氧气直接氧化苯制备苯酚

苯酚是重要的化工原料,其工业生产主要是通过异丙苯氧化法制备,该方法存在制备流程长、消耗丙烯多以及产生大量副产物等不足。苯直接氧化制备苯酚,特别是氧气直接氧化苯制备苯酚,因其步骤少、操作成本低、环境友好等特点已成为苯酚绿色制备的研究热点。本文较为系统地总结了氧气氧化苯液相法合成苯酚的研究工作,综述了该反应体系下的反应机理以及所使用的催化剂、还原剂等;归纳了反应温度、反应压力、还原剂用量及反应溶剂等反应条件对苯酚产率的影响;分析了目前氧气直接氧化苯液相法制苯酚研究中存在的问题,并总结了未来的研究方向。     

FeZSM-5/N2O催化氧化苯制苯酚

苯一步氧化制苯酚 ,是有机物氧化合成中富有挑战性的研究课题之一。该文着重论述了在Fe ZSM- 5及其一系列沸石催化剂上 ,应用氧化亚氮作为氧化剂使苯直接氧化制苯酚的研究进展。这一系列催化剂体系的特殊之处在于通过氧化亚氮在沸石分子筛上的分解获得具有催化活性的 α-氧。详细讨论了在沸石分子筛上形成特殊结构的铁氧化物作为催化活性中心这一观点。由于这种催化体系对苯直接氧化制苯酚的反应有着很高的选择性 ,因此 ,这种比较经济和安全的制备苯酚的方法引起了人们的广泛关注     

FeZSM-5/N2O催化氧化苯制苯酚

苯一步氧化制苯酚，是有机物氧化合成中富有挑战性的研究课题之一。该文着重论述了在FeZSM-5及其一系列沸石催化剂上，应用氧化亚氮作为氧化剂使苯直接氧化制苯酚的研究进展。这一系列催化剂体系的特殊之处在于通过氧化亚氮在沸石分子筛上的分解获得具有催化活性的a－氧。详细讨论了在沸石分子筛上形成特殊结构的铁氧化物作为催化活性中心这一观点。由于这种催化体系对苯直接氧化制苯酚的反应有着很高的选择性，因此，这种比较经济和安全的制备苯酚的方法引起了人们的广泛关注。     

分子氧催化氧化苯直接合成苯酚

苯酚是重要的有机合成中间体,当前主要通过异丙苯法合成苯酚的技术路线存在制备流程长、消耗丙烯、副产丙酮等不足。以分子氧为氧化剂由苯氧化直接合成苯酚则具有潜在重大的经济效益、社会效益和环境效益，已成为催化与有机合成等研究领域中极具挑战性的热点课题之一。本文较为系统地总结了分子氧氧化苯通过一步法合成苯酚的研究工作，着重综述了用于该反应的催化剂如Pd、Cu、V等金属或其化合物，也归纳了影响此反应的主要因素，并介绍相应的反应机理。最后，对分子氧催化氧化苯合成苯酚反应的研究提供了一些建议和展望。     

硅钼钒和硅钨钒杂多酸的制备及其在苯直接羟基化制苯酚中的活性研究

本文采用分步反应、分步酸化法制备了硅钼钒和硅钨钒杂多酸,用等离子原子发射光谱、热重分析、红外、紫外、粉末X射线对制备的化合物进行了表征。结果表明,制备所得化合物为Keggin结构的杂多酸。同时,本文还用该杂多酸作催化剂,研究了其对由苯直接氧化羟基化合成苯酚的催化活性,结果显示,在本文条件下,用所合成的杂多酸作催化剂,可获得17.2%苯酚收率和高于90%的苯酚选择性。     

碳铁催化剂的研究进展

Fe_xO_y/C复合材料作为催化剂,在有机化合物的催化氧化方面表现出非常高的活性,如对苯甲醇催化氧化苯甲醛,苯乙烯催化氧化苯甲醛,苯甲醛催化氧化苯甲酸,苯催化氧化苯酚,是最高效的催化剂之一。近年来的研究报道中,Fe_xO_y/C复合材料的制备方法主要有水热合成法,浸渍法和超声喷雾热解法。比较了三种方法各有利弊,以期寻找一种更加高效,方便,省时的制备Fe_xO_y/C复合材料的方法。其中溶液燃烧法尤为重要,溶液燃烧法给Fe_xO_y/C复合材料的制备带来了新的机遇。     

几种载体载Ni催化剂上苯直接羟基化制备苯酚的研究

本文利用浸渍法制备了一系列不同载体的镍基催化剂,并将其用于苯的羟基化反应.用等离子原子直读光谱、粉末X射线衍射分析、比表面测试等对所制备的催化剂进行了表征.发现在所制备的催化剂中,以γ-Al2O3为载体的Ni1.7/γ-Al2O3 催化剂在苯的羟基化反应中具有相对较好的催化活性和选择性,而在Ni/TiO2和Ni/NaX上,则苯酚的深度氧化严重.     

钒钼磷杂多酸催化苯直接羟化为苯酚的动力学研究

以钒钼磷杂多酸作为催化剂,用紫外可见分光光度法研究了过氧化氢直接将苯氧化羟基化为苯酚反应的动力学行为。结果表明,该氧化羟化反应速率对底物苯、氧化剂和催化剂都是一级反应,反应的活化能为57.73kJ.mol-1。本文推测了杂多酸配合物催化苯氧化羟化为苯酚反应的过程,建立了该反应动力学数学模型,模型很好地解释了实验结果。     

基于多金属氧酸盐的介孔离子催化剂催化苯一步氧化制苯酚（英文）

苯酚是一种重要的有机化工原料,工业上主要采用合成路线长、原子利用率低、能耗高、环境污染严重的异丙苯法生产.当前,随着绿色化学的普及,H_2O_2催化苯一步氧化制苯酚受到越来越多的关注.在研究的众多催化剂中,钒取代杂多酸被认为是该反应最有效的催化剂之一.然而,纯杂多酸易溶于H_2O_2催化的苯羟基化反应体系,导致污染严重、后处理和分离困难.为了获得可回收的固体杂多酸催化剂,通常将其负载于多孔载体上,但这种方法常伴随着活性组分易溶脱,反应速率慢等缺点.因此,在H_2O_2催化苯一步氧化制苯酚体系中获得高效、可重复使用的杂多酸基固体催化剂仍然是一个挑战.采用有机单元修饰杂多酸是制备杂多酸基固体催化剂的有效方法.研究表明,有机基团的引入可以有效调控杂多酸的溶解性和氧化还原性.另一方面,催化剂中的疏水微环境也能有效促进非极性底物与催化活性中心的相互作用,提高反应速率,改善催化活性.因此,我们通过离子交换法将对二甲苯型双核咪唑离子液体阳离子与含钒杂多阴离子结合,研究制备了一种具有疏水微环境的介孔杂多酸基离子固体催化剂.采用傅里叶变换红外光谱、X射线衍射、扫描电镜、N2吸附-脱附和CHN元素分析等表征手段对催化剂进行全面分析.结果表明,该催化剂是一种具有较高比表面积的半无定形疏水有机杂多酸盐.在H_2O_2催化的苯一步氧化制苯酚反应中引导了液-固两相催化体系,在反应时间1 h,反应温度70 oC,苯酚产率可达到28.9%,与均相纯杂多酸的催化活性基本相当,且催化剂重复使用性能良好.催化剂构效关系和反应动力学研究表明,高比表面积和疏水微环境的构建加快了苯与催化活性中心的相互作用,提高了催化反应速率和产物选择性.同时,咪唑基离子液体阳离子通过分子内的电子相互作用改善了杂多阴离子的氧化还原能力,也赋予固体催化剂更高的催化活性.该研究为H_2O_2催化苯一步氧化制苯酚反应提供了一种制备简单,经济高效,可重复使用的杂多酸基固体催化剂.     

PdCl_2－CuCl_2／海泡石催化剂对苯一步氧化法制苯酚的催化作用

ＰｄＣｌ２┐ＣｕＣｌ２／海泡石催化剂对苯一步氧化法制苯酚的催化作用＊曹声春杨礼嫦黄孟光（湖南大学化工系，长沙４１００８２）关键词氯化钯，氯化铜，海泡石，负载型催化剂，苯，苯酚，催化机理国内外现行的由苯合成苯酚的方法有磺化法、氯苯法、Ｒａｓｃｈｉｎｇ－...     

Oxidation of benzene with hydrogen peroxide catalyzed with ferrocene in the presence of pyrazine carboxylic acid

It is found that ferrocene in the presence of small amounts of pyrazine carboxylic acid (PCA) effectively catalyzes the oxidation of benzene to phenol with hydrogen peroxide. Two main differences upon the oxidation of two different substrates, i.e., cyclohexane and benzene, with the same H₂O₂-ferrocene-PCA catalytic system are revealed: the rates of benzene oxidation and hydrogen peroxide decomposition are several times lower than the rate of cyclohexane oxidation at close concentrations of both substrates, and the rate constant ratios for the reactions of oxidizing particles with benzene and acetonitrile are significantly lower than would be expected for reactions involving free hydroxyl radicals. The overall rate of hydrogen peroxide decomposition, including both the catalase and oxidase routes, is lower in the presence of benzene than in the presence of cyclohexane. It is suggested on the grounds of these data that a catalytically active particle different from the one generated in the absence of benzene is formed in the presence of benzene. This particle catalyzes hydrogen peroxide decomposition less efficiently than the initial complex and generates a dissimilar oxidizing particle that exhibits higher selectivity. It is shown that reactivity of the system at higher concentrations of benzene differs from that of an initial system not containing an aromatic component with the capability of π-coordination with metal ions.     

Hydroxylation of benzene in the system vanadium(V)-hydrogen peroxide-acetic acid

Hydroxylation of benzene in acetic acid at 323 K was studied in the presence of a sodium orthovanadate catalyst. With hydrogen peroxide as aqueous solution, the yield of phenol was 12–14%. With hydrogen peroxide generated from dry sodium peroxide, the yield of phenol could be improved to 21–23%. The apparent decomposition rate constants of hydrogen peroxide in acetic acid are presented.     

磷钼钒杂多酸催化苯制苯酚的研究

将磷钼钒杂多酸应用于以过氧化氢作氧化剂,冰醋酸作溶剂的苯一步氧化制苯酚反应中,分别考察了杂多酸、过氧化氢和冰醋酸的用量,以及反应温度和反应时间等因素对苯制苯酚反应的影响,并通过单因素实验方法确定了较为适宜的工艺条件.     

硅钼钒和硅钨钒杂多酸催化过氧化氢直接氧化苯制苯酚的活性研究

以自制的两种Keggin型杂多酸,硅钼钒杂多酸和硅钨钒杂多酸作催化剂,冰醋酸作溶剂,过氧化氢作氧化剂,研究了由苯直接羟基化制苯酚的催化活性,发现对于所研究的体系,即苯为0.02mol,过氧化氢为0.16mol,冰醋酸为0.24mol,当杂多酸的用量为0.10~0.15mmol、反应温度323K、反应时间80min时,硅钼钒和硅钨钒上苯酚的收率分别可达17.2%和4.3%,选择性达90.3%和87.4%.     

Effect of solvent nature on the catalytic activity of iron-containing pyrocatecholsulfonic cationite in the reactions of H<Subscript>2</Subscript>O<Subscript>2</Subscript> decomposition and benzene hydroxylation

Kinetics of hydrogen peroxide decomposition under the conditions of heterogenous catalysis with iron-containing pyrocatecholsulfonic cationite at 50°C in dimethyl sulfoxide, tetrahydrofuran, dioxane, acetonitrile, and nitromethane was studied. The value of rate constant of hydrogen peroxide decomposition in these solvents was found to diminish with increase of solvent nucleophilicity. At the hydroxylation of benzene in the aqueous acetonitrile medium the formation of phenol was observed. The phenol yield was found to depend on the composition of the binary solvent acetonitrile-water.     

苯直接羟基化制苯酚研究进展

综述了苯直接羟基化制苯酚的几种催化反应,包括阳极氧化法、N₂O氧化法、H₂O₂氧化法、O₂直接氧化法,这些反应均具有良好的原子经济性和环境效益.同时重点介绍了相关的催化剂及其活性中心,探讨了这些新型方法的工业应用前景.     

Ni-Zr-Ce／Al2O3催化剂上H2O2作氧化剂直接使苯氧化胺化一步合成苯胺研究

设计制备了Ni-Zr-Ce/Al_2O_3催化剂,研究了其上用H_2O_2直接将苯氧化胺化 合成苯胺的活性。发现在常压、50 ℃的温和条件下,该催化剂对苯、氨水与 H_2O_2直接氧化胺化生成苯胺有较好活性,并且其对苯胺的选择性远远大于对苯酚 的选择性。提高反应原料中氨水对苯的比例,能提高苯胺的收率,且不会增加苯酚 的生成量。本方法能耗低,原子利用率高,为苯胺的绿色合成提供了一条新的路径 。     

Transition metal substituted polyoxometalates and their application in the direct hydroxylation of benzene to phenol with hydrogen peroxide

A series of transition metal substituted polyoxometalates with a Keggin structure were prepared and utilized for the hydroxylation of benzene to phenol. Among the compounds tested, [(CH₃)₄N]₄PMo₁₁VO₄₀ exhibits the highest phenol yield (13.0%) and selectivity (90.6%) in acetic acid/acetonitrile. Vanadium peroxo is the active site of the reaction, and ammonium also plays an important role. The influence of various reaction parameters, such as solvent, reaction time, reaction temperature, and amount of hydrogen peroxide used were investigated to obtain the optimal reaction conditions.     

Determination of hydroxyl radical photoproduction rates in natural waters.

The photochemical formation rates of hydroxyl radicals (OH radicals) in river water and seawater were determined by a simple, rapid and sensitive benzene probe method, in which phenol formed by the reaction between benzene and photochemically-generated OH radicals was analyzed by on-line preconcentration HPLC. The OH radical formation rates from well-known OH radical sources, such as nitrate, nitrite and hydrogen peroxide, were in good agreement with those reported previously. River water samples containing high concentrations of nitrate and nitrite were found to show high OH radical formation rates. Ten to 80% of the OH radical formation in river water and seawater was due to the photolysis of nitrate and nitrite, but OH radical formation from hydrogen peroxide was negligible. The OH radical formation from unknown sources other than nitrate, nitrite and hydrogen peroxide was strongly correlated to the amount of fluorescent matter.     

Catalytic activity of iron-containing polymers in hydroxylation of benzene with hydrogen peroxide

Hydroxylation of benzene with hydrogen peroxide in aqueous acetonitrile at 50°C was studied. The KU-2-8 and KU-1 cation exchangers, and also specially synthesized cation exchangers and phenolformaldehyde resins derived from pyrocatechol and resorcinol, all modified with Fe(III) cations, were used as catalysts. The macrocomplex KU-2-8/Fe³⁺ showed the highest catalytic activity and ensured 32% yield of phenol in 15 min. The formation of phenol depends in a complex fashion on the initial concentration of hydrogen peroxide, content of Fe(III) ions in the polymer, and reaction time.