硝基苯加氢制备苯胺的最新研究进展

苯胺(AN)作为一种化工中间体,在化工行业中有着重要地位,被广泛的应用于医药、印染和农药等与人们息息相关的行业。通过硝基苯催化加氢法制备苯胺不仅对环境污染小,而且操作工艺简单,在工业生产中具有广阔的发展空间,其催化体系主要有Ni系、Cu系和贵金属系等。综述了近些年有关硝基苯催化加氢制备苯胺的最新研究进展,为后继工作者进行加氢催化剂的改进与创新提供参考。     

硝基苯液相催化加氢制苯胺催化剂研究进展

介绍了苯胺生产中硝基苯液相催化加氢制苯胺工艺,着重介绍了液相加氢催化剂体系中的镍系催化剂和贵金属催化剂的研究进展。液相催化加氢多采用贵金属催化剂和高活性、制备工艺复杂的催化剂,生产成本较高,开发价廉、高效并能满足绿色化工要求的新型催化剂是今后工作的重点。     

MoS_2/C催化剂上硝基苯催化加氢的反应研究

采用浸渍法制备了负载型MoS2/C催化剂,研究了该催化剂上硝基苯催化加氢反应。结果表明,在压力1.5 MPa,温度80℃条件下,硝基苯的转化率可达95%,其加氢主产物为苯胺,副产物主要有乙基苯胺类、甲基苯胺类、喹啉类。该催化剂反应活性较高,反应条件比较温和、操作简单,但产物相对复杂。     

Ni-B/SiO2催化剂上硝基苯选择加氢制备苯胺

以KBH4为还原剂,用浸渍-还原法制备了Ni-B/SiO2催化剂,并用于硝基苯催化加氢制苯胺的反应,讨论了制备条件（Ni、B用量及焙烧温度）及反应条件（压力、温度）对硝基苯的转化率及苯胺选择性的影响。结果表明,Ni-B/SiO2催化剂具有很高的催化活性。适当增加Ni和B的用量,可以提高催化剂对硝基苯的转化率和转化频率及苯胺的选择性。催化剂前驱体的焙烧温度在453K时,硝基苯的转化率可达到98.5%,对苯胺选择性为97.0%。过高的焙烧温度不利于催化剂活性的提高。适当提高加氢反应压力以及温度,可以提高催化剂的加氢活性及对苯胺的选择性。     

硝基苯加氢合成对氨基苯酚的催化剂研究进展

对氨基苯酚是一种重要的医药、农药、染料中间体。以硝基苯为原料直接一步催化加氢合成对氨基苯酚具有成本低、收率高、三废排放少等优点,是一条绿色的合成路线。详细综述了硝基苯加氢生成羟基苯胺及羟基苯胺Bamberger重排生成对氨基苯酚的反应机理,加氢及重排催化剂研究等方面的研究进展,介绍了表面活性剂助剂对对氨基苯酚选择性及收率的影响。     

氯代硝基苯合成氯代苯胺的进展

氯代苯胺是一类重要的化工原料,广泛用于染料、香料、医药及橡胶助剂等行业。本文综述了氯代硝基苯还原制备氯代苯胺的几类方法,对各类方法进行了对比和讨论,其中环境友好的催化加氢还原法可通过添加脱氯抑制剂和改善催化剂性能两条途经来提高反应的选择性。认为催化加氢法是制备氯代苯胺的首选方法。     

4-氨基二苯胺的合成方法综述

综述并评述了4-氨基二苯胺的合成方法。同时指出，硝基苯和苯胺缩合，催化加氢合成4-氨基二苯胺的硝基苯法颇具竞争力。     

硝基苯液相催化加氢制苯胺催化剂研究进展

介绍了硝基苯液相催化加氢制苯胺的工艺过程,同时对该工艺所用催化剂体系(非贵金属类催化剂和贵金属类催化剂)进行了详述。非贵金属催化剂不仅存在对苯胺选择性差还存在对环境污染的问题;贵金属催化剂活性高,但成本也较高。开发催化活性高、稳定性好、寿命长、损耗低且环境友好型催化剂是硝基苯液相加氢催化剂发展的主研方向。     

非晶态镍-硼合金柱撑膨润土催化剂的制备及其加氢性能的研究

采用浸渍-化学还原法制备了非晶态镍-硼合金柱撑膨润土催化剂,考察了催化剂不同制备条件对其催化硝基苯加氢制苯胺反应性能的影响;并对催化剂的晶相、形貌和比表面积等方面进行了表征。结果表明,非晶态镍-硼合金柱撑膨润土催化剂具有较大的比表面积,非晶态镍-硼在柱撑膨润土孔道中分散性较好,具有较好的催化加氢性能和稳定性。非晶态镍-硼柱撑膨润土催化剂在加氢反应的初始压力为2.0 MPa、温度为110 ℃、反应时间为2 h条件下,催化硝基苯加氢制苯胺的转化率和选择性分别达到92.6%和96.1%,并且催化剂在连续使用6次后硝基苯的转化率和苯胺的选择性分别为88.9%和93.8%。     

硝基苯液相催化加氢制备苯胺的研究进展

介绍了苯胺生产中硝基苯液相催化加氢制苯胺工艺,并对目前研究的硝基苯乙醇重整制氢、CO/H2O还原、超临界二氧化碳低温合成苯胺的工艺做了简述,说明我国应继续研究和推广催化加氢制取苯胺清洁生产工艺;另外着重介绍了液相加氢催化剂体系中的镍系催化剂和贵金属催化剂的研究进展。液相催化加氢多采用贵金属催化剂和高活性、制备工艺复杂的催化剂,生产成本较高,开发价廉、高效并能满足绿色化工要求的新型催化剂是今后工作的重点。     

非晶态Ni-P合金上硝基苯催化加氢制苯胺的本征动力学

Ni-P非晶态合金催化剂因其晶体结构的特殊,具有较好的催化活性。以硝基苯液相催化加氢合成苯胺为目标反应,运用Matlab软件并借助Levenberg-Marquardt算法估计反应动力学模型的参数,根据参数估计结果筛选动力学机理模型,对新型Ni-P非晶态合金催化剂的本征动力学进行研究,为催化剂的进一步开发和反应器设计提供理论依据。结果表明,Ni-P非晶态合金催化剂的颗粒较小,过程内扩散的影响可以忽略不计,当搅拌速率达到600 r·min^-1时,反应过程的外扩散影响也可忽略。在（373.15~403.15） K、氢压1.0 MPa、非晶态Ni-P催化剂质量0.2 g、硝基苯质量2.0 g和无水乙醇质量8.0 g条件下,硝基苯分子不吸附,硝基苯分子与解离吸附的氢原子在催化剂表面反应,苯胺脱附为硝基苯加氢合成苯胺反应的速率控制步骤,本征动力学模型为：r_j=kc_A/1+b_H2α_H2p_H2,表面反应的指前因子为1.08×105 min^-1,活化能为51.81 kJ·mol-1,氢气吸附热为64.12 kJ·mol^-1。     

PROMOTION EFFECT OF Mo IN AMORPHOUS Ni-P CATALYSTS FOR THE LIQUID-PHASE CATALYTIC HYDROGENATION OF NITROBENZENE TO ANILINE

Amorphous Ni-P catalysts were prepared by a chemical reduction method, and the promotional effects of Mo on the hydrogenation of nitrobenzene to aniline on Ni-P catalyst were investigated. However, the two crystallization temperatures of the 1% Ni-Mo-P catalyst were 644 K and 723 K, which were 15 K and 43 K higher, respectively, than those of the Ni-P catalyst itself; these results indicate that the presence of Mo increased the thermal stability of the Ni-P catalysts. SEM results showed that the particle size of the active component of Ni-P in the 1.0% Ni-Mo-P catalyst was smaller than that in the amorphous Ni-P catalyst. The N₂ adsorption isotherms for the amorphous Ni-Mo-P catalysts were the III-type, and the N₂ isothermal adsorption-desorption curves exhibited H₃-type hysteresis loops. H₂-TPR results showed that the addition of Mo had no effect on the reduction of NiO in the catalyst but negatively affected the reduction of Ni-P-O. H₂-TPD results showed that the hydrogen adsorption capacity of the amorphous Ni-P catalysts can be enhanced through the addition of Mo, and the optimal amount of Mo was determined to be 1.0%. The XPS results indicated the presence of a small amount of free metallic Mo in the amorphous Ni-Mo-P catalysts in addition to the Mo in MoO₃. The use of 1% amorphous Ni-Mo-P catalyst at 383 K and under 1.0 MPa of hydrogen for 3.0 h resulted in a nitrobenzene conversion rate and aniline selectivity of 64.5% and 98.8%, respectively.     

Promotion of the electrochemical hydrogenation of nitrobenzene at hydrogen storage alloys studied using a solid electrolyte method

The electrocatalytic properties of an AB₅-type hydrogen storage alloy towards the electrochemical hydrogenation of unsaturated organic compounds have been studied by a solid electrolyte method using electrochemical hydrogenation of nitrobenzene as a model reaction. Voltammetric studies reveal that the kinetics of the nitrobenzene electro-reduction on the hydrogen storage alloy electrode is similar to that on a Ni electrode. Aniline and p-aminophenol are produced as the reaction products. Compared to the Ni electrode, the production of aniline is considerably promoted on the hydrogen storage alloy electrode. Modifying the alloy surface with a thin layer of Cu enhances the reaction selectivity and current efficiency for aniline formation. Compared to a Cu electrode, the electrochemical hydrogenation of nitrobenzene to aniline is promoted on the Cu-modified alloy electrode. The hydrogenation promotion effect is attributed to the chemical reaction between nitrobenzene and metal hydrides that are electrochemically generated in situ. Hydrogen storage alloys therefore make it possible to intensify the electrochemical hydrogenation process of unsaturated organic compounds.     

Kinetic investigations of the deactivation by coking of a noble metal catalyst in the catalytic hydrogenation of nitrobenzene using a catalytic wall reactor

The vapour phase hydrogenation of nitrobenzene to aniline is a highly exothermic reaction deactivated by coking of the palladium catalyst supported on -alumina carrier. For studying the deactivation of the catalyst a catalytic wall reactor was used in order to ensure isothermal reaction conditions for the kinetic measurements. Furthermore, the catalytic wall reactor allowed the determination of axial coke profiles by total carbon analysis of different wall segments. On the assumption that the main reaction and the deactivation of the catalyst can be assumed separable both the steady state and the unsteady state kinetics were studied. Nitrobenzene was identified as the relevant coke precursor whereas aniline has neither an influence on the main reaction nor on the deactivation. It could be shown that the hydrogenation of nitrobenzene to aniline follows a Langmuir–Hinshelwood mechanism considering the surface reaction of the adsorbed nitrobenzene molecule and one adsorbed hydrogen atom as the rate determining step. The differentiation of coke on the active sites and coke on the support must be taken into account to model the kinetics of coke formation with sufficient accuracy.     

Preparation and characterization of Ni-B/SiO2sol amorphous catalyst and its catalytic activity for hydrogenation of nitrobenzene

Supported Ni-B/SiO₂sol amorphous alloy catalyst was prepared by a sol-gel and impregnation-chemical reduction method, and the effects of the tetraethyl orthosilicate (TEOS) and ammonia ratio, and the nickel loading amount on the nitrobenzene hydrogenation were also investigated. The results showed that Ni-B amorphous alloy catalyst supported on the silica sol increased the specific surface area of catalysts, improved the catalytic activity of Ni-B amorphous alloy catalyst, and the Ni species on the surface existed in the form of Ni²⁺. The optimal TEOS and ammonia ratio and nickel loading amount was 1.0 and 10%, respectively, and when using this optimal Ni-B/SiO₂sol catalyst, the nitrobenzene conversion was 99.9% with an aniline selectivity of 99.8%, and after 5 recycles, the Ni-B/SiO₂sol maintained a good stability.     

碳基固体酸在硝基苯加氢制备对氨基苯酚中的应用

考察了以马铃薯淀粉为碳源制备的碳基固体酸催化剂和质量分数3%的Pt/C为加氢催化剂作用下硝基苯加氢制备对氨基苯酚的反应条件，在以酸度为2.316mmol/g的固体酸为酸性催化剂时，优化的反应条件下硝基苯的转化率100%，对氨基苯酚的选择性67.6%。总结了硝基苯加氢制备对氨基苯酚的反应机理：(1)硝基苯在Pt/C催化剂上发生加氢反应生成中间产物苯基羟胺；(2)苯基羟胺在固体酸催化剂上发生Bamberger重排反应生成对氨基苯酚；(3)主要的副反应包括：苯基羟胺进一步加氢生成苯胺，苯基羟胺歧化反应生成苯胺和亚硝基苯，苯基羟胺与亚硝基苯发生缩合反应生成副产物氧化偶氮苯。通过机理分析和实验验证，提出要提高对氨基苯酚的收率，需综合考虑硝基苯加氢过程和Bamberger重排反应过程。     

Ni-Mo-B非晶态合金催化剂制备及其催化加氢性能研究

采用化学还原法,以Ni(Ac)2.4H2O和NH4Mo9O24.4H2O为原料,KBH4为还原剂,制备了Ni-Mo-B非晶态合金催化剂。以硝基苯加氢为探针反应,考察了制备条件对Ni-Mo-B催化剂的结构和性能以及反应温度、压力与催化剂用量等反应条件对催化加氢性能的影响。研究结果表明,适当添加Mo可以提高Ni-B催化剂活性。当Mo掺杂量为Ni质量的5%时,Ni-Mo-B催化剂活性最佳。Mo主要以MoO3的形式存在,MoO3的分散作用可防止Ni-B合金粒子的团聚,提高了催化剂比表面积,稳定了Ni-Mo-B催化剂的非晶态结构。     

二氧化硅接枝黑荆树单宁负载钯催化剂的制备及其性能

以二氧化硅接枝黑荆树单宁为载体,制备了一种新型的负载型钯催化剂,并将其用于硝基苯的液相催化加氢。结果表明,二氧化硅接枝黑荆树单宁负载钯催化剂(SiO2-BT-Pd)对硝基苯的液相加氢具有很高的催化活性。当以甲醇为溶剂,在温度为50℃和H2压力1.0MPa的条件下进行反应时,SiO2-BT-Pd对硝基苯的初始催化转化频率(TOF)高达2061.5mol/(mol·h),转化率在80min达到100%,转化为苯胺的选择性为99.5%。该催化剂重复使用4次后,其催化活性及选择性没有明显降低。这表明SiO2-BT-Pd是一种具有高催化活性和高选择性的负载型催化剂。     

催化加氢制备3-氯-4-氟苯胺的研究

研究了以Pt-Cu-S/C作催化剂,3-氯-4-氟硝基苯常压加氢制备3-氯-4-氟苯胺的方法,考察了该催化剂对3-氯-4-氟硝基苯的催化加氢反应的性能,探讨了影响加氢反应的主要因素。实验表明,催化剂具有较高的催化活性和选择性。当催化剂中Pt的质量分数为1%,Cu的质量分数为0.1%,S的质量分数为0.03%,催化剂用量为硝基物质量的0.5%,溶剂用量2 m L甲醇/1 g硝基物,反应温度80℃,压力为1.5 MPa时,3-氯-4-氟苯胺的产率为98%,纯度达99.5%以上。