Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen cartier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction. Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox re-action decreased over La0.8Sr0.2Fe0.9Co0.1O3 oxide, while LaFeO3 and Lao.sSro.2FeO3 exhibited excellent structural stability and continuous oxygen supply.     

无气相氧条件下La0.8Sr0.2Fe0.9Co0.1O3钙钛矿氧化物的氧物种直接氧化甲烷

以La0.8Sr0.2Fe0.9CO0.1O3钙钛矿氧化物作氧载体,采用连续流动反应和连续顺序Redox反应考察了氧物种氧化甲烷的反应性能.结果表明,连续流动反应中La0.8Sr0.2Fe0.9CO0.1O3氧化物的氧物种能选择氧化甲烷生成合成气.在适宜的再氧化条件下,通过连续顺序Redox反应实现了La0.8Sr0.2Fe0.9CO0.1O3氧化物的氧物种氧化甲烷连续生成合成气,消耗的氧物种可通过与气相氧反应而得到补充.但随着Redox反应的进行,氧化物的持续供氧性能下降,钙钛矿结构被破坏.     

Hydrogen production from a combination of the water-gas shift and redox cycle process of methane partial oxidation via lattice oxygen over LaFeO3 perovskite catalyst

A redox cycle process, in which CH4 and air are periodically brought into contact with a solid oxide packed in a fixed-bed reactor, combined with the water-gas shift (WGS) reaction, is proposed for hydrogen production. The sole oxidant for partial oxidation of methane (POM) is found to be lattice oxygen instead of gaseous oxygen. A perovskite-type LaFeO3 oxide was prepared by a sol-gel method and employed as an oxygen storage material in this process. The results indicate that, under appropriate reaction conditions, methane can be oxidized to CO and H2 by the lattice oxygen of LaFeO3 perovskite oxide with a selectivity higher than 95% and the consumed lattice oxygen can be replenished in a reoxidation procedure by a redox operation. It is suggested that the POM to H2/CO by using the lattice oxygen of the oxygen storage materials instead of gaseous oxygen should be possibly applicable. The LaFeO3 perovskite oxide maintained relatively high catalytic activity and structural stability, while the carbonaceous deposits, which come from the dissociation of CH4 in the pulse reaction, occurred due to the low migration rate of lattice oxygen from the bulk toward the surface. A new dissociation-oxidation mechanism for this POM without gaseous oxygen is proposed based on the transient responses of the products checked at different surface states via both pulse reaction and switch reaction over the LaFeO3 catalyst. In the absence of gaseous-phase oxygen, the rate-determining step of methane conversion is the migration rate of lattice oxygen, but the process can be carried out in optimized cycles. The product distribution for POM over LaFeO3 catalyst in the absence of gaseous oxygen was determined by the concentration of surface oxygen, which is relevant with the migration rate of lattice oxygen from the bulk toward the surface. This process of hydrogen production via selective oxidation of methane by lattice oxygen is better in avoiding the deep oxidation (to CO2) and enhancing the selectivity. Therefore, this new route is superior to general POM in stability (resistance to carbonaceous deposition), safety (effectively avoiding accidental explosion), ease of operation and optimization, and low cost (making use of air not oxygen).     

Partial Oxidation of Methane to Syngas Using Lattice Oxygen of La1-xSrxFeO3

Catalytic partial oxidation of methane to syngas using the lattice oxygen of La1-xSrxFeO3 perovskite oxide catalysts in place of molecular oxygen was studied. La1-xSrxFeO3 (x＝0, 0.1, 0.2,0.5) perovskite oxides were prepared by the "auto-combustion method". XRD analysis showed that all La1-xSrxFeO3 samples have a single-phase perovskite-type oxide. The redox properties of the catalysts were investigated by temperature programmed reduction with hydrogen (H2-TPR). Reducibility of the catalysts increase with the increasing of the Sr2+ content. The oxygen species of the catalysts and their reaction with CH4 were studied by the temperature programmed surface reaction (CH4-TPSR). In the absence of gas phase oxygen, there exist two kinds of oxygen species on the catalysts. One kind of the oxygen species with strong oxidative ability is produced first, which can oxidize CH4 completely to CO2 and H2O.Then, the second oxygen species with weak oxidative ability is formed, which can oxidize CH4 partially to CO and H2 with high selectivity. The number of the oxygen species with strong oxidative ability in the CH4-TPSR tends to become zero at low x values (x≤0.1). Under suitable reaction conditions, switching alternatively the reactions of 11% O2-Ar and 11% CH4-He over a La0.sSr0.2FeO3 catalyst at 900 ℃ allows methane to be selectively converted to synthesis gas (CH4 conversion ～90%, CO selectivity ＞93%) using the lattice oxygen of the perovskite oxide catalyst in a redox mode.     

LaMO3纳米复合钙钛矿氧载体化学循环重整甲烷制合成气

采用溶胶-凝胶法制备了不同B位可变价离子的LaMO3 (M= Cr,Mn,Fe,Co)复合氧化物氧载体,采用X射线衍射、N2吸附-脱附、扫描电镜及CH4程序升温表面反应等手段对氧载体进行了表征,并用于直接选择氧化CH4的反应中.结果表明,Cr,Mn,Fe 和Co均能形成LaMO3纳米复合钙钛矿结构,其氧物种氧化能力大小...     

Lan+1NinO3n+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)(ABO3)n(A=La, B=Ni, n-1～4)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-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, CH4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。     

La2-xSrxCuO4-λ复合氧化物的合成、表征和氨的氧化催化性能的研究

合成了x值不同的La2-xSrxCuO4-λ(x=0~1)系列复合氧化物, 用XRD研究了这一系列氧化物的结构, 结果表明x在0~0.3之间可形成K2NiF4结构单相化合物。用化学分析方法测定了过渡金属Cu的价态及含量, 并计算出复合氧化物中的非计量氧数。用TPD, TPR, TG, XPS, SEM等方法研究了这类复合氧化物的氧化还原性能, 所含氧种及表面形态, 考察了对NH3氧化的催化活性, 并对其催化活性与化学组成及结构的关系进行了讨论。     

原位FT-IR研究甲烷和氧与SrO-La_2O_3/CaO催化剂表面的相互作用和反应(英文)

用原位FT－IR研究了甲烷和氧与纯CaO,La_2O_3和SrO氧化物以及LC和SLC催化剂的相互作用和反应．当不存在气相氧时,引入的甲烷与表面晶格氧反应生成碳酸盐物种。在室温或高温下,在这些氧化物和催化剂上不能检测到CH_4或O_2的吸附物类。但是,当CH_4和O_2同时存在时,在La_2O_3和LC催化剂上能检测到1118cm~－1的新谱带、这一谱带可能来自于表面碳酸盐在高温下氧气氛中的分解,并可归属为物种。甲烷与这一活性氧物种反应生成C_2H_4。但对SLC催化剂,在高温下不能检测到物种,而甲烷和氧在高温下反应也能产生表面碳酸盐并在气相中形成乙烯,这就表明,气相氧对这些催化剂也起着关键作用,但是在LC和SLC催化剂上甲烷氧化偶联反应可能有本质上的差别。     

Simple syntheses, structural diversity, and Tishchenko reaction catalysis of neutral homoleptic rare earth(II or III) 3,5-di-tert-butylpyrazolates--the structures of

The homoleptic rare-earth pyrazolate complexes [Sc(tBu2pz)3], [Ln2(tBu2pz)6] (Ln = La, Nd, Sm, Lu), [Eu4(tBu2pz)8] and the mixed oxidation state species [Yb2(tBu2pz)5] (tBu2pz = 3,5-di-tert-butylpyrazolate) have been prepared by a simple reaction between the corresponding rare-earth metal and 3,5-di-tert-butylpyrazole, in the presence of mercury, at elevated temperatures. In addition, [Yb2(tBu2pz)6] was prepared by redox transmetallation/ligand exchange between ytterbium, diphenylmercury(II) and tBu2pzH in toluene, whilst the same reactants in toluene under different conditions or in diethyl ether gave [Yb2(tBu2pz)5]. The complexes of the trivalent lanthanoids display dimeric structures [Ln2(tBu2pz)6] (Ln = La, Nd, Yb, Lu) with chelating eta2-terminal and eta2:eta2-bridging pyrazolate coordination. The considerably smaller Sc3+ ion forms monomeric [Sc(tBu2pz)3] of putative D3h molecular symmetry, with pyrazolate ligands solely eta2-bonded. [Eu4(tBu2pz)8] is a structurally remarkable tetranuclear EuII complex with two types of europium centres in a linear array. The outer two are bonded to one terminal and two bridging pyrazolates, and the inner two are coordinated by four bridging ligands. Unprecedented mu-eta5:eta2 pyrazolate ligation is observed, with each outer Eu2+ sandwiched between two eta5-bonded pyrazolate groups, which are also eta2-linked to an inner Eu2+. The two inner Eu2+ ions are linked together by two equally occupied components of each of two symmetry related, disordered pyrazolate groups with one component eta4:eta2 bridging and one eta3:eta2 bridging. [La2(tBu2pz)6] has also been shown to be a Tishchenko reaction catalyst with several organic substrates.     

稀土取代的复合氧化物Eu_（0．5）RE_（0．5）Fe_（0．5）Mn_（0．

利用固相反应合成了稀土取代的复合氧化物Ｅｕ_（０．５）ＲＥ_（０．５）Ｆｅ_（０．５）Ｍｎ_（０．５）Ｏ_３（ＲＥ＝Ｌａ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔｍ，Ｙｂ）．测量了这些化合物的ＸＲＤ和ＸＰＳ谱。在ＸＰＳ研究中发现，稀土取代而使稀土元素本身的结合能相对于其倍半氧化物中的有所降低；在取代的复合氧化物中，随着ＲＥ离子半径的减小，Ｆｅ、Ｍｎ的结合能随之增加。     

Influence of support on resistance to carbon-deposition of catalyst for CH4, CO2 with O2 to synthesis gas

In the reaction of catalytic oxidation of CH4,CO2 with O2 to synthesis gas, carbon-deposition is an important factor for deactivation. By adding different oxides to Ni/AI2O3 catalyst, its resistance to carbon-deposition was improved. The experimental results indicate that the order of resistance to carbon-deposition is as follows: Ni/CaO-AI2O3>Ni/MgO-AI2O3>Ni/ TiO2-AI2O3>Ni/CeO2-AI2O3>Ni/La2O3-AI2O3>Ni/Y2O3-AI2O3>Ni/Fe2O3-AI2O3>Ni/AI2O3. The catalysts were characterized by CO2-TPD, O2-TPD and XPS methods. Here the relation between the order of resistance to carbon-deposition and performance of catalyst is discussed.     

甲烷氧化偶联La－Me－O（Me＝Mg，Ca，Sr，Ba）系催化剂表面氧种的研究

利用ＣＯ_２－ＴＰＤ法考察了Ｌａ－Ｍｅ－Ｏ（Ｍｅ＝Ｍｇ，Ｃａ，Ｓｒ，Ｂａ）系催化剂的表面碱性，并用Ｏ_２－ＴＰＤ、ＣＨ_４－ＴＰＤ法对该体系的表面活性氧种进行了表征，并与催化性能相关联。结果表明，Ｌａ－Ｂａ－Ｏ催化剂由于表面强碱性中心数目多，产生活性氧种的数目也多，有利于甲烷的活化，因而具有最高的甲烷转化率和Ｃ_２烃选择性。脉冲反应表明，在无气相氧存在下，表面晶格氧参与了氧化偶联，而且是选择氧化的活性氧种。     

稀土和碱土钼氧化物上甲烷选择氧化

白钨石ABO_4复合氧化物在烯烃氧化中起着重要作用,但在烷烃催化氧化中的研究并不多,有关稀土氧化物催化剂的研究则更少。本文以Mg、La、Ce、Eu的钼酸盐作为甲烷选择氧化催化剂,每种催化剂制成不同A/B值系列,以考察催化剂结构和氧化活性的关系。     

THE ROLE OF LATTICE AND GASEOUS OXYGEN ON THE OXIDATIVE COUPLING OF METHANE STUDIED BY A PULSE REACTION TECHNIQUE

A comparative study of the role of lattice and gaseous oxygen in theoxidative coupling of methane over Na~ /Cao and Ca_xSr_(1-x)TiO_3 perovskiteoxide catalysts was performed by using a pulse reaction technique with CH_4,O_2 and mixtures of CH_4and O_2.It was found that there is an oxygen species onthe Surface of Cao which is active only for the total oxidation of methane at thereaction temperature.These oxygen species.once reacted with methane andconsumed,can be regenerated by the adsorption of oxygen molecules from thegas phase or by the migration of the lattice oxysen from the bulk onto thesurface.In contrast,no such oxygen species and no reaction can be detected bymethane pulsed over Ca_xSr_(1-x)TiO_3perovskite oxide catalysts.Na~ can heavilysuppress the non-selective oxygen species on the surface,and When 5mol%Na~ was incorporated onto the surface of Cao,the sample showed no reactivityto methane.When oxygen exists in the gas phase,or the pulse containsmethane and oxygen,the reaction over(Cao is mai     

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9CO0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction, Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox reaction decreased over La0.8Sr0.2Fe0.9Co0. 1O3 oxide, while LaFeO3 and La0.8Sr0.2FeO3 exhibited excellent structural stability and continuous oxygen supply.     

希土硼氢化物的研究 Ⅹ.含[B_(10)H_9NH_2COCH=CH_2]~-的双苯甲酰丙酮缩1,3—丙二胺希土(Ⅲ)配合物的研究

将闭式+氢+硼酸阴离子酰胺衍生物[B_(10)H_9NH_2COCH=CH_2]~-、双苯甲酰丙酮缩1,3-丙二胺C_6H_5C(OH)=CHC(CH_3)=N(CH_3)CH=C(OH)C_6H_5(Bapn)及希土氯化物在丙酮-乙醇混合溶剂中进行反应,得到分子式为Ln(Bapn)_3[B_(10)H_9NH_2COCH=CH_2]_3(Ln=La,Nd,Sm,Eu,Gd,Dy)的混式配体希土配合物。通过元素分析、IR、~1H NMR及摩尔电导率的测定对配合物进行了表征,还通过DTA-TG方法研究了它们的热性质。     

New solid-gas metathetical synthesis of binary metal polysulfides and sulfides at intermediate temperatures: utilization of boron sulfides

A new simple synthetic method for binary metal polysulfides and sulfides was developed by utilizing an in situ formation of boron sulfides and their subsequent reactions with metal-source oxides in a closed container at intermediate temperatures above 350 degrees C at which the boron sulfides react in a gaseous form. The versatility of the new method is demonstrated with oxides of various transition metals (Ti, V, Mn, Fe, Ni, Nb, Mo, Ru, and W) and rare-earth metals (Y, Ce, Nd, Sm, Eu, Tb, and Er) as starting materials that exhibit different chemical characteristics. Regardless of the oxidation states of metals in the starting materials, the sulfidation reactions occurred quantitatively with stoichiometric mixtures of boron and sulfur, and within 24 h the reactions yielded pure products of TiS(2), TiS(3), VS(4), FeS(2), NiS(2), NbS(3), MoS(2), RuS(2), WS(2), Y(2)S(3), and RS(2) (R = Ce, Nd, Sm, Eu, Tb, and Er) which were the thermodynamically stable phases under the reaction conditions. The scope and implications of the new sulfidation method are also discussed.     

Effect of La on Partial Oxidation of Ethanol to Hydrogen over Ni／Fe Catalysts

The partial oxidation of ethanol to hydrogen was investigated over Ni/Fe/La catalysts prepared by the co-precipitantion method.the effects of introduction of La promoter and the reaction temperature on the catalytic performance were studied.It was found that the introduction of La into Ni/Fe catalysts is helpful to increase the selectivity to hydrogen and the stability of the catalysts.The results of XRD and XPS characteri-zation show that the structure of the catalyst was changed during the reaction.The existence of LaFeO3 species is possibly the main reason of the increase of the catalyst stability.     

The Effect of Rare Earth on the Activity of Methanol Synthesis Catalyst

AlthoughtheCuO/ZnO/Al=O,cataIysthasbeenusedasasuccessfulmethan0lsynthesiscatalystfromCOhydrogenationformanyyears,itscatalyticactivityisnothighenoughf0rmethan0Isynthesisfr0mpureCO,hydrogenati0n.Manynewsynthesismethods,includingsol-gelco-precipitati0nmethodandultrasonicsynthesismeth0d,wereusedtopreparethemethanolsynthesiscatalyst"'.Intheliterature,manymetal0xidessuchasZrO,,Cr,O,,Ga,O,,Al,O,,SiO,andTiO,etc.wereaddedintocatalystt0improveitscatalyticactivityandmethanoIselectivity'~'.Howev…     

稀土金属有机配合物的红外和拉曼光谱研究

利用新合成的配体N,N,N′,N′－四正丁基己二酰胺Bu2NCO(CH2)4OCNBu2(TBAA)(Bu=正丁基）与一系列稀土金属硝酸盐反应,得到了一系列配合物Ln2(TBAA)3(NO3)6(Ln=La,Nd,Sm,Eu,Gd,Tb,Dy,Tm,Lu)。研究表明,该系列配合物具有相似的红外和拉曼光谱特性,有机配体以羰基中的氧通过双龄和桥连方式与Ln^3 配位,每个Ln^3 的配位数为9。