本期推荐——苯系列化合物

苯甲酸加氢方法 本发明公开的一种苯甲酸加氢方法是将熔融苯甲酸在Pd／C催化剂和镍助剂存在下，与氢气接触反应后，采用旋液、离心和磁分离3级分离过程，将催化剂从混合物中分离并循环回反应器，其中旋液分离后的浊液循环回反应器，清液进入离心分离器，经分离后下部的催化剂循环回反应器，上部清液进行磁分离，分离出镍基助催化剂循环回反应器。该方法可有效分离镍助剂，进一步提高Pd／C的活性，具有更高的反应处理能力和生产效率。     

Pd/Al2O3液相选择加氢催化剂抗硫性能研究

研究了助剂对Pd/Al2O3催化剂裂化汽油液相选择加氢活性及其抗硫性能的影响。着重探讨了Co助剂的作用规律。结果表明，助剂对Pd/Al2O3催化剂的加氢活性有不同影响，其中加入Ag、Cu和Co助剂时，可以提高催化剂加氢活性，而Co助剂的提高最为明显，通过对催化剂进行XPS和反应后催化剂硫含量的分析，表明Co助剂改善Pd/Al2O3催化剂液相加氢活性的作用有两方面，一是与Pd金属产生电子相互作用，改变其电子状态，减弱对硫化物的吸附；二是Co具有吸硫作用，使部分硫化物吸附在助剂Co上，从而减少了在活性中心Pd上的吸附，导致Pd－Co/Al2O3催化剂具有良好的液相选择加氢活性。     

一步法合成N-(1-乙基丙基)-3,4-二甲基苯胺

以自制的Pd－Pt/C为加氢催化剂，有机酸为助催化剂，3，4－二甲基硝基苯和3－戊酮为原料，通过硝基加氢、酮胺加成、脱水与碳氮双键加氢一系列反应一步法合成了N－（1－乙基丙基）－3，4－二甲基苯胺。考察了不同加氢催化剂、助催化剂和反应温度对该反应的影响：在较佳的反应工艺条件下，四步反应的总收率达98．6％，比文献值收率提高10％。     

环戊二烯加氢制环戊烯的研究

研究了环戊二烯加氢制环戊烯的工艺技术，重点考察了氢气压力，搅拌速度，催化剂投入量，反应温度和催化剂活性稳定性等加氢工艺条件，环戊二烯加氢的条件为：催化剂投料量0．3％－0．6％，氢气压力为0．8－1．5MPa，搅拌速度大于600转／分，加氢温度小于32℃，在理想的条件下，使用细颗粒Pd/C催化剂，环戊二烯转化率大于95％，环戊烯选择性大于90％。     

烷基苯酚加氢用Pd/C催化剂性能研究

采用浸渍法制备不同助剂改性的Pd/C催化剂,并与未添加助剂的Pd/C催化剂对比,考察不同助剂对苯酚加氢制备环己酮用Pd/C催化剂性能影响。结果表明,助剂Zn对催化剂活性和选择性影响较小,助剂Mg、Fe、Co使烷基苯酚加氢用Pd/C催化剂活性和选择性均有所提升,且以CoCl2为Co源,质量含量为2.0%Co修饰的Pd/C催化剂效果较优,催化剂重复使用性能良好。     

制备工艺对负载型Pd催化剂催化加氢性能的影响

介绍了Pd催化剂催化加氢反应的机理,以及Pd催化剂在工业加氢反应中的应用现状和研究进展。重点讨论了负载型Pd催化剂的制备方式、载体、助催化剂等因素对其催化加氢性能的影响,以期为新型负载型加氢Pd催化剂的研究和开发提供参考。     

C_5石油树脂加氢改性用Pd/Al_2O_3催化剂及其失活原因

研究了Pd/Al2O3催化C5石油树脂的加氢反应时催化剂失活的原因,采用物理吸附(BET)法、X射线衍射(XRD)法、高分辨透射电镜(HRTEM)和电感耦合等离子体质谱(ICP-MS)法等对加氢前后Pd/Al2O3催化C5石油树脂的性能进行了分析。研究结果表明:在加氢过程中,从原料中脱除的S杂质吸附在催化剂表面上,致使催化剂失活;高温氧化脱除催化剂上吸附的S杂质后,该催化剂可恢复加氢活性。     

Ag-Pd/C催化四氯化碳液相加氢反应的研究

制备了Ru-Pd/C,Fe-Pd/C,Ni-Pd/C,Cu-Pd/C和Ag-Pd/C催化剂,并考察了它们对四氯化碳液相加氢脱氯成氯仿的反应性能,重点考察了Ag/Pd摩尔比对Ag-Pd/C催化剂反应性能的影响。结果表明,在所有考察的催化剂中,Ag加入到Pd/C可有效抑制副产物甲烷的生成,显著提高氯仿的选择性。在Ag-Pd/C(2:1)催化剂上四氯化碳转化率为100%时,氯仿选择性高达97%。在Ag-Pd合金催化剂中,Ag可能主要起断裂C-Cl键的作用,而Pd主要提供加氢所需的活化H原子。溶剂对Ag-Pd/C催化剂四氯化碳液相加氢脱氯反应的活性和选择性有重要的影响,四氯化碳液相加氢生成CHCl3和CH2Cl2的反应在甲醇溶剂中是平行反应,而在正庚烷溶剂中则是连串反应。     

Pd/C催化剂制备条件优化及其在4-氨基二苯胺生产中的应用

采用浸渍法制备了Pd/C催化剂,考察了催化剂制备过程中加料方式、还原方法、载体种类、钯质量分数和浸渍液质量浓度对催化剂性能的影响,得到了制备Pd/C催化剂的优化工艺条件:载体为NH-03型活性炭,浸渍液质量浓度为20 g/L,采用滴加的方式将PdCl_2溶液加至活性炭浆液中,还原剂为(w)20%的次亚磷酸钠溶液,钯质量分数为5%。优化制备条件下制得的Pd/C催化剂用于催化加氢制备4-氨基二苯胺,表现出较好的活性,其中4-硝基二苯胺和4-亚硝基二苯胺转化率均可达到100%,4-氨基二苯胺选择性大于99%,加氢反应时间小于30 min。催化剂SEM表征结果表明:自制的Pd/C催化剂表面活性炭载体凸起部分与Pd粒子粒径相当,有利于Pd粒子在活性炭表面的负载,提高Pd粒子的吸附牢固度和分散性,进而提高了Pd/C催化剂的活性。     

超临界CO_2中对苯二酚催化加氢反应的研究

通过超临界CO2介质中对苯二酚催化加氢的研究,探讨了催化剂、超临界CO2压力等反应条件的影响,研究了Pt/C、Pd/C、Ru/C和Rh/C几种催化剂对反应转化率和主要产物1,4-环己二醇选择性的影响,结果表明:Ru/C催化剂的活性最好。研究了超临界CO2压力、反应温度、氢气压力、反应时间等对反应转化率和选择性的影响,根据产物的选择性对该反应路径进行了初步分析。     

Effects of iron-tetrasulfophthalocyanine on the catalytic activities of Pt/C,PtRu/C,and Pd/C catalysts in a multi-anode direct formic acid fuel cell

This paper reports a systematic study of the effects of a promoter, iron-tetrasulfophthalocyanine (FeTSPc), on the catalytic activities of carbon supported Pt, PtRu, and Pd catalysts (Pt/C, PtRu/C, and Pd/C) for formic acid oxidation. A multi-anode direct formic acid fuel cell (DFAFC) was used to compare the effects on each catalyst of adding FeTSPc to the fuel stream. The FeTSPc significantly enhanced the activity of the Pt/C catalyst, but had little effect on the PtRu/C catalyst. The activity of the Pd/C catalyst was inhibited by the FeTSPc. A FeTSPc modified Pt/C was also evaluated in a conventional 5 cm² DFAFC.     

延长Pd/C催化剂使用寿命

本文围绕延缓Pd/C催化剂中Pd晶粒的烧结及减少Cu、Fe等离子对催化剂的污染的原理方面进行了工艺实验 ,提出了在使用初期 ,采取比原来值高的H2 供应量 ;中期控制在设计范围内 ;在使用后期 ,特别是超过设计寿命时 ,采取强化工艺 ,提高H2 分压 ,有效地保护Pd晶粒的活性中心 ,以延缓Pd/C催化剂中的Pd烧结及减少杂质离子的污染。并对受到污染而活性下降的Pd/C催化剂用碱洗恢复活性的方法进行了有关实验 ,常温下先用 2 0 %NaOH溶液浸泡 4h ,再用 5 %NaOH溶液浸泡 4h ,即能够有效地去除污染物 ,恢复催化剂的活性。延缓Pd/C催化剂中的Pd烧结和碱洗均能延长Pd/C催化剂使用寿命     

苯甲酸加氢用钯碳催化剂的制备、失活及再生研究

研究了苯甲酸加氢用钯碳催化剂的制备、失活及再生。提出了钯碳催化剂的制备关键、加入甲烷化助剂可以延长钯碳催化剂寿命、利用超临界流体再生方法可以有效再生失活钯碳催化剂。     

Selective hydrogenation of 4-isobutylacetophenone over a sodium-promoted Pd/C catalyst

The effect of sodium promotion on the selective hydrogenation of 4-isobutylacetophenone, 4-IBAP, was investigated over a Pd/C catalyst. A precipitation and deposition method was used to prepare the catalyst, and sodium was promoted on the Pd/C catalyst via post-impregnation while varying the sodium content. The sodium-promoted Pd/C catalyst resulted in a significantly improved yield greater than 96% of the desired product, 1-(4-isobutylphenyl) ethanol (4-IBPE), compared with the non-patented literature results under a mild hydrogenation condition. A detailed hydrogenation network over the Pd/C catalyst was suggested. The reaction mechanism for the yield and selectivity enhancement of 4-IBPE induced-by the promoted Pd/C was elucidated in relation to the geometric and electronic effects of reactant molecules in the microporous support depending on the reaction steps.     

EDS表面分析研究Pd／C催化剂的失活原因

利用Ｘ射线能谱仪及原子吸收研究了对苯二甲酸加氢精制过程中失活的钯炭催化剂的失活原因,结果表明,原料中的含硫化合物,以二甲苯氧化工段的催化剂四溴乙铵,设备腐蚀和溶剂水中的离子均会沉积在钯炭催化剂的表面,引起催化剂加氢活性的下降,利用ＥＤＳ分析把炭催化剂及断面的元素沉积是分析催化剂失活原因的有效方法。     

Hydrogenation of carbon dioxide to methanol over palladium-promoted Cu/ZnO/A12O3 catalysts

The effect of Pd on a Cu/ZnO/A1₂O₃ catalyst for methanol synthesis from CO₂/H₂ has been investigated. Activities of impregnated catalysts and physical mixtures were studied in an internal recycle reactor under 5 MPa, 250°C and a range of conversions. In all cases, the promotion of methanol production was greater at higher flow rates (lower conversions). The promotion achieved by use of Pd/A1₂O₃+ Cu/ZnO/Al₂O₃ physical mixtures was found to increase with Pd content. Greater promotion was observed over the Pd impregnated Cu/ZnO/Al₂O₃ catalysts, although this was insensitive to the particular Pd loadings used. The results are consistent with the proposal that hydrogen spillover is responsible for the observed promotion. The effectiveness of Pd as a promoter for the reduction of CuO in the catalysts was studied by TPR and was found to be related to the level of promotion in methanol production.     

Highly active carbon-supported PdNi catalyst for formic acid electrooxidation

A new carbon-supported PdNi (PdNi/C) catalyst is prepared by a simple simultaneous reduction reaction with sodium borohydride in glycol solution. The results show that the performance of PdNi/C catalyst for formic acid oxidation is greatly improved compared with that of Pd/C. X-ray diffraction (XRD) results show that Ni exists in the catalyst both as NiO and as PdNi alloy. The value of the apparent activation energy shows that the activity of formic acid oxidation on the PdNi/C is more sensitive to temperature compared with Pd/C.     

对苯二甲酸精制钯炭催化剂载体活性炭的研究

分析了不同厂家生产的对苯二甲酸精制用钯炭催化剂载体活性炭的各种物性指标。实验结果表明,各种活性炭比表面相同时,其吸附量基本相近,但孔结构有较大差异,尤其是中孔孔容相差较大。中孔孔容增大,有利于钯炭催化剂分散度的提高和热稳定性增强.活性炭的表面基团对催化剂分散度也有影响,表面酸性基团含量增加,值化剂分散度提高.     

Integration of methanation into the hydrogenation process of benzoic acid

The traditional industrial process for hydrogenation of benzoic acid to cyclohexanecarboxylic acid (CCA) has drawbacks of low‐activity and fast deactivation of the Pd/C catalyst due to the poisoning of CO arising from the decarboxylation of CCA. A novel rapidly quenched skeletal NiCrFe promoter (RQ NiCrFe) is developed for the methanation of CO to harmless CH₄. Evaluations in bench‐scale autoclave and in traditional industrial equipment verified that RQ NiCrFe was very effective in promoting the activity of the Pd/C catalyst in the hydrogenation of benzoic acid. In order to solve the catalyst recycle and separation problem introduced by RQ NiCrFe, the industrial process was modified by incorporating a hydraulic cyclone and a magnetic separator to the separation unit. The modified process showed merits of lower costs of catalyst and operation, higher productivity, and better product purity than the traditional process. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

Oxidation of methane over Pt and Pd supported on alumina in lean-burn natural-gas engine exhaust

Catalytic oxidation of hydrocarbons in lean-burn natural-gas engine exhaust has been studied for Pt and Pd supported on alumina. A Pt–Pd/alumina catalyst exhibited higher and longer-lasting hydrocarbon oxidation activity than Pt–Rh/alumina, Pt/alumina, and Pd/alumina catalysts. Increasing the palladium content in Pt–Pd/alumina catalyst increased the oxidation activity and had more durability. While increasing the platinum content a little bit also improved the activity, adding much more did not. Supporting the platinum on alumina retarded the sintering of Pd and PdO, thus lengthening the oxidation activity of the Pt–Pd/alumina catalyst.