SYNTHESIS, CHARACTERIZATION AND CATALYTIC BEHAVIOR OF LA2-XSRXCOO4+/-LAMBDA (X=0-2) IN COMPLETE OXIDATION

A series of mixed oxides La2-xSrxCoO4+/-lambda (x=0-2) with varying x values was synthesized. The crystal structure of this series of mixed oxides was studied by using XRD. The result showed that when x=0.25-1.5 the mixed oxides possessing K2NiF4 structure are formed. The valences of the transition metal Co and the relation between +/-lambda content and x value by using chemical analysis method have been measured, too. The redox property of this series of mixed oxides and different kinds of oxygen species were studied by IR, TPD, TPR, XPS and SEM methods. The catalytic activity in the complete oxidation of CO and CH4 was investigated and the relationships between the activity, composition and structure of the mixed oxides have been elucidated.

A STUDY OF SURFACE OXYGEN SPECIES FROM LA-ME-O (ME=MG, CA, SR, BA) CATALYSTS FOR METHANE OXIDATIVE COUPLING

CO2-TPD was used to study the surface basicity of La-Me-O mixed oxides and O-2-TPD, CH4-TPD were employed to study the surface active oxygen species. Comparing the CO2-TPD with O-2-TPD, we can see that the basicity of catalyst is in parallel with the catalystic activity. The stronger basicity is more profitable for the catalyst to adsorb oxygen to form active oxygen species and to activate CH4 by breaking a C-H bond, By comparing the catalytic activity, the results showed that La-Ba-O(La/Ba=7/3) catalyst had the strongest basicity, and it gave the highest CH4 conversion and C-2 selectivity, The results from the pulse reaction showed that the lattice oxygen participated in the OCM reaction without gas oxygen, and it was the selective oxygen species.

甲烷氧化偶联Ti-La-Li系多元氧化物催化剂的表面碱性和表面活性氧种

利用CO2-TPD方法考察了Ti-La-Li系多元氧化物催化剂的表面碱性,实验发现:C2 选择性与表面碱强度呈顺变关系,而CH4 转化率与CO2 的脱附峰面积呈顺变关系.同时,利用XPS,O2-TPD等方法对该体系催化剂的表面活性氧种进行了表征与研究,结果表明:催化剂的表面晶格氧与C2 选择性有关,表面吸附氧与甲烷转化(包括偶联和深度氧化)有关.O2 -TPD实验发现催化剂的表面存在三种氧:α( 100℃≤t≤450℃),β(450℃

La_(n+1)Ni_nO_(3n+1)(n=1～4)复合氧化物的制备、表征和催化性能的研究

合成了(AO)(ABO_3)_n(A=La,B=Ni,n=l～4)型系列复合氧化物.用XRD,XPS,IR,TPD,TPR等方法对其进行了表征,研究了结构特征,氧化一还原性能.用化学分析方法测定了镍的价态及氧缺陷.考察了该系列复合氧化物对CO,CH_4的完全氧化活性,并对其活性与化学组成及结构间的关系进行了讨论.

La_(2—x)Sr_xCoO_4±λ(x=0～2)的合成,表征和完全氧化催化性能的研究

合成了x值不同的La_(2-x)Sr_xCoO_4±λ(x=0～2)系列复合氧化物.用XRD研究了这一系列氧化物的晶体结构,结果表明x在0.25～1.5之间可形成具有K_2NiF_4结构的复合氧化物.用化学分析方法测定了过渡金属Co的价态和±λ含量与x值的关系.用IR,TPD,TPR,XPS,SEM等方法研究了这类复合氧化物的氧化还原性能,所含不同氧种,考察了对CH_4,CO的完全氧化活性,并对其活性与化学组成及结构间的关系进行了讨论.

A STUDY OF CATALYTIC PROPERTIES OF PEROVSKITE-TYPE OXIDES LAMNYCO1-YO3 .1. THE RELATIONSHIP BETWEEN THE TYPE OF OXYGEN SPECIES AND THE CATALYTIC PROPERTY IN AMMONIA OXIDATION

The type of oxygen species in perovskite-type oxides LaMnyCo1-yO3 (y = 0.0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0) has been studied by means of XRD, XPS and TPD. The catalytic activity in ammonia oxidation was also investigated. It was found that there were three desorption peaks in TPD curve corresponding to three types of oxygen species (alpha, beta, beta'). The desorption temperatures were 293 K less-than-or-equal-to T(alpha) less-than-or-equal-to 773 K, 773 K less-than-or-equal-to T(beta) less-than-or-equal-to K and T(beta') greater-than-or-equal-to 1073 K respectively. The relationship among the composition, structure and the catalytic property of.the catalyst was correlated and could be explainned with a model based on solid defect reaction and the interaction between Co and Mn ions. The adsorption strength and quantity of a oxygen are proportional to the catalytic activity. The, result indicates that the synergetic effect between B-site ions seems to the benefit of the ammonis oxidation reaction.

钙钛石型复合氧化物催化剂LaMn_yCo_(1-y)O_3的催化性能研究——Ⅰ.在氨氧化反应中氧的形态和催化性能的关系

用XRD,XPS和TPD等手段研究了钙钛石(ABO_3)型复合氧化物催化剂LaMn_yCo_(1-y)O_3中氧的形态;研究了催化剂在氨氧化反应中的活性,发现这类氧化物中存在三种形态的氧种(α,β,β’).它们所对应的脱附温度分别为293K≤T_α≤773K,773K≤T_β≤1073K,T_β’≥1073K.研究了它们与催化剂组成、结构及催化性能之间的关系,并用缺陷化学反应和B位离子之间的相互作用模型进行了解释.α氧的吸附强度和吸附量与催化活性成正比关系.B位离子之间的协同作用有利于氨氧化反应的进行.

ROLE OF H2S IN THE REDUCTION OF MOO3/AL2O3

MoO3/Al2O3 is reduced at least partly by sulfur which is formed from H2S in sulfidation with H2S/N2 mixture. SO2 formation during TPD of MoO3/Al2O3 with presorbed H2S provides evidence for the explanation.

THE CATALYTIC BEHAVIOR AND REACTION-MECHANISM OF THE BI-CE-O SYSTEM CATALYSTS IN THE OXIDATIVE DEHYDROAROMATIZATION OF PROPYLENE

Oxidative dehydroaromatization of propylene was investigated by the pulse technique over two kinds of single oxide catalysts. With the Bi2O3 catalyst, the main dimer product was 1,5-hexadiene, and the dimerization activity was stable to pulse number even if the catalyst was partly reduced to the bulk. With the CeO2 catalyst, benzene was mainly formed instead of 1,5-hexadiene, but the activity decreased rapidly with increasing pulse number, indicating that only the lattice oxygen near the catalyst surface could be used for oxidative dimerization and the further aromatization. The Bi-Ce-O system catalyst was found in this study to give higher aromatization activity and showed better stability, compared to the Bi-Sn-O catalyst. Although the Bi-Ce-O catalyst was only a mixture of the two component oxides from X-ray diffraction analysis, there was a significant combination effect on the selectivity to benzene. The highest and the most stable selectivity of benzene was obtained at Bi/Ce = 1. In the TPD spectrum of Bi-Ce-O catalyst, there are not only the lattice oxygen (beta-oxygen) over 620-degrees-C due to the reduction of Bi2O3, but also a great deal of the alpha-oxygen desorbed about 400-degrees-C, which is considered the absorbed oxygen in the bulk. This absorbed oxygen could probably be a compensation of the lattice oxygen through the route of gaseous --> absorbed --> lattice oxygen in the binary catalyst system. By the kinetic study on the Bi-Ce-O catalyst, the dimer formation rate was the first-order with respect to the partial pressure of propylene and zero-order of oxygen. Although detail investigation would be made further, it was considered that the complete oxidation of propylene would mainly take place parallelly on some different sites, and the rate-determining step of propylene dimerization occurred probably between an adosrbed propylene and a gaseous one by an Eley-Rideal type mechanism.

Sb-Fe催化剂的活性结构和在丙烯氨氧化中的催化作用机理研究

用XRD,Mossbauer,XPS和TPD研究了Sb-Fe催化剂的活性组分和它们的催化行为以及TPD的产物分布。XRD测定表明,活性组分可能有FeSbO_4和Sb_2O_4。穆斯堡尔谱结果确定活性组分除有FeSbO_4外,还有FeSb_2O_6。由富锑催化剂的XPS分析,出现结合能为709.3eV的肩峰,进一步证明含Fe_(2+)新活性组分FeSb_2O_6的存在。由Fe_(3+)和Fe_(2+)含量与活性的关系可以得出结论,催化作用取决于FeSbO_4,FeSb_2O_6和Sb_2O_4的协同作用,FeSb_2O_6是表面活性中心。最后,由催化剂的活性组分和催化作用以及TPD产物分布初步探讨了催化作用机理。

多组分钼酸盐催化剂的活性结构及其在丙烯氨氧化中的催化作用机理

用XRD,IR,Mossbauer,ESR,XPS和TPD研究了50％Ni_3Co_5Fe_xBiPK_(0.1)Mo_(12)O_(48.05+(3/2)x)-50％SiO_2催化剂的活性组分、催化行为和产物分布。结果表明,活性组分有Fe_2(MoO_4)_3,Bi_2O_3·3MoO_3,CoMoO_4和NiMoO_4。Bi_2O_3·3MoO_3是表面活性中心,起选择氧化作用;Fe_2(MoO_4)_3则起氧化还原的促进作用;CoMoO_4和NiMoO_4起结构稳定作用。还探讨了催化作用机理。

LaMn_(1-y)Fe_yO_3对CH_4和CO的催化氧化作用

用程序升温脱附试验考察了LaMn_(1-y)Fe_yO_3型催化剂中B位元素对Co、CH_4氧化活性的影响。发现催化剂的活性与TPD谱上脱氧峰的位置及面积有关,同一催化剂对CO与CH_4的氧化活性中心并不一致。以γ-Al_2O_3为载体制得的锰系ABO_3型催化剂在浸渍微量氧化物助催化剂后,能使CO在130℃完全氧化,CH_4的氧化温度为300～500℃。

Li/La_2O_3的表面活性氧及其在甲烷氧化偶联中的催化行为

甲烷氧化偶联反应近年来研究十分活跃。Lunsford等报道了载有碱金属的碱土氧化物是对此反应有效的催化剂,并提出晶格取代型活性中心[M~+O~-〕和表面活化、气相偶联的反应机理。Otsuka等系统地研究了稀土氧化物的甲烷氧化偶联活性,本文通过氧化镧中添加锂前后的对比,运用骤冷技术与ESR法研究了催化剂的表面活性氧,以低温TPD法研究了甲烷在催化剂表面上的吸附与活化,以及在甲烷氧化偶联中的催化行为。

Methane dehydro-aromatization over a Mo/phosphoric rare earth-containing penta-sil type zeolite in the absence of oxygen

The dehydro-aromatization of methane over a Mo-modified penta-sil type high-silica zeolite containing phosphoric and rare earth oxide (abbreviated as Mo/HZRP-1) was investigated. As a modification of HZSM-5, HZRP-1 is also a good support for the preparation of Mo-based zeolite catalysts, and is active for methane dehydro-aromatization. Mo/HZRP-1 catalysts are more active at high Mo loadings compared with Mo/HZSM-5 catalysts. Al-27 MAS NMR spectra of Mo/HZRP-1 reveal that there are two kinds of framework Al in HZRP-1. It is suggested that only the tetrahedral coordinated Al atoms in the form of Al-O-Si species in the zeolite, in the proton forms, are responsible for the formation of aromatics.

MAS NMR studies of modified HY zeolites

The variations in structure and acidity on the internal and external surfaces of HY zeolites modified by MgO and SiO2 have been studied by MAS NMR, together with the selective adsorption of perfluorotributyl-amine. Al-27 and Si-29 MAS NMR spectra revealed that the modifications led to significant changes of the framework owing to the migration of some non-framework Si and Al into the framework in the course of the modifications. H-1 MAS NMR spectra showed that the modifications decreased the acidity of the zeolite surfaces. With an increasing of the loading of the oxides, the acidity of the surface decreased further. Both of the two kinds of Bronsted acidity of the MgO-modified HY zeolites decreased, particularly those in the supercages, while those of the SiO2-modified HY zeolites decreased less, and this result is consistent with that of NH3-TPD, from the adsorption of perfluorotributyl-amine, it was found that the acidic sites on the external surface of the HY zeolite can be completely covered by SiO2 after being modified by the chemical liquid deposition (CLD) method.