双金属催化剂还原性能研究

采用共沉淀法制备CuO-CoO和CuO-Fe₂O₃催化剂。采用程序升温还原(TPR)技术测定纯CuO、Co₃O₄、Fe₂O₃和CuO-CoO、CuO-Fe₂O₃催化剂的还原动力学参数。结果表明，添加CuO能促进Co₃O₄和Fe₂O₃的还原，两种催化剂的还原温度向低温方向偏移，还原活化能明显降低。并且，Cu的存在还改变了氧化铁的还原历程。     

Co-Fe2O3纳米载氧体作用下CO化学链燃烧富集CO2

制备了不同量级Co掺杂Fe₂O₃载氧体Co-Fe₂O₃,利用BET和TEM对载氧体结构进行表征。通过在不同温度下Co-Fe₂O₃与气体燃料CO的还原反应,考察Co-Fe₂O₃对CO化学链燃烧特性。结果表明,同一温度条件下,掺杂量越高,还原反应转化率越高;掺杂量不变的情况下,温度升高促使还原程度加深,缩短了载氧体完全还原转化的时间。根据TGA曲线进行了化学动力学分析,发现Co_0.2Fe还原反应过程在344.7～391.0℃和414.7～472.5℃温度范围反应动力学对应扩散控制的Jander方程模型,607.6～681.5℃温度范围对应二维扩散反应模型,并分别计算出相应模型的表观活化能和频率因子。结果可为化学链燃烧技术应用提供理论指导。     

铁氧化物在流化床温度和CO气氛下的形态迁移及其对NO催化还原

利用小型固定床实验台实验研究了铁氧化物在典型流化床温度和CO还原性气氛下的形态迁移及其生成物对NO的催化还原作用,采用分级还原结合X射线衍射（XRD）表征分析,确定铁氧化物与CO和NO反应后生成物的价态及各种铁氧化物对NO的还原机制。结果表明,Fe₂O₃在实验条件下可依次被CO还原为Fe₃O₄、FeO和单质铁,反应过程中随着还原度的增加,还原速率逐级下降,从Fe₂O₃还原到Fe₃O₄的速率最高,FeO还原到Fe速率最低,在实验温度范围内,床温升高有利于提高Fe₂O₃到Fe₃O₄的还原速率和还原度。不同形态的铁氧化物对NO的催化还原特性不同,Fe₂O₃及其部分还原后生成的Fe₃O₄都不能直接与NO反应,Fe₂O₃对CO催化还原NO的效果很弱,而Fe₃O₄对CO还原NO的反应却有很强的催化作用,而进一步还原生成FeO与单质铁还可直接与NO反应。     

钙钛矿型复合氧化物对甲烷的部分氧化及在混合太阳能氧化还原过程的应用

利用固相法合成了3种钙钛矿型复合氧化物Fe₂O₃-CaTi_xM_1-xO₃,研究了其结构、晶型和氧化还原活性。在固定床反应器中考察了该氧化物对两步法甲烷催化氧化制合成气及水分解制氢的活性及选择性。X射线衍射结果表明3种钙钛型复合氧化物均由正交晶系钙钛矿相和赤铁矿相组成。3种钙钛矿复合氧化物对甲烷的氧化活性顺序为Fe₂O₃-CaTi_0.85Ni_0.15O₃ >Fe₂O₃-CaTi_0.85Co_0.15O₃ >Fe₂O₃-CaTi_0.85Fe_0.15O₃。固定床反应结果表明,以Fe₂O₃-CaTi_0.85Ni_0.15O₃为氧载体催化剂,CH₄转化率可达96%,CO和H₂产率达71%,同时水分解反应的转化率为40%。利用Aspen Plus^®对Fe₂O₃-CaTi_0.85Ni_0.15O₃在混合太阳能氧化还原过程的效率及合成油和H₂产率进行了模拟。模拟计算结果证明基于复合氧化物的混合太阳能氧化还原过程可以有效提高CH₄利用率。     

基于甲烷脉冲法的Fe2O3-Al2O3载氧体还原特性研究

开发高效廉价铁基载氧体是天然气化学链重整制氢技术走向应用的关键。为探究高效铁基载氧体设计的基本依据,利用自行设计的脉冲反应器和气体产物全量同步在线分析系统,在800℃和无内外扩散影响的条件下研究了不同Fe₂O₃质量分数的Fe₂O₃-Al₂O₃载氧体的甲烷脉冲法还原特性。结果表明：Fe₂O₃的还原反应依两段机理进行,随载氧体颗粒内Fe₂O₃含量的多少可停止于Fe₃O₄,也可完全进行至FeO;气相产物中CO₂与CO的摩尔比随CH₄脉冲次数的变化规律也与Fe₂O₃含量密切相关。对用α-Al₂O₃粉末稀释高Fe₂O₃质量分数载氧体粉末的方法制备的低Fe_...     

化学链过程中Cu低浓度掺杂改性Fe-基载氧体反应性能：实验与理论模拟

基于热重实验（TGA）和密度泛函理论（DFT）计算,对Cu低浓度掺杂Fe₂O₃载氧体（Cu-Fe₂O₃）与H₂在化学链燃烧过程中反应活性和微观分子反应机理进行研究。TGA结果显示,Cu低浓度掺杂降低Fe₂O₃载氧体与H₂反应表观活化能E_a （从83.9 kJ/mol降低至72.3 kJ/mol）,因此,低浓度Cu掺杂由于原子尺度Cu掺杂缺陷的引入的确提高了Fe₂O₃载氧体转化率和晶格氧释放速率。DFT计算从分子水平证实Cu低浓度掺杂改变了Fe₂O₃载氧体与H₂反应路径,路径分析表明,Cu掺杂使Fe₂O₃载氧体与H₂反应能垒从2.30 eV分别降低至1.81 eV（Fe原子top位反应）和1.68 eV（Cu原子top位反应）,Cu掺杂的Fe-基载氧体的氢还原反应优先发生在掺杂的Cu原子位,其次为Fe原子位。此外,计算结果表明,因Cu-O和Cu-Fe键的引入,低浓度Cu掺杂改变了Fe₂O₃载氧体微观结构,这对于载氧体的晶格氧快速释放是有利的。     

污泥热解炭脱除NO特性

以废水污泥热解产生的污泥热解炭为原料,通过酸洗、活化、负载Fe、H₂还原等方式考察不同污泥热解炭样品对脱硝性能的影响。结果表明,污泥原样中的Fe₂P、FeS等低价态的铁具有良好的脱硝性能,450～500℃时最大脱硝效率达到81%。经过HNO₃酸洗和KOH活化后的污泥热解炭,因为去除了Fe₂P、FeS等低价态的铁,脱硝效率大幅下降,在450～500℃的最大效率分别仅为30%和53%。而热解污泥负载样中的Fe主要以Fe₂O₃形式存在,其最大脱硝效率在450～500℃时只有50%。经过H₂还原后,负载样中的Fe₂O₃被还原为Fe₂P、FeS等低价态的铁,其最大脱硝效率在450～500℃时上升至94%。     

MgFeMn-HTLcs的制备、改性及其CO加氢性能

采用沉淀-水热法制备了系列不同Mg/Fe/Mn配比的MgFeMn-HTLcs类水滑石前体,经焙烧、浸渍法K改性用于CO加氢制烯烃反应。采用XRD、SEM、TG、N₂吸附-脱附、H₂-TPR、XPS等手段对催化剂进行了表征。结果表明,制备的Mg-Fe-Mn前体均具有类水滑石层状结构,Mn的添加使结晶度下降;焙烧后,Mg-Fe样品主要生成MgO,Mg-Fe-Mn样品生成Mg₂MnO₄、MgO和MgFe₂O₄物相;反应后主要为MgCO₃和FeCO₃混合物相,伴随FeO-MnO和Fe_xC_y的生成;与K/Mg-Fe样品相比,Mn的加入进一步促进了Fe的分散,使得Fe₂O₃到Fe₃O₄还原度增加,其供电子效应促使Fe电子结合能向低偏移。在CO加氢反应中,K/Mg-Fe-Mn催化剂均表现出较高的反应活性和烯烃选择性。其中,K/3Mg-1Fe-2Mn催化剂的效果较好,CH₄含量较低,O/P值达5.20,C₂⁼～C₄⁼质量分数为43.03%。     

化学链燃烧过程Fe2O3/Al2O3载氧体表面CH4反应：ReaxFF-MD模拟

借助ReaxFF-MD方法,对化学链燃烧过程Al₂O₃负载Fe₂O₃载氧体（Fe₂O₃/Al₂O₃）表面CH₄反应过程模拟,探究Al₂O₃惰性载体对Fe₂O₃-CH₄体系燃烧过程的调控机制。研究发现添加Al₂O₃惰性载体改变了化学链燃烧过程中Fe₂O₃载氧体反应性和Fe₂O₃/Al₂O₃-CH₄反应体系的热力学和动力学行为。主要是促进了Fe₂O₃载氧体表面CH₄氧化,并对CH₄反应过程、中间体、产物及其反应速率和放热量等均具有显著促进和调控作用。原因在于Al₂O₃惰性载体对Fe₂O₃活性相中晶格氧的活化作用促进了晶格氧的迁移-扩散-释放。添加惰性载体增强了Fe₂O₃载氧体在化学链燃烧过程晶格氧释放速率和释放量,有利于CH₄氧化燃烧向合成气的高效、清洁转化,强化了化学链燃烧过程,满足当前能源高效转化和碳减排目标。     

化学链燃烧过程Fe2O3/Al2O3载氧体表面CH4反应：ReaxFF-MD模拟

借助ReaxFF-MD方法,对化学链燃烧过程Al₂O₃负载Fe₂O₃载氧体（Fe₂O₃/Al₂O₃）表面CH₄反应过程模拟,探究Al₂O₃惰性载体对Fe₂O₃-CH₄体系燃烧过程的调控机制。研究发现添加Al₂O₃惰性载体改变了化学链燃烧过程中Fe₂O₃载氧体反应性和Fe₂O₃/Al₂O₃-CH₄反应体系的热力学和动力学行为。主要是促进了Fe₂O₃载氧体表面CH₄氧化,并对CH₄反应过程、中间体、产物及其反应速率和放热量等均具有显著促进和调控作用。原因在于Al₂O₃惰性载体对Fe₂O₃活性相中晶格氧的活化作用促进了晶格氧的迁移-扩散-释放。添加惰性载体增强了Fe₂O₃载氧体在化学链燃烧过程晶格氧释放速率和释放量,有利于CH₄氧化燃烧向合成气的高效、清洁转化,强化了化学链燃烧过程,满足当前能源高效转化和碳减排目标。     

The kinetics of the reduction of iron oxide by carbon monoxide mixed with carbon dioxide

Results are reported for the repeated reduction of iron oxide particles, 300–425 μm diameter, by a mixture of CO, CO₂, and N₂ in a fluidized bed of 20 mm internal diameter. The conclusions were as follows: (1) Reduction of either Fe₂O₃ to Fe₃O₄ or of Fe₃O₄ to Fe_0.947O is first‐order in CO. (2) With the particle sizes used, the rates of the reduction reactions are controlled by intrinsic chemical kinetics. Activation energies and pre‐exponential factors are reported. (3) The first cycle gave anomalous results, but (a) the rate of reduction of Fe₂O₃ to Fe₃O₄ remained constant over cycles 2–10; (b) the rate of reduction of Fe₃O₄ to Fe_0.947O declined by 60–85% over cycles 2–10. (4) The rates of reduction declined with solids conversion down to zero at 80% conversion. The rates were incorporated into a conventional model of a fixed bed, which was used to predict, satisfactorily, the reduction behavior of iron oxide. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Microwave-assisted catalytic oxidative dehydrogenation of ethylbenzene on iron oxide loaded carbon nanotubes

The catalytic performance of multi-walled carbon nanotubes (MWCNTs) modified by iron oxide has been investigated for oxidative dehydrogenation of ethylbenzene in an integral fixed-bed reactor conventionally-heated and under microwave-assisted conditions. The morphology and microstructural characteristics of the obtained composites before and after the catalytic reaction were characterized by transmission electron microscopy and X-ray diffraction. The content 3wt.% of iron oxide supported on MWCNTs was found optimal in respect of the ethylbenzene conversion and styrene selectivity. All prepared composites were found more selective in a microwave field in the temperature range 380-450 °C. The transformation of Fe₂O₃ into Fe nanocrystals encapsulated by polyhedral graphite shells was observed only under microwave-assisted reaction conditions.     

Room temperature in situ chemical synthesis of Fe3O4/graphene

A simple, cost-effective, efficient, and green approach to synthesize iron oxide/graphene (Fe₃O₄/rGO) nanocomposite using in situ deposition of Fe₃O₄ nanoparticles on reduced graphene oxide (rGO) sheets is reported. In the redox reaction, the oxidation state of iron(II) is increased to iron(III) while the graphene oxide (GO) is reduced to rGO. The GO peak is not observed in the X-ray diffraction (XRD) pattern of the nanocomposite, thus providing evidence for the reduction of the GO. The XRD spectra do have peaks that can be attributed to cubic Fe₃O_4. The field emission scanning electron microscopy (FESEM) images show Fe₃O₄ nanoparticles uniformly decorating rGO sheets. At a low concentration of Fe²⁺, there is a significant increase in the intensity of the FESEM images of the resulting rGO sheets. Elemental mapping using energy dispersive X-ray (EDX) analysis shows that these areas have a significant Fe concentration, but no morphological structure could be identified in the image. When the concentration of Fe²⁺ is increased, the Fe₃O₄ nanoparticles are formed on the rGO sheets. Separation of the Fe₃O₄/rGO nanocomposite from the solution could be achieved by applying an external magnetic field, thus demonstrating the magnetic properties of the nanocomposite. The Fe₃O₄ particle size, magnetic properties, and dispersibility of the nanocomposite could be altered by adjusting the weight ratio of GO to Fe²⁺ in the starting material.     

An integrated surface science approach towards metal oxide catalysis

The function of a metal oxide catalyst was investigated by an integrated approach, combining a variety of surface science techniques in ultrahigh vacuum with batch reactor conversion measurements at high gas pressures. Epitaxial FeO(111), Fe₃O₄(111) and α‐Fe₂O₃(0001) films with defined atomic surface structures were used as model catalysts for the dehydrogenation of ethylbenzene to styrene, a practized selective oxidation reaction performed over iron‐oxide‐based catalysts in the presence of steam. Ethylbenzene and styrene adsorb onto regular terrace sites with their phenyl rings oriented parallel to the surface, where the π‐electron systems interact with Lewis acidic iron sites exposed on Fe₃O₄(111) and α‐Fe₂O₃(0001). The reactant adsorption energies observed on these films correlate with their catalytic activities at high pressures, which indicates that the surface chemical properties do not change significantly across the pressure gap. Atomic defects were identified as catalytically active sites. Based on the surface spectroscopy results a new mechanism was proposed for the ethylbenzene dehydrogenation, where the upward tilted ethyl group of flat adsorbed ethylbenzene is dehydrogenated at Brønsted basic oxygen sites located at defects and the coupling of the phenyl ring to Fe³⁺ terrace sites determines the reactant adsorption–desorption kinetics. The findings are compared to kinetic measurements over polycrystalline catalyst samples, and an extrapolation of the reaction mechanism found on the model systems to technical catalysts operating under real conditions is discussed. The work demonstrates the applicability of the surface science approach also to complex oxide catalysts with implications for real catalysts, provided suitable model systems are available.     

Carbon incorporated FeN/C electrocatalyst for oxygen reduction enhancement in direct methanol fuel cells: X-ray absorption approach to local structures

The C-containing iron nitride electrocatalyst is fabricated by chelating N-containing species and Fe²⁺ with a carbon support under heat treatment in an NH₃ atmosphere, which induces the oxygen reduction reaction activity. This is the first demonstration of forming Fe_xC species on iron nitride materials. The correlation between the electrochemical properties and structures are aided to elucidate their features under investigation by using X-ray absorption spectroscopy. A rotating ring disk electrode test is conducted in sulfuric acid solution and the results reveal the low H₂O₂ yield and approximately 4e⁻ transfer process of the carbon-containing FeN/C electrocatalyst.     

Catalytic application of metallic iron from the dyeing sludge ash for benzene steam reforming reaction in tar emitted from biomass gasification

Because it is the most promising method for reforming tar in a gasification system, a catalytic steam reforming reaction of tar using a dyeing sludge ash catalyst that contains mostly iron oxide has been modeled using benzene to investigate whether a steam reforming catalyst produced from waste is viable. The catalytic activity of the ash catalyst is similar to that of the commercially available iron-chrome-based catalyst for the same equivalent total amount of Fe₂O₃. The activity over the ash catalyst has been examined in terms of the weight hour space velocity (WHSV) and the reaction temperature to develop a model for the reaction kinetics. Using a power law model, the reaction order coefficients of the benzene and steam were estimated to be 0.43 and 0, respectively. The activation energy required for the ash catalyst was approximately 187.6 kJ mol^?1. In addition, the reductive properties of the iron oxide in the ash catalyst were also examined via XRD and H₂-TPR analyses.     

The electrochemical behaviour of iron oxides in dilute sulphuric acid and the interpretation of the flade potential of iron

The cathodic reduction of Fe₂O₃, FeOOH, and Fe₃O₄ in dilute sulphuric acid has been directly investigated using graphite paste electrodes containing the oxides. It has been found that these oxides sustain redox reactions at a high positive potential which is stabilised by the presence of ferrous sulphate in the solution and, at saturation, tends to coincidence with the Flade potential. The redox process can be formulated, for example, as Fe₂O₃(its)+2H⁺+2H₂SO₄+2e^?=2FeSO₄s+3H₂O(1) and the potential derived from the free energy change is approximately right. γ-oxides and hydroxyoxides of iron enter into reaction more readily than their α-analogues, and this would be expected on structural grounds.     

Kinetics of the dehydrogenation of ethylbenzene to styrene over unpromoted and K-promoted model iron oxide catalysts

The dehydrogenation of ethylbenzene to styrene over unpromoted and potassium-promoted model iron oxide catalysts has been studied using ultrahigh vacuum techniques in conjunction with elevated pressure reaction kinetics. Model iron oxide catalysts were prepared by oxidizing a polycrystalline Fe sample that was subsequently dosed with metallic potassium. At 875 K the unpromoted catalyst exhibited a turnover frequency of 5×10^–4 molecules/ site s and an activation energy of 39 kcal/mol, both in excellent agreement with the results found for an analogous iron oxide powder catalyst. Potassium promotion increased the turnover frequency to 1.0×10^–3 molecules/site s and lowered the activation energy to 36 kcal/mol for the dehydrogenation reaction. Similarities between the activation energies on the unpromoted and promoted catalysts indicate that the active site is the same on both catalysts. Creation of the active site was dependent upon the formation of an Fe³⁺ metastable species, consistent with the formation of a KFeO₂ phase, upon the addition of potassium.     

Effect of iron oxide on vulcanization kinetics and electrical conductance of butyl rubber composites

This paper investigates the effect of iron oxide concentration on the vulcanization process, electrical conductance during swelling in kerosene, and sheds some light on the possible mechanism of vulcanization kinetics. The rate and degree of crosslinking have been evaluated as a function of Fe₂O₃ concentration. It was found that the characteristic time constant during vulcanization decreases as the Fe₂O₃ concentration increases. The activation energy of the crosslinking reaction is calculated. An abrupt decrease in electrical conductance appears after a characteristic time of swelling. A modified model is suggested to calculate the separation distance in the conductive rubber matrix. The effect of microwave irradiation on electrical conductance and separation distance between conductive aggregate of butyl rubber (IIR) composites is also studied. Fe₂O₃ inhibits the degradation of IIR composites and microwave irradiation enhances the texturing microstructure of rubber matrix. © 2000 Society of Chemical Industry     

Oxygen carriers for chemical looping combustion of solid fuels

A thermal analyzer-differential scanning calorimeter-mass spectrometer (TG-DSC-MS) was used to study oxygen carriers (OC) for their potential use for the application of chemical looping combustion (CLC) to solid fuels. Reaction rates, changes in reaction rates with repeated oxidation-reductions, exothermic heats during oxidation, and the effect of changing reduction gas compositions were studied. Oxidation rates were greater than reduction rates and reaction rates were reproducible through multiple oxidation-reduction cycles except where agglomeration occurred with powders. Iron oxide (Fe₂O₃ powder) and iron-based catalysts were found suitable for CLC of solid fuels having rapid reduction rates which increased with higher reducing gas concentrations. Fe₂O₃ powder was used to oxidize a high carbon coal char in an inert gas removing 88% of the carbon from the char. Other properties such as cost and durability indicated iron oxide OCs potential use for CLC of solid fuels.