钴基催化剂上乙烷氧化脱氢的催化作用

比较了氧化钴、氧化镍分别对乙烯、乙烷氧化的催化性能，结果发现：乙烯在氧化钴较氧化镍上更易进一步深度氧化生成CO2．通过对新制担载型Co-基催化剂随反应温度反复升、降温的乙烷氧化脱氢(ODHE)性能研究，展现了氧化钴活性相与SiO2载体相互作用对催化性能的影响．Weiss原位磁研究结果表明：SiO2担载的氧化钴催化剂较难还原，即使在反应气中氧被完全耗完时，钴仍停留在Co^2 的价态上．通过对数十个担载和未担载、不同载体、不同担载量的Co-基催化剂的ODHE性能考察表明：在Co-基催化剂上ODHE反应机理一般遵从Hetero-homogeneous机理．     

纳米Cr2O3系列催化剂上CO2氧化乙烷脱氢制乙烯反应

 采用溶胶－凝胶法和共沸蒸馏法耦合技术制备了纳米Cr2O3催化剂，并采用共沉淀法和共沸蒸馏法耦合技术制备了纳米Cr2O3／Al2O3，Cr2O3／ZrO2和Cr2O3／MgO复合催化剂．应用BET，XRD，XPS，TPR和TEM等物理化学方法对催化剂的结构和物化性质进行了表征，并考察了该系列催化剂上CO2氧化乙烷脱氢制乙烯的反应性能．结果表明，纳米Cr2O3催化剂上乙烷和CO2的转化率均明显高于常规Cr2O3催化剂，但乙烯的选择性低于常规Cr2O3催化剂；纳米复合催化剂中的复合成分显著影响催化剂的催化性能．其中，10％Cr2O3／MgO纳米复合催化剂在温度为973K时，乙烷转化率和乙烯选择性分别可达到61．54％和94．79％．纳米催化剂表面Cr的还原性以及Cr6＋／Cr3＋比值是影响乙烷转化率和乙烯选择性的重要因素．     

Co-MCM-41催化剂上临CO2-乙烷脱氢反应的研究

合成了不同Co掺杂量的Co-MCM-41分子筛.用XRD,FTIR和TG-DTA等技术对所制样品进行表征.在常压连续流动固定床反应器上考察了它们对临CO₂-乙烷脱氢制乙烯反应的性能,结果表明,3%Co-MCM-41在973K可使乙烷的转化率达到39.54%,乙烯的选择性达到98.59%,收率达到38.98%.Co的掺杂量和反应温度等条件对该反应均有一定影响.Co-MCM-41对乙烷催化脱氢制乙烯同样也有很高的活性.引入CO₂可消除积炭对催化剂活性的影响,更有利于催化反应的进行.     

负载Ni催化剂用于乙二醇蒸汽重整制氢催化性能研究

采用等体积浸渍法和共沉淀法制备了Ni催化剂,在固定床反应器上考察了Ni负载量、焙烧温度、反应温度等因素对乙二醇低温重整制氢反应活性和选择性的影响。应用X射线衍射、氮物理吸附、H₂程序升温还原等技术对负载型Ni催化剂进行了表征。结果表明,共沉淀法制备的Ni/CeO₂催化剂具有较小的NiO颗粒与CeO₂载体颗粒粒径,催化活性较高。添加少量氧化钴到Ni/CeO₂催化剂中可使H₂收率达72.6%,EG转化率达93.1%。在CeO₂中添加Al₂O₃能提高负载Ni催化剂的活性,乙二醇转化率达94.0%,H₂收率达67.0%;但添加SiO₂则使其活性明显变差。     

Experimental investigation of fluidized-bed reactor performance for oxidative coupling of methane

Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane (C2) yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.     

甲烷氧化偶联锂/氧化镁催化剂和纳米催化剂

The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products (ethane and ethylene) compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.     

Effects of Preparation Methods and Interaction between Support and Oxide for Oxidative Dehydrogenation of Ethane over NiO/ZrO2

The previous studies indicated that the unsupported and alumina supported nickel oxide catalysts are the attractive candidates for the oxidative dehydrogenation of ethane (ODE) reaction at lower reaction temperature^[1,2]. In the present study, NiO/ZrO₂ catalysts were prepared by the impregnation, complex of ammonia and coprecipitation, respectively, using the conventional incipient wetness technique. Over all samples used in this study, no NiO crystal structure was detected by XRD measurements carried out in parallel with the present work, which indicated the nickel oxide was highly dispersed on the support The blank testing indicated that the support ZrO₂ had very little activity below 600℃. Comparing with the unsupported nickel oxide, it was found that the activity of NiO/ZrO₂ catalysts prepared by the methods mentioned above decreased slightly and the selectivity for ethylene improved. With the increasing temperature, the ethane conversion increased and the selectivity for ethylene decreased However, the cracking of the ethane occurred at ca.450℃ on all samples prepared by different methods. The optimum catalytic behavior could be obtained on 5wt%NiO/ZrO₂ prepared by coprecipitation, with the ethane conversion of 26.2% and selectivity for ethylene of 51.8% at as low temperature as 350℃. The sample prepared by coprecipitation and calcined at 500℃ was calcined again at 600℃ for 5 h,the activity decreased obviously, which may be attributed to the existence of the interaction between nickel oxide and support taking into account for the high dispersion of NiO on ZiO₂.     

Effect of methane co-feeding on the selectivity of ethylene produced from oxidative dehydrogenation of ethane with CO2 over a Ni-La/SiO2 catalyst

A Ni-La/SiO₂ catalyst was prepared through the incipient wetness impregnation method and tested in the oxidative dehydrogenation of ethane (ODHE) with CO₂. The fresh and used catalysts were characterized by XRD and SEM techniques. The Ni-La/SiO₂ catalyst exhibited catalytic activity for the oxidative dehydrogenation of ethane, but with low ethylene selectivity in the absence of methane. The selectivity to ethylene increased with increasing molar ratio of methane in the feed. The carbon deposited on the catalyst surface in the sole ODHE with CO₂ was mainly inert carbon, while much more filamentous carbon was formed in the presence of methane. The filamentous carbon was easy to be removed by CO₂, which might play a role in improving the conversion of ethane to ethylene. The introduction of methane might affect the equilibrium of the CO₂ reforming of ethane and the ODHE with CO₂. As a consequence, the synthesis gas produced from CO₂ reforming of methane partly inhibited the reaction of ethane and promoted the ODHE with CO₂, thus increasing the selectivity of ethylene.     

Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.     

添加碱金属对甲烷与空气制合成气的催化剂性能的影响

考察了添加在镍基催化剂中的碱金属助剂 ,对甲烷与空气制合成气的催化反应性能的影响 ;并用 TPO、TPR、CO2 程序升温脱附 (TPD)、XPS及 CO脉冲色谱技术 ,对催化剂进行了表征 .实验表明 ,碱金属助剂对降低催化剂结炭有一定的作用 ,催化剂的抗积炭性能为 Ni- K2 O/Ca O- Al2 O3>Ni- L i2 O/Ca O- Al2 O3>Ni- Na2 O/Ca O-Al2 O3>Ni/Ca O- Al2 O3.在实验中发现 ,碱金属的添加 ,可使催化剂的 Ni比表面积变小、吸附 CO2 的能力增强 ,且结合能可发生不同程度的改变 .从而解释了碱土金属助剂对催化剂活性和抗积炭性的影响 .实验显示 ,Ni-L i2 O/Ca O- Al2 O3具有较好的活性和抗积炭性能     

Oxidative coupling of methane over La-promoted CaO catalysts： Influence of precursors and catalyst preparation method

The oxidative coupling of methane to C2 hydrocarbons has been studied over a series of La-promoted CaO (La/Ca = 0.05) catalysts, prepared using different precursor salts for CaO and La2O3 (viz. acetates, carbonates, nitrates and hydroxides) and catalyst preparation methods (viz. physical mixing of precursors, co-precipitation using ammonium carbonate/sodium carbonate as a precipitating agent), under different reaction conditions (temperature: 700-850℃, CH4/O2 ratio: 4.0 and 8.0, and GHSV: 51360 cm3 g-1 h-1)...     

Dry reforming reaction over nickel catalysts supported on nanocrystalline calcium aluminates with different CaO/Al2O3 ratios

Nanocrystalline calcium aluminates with different CaO/Al2O3 ratios were prepared by a facile co-precipitation method using Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG, MW: 5800) as a surfactant. They were employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction (XRD), N2 adsorption (BET), temperature-programmed reduction and oxidation (TPR-TPO), and scanning electron microscopy (SEM) techniques. Catalysts showed a relatively high catalytic activity and stability. TPR analysis revealed that the catalysts with higher CaO content are more difficult to be reduced. TPO analysis showed that the 5 wt%Ni/CA and 5 wt%Ni/C12A7 catalysts with higher CaO amount were effective against coke deposition.     

Catalytic performance of silica-supported chromium oxide catalysts in ethane dehydrogenation with carbon dioxide

The oxidative dehydrogenation of ethane into ethylene by CO₂ over a series of silica-supported chromium oxide catalysts was investigated. The results showed that the catalysts were effective for the reaction and CO₂ in the feed promoted the catalytic activity. The 5%Cr/SiO₂ catalyst exhibited the excellent performance with 30.7% ethane conversion and 96.5% ethylene selectivity at 700^oC. ESR and UV-DRS were used to probe the active sites and the species with high valent states (Cr⁵⁺ and/or Cr⁶⁺) were found to be important for the reaction.     

Oxygen species on NiO/Al2O3 and their reactivities

Oxygen species on fresh and treated NiO/Al₂O₃ and their activities for oxidation of ethane and ethylene were investigated using catalytic property measurements, ethane and ethylene pulse experiments and O₂–TPD–MS experiments. The results revealed that there are two kinds of active oxygen species (the more active one and the less active one) on fresh NiO/Al₂O₃ catalyst, but there is only one active oxygen species, the less active one, on treated NiO/Al₂O₃ catalyst. The more active oxygen species can convert ethane or ethylene to carbon dioxide by one step while the less active one can only convert ethane to ethylene, but cannot convert ethane and/or ethylene to carbon dioxide. The more active oxygen species can be removed from the catalyst by heating from 350 to 850 °C. The amounts of desorption oxygen on the catalysts are proportional to their selectivity to carbon dioxide.     

锂在甲烷氧化偶联催化剂中的助催化作用

自Lunsford等首次报道在Li/MgO催化剂上的甲烷氧化偶联(OCM)以来,许多研究者相继报道了添加碱金属对该反应的影响,其中以Li的添加最受关注。Li在OCM反应中对提高C_2烃选择性的作用最为明显,因而弄清Li在这一反应中的作用十分必要。本文讨论了Li在几个有代表性的碱土(CaO)及稀土(La_2O_3)中的存在形式与生成C_2产物的关系。     

CeO2、CaO助剂对甲烷部分氧化制合成气Ni/MgOAl2O3催化剂结构和性能的影响

采用BET、H2 TPR、XRD、TEM和活性评价等表征手段，考察了CeO2、CaO助剂对Ni/MgOAl2O3催化剂物化性质和甲烷部分氧化制合成气反应性能的影响。实验结果表明，单独加入CeO2或CaO助剂可以改善Ni/ MgOAl2O3催化剂中镍物种的还原性能，以CaO尤为明显；CaO作为结构助剂可以降低还原态催化剂中的镍晶粒尺寸，使改性的催化剂具有较好的活性，而CeO2对催化剂的活性未产生显著影响。当CeO2与CaO两种助剂同时对Ni/MgOAl2O3进行改性时，虽然催化剂中镍物种的还原性能没有发生明显变化，但仍具有很好的反应性能，这与CeO2与CaO能够形成CaO-CeO2固溶体有关。CaO-CeO2固溶体不仅与镍物种间存在相互作用，提高了镍物种的分散度、减小了镍晶粒尺寸，还可以提高催化剂的储氧能力和晶格氧的流动性，从而有利于改善其甲烷部分氧化反应性能。     

固体酸WO3/TiO2负载锂锰催化剂组成对其甲烷氧化偶联反应性能的影响

The selective oxidation of methane to basic petrochemicals (ethylene and ethane) is desirable and has attracted extensive research attention. The oxidative coupling of methane (OCM) is considered a promising one-step route for the production of C₂ compounds (ethylene and ethane) from methane, and has been the focus of industrial and fundamental studies. It is widely accepted that the composition is a crucial factor governing the activity of a catalyst system. It was found that the phase structures, basicity, existing status and distribution of the active components, oxygen species, and chemical states of the catalyst were influenced by the composition and ratio, resulting in different catalytic performances for the OCM. In this study, a series of solid acid WO₃/TiO₂-supported lithium-manganese oxide catalysts for OCM were synthesized via the impregnation method. The impacts of diverse compositions, such as the individual contents (Li and Mn) and dual contents (Li-Mn), on the OCM were investigated in detail, using inductively coupled plasma optical emission spectrometry, X-ray diffraction, high-resolution transmission electron microscopy, CO₂-temperature-programmed desorption, O₂-temperature-programmed desorption, H₂-temperature-programmed reduction, Raman spectroscopy, X-ray photoelectron spectroscopy, and CH₄-temperature-programmed surface reaction. The addition of Li content to the catalyst not only led to the anatase-to-rutile crystal structure transformation of TiO₂, and the reduction of the high-valence-state Mn species to low-valence-state Mn, but also increased the content of surface lattice oxygen and decreased the surface basicity. The observed effects on the structures and catalytic performance suggest that the Li content is helpful in suppressing the formation of completely oxidized CO₂, and increases the C₂ selectivity. Moreover, increasing the Li content of the catalyst facilitated the mobility of the lattice oxygen, which triggered the promotion of CH₄ activation, thereby enhancing the OCM catalytic performance. The Mn content acted as the active sites for OCM; therefore, the performance of the catalyst was closely related to the Mn concentration and valence state. However, the WO₃/TiO₂-supported catalyst with excessive Mn content exhibited a high surface basicity, high valence state of Mn, and low abundant lattice oxygen, which was unfavorable for C₂ selectivity. The Raman spectroscopy results revealed that MnTiO₃ was formed due to the co-existence of Li and Mn on WO₃/TiO₂, and played an essential role in improving the low-temperature OCM performance. There was a synergic effect of the Li and Mn components on the OCM. The optimal performance (16.3% C₂ yield) was achieved over the WO₃/TiO₂-supported lithium-manganese catalyst with n(Li) : n(Mn) = 2 : 1 at 750 ℃.     

Effect of barium on reducibility and activity for cobalt-based Fischer-Tropsch synthesis catalysts

Barium modified Co/Al2O3 catalysts were prepared by incipient wetness impregnation. The catalysts were characterized by XRD, TPD and DRIFTS. The catalytic activity for Fischer-Tropsch synthesis was measured in a continuously stirred tank reactor. It was found that small amounts of BaO (≤ 2 wt%) improved the cobalt reducibility, which led to more cobalt active sites on the catalyst surface, and then resulted in higher CO conversion and C5+ selectivity. However, for the catalysts with high BaO loadings negative effects on the catalytic activity and selectivity for high hydrocarbons were observed because of low cobalt reducibility.     

镍盐前驱体对Ni/C催化剂乙醇气相羰化活性的影响

采用等体积浸渍法制备了分别以乙酰丙酮镍、氯化镍、硝酸镍和醋酸镍为前驱体负载在活性炭上的四种催化剂。用BET、金属分散度、H2-TPR、CO-TPD和XRD等方法研究了四种催化剂的结构特点和乙醇气相羰化活性。结果表明,以醋酸镍制备的Ni/C催化剂的羰化活性最高,乙醇转化率和丙酸选择性分别为96.1%和95.7%,而以乙酰丙酮镍制备的Ni/C催化剂的羰化活性最低,乙醇转化率和丙酸选择性分别为68.9%和27.1%。这种活性的差异与镍盐前驱体和活性炭之间的相互作用强弱有着密切关系。醋酸镍组分与活性炭之间的相互作用较强,浸渍组分易在活性炭表面充分吸附,活性中心Ni0在240－340 ℃温度范围内对CO吸附量最大,还原后金属镍的分散度较好且晶粒较小。     

多氮螯合配位后过渡金属络合物烯烃聚合催化剂

A2二亚胺镍、钯络合物和吡啶二亚胺铁、钴络合物是近几年来发现的新一代烯烃均相聚合后过渡金属催化剂。这类催化剂具有活性高、选择性易调变、聚合物性质可控制的特点, 尤其是对官能团中的杂原子的稳定性方面优于前过渡金属催化剂。本文将近年来的有关报道归纳为4 个方面进行评述: 络合物的合成和结构; 配体结构因素对络合物催化性能的影响; 催化烯烃高聚、齐聚和共聚以及催化反应机理。