Ni-Ce-P非晶态合金催化剂用于氯代硝基苯液相加氢制氯代苯胺

 采用化学还原法制备了Ni-Ce-P非晶态合金催化剂,用X射线能谱、 X射线衍射、 选区电子衍射、 透射电子显微镜和差热分析等方法对催化剂的组成、结构、形貌及热稳定性进行了表征,讨论了Ni-Ce-P非晶态合金催化剂的催化性能和结构的关系,并以氯代硝基苯液相加氢合成氯代苯胺为探针反应考察了所制备催化剂的加氢性能. 研究结果表明,在不加脱卤抑制剂的情况下,在110 ℃下反应时所选4种反应物的转化率均可达99.8%, 脱卤率小于1.8%, 且Ni-Ce-P非晶态合金的活性为Ni-P非晶态合金催化剂的2倍,表现出较高的加氢性能和抑制脱卤性能.     

Ni-Co-B非晶态合金催化剂用于氯代硝基苯液相加氢制氯代苯胺

 用化学还原法制备了 Ni-Co-B 非晶态合金催化剂,并采用透射电子显微镜、扫描电子显微镜、选区电子衍射、X射线衍射、X射线能谱和差热-热重分析等表征手段研究了催化剂的非晶性质和原子组成等. 将此催化剂用于邻氯硝基苯和 3,4-二氯硝基苯的液相催化加氢反应,结果表明,当Co/(Co+Ni)=0.5 (摩尔比)时, Ni-Co-B 催化剂具有较好的加氢性能和较高的抑制脱卤性能. 在不加脱卤抑制剂的情况下,两种氯代硝基苯的转化率均接近100%, 脱卤率分别为1.12%和0.42%, 优于使用 Ni-B 和 Co-B 非晶态合金催化剂时的结果. 还讨论了将Co引入到 Ni-B 非晶态合金催化剂时对其性能的影响.     

水溶性纳米ni催化氢化氯代硝基苯制备氯代苯胺

水溶性纳米镍;催化加氢;氯代硝基苯;氯代苯胺     

负载型镍基非晶态催化剂催化氯代硝基苯加氢合成氯代苯胺

分别以碳纳米管(CNTs), SiO_2, TiO_2, γ-Al_2O_3, TiO_2-SiO_2和活性炭(AC)为载体(M),以Ni和B为活性组分,采用浸渍-化学还原法制备了一系列负载型Ni-B非晶态合金催化剂(Ni-B/M).采用电感耦合等离子体光谱(ICP), XRD, TEM和DSC研究了Ni-B/CNTs的非晶性质,Ni的担载量及其热稳定性.将Ni-B/M用于催化三种氯代硝基苯液相加氢合成氯代苯胺的反应.结果表明,Ni-B/M在反应中表现出较高的活性和良好的选择性,其中Ni-B/CNTs可使三种氯代硝基苯的转化率均高于99.8%,加氢脱氯率小于3%.讨论了CNTs和Ni-B之间的相互作用对催化剂性能的影响.     

活性炭负载Pt-Fe双金属催化剂催化对氯硝基苯选择性加氢

采用浸渍还原法制备了活性炭负载Pt-Fe双金属催化剂(Pt-Fe/AC),考察了其催化对氯硝基苯加氢性能。 与Pt/AC催化剂比较,该催化剂对催化对氯硝基苯加氢表现出高活性和优异的抑制脱氯性能,在乙醇为溶剂、催化剂Pt_0.003-Fe_0.04/AC(下标为元素在催化剂中的质量分数)用量为0.02 g/g对氯硝基苯、1 MPa H₂和30 ℃条件下反应150 min,对氯硝基苯完全转化为对氯苯胺,而且即使在较高的反应温度和H₂压力下,脱氯反应也得到了完全抑制。 采用X射线衍射(XRD)、透射电子显微镜(TEM)及X射线光电子能谱(XPS)等技术手段对Pt-Fe/AC催化剂进行了表征。 结果表明,Pt、Fe高度分散在活性炭上,Pt与Fe之间的相互作用对纳米Pt粒子的电子结构有一定的调变作用,使纳米Pt处于缺电子态,减弱了Pt与对氯苯胺苯环之间的电子反馈,这可能是Pt-Fe/AC对催化对氯硝基苯加氢表现出高活性和优异的抑制脱氯性能的主要因素。     

Sn4+离子修饰的Pd/γ-Al2O3催化卤代芳香硝基化合物选择性加氢

用乙醇．水混合溶液还原方法制备了以聚乙烯吡咯烷酮（PVP）稳定的Pd／γ-Al2O3负载型单金属催化剂，用于二氯代硝基苯中硝基的选择性加氢．实验结果表明，在催化反应体系中直接加入Sn^4＋作为修饰剂，虽在一定程度上降低了Pd／γ-Al2O3的催化活性，却大大提高了二氯苯胺的选择性．在其它反应条件相同的情况下，当不添加和添加Sn^4＋时，二氯代硝基苯的转化率分别在80℃和110℃达100%，而2，5-、2，4-、2，3-二氯苯胺的选择性分别由不加修饰剂的84．5％、76．1％、86．8％上升到Sn^4＋修饰后的98．7％、100％、100％．Sn^4＋的添加方式影响对催化剂的修饰效果．     

稀土在聚合物负载铂催化氢化氯代硝基苯反应中的作用研究

研究了稀土元素对高分子负载Pt催化剂催化氢化氯代硝基苯反应的影响. 结果表明 稀土元素的存在抑制了氯代硝基苯加氢反应活性, 对产物氯代苯胺的选择性有不同程度的提高; 碱NaOH存在时, PVP-Pr-Pt给出了90.8%的邻氯苯胺选择性, 使用PVP-La-Pt时得到97.2%的间氯苯胺选择性, PVP-Ce-Pt催化体系获得了98.2%的对氯苯胺选择性.     

高活性Ni/HY催化剂加氢催化合成苯胺类化合物的研究

采用浸渍沉淀法制备Ni/HY催化剂,用BET、XRD、TEM、TPR等方法对其进行表征,并将其应用于硝基化合物液相加氢合成苯胺类化合物反应中.结果表明,Ni/HY催化剂具有较高的催化活性,在温和的反应条件下,反应0.5 h后,硝基化合物的转化率和苯胺类化合物的选择性均高达99.0%以上.该催化剂能储存于150℃以下的空气气氛中,活性组分分散度高,且具有良好的磁分离性能.     

原位液相催化加氢法合成N-乙基苯胺和N，N-二乙基苯胺

以硝基苯为原料,Pt/γ-Al2O3为催化剂,乙醇水溶液为溶剂和氢供体,采用原位液相加氢一步法合成了N-乙基苯胺和N,N-二乙基苯胺.采用低温N2吸附-脱附、电感耦合等离子体发射光谱、X射线衍射、程序升温化学吸附和透射电子显微镜等对Pt/γ-Al2O3催化剂进行了表征,并考察了所制备催化剂的原位液相加氢性能.结果表明,在温度为503K、压力为5.0MPa、空速为3.2h-1、溶剂水含量为30%以及硝基苯浓度为8%的反应条件下,在Pt/γ-Al2O3催化剂上原位液相加氢合成N-乙基苯胺及N,N-二乙基苯胺有较好的结果,硝基苯转化率达到100%,N-乙基苯胺和N,N-二乙基苯胺的总收率达到99.5%.讨论了硝基苯原位液相加氢合成N-乙基苯胺和N,N-二乙基苯胺的反应机理.     

Deactivation of silica supported Pd catalysts during liquid-phase hydrogenation

Summary Large pore MCM-41 was found to provide a better stabilization of Pd particles than amorphous SiO₂ during liquid phase hydrogenation. Pd/large pore MCM-41 exhibited higher hydrogenation activities as well as lower amount of metal loss by Pd leaching.     

Ru-Ni/Al2O3催化马来酸二甲酯加氢性能研究

以Al₂O₃为载体,RuCl₃·xH₂O及Ni（NO₃）₂·6H₂O为活性组分前驱体,采用吸附-沉淀法制备系列Ru-Ni/Al₂O₃催化剂,以马来酸二甲酯（DMS）催化加氢为探针反应,考察了活化条件和Ni的添加量对催化剂性能的影响。随Ni负载量的升高,Ru-Ni/Al₂O₃催化剂活性呈现先升高后降低的趋势,在Ni：Ru的原子比为6：1时（催化剂Ru₁Ni₆/Al）催化活性最高。催化剂Ru₁Ni₆/Al在氢气中200 ℃直接还原后的平均转化率与氢气中400 ℃还原后的平均转化率接近,达到了单组分Ru/Al催化剂的1.5倍以上。XPS、XRD、H₂-TPR数据表明,Ru与Ni之间发生了较强的相互作用,Ni的加入促进了金属Ru在载体上的分散,提高了催化活性。     

La2O3助剂对Rh/SiO2催化CO加氢反应性能的影响

采用溶胶凝胶法制备了SiO_2和La_2O_3-SiO_2载体,再通过浸渍法分别引入Rh-La和Rh组分,研究考察了La引入方式对Rh/SiO_2催化CO加氢反应性能的影响。结果表明,La的添加有利于提高Rh的分散度,促进Rh+中心数的增加,有效地抑制产物中CO2的生成,提高含氧化合物选择性。此外,La的引入方式会影响La与Rh间的相互作用强弱,Rh和La共浸渍制得的2Rh-5La_2O_3/SiO_2催化剂中Rh-La相互作用较强,削弱的Rh-CO键有利于反应过程中CO的插入反应,使得产物以C_(2+)含氧化合物为主。而La以助剂形式掺入SiO_2制得的2Rh/5La_2O_3-SiO_2催化剂具有较弱的La-Rh相互作用,其产物则以甲醇、乙醇等低碳醇为主。     

胶原纤维接枝多酚负载纳米钯的制备及其对硝基苯加氢的催化特性

以胶原纤维(CF)接枝表棓儿茶素棓酸脂(EGCG)为载体,制备了新型非均相钯(Pd)纳米催化剂(CF-EGCG-Pd).EGCG作为"桥分子"不仅对Pd纳米颗粒具有锚定作用,而且能控制Pd纳米颗粒的大小及分布.通过SEM、TEM、XRD、XPS对该催化剂的形貌和物理特性能进行了表征,发现该催化剂具有规整的纤维结构,在胶原纤维的外表面形成了高分散的平均粒径在3.8 nm的Pd纳米颗粒.将该催化剂用于硝基苯液相催化加氢反应,结果表明在308 K和1.0 MPa氢压下,硝基苯转化速率(TOF)达到34.13 mol·mol-1·min-1,苯胺选择性为100%,催化剂重复使用3次其催化活性基本不变.     

Fe2O3晶型对Fe基催化剂的CO2加氢性能影响

以共沉淀法制备FeAl母体,采用浸渍法添加Zn、K和Cu助剂制成催化剂,利用低温N2物理吸附、XRD、H2-TPR等手段对FeAl母体和催化剂进行表征,并用固定床反应器考察它们的CO₂加氢反应性能。XRD结果表明,加入Al助剂、并采用无水乙醇洗涤沉淀能促进酌-Fe₂O₃晶相生成,其中,Al₂O₃/Fe₂O₃质量比为10%的母体具有最强的酌-Fe₂O₃衍射峰;加入Al使得母体中的a-Fe₂O₃晶粒粒径变小,引起比表面积明显增大;浸渍助剂过程没有改变上述两种效应。母体比表面积增大提高了助剂Cu的分散度,促进了催化剂还原,但酌-Fe₂O₃晶相的生成才是催化剂的CO₂加氢反应活性被提高的主要原因。     

Ni／ZrO2-Al2O3制备表征及催化性能的研究

本文采用浸渍沉淀法制备了不同配比的ZrO2-Al2O3复合载体。并通过浸渍法制备Ni/ZrO2-Al2O3催化剂,以苯加氢制环己烷反应为探针,考察了ZrO2与Al2O3的配比对Ni催化剂催化加氢性能的影响;采用X射线衍射(XRD)、程序升温还原(TPR)、程序升温脱附(TPD)等技术考察复合载体对Ni催化剂的体相结构、还原性能以及表面吸附性能的影响。研究结果表明,ZrO2质量分数为20%的复合载体所负载的Ni催化剂有很好的加氢活性,优于单组分载体负载的Ni催化剂;采用浸渍沉淀法制备的ZrO2-Al2O3复合载体中ZrO2以非晶态形式存在,这是由于Al2O3的存在影响了ZrO2的内部结构;该载体负载的Ni催化剂较其他催化剂更容易被还原,吸附中心数量增加。     

Promotion of hydrocarbon selectivity in CO2 hydrogenation by Ru component

We investigated catalytic behavior of iron in CO₂ hydrogenation with and without a ruthenium component. Calcined iron-based catalysts were reduced by H₂ and characterized by XRD, BET surface area and CO₂, CO and C₂H₄ temperature-programmed desorption (TPD), and tested for CO₂ hydrogenation. When Fe-K/γ-Al₂O₃ was used as a catalyst, CO₂ conversion was 36%, but when Fe-Ru-K/γ-Al₂O₃ was used, CO₂ conversion was 41%. The product selectivities for catalysts with and without the ruthenium component were also compared. Fe-K/γ-Al₂O₃ exhibited higher methane (16 mol%) and C₂–C₄ selectivity (39.6 mol%) than Fe-Ru-K/γ-Al₂O₃. The main products obtained with Fe-Ru-K/γ-Al₂O₃ were higher hydrocarbons such as C₅⁺ hydrocarbons. For Fe-Ru-K/γ-Al₂O_3, the product distribution followed the Anderson–Schultz–Flory (ASF) distribution. However, in the case of Fe-Ru-K/γ-Al₂O₃, the hydrocarbon distribution deviates from the ideal ASF distribution. It is concluded that the readsorption rates of the primary hydrocarbon product increase exponentially with chain length in the ruthenium promoted catalytic system. The behavior of catalysts with and without the ruthenium will be explained by the CO₂-, CO- and C₂H₄– profiles. In this study, it was confirmed that ruthenium component promoted the readsorption ability of -olefin, and then the chain length of hydrocarbon is higher. In addition, the microcrystalline wax produced in CO₂ hydrogenation was a high-crystalline and olefin-rich hydrocarbon.     

Enhanced catalytic performance of Pd‐Ga bimetallic catalysts for 2‐ethylanthraquinone hydrogenation

A series of Pd and Pd‐Ga bimetallic catalysts were prepared by a co‐impregnation method for 2‐ethylanthraquinone (EAQ) hydrogenation to produce hydrogen peroxide. Compared with 0.6Pd catalyst, the hydrogenation efficiency of 0.6Pd1.2Ga catalyst (11.9 g L^?1) increases by 32.2%, and the stability of 0.6Pd1.2Ga catalyst is also higher than that of 0.6Pd catalyst. The structures of the samples were determined by N₂ adsorption–desorption, ICP, XRD, CO chemisorption, TEM, H₂‐TPR, in situ CO‐DRIFTS and XPS. The results suggest that incorporation of Ga species improves Pd dispersion and generates a strong interaction between Ga₂O₃ and Pd interface or between Pd and support. DFT calculation results indicate that the strong adsorption of carbonyl group on Ga₂O₃/Pd interface facilitates the activation of EAQ and promotes the hydrogenation efficiency.     

Selective hydrogenation of phenol in supercritical carbon dioxide

Liquid phase hydrogenation of phenol over Pt/C catalysts was investigated under conventional conditions and supercritical carbon dioxide (scCO2). The equivalent ration of hydrogen to phenol shows a significant effect on the product selectivity. Hydrogenation of phenol in different solvents was also studied, the experimental results show that polarity of solvents influences the yield of cyclohexanone remarkably, scCO2 has the highest one. Catalytic hydrogenation of phenol in scCO2 or sub-scCO2 was emphatically researched. The result is that near the critical point of CO2 phenol has higher reaction activity than that of normal organic solvents, cyclohexanone has 47% in yield and 87% in selectivity.     

Catalytic oxidation of cyclohexene to cyclohexanone by a triple system in acidic aqueous acetonitrile medium

The catalytic oxidation of cyclohexene to cyclohexanone using Pd(OAc)2/HQ/FePc was investigated in an acidic aqueous solution of acetonitrile. The role of each component of this system in the oxidation of cyclohexene was explored by means of UV-VIS, IR, XPS spectroscopy and cyclic voltammetry, respectively. Based on the experimental results, the mechanism of the oxidation of cyelohexene catalyzed by Pd(OAc)2/HQ/FePc was elucidated.