取邻苯二酚的研究

以Ｌａ－ＴｉＯ２作为苯酚选择氧化催化剂,用过氧化氢氧化,得到邻苯二酚选择性高达９０％的良好结果,讨论了溶剂,反应温度,反应时间,过氧化氢浓度,催化剂用量,过氧化氢用量等工艺条件对苯酚羟基化作用的影响。     

苯酚在Ln—ZrO2催化剂上直接氧化制取邻苯二酚地研究

以Ｌｎ－ＺｒＯ２作为苯酚选择氧化催化剂，用过氧化氢氧化，得到邻苯二酚选择性高达８５．７％的良好结果，添加稀土元素镧，钕的氧化锆催化剂的单纯的二氧化钛催化剂相比，邻苯二酚选择性分别提高了７３．５％和６７．８％。     

多波长线性回归—导数分光光度法测定对苯二酚,邻苯二酚和苯酚

本文将导数分光光度法与多波长线性回归法联用，测定了电有机合成产品中的对苯二酚，邻苯二酚和苯酚的含量，回收率在９５．０％～１００．１％之间，模拟合成样品分析结果的相对误差对０．１％～６．６％。方法简便。     

苯酚在Ln-ZrO_2催化剂上直接氧化制取邻苯二酚的研究

以ＬｎＺｒＯ２作为苯酚选择氧化催化剂，用过氧化氢氧化，得到邻苯二酚选择性高达８５７％的良好结果，添加稀土元素镧、钕的氧化锆催化剂与单纯的二氧化钛催化剂相比，邻苯二酚选择性分别提高了７３５％和６７８％。     

TS－1分子筛催化苯羟基化反应

ＴＳ－１分子筛对苯羟基化反应有着较高的催化活性及选择性．在反应体系中加入适量的无机酸，可提高反应的选择性；增加催化剂ＴＳ－１及Ｈ２Ｏ２的加入量，由于转化率的提高，反应选择性略有下降，而产物分布中苯酚的含量减少，苯醌的含量增大．ＴＳ－１催化苯羟基化反应是一个复杂的串连反应过程，即首先是苯氧化为苯酚，然后苯酚进一步氧化为苯二酚（对苯二酚为主），苯二酚再进一步氧化为醌．提高反应温度，Ｈ２Ｏ２的转化率和选择性随之提高，并且产物分布中苯酚的含量增大，醌的含量减少，这可能是热力学因素所致     

双杂原子Ti-Mn-β沸石的合成、表征及催化苯酚羟化反应

采用水热合成法在SiO2-TiO2-MnO2-(TEA)2O-H2O-NH4F体系中合成了Ti-Mn-β沸石。 运用X射线衍射、红外光谱、固体紫外可见漫反射、热重-差热、扫描电子显微镜和X射线光电子能谱等技术手段对样品进行了表征,探讨了影响Ti-Mn-β沸石合成的因素。 Ti-Mn-β沸石在以H2O2为氧化剂的苯酚羟基化反应中表现出较好的催化活性,苯酚的转化率为29.8％,邻苯二酚和对苯二酚的选择性分别为70.9％和26％。     

超导型复合氧化物在苯酚羟化反应中催化作用

采用柠檬酸络合法合成了一系列含铜复合氧化物(超导体)．用化学滴定方法和 O2-TPD等技术对所合成的复合氧化物的组成和表面性质进行了测定．通过探讨催化 剂结构与活性的关系，发现含铜复合氧化物中的非化学计量氧和铜离子的平均价态 与苯酚经化活性和过氧化氢分解活性密切相关．在实验中观察到酪类化合物在苯酚 经化反应循环中具有增强电子传递功能，在此基础上提出了酮类化合物参与催化循 环的机理．     

Pyridine-keggin heteropoly compounds as catalyst for hydroxylation of phenol using hydrogen peroxide as oxidant

The pyridine-heteropoly compounds are very active catalysts for phenol hydroxylation to dihydroxybenzenes with hydrogen peroxide as oxidant in aqueous solutions. The conversion of phenol reaches 77.8%, and the selectivity for dihydroxybenzenes reaches 99%.     

催化苯酚羟基化制邻、对苯二酚的研究进展

概述了苯酚双氧水羟基化催化剂的研究进展,指出水滑石类催化剂催化苯酚羟基化反应具有良好的应用前景,并对苯酚双氧水羟基化反应的影响因素和催化反应机理进行了讨论。     

苯酚羟化反应中焦油的分离与分析

利用高速离心、减压蒸馏和萃取等方法分离和定量分析苯酚催化羟化反应中所产生的副产物焦油,讨论各种方法的特点.使用萃取方法系统地考察了各种条件下,以Cu2(OH)PO4为催化剂时苯酚羟化反应体系中焦油的生成量.     

铜铝水滑石类化合物催化苯酚羟化反应的研究

利用共沉淀法合成了不同Cu/Al比例的铜铝水滑石类化合物, 且利用XRD, IR对此类化合物进行了表征。首次用于催化苯酚羟化反应,并获得了较好的结果, 同时探讨了Cu/Al比例, 反应温度, 反应介质及介质的pH值对反应活性的影响。初步提出了反应机理。     

Surface characterization and catalytic evaluation of copper-promoted Al-MCM-41 toward hydroxylation of phenol

The Mobil Composition of Matter No. 41 (MCM-41) containing Cu and Al with Si/Al ratios varying from 100 to 10 and 1 to 6 wt.% of Cu was synthesized under hydrothermal and impregnation conditions, respectively. The samples were characterized by nitrogen adsorption–desorption measurements, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS), temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), and ²⁹Si and ²⁷Al magic-angle spinning–nuclear magnetic resonance (MAS–NMR) spectra. X-ray diffraction patterns indicate that the modified materials retain the standard MCM-41 structure. TPR patterns show the two-step reduction of Cu species. TPD study shows that Cu-impregnated Al-MCM-41 samples are more acidic than Al-MCM-41. From the MAS–NMR it was confirmed that most of the Al atoms are present tetrahedrally within the framework and some are present octahedrally in extraframework position. Impregnation of Cu shifted Al to the extraframework position. The catalytic activity of the samples toward hydroxylation of phenol in aqueous medium was evaluated using H₂O₂ as the oxidant at 80 °C. The effects of reaction parameters such as temperature, catalyst amount, amount of H₂O₂, and solvent were also investigated. Sample containing 4 wt.% copper-loaded Al-MCM-41-100 showed high phenol conversion (78%) with 68% catechol and 32% hydroquinone selectivity.     

Pyridine-H_5PMo_(10)V_2O_(40) hybrid catalysts for liquid-phase hydroxylation of benzene to phenol with molecular oxygen

Pyridine(Py)-modified Keggin-type vanadium-substituted heteropoly acids(PynPMo10V2O40,n=1 to 5) were prepared by a precipitation method as organic/inorganic hybrid catalysts for direct hydroxylation of benzene to phenol in a pressured batch reactor and their structures were detected by FT-IR.Among various catalysts,Py3PMo10V2O40 exhibits the highest catalytic activity(yield of phenol,11.5%),without observing the formation of catechol,hydroquinone and benzoquinone in the reaction with 80 vol% aqueous acetic ...     

Catalysis of the rare earth containing mixed oxides Ln_2CuO_4 in phenol hydroxylation

Mixed oxides Ln2CuO4±λ(Ln=La,Pr,Nd,Sm,Gd) with K2NiF4 structure were prepared Their crystal structures were studied with XRD and IR spectra.Meanwhile,the average valence of Cu ions and non stoichiometric oxygen (λ) were determined through chemical analyses.Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated.Results show that the catalysis of these mixed oxides has close relation with their structures and composition.Substitution of A site atom in Ln2CuO4λ has a great influence on then eatalysis in the phenol hydroxylation.     

Catalysis of the rare earth containing mixed oxides Ln2CuO4 in phenol hydroxylation

Mixed oxides Ln₂Cu0_{4 ± λ} (Ln = La, Pr, Nd, Sm, Gd) with K₂NiF₄ structure were prepared. Their crystal structures were studied with XRD and IR spectra. Meanwhile, the average valence of Cu ions and nonstoichiometric oxygen (λ) were determined through chemical analyses. Catalysis of the above-mentioned mixed oxides in the phenol hydroxylation was investigated. Results show that the catalysis of these mixed oxides has close relation with their structures and composition. Substitution of A site atom in Ln₂CuO_4±λ has a great influence on their catalysis in the phenol hydroxylation. Project supported by the National Natural Science Foundation of China.     

Kinetics and reaction mechanism of phenol hydroxylation catalyzed by La-Cu_4FeAlCO_3

Phenol hydroxylation is an industrially important reaction, whose main products are catechol and hy-droquinone being diverse applications which are im-portant intermediates for perfumes, drugs, and phar-maceuticals and so on[1]. The processes using H2O2 a…