CuNi纳米晶的可控合成及Pt/CuNi催化剂催化肉桂醛加氢性能

采用水热法制备了CuNi二元金属纳米晶。以水合肼为还原剂,探究水热合成温度、表面活性剂[乙二胺（EDA）、聚乙烯吡咯烷酮（PVP）、十六烷基三甲基溴化铵（CTAB）]对CuNi纳米晶形貌的影响。随水热合成温度的升高（60℃、90℃、120℃、150℃）,Cu²⁺、Ni²⁺的还原速率加快,有利于形成Cu@Ni核壳结构。以EDA为表面活性剂时,制备的CuNi二元金属纳米晶在120℃和150℃时分别呈现花状和海胆状。此外,以CuNi纳米晶为催化剂载体,采用化学置换法负载贵金属Pt合成了Pt/CuNi三元金属催化剂。X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、扫描电镜X射线能谱（SEM-EDS）、X射线光电子能谱（XPS）、高角度环形暗场扫描透射（HAADF-STEM）和元素面扫（STEM-EDS）表征结果表明,Pt/CuNi催化剂纳米结构为小岛状的Pt纳米团簇负载于CuNi纳米晶。其中,Pt/CuNi-120-EDA（120为水热合成温度,EDA为制备CuNi纳米晶时添加的表面活性剂）催化剂表面具有较丰富的缺陷位和活性位点,使其在肉桂醛加氢反应中表现出最佳的催化性能（80℃下对苯丙醇的产率达100%）。     

纳米金催化剂的制备及其对肉桂醛选择性加氢的催化性能

以多壁碳纳米管和椰壳活性炭为载体,分别采用溶胶固载法和等体积浸渍法制备负载型纳米金催化剂。采用N_2吸附-脱附、XRD、TEM和XPS等对碳载体和纳米金催化剂样品进行表征,并研究纳米金催化剂在肉桂醛选择性加氢反应中的催化性能。结果表明,HNO_3-H_2SO_4预处理可以增加碳载体表面的含氧基团和含氮基团,在肉桂醛加氢反应中,溶胶固载法得到的更小尺寸的纳米金催化剂对C=C双键加氢选择性高,等体积浸渍法制备的纳米金催化剂对C=O双键加氢选择性高,椰壳活性炭为载体催化剂的C=C加氢催化活性优于多壁碳纳米管。     

Effect of the support in Pt and PtSn catalysts used for selective hydrogenation of carvone

In this paper, a study on the hydrogenation of carvone by using Pt/Al₂O₃, PtSn/Al₂O₃, PtGe/Al₂O₃, Pt/C and PtSn/C is reported. TPR, H₂ chemisorption, XPS and test reaction results show that the addition of a second metal to Pt leads to important modifications of the structure of the metallic phase, though these modifications are different according to the nature of the support (Al₂O₃ or C). The activity and selectivity of these catalysts in carvone hydrogenation depend not only on the composition of the metallic phase, but also on the nature of the support. Thus, adding Sn or Ge to Pt/Al₂O₃ enhances the selectivity to unsaturated ketones (at a fixed carvone conversion, X_carv=1). When Pt is supported on activated carbon, small amounts of unsaturated alcohols are observed. The Sn addition to Pt/C sharply enhances the selectivity to carveol formation (the doubly unsaturated alcohol) reaching values close to 100% at the initial stages of the reaction.     

去氢芳樟醇加氢催化剂的制备与活性评价

采用浸渍法制备了Pd-Pb-Bi/CaCO3催化剂,考察了钯质量分数对催化剂活性的影响,并对催化剂加氢性能进行了评价。结果表明,钯质量分数为1.5%的催化剂活性较高,在反应温度为60～65 ℃,系统压力为0.6 MPa,催化剂用量为原料质量的0.5％,去氢芳樟醇转化率大于99%时,芳樟醇选择性大于96%,催化剂套用7次后,利用ICP对使用前后催化剂的组成进行分析后,根据反应结果分析了Pb和Bi对加氢反应的作用。     

稀土掺杂调变催化剂多相催化加氢性能研究进展

通过不同方法向分子筛中掺杂不同稀土离子能有效提高分子筛催化剂活性、结构稳定性和抗中毒能力,且有利于促进稀土资源的高值化应用.对稀土掺杂的分子筛催化剂的主要合成方法以及催化剂改性方面进行阐述,总结掺杂稀土元素种类及含量对加氢催化剂结构、选择性、活性以及稳定性的影响,且对含稀土加氢催化剂的回收及未来发展提出展望.     

The influence of zeolite acidity for the coupled hydrogenation and ring opening of 1-methylnaphthalene on Pt/USY catalysts

The influence of framework and extraframework composition of USY zeolite on the catalytic performance of bifunctional Pt/USY (1 wt.% Pt) catalysts for the coupled hydrogenation and ring opening of 1-methylnaphthalene (1-MN) has been studied on a continuous fixed bed high pressure reactor. All Pt/USY catalysts showed very high methylnaphthalene (MN) conversions under the reaction conditions studied (T=300–375 °C, P=4.0 MPa, WHSV=2 h⁻¹, H₂/1-MN=30 mol/mol). Product yields and selectivities were mainly determined by the zeolite composition (i.e. acidity). Selectivity to products with the same number of carbon atoms than the feed (C11) increased, at constant temperature, with decreasing the Brönsted acidity of the USY zeolite, that is, with decreasing the concentration of framework Al (FAL) and increasing extraframework Al (EFAL). Selectivity to high cetane ring opening products (ROP=C11-alkylbenzenes (C11AB) and C11-alkylcycloalkanes) within the C11 fraction was higher for the less acidic catalysts. A maximum yield of ROP of ca. 15 wt.% at a C11 yield of ca. 73 wt.% was obtained at 350 °C (P=4.0 MPa, WHSV=2 h⁻¹, H₂/1-MN=30 mol/mol) for a USY zeolite with an intermediate degree of dealumination (a₀=24.33 Å) and containing all the EFAL (bulk Si/Al ratio of 2.6). For this catalyst, a slight increase in ROP yield (ca. 17 wt.%) at similar C11 yield (ca. 74 wt.%) was obtained by working at lower temperature (300 °C) and lower space velocity. Increasing the reaction pressure above 4.0 MPa had only a marginal influence on product yields and selectivities.     

载体对肉桂醛选择性加氢钴基催化剂的影响

以肉桂醛选择性加氢制肉桂醇为探针反应,通过反应筛选出对催化作用有利的载体,并确定催化剂的最佳负载量。催化剂表征结果表明,酸性载体较碱性载体好,在酸性载体中硅藻土具有更好的助催化作用,钴负载在硅藻土上的最佳负载质量分数为12%,载体存在颗粒效应及催化剂金属与载体存在强相互作用,载体影响催化剂的分布、晶体的形状及活性中心的多少。     

Enantioselective hydrogenation of ethyl pyruvate Long-term performance of chirally modified Pt/zeolite catalysts

The long-term performance of 5 wt.% Pt/zeolite catalysts (HNaY with different degrees of ion exchange) modified with (−)cinchonidine was studied. The enantioselective hydrogenation of ethyl pyruvate to R(+)ethyl lactate was used as the model reaction. The Pt/zeolites are effective catalysts for long-term use, if the chiral modifier is added before each cycle of hydrogenation. The optimal ratio between the amount of catalyst and chiral modifier essentially depends on both the specific Pt surface area of the catalyst and the solvent used. It is found that the use of acetic acid as solvent results in a higher long-term performance than cyclohexane. This is due to the competitive adsorption between the chiral auxiliary and acetic acid on the Pt surface. Furthermore, the acidity of the solvent results in a weakening of the (−)cinchonidine/Pt interaction, which prevents an overloading of the Pt surface area with (−)cinchonidine or its decay products. This effect was determined by means of differential thermal analysis and elemental analysis. When cyclohexane is used as the solvent, the long-term performance is significantly improved by raising the carrier acidity.     

Pt catalysts supported on zeolitized-pumice for the selective hydrogenation of campholenic aldehyde: A characterization and kinetic study

A detailed characterization study of Pt catalysts supported on a novel zeolitized-pumice (Z-PM) support is reported. Two catalysts, named Pt(Cl)/Z-PM and Pt(Ac)/Z-PM, prepared by impregnation from H₂PtCl₆ and Pt(acac)₂ as precursors and subsequent reduction under H₂ at 623 K, were investigated in terms of microstructure, chemical and surface properties by using X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS).Characterization data showed that the microstructural stability of the support was preserved by using Pt(acac)₂ as precursor. It was verified instead that, by using H₂PtCl₆, the microstructure of the support changed during the thermal activation step under hydrogen, favouring a strong interaction between Pt and support as well as the formation of bimetallic Pt–Fe alloys. Moreover, a moderate increase of Pt d-band vacancies with respect to metallic Pt was observed in this catalyst by XPS.The above catalysts were tested in the selective hydrogenation of campholenic aldehydes to the corresponding unsaturated alcohol, naturanol. In comparison to the Pt(Ac)/Z-PM sample, the ex-chloride Pt(Cl)/Z-PM catalyst showed a higher selectivity to naturanol. This behaviour was interpreted on the basis of the different microstructural and electronic properties as evinced by the characterization data.     

催化裂解汽油加氢催化剂及工艺研究

根据催化裂解汽油组成特点,开发了“切C5-脱砷-切C9-两段加氢”工艺技术路线及配套的一、二段加氢催化剂.采用该工艺技术路线,利用自制催化剂对催化裂解汽油进行加氢处理,500 h稳定性评价结果表明,开发的工艺技术路线合理、可靠,催化剂性能稳定,产品溴价小于1.0 g Br/100 g,硫含量小于1.0 μg/g,满足芳烃抽提要求.     

Ni supported on sepiolite catalysts for the hydrogenation of furfural to value-added chemicals: influence of the synthesis method on the catalytic performance

Topics in Catalysis - Nickel-based catalysts supported on sepiolite catalysts, with a nickel loading between 1 and 10 wt%, have been synthesized by several synthetic strategies...     

Pt掺杂对Cu-Mn-Ce复合氧化物催化燃烧性能的影响

为提高复合氧化物催化剂的催化燃烧性能和热稳定性,采用溶胶-凝胶法制备一系列贵金属Pt改性的Cu-Mn-Ce催化剂,采用XRD、BET、H2-TPR、Raman对催化剂进行了表征,并以甲苯催化燃烧为模型反应考察了催化活性。结果表明,Pt掺杂会导致Cu-Mn-Ce晶相结构中出现较多的缺陷位,并使比表面积和表面氧数量增加,增强了催化剂的氧化-还原能力。活性测试表明,Pt相似文献   

肉桂醛选择性加氢Co-Fe/硅藻土催化剂稳定性考察

通过肉桂醛在高压微反固定床上24 h的催化加氢反应,考察了肉桂醛选择加氢的催化剂Co-Fe/硅藻土稳定性。结果表明,肉桂醛选择加氢催化剂Co-Fe/硅藻土在反应初期存在反应的诱导期,诱导期后,肉桂醛转化率70%,肉桂醇选择性80%,肉桂醇收率可达60%以上,且催化性能趋于平稳,表现出良好的催化性能和稳定性。利用XRD、SEM、TG-DSC对反应前后催化剂结构进行表征,发现催化剂经24 h反应,结构不变,表面颗粒分布更细化,无积炭迹象。     

低温选择催化还原NO催化剂的制备及其性能研究

采用等体积浸渍法制备Mn-Ti-PILC、Co-Ti-PILC、Fe-Ti-PILC、Cu-Ti-PILC和V-Ti-PILC催化剂,并应用于丙烯选择催化还原NO(C3H6-SCR)体系中。结果显示,N2最高收率由高到低的顺序依次为Cu-Ti-PILCFe-Ti-PILCV-Ti-PILCMn-Ti-PILCCo-Ti-PILC,N2最高收率所对应的反应温度由低到高的顺序依次为Mn-Ti-PILCCu-TiPILCFe-Ti-PILC=Co-Ti-PILCV-Ti-PILC。     

低温选择催化还原NO催化剂的制备及其性能研究

采用等体积浸渍法制备Mn-Ti-PILC、Co-Ti-PILC、Fe-Ti-PILC、Cu-Ti-PILC和V-Ti-PILC催化剂,并应用于丙烯选择催化还原NO(C3H6-SCR)体系中。结果显示,N2最高收率由高到低的顺序依次为Cu-Ti-PILC>Fe-Ti-PILC>V-Ti-PILC>Mn-Ti-PILC>Co-Ti-PILC,N2最高收率所对应的反应温度由低到高的顺序依次为Mn-Ti-PILC相似文献   

金属改性对多环芳烃选择性开环Pt/Beta催化剂性能的影响

以离子交换法对Beta分子筛进行Mg、Ce、Ga金属改性,并制得不同金属改性的Pt/Beta催化剂。本文采用XRD、XRF、NH₃-TPD、Py-IR、H₂-O₂、TEM、H₂-TPR、H₂-TPD及XPS等手段表征了改性前后样品的物化性质,并考察了改性前后样品的多环芳烃选择性开环性能。结果表明,改性金属对B酸中心的取代效应和对L酸中心的补偿效应,可显著调控分子筛酸性位的类型与强度。改性金属可增强金属-载体强相互作用（SMSI）,一方面促进贵金属铂的分散,提高铂纳米颗粒的热稳定性;另一方面产生铂纳米颗粒向载体的电子偏移或离域,影响H₂在铂纳米颗粒上的活化与脱附。此外,金属Ga可以选择性毒化铂纳米颗粒的活性位。改性金属显著影响Pt/Beta催化剂转化甲基萘的活性、稳定性及轻芳烃选择性,金属Ga、Ce改性可显著提高催化剂的稳定性,Ga改性催化剂的轻芳烃选择性最优。     

Diastereoselective catalytic hydrogenation on heterogeneous metal catalysts

The application of diastereoselective hydrogenation catalyzed by heterogeneous catalysts for the asymmetric synthesis of organic compounds is illustrated in the reduction of several functional groups. In that approach, the chiral information is provided by the prior attachment of a chiral auxiliary to the substrate to be hydrogenated. The optically active hydrogenated product is then disconnected from the chiral auxiliary. Proper choice of the inductor, of the catalyst and of reaction conditions may result in high diastereoselectivities. This revised version was published online in June 2006 with corrections to the Cover Date.     

硅藻土负载Co-Fe肉桂醛选择加氢催化剂的制备与表征

以肉桂醛选择性加氢制肉桂醇为探针反应,通过制备不同Fe含量的Co-Fe/硅藻土催化剂并进行催化性能评价。结合XRD、SEM和正电子寿命谱等进行表征,结果表明,Fe对Co₃O₄晶体的完整程度产生影响,导致晶体缺陷数增加。Fe引入使活性助分在载体硅藻土表面分散性更好,分散的单层性明显,负载在硅藻土上催化剂的晶粒粒径也有变小趋势。     

Novel cluster-derived catalysts for the selective hydrogenation of crotonaldehyde

The controlled pyrolysis of transition metal cluster substituted metal carboxylates, e.g., M₄O[(CO)₉Co₃CCO₂]₆, where M = Co and Zn, and M'₂(CO)₉Co₃CCOO₄, where M' = Co, Mo, and Cu, results in the formation of high surface area, amorphous solids that are active and selective catalysts for the hydrogenation of crotonaldehyde. In contrast to conventional metal catalysts that are selective for the double bond hydrogenation, these new solids exhibit high regioselectivities for the conversion of crotonaldehyde (2-butenal) to crotyl alcohol (2-butenol). Further, the observed selectivities depend on the metal cluster carboxylate structure.