Synthesis of p‐aminophenol from the hydrogenation of nitrobenzene over metal–solid acid bifunctional catalyst

BACKGROUND: A single‐step conversion of nitrobenzene (NB) to p‐aminophenol (PAP) through catalytic hydrogenation is a widely used synthesis route for PAP. The main shortcoming of this route is the use of sulfuric acid for rearrangement of the phenylhydroxylamine (PHA) intermediate. In this paper, S₂O₈^2?/ZrO₂ (PSZ) solid acid and Pt‐S₂O₈^2?/ZrO₂ (Pt‐PSZ) bifunctional catalysts were prepared for the synthesis of PAP in non‐acid medium. RESULTS: Calcination temperature has a substantial effect on the acidity, structure and activity for PHA rearrangement of PSZ. The highest PAP yield was 33.8% over PSZ calcined at 823 K when the reaction was carried out in water at 423 K. A high PAP yield of 23.9% was achieved by a single‐step reaction of nitrobenzene over Pt‐PSZ bifunctional catalysts. CONCLUSION: PSZ solid acid exhibits high activity for PHA rearrangement. Perfect tetragonal ZrO₂ and much stronger acid sites play important roles in catalytic activity. Inhibiting the hydrogenation activity by reducing the amount of Pt loading on Pt‐PSZ can improve the competition of PHA rearrangement on acid sites with hydrogenation of PHA on metal active sites, resulting in better selectivity to PAP. Copyright © 2008 Society of Chemical Industry     

Reactant induced restructuring and corrosion of germanium-palladium catalysts during hydrogenation reactions

An anomalous rate enhancement with increasing conversion has been observed during the liquid phase hydrogenation of nitrobenzene and crotonaldehyde over Ge/Pd/C catalysts at ambient temperature and atmospheric pressure. Inductive coupled plasma atomic emission spectroscopy and electrochemical measurement of the oxidation state of catalysts during reaction revealed that the bimetallic particles were partially oxidized by the reactants, which resulted in Ge-dissolution and increased exposure of Pd on the surface. It is proposed that the surface and bulk composition of Ge/Pd catalysts are a function of their oxidation state. This behaviour is due to the unusually high mobility of Ge in the Pd lattice and to the good solubility of GeO₂ in polar solvents. The influence of hydrogen transport on the corrosion process and the stability of other X/Pd type bimetallic catalysts during liquid phase hydrogenation are also discussed.     

差分脉冲极谱法测定苯胺中微量硝基苯

建立了测定苯胺中微量硝基苯的差式微分脉冲极谱法。试验发现硝基苯在-0.57V(vs.Ag/AgCl)处有一个良好的差分脉冲极谱峰。硝基苯质量浓度在1～600μg/mL的范围内,质量浓度与差分脉冲极谱峰的峰高呈线性关系。此法简便、快速、灵敏,结果准确。     

间溴苯甲醚的合成研究

硝基苯经过溴化、还原、重氮化、甲基化得到间溴苯甲醚,总收率为40%。     

处理硝基苯类废水的Fenton催化氧化技术研究现状

硝基苯类化合物是高毒性物质,难以生物降解且对生化反应有抑制和毒害作用.因此,硝基苯对环境的污染问题越来越受到科学研究者的关注.目前,采用Fenton氧化技术降解硝基苯类化合物的机理和工艺研究越来越活跃.作者就近几年来国内外Fenton催化氧化技术降解硝基苯类废水的研究现状进行了综述.     

硝基苯加氢制备对氨基苯酚的工艺要素研究

在稀硫酸介质中,Pt/C催化,硝基苯加氢还原、转位得到目标化合物对氨基苯酚。工艺要素研究表明:硝基苯20mL,氢气压力为1kPa的水封压力,温度85～90℃,十六烷基三甲基溴化铵用量为0.1g,2%Pt/C催化剂0.5g,反应时间为5h时,所得产品质量达到并优于日本JISK4144 1986标准要求。     

Reaction Coupling of Ethylbenzene Dehydrogenation with Nitrobenzene Hydrogenation

The chemical equilibrium for the coupling of ethylbenzene dehydrogenation with nitrobenzene hydrogenation, to produce styrene and aniline simultaneously, has been calculated on the basis of the Soave–Redlich–Kwong equation of state. The dehydrogenation of ethylbenzene in the presence of nitrobenzene over the catalysts -Al₂O₃, ZSM-5, activated carbon and platinum supported on activated carbon has been carried out at 400 °C. The effects of Pt loading and the pretreatment of the catalysts have been investigated. It has been revealed that the conversion of ethylbenzene can be greatly improved by the reaction coupling due to the elimination of the hydrogen produced in the reaction by the hydrogenation of nitrobenzene. Platinum supported on the activated carbon has been suggested as a suitable catalyst. The best results with ethylbenzene conversion of 33.8% and styrene selectivity of 99.2% were obtained over Pt(0.02 wt%)/AC at 400 °C. Moreover, such process is also energetically favored since the necessary process heat to drive the ethylbenzene dehydrogenation can be provided by the coupling with the exothermic nitrobenzene hydrogenation reaction.     

二价铁离子对零价铁还原硝基苯的影响

为了解地下水环境中铁离子对零价铁(zero valention)还原作用的影响,采用批次实验,研究不同质量浓度二价铁离子对ZVI还原硝基苯的影响,利用HPLC和GC-MS作为分析工具,观测反应过程中硝基苯的质量浓度,同时跟踪溶液中Fe2+、pH、ORP的变化.结果表明,有无Fe2+存在,硝基苯均可被ZVI还原为苯胺,Fe2+没有改变还原产物;溶液中投加Fe2+后,ZVI还原硝基苯的反应速率明显加快,溶液中Fe2+对于还原反应起促进作用;溶液中Fe2+对ZVI体系pH起缓冲作用,含有Fe2+的ZVI体系ORP下降明显.反应动力学分析表明,硝基苯的还原反应符合假一级动力学模型,表观速率常数kobs值随Fe2+质量浓度的升高而增加,Fe2+离子的存在有助于ZVI对硝基苯的还原.     

原水输水渠道中粉末活性炭吸附污染物的模拟研究

在原水输水管渠中投加粉末活性炭,对污染原水进行预处理,已经成为水源地突发污染事故条件下的应急处理技术手段。本文提出了原水输水渠道中粉末活性炭动态沉降条件下,粉末活性炭—污染物耦合数学模型,以水源地硝基苯浓度超标为例(分别超标2、5和10倍),模拟了粉炭对硝基苯的吸附净化效果。得出基本结论为:粉炭吸附污染物的效果既与水流条件(实际水流剪应力或供水水量)有关,也与输水渠道的断面水深有关。在相同的粉炭投加浓度条件下,水流剪应力越低,断面水深越低,污染物吸附平衡浓度就越高。当水源地水质严重超标时(超标5–10倍),应将增加粉末活性炭投加量作为解决方案;而当水源地水质超标不明显时(超标2倍),可在合理调控供水水量和粉炭投加量的条件下,达到供水水质要求。该研究建立的数学模型,对突发污染事故条件下城市应急供水,具有借鉴意义。     

天然藻类对硝基苯富集与释放能力研究

对硝基苯(Nitrobenzene,NB)在水生生物(藻类)体内的生物富集与释放规律进行了研究,为硝基苯的生态环境效应和生态风险评价提供科学依据.本文主要研究内容和结果如下:松花江水中天然藻类,经过无机盐培养液富集培养后,转入硝基苯浓度8.3±1.0 mg/L的培养液中进行实验.结果表明:藻类对硝基苯的富集与释放速率均很快.