龙泉窑铁胎青瓷产品的烧制技艺

通过龙泉窑铁胎的烧成试验，证明了铁胎在还原气氛下的烧结温度比氧化气氛下的烧结温度要低，并且最大收缩率和收缩速度均比氧化气氛大。其主要原因在于龙泉窑铁胎Fe₂O₃含量较高，在还原气氛下转化为FeO,FeO起熔剂的作用，使坯体在较低温度下出现液相。另外，通过龙泉窑铁胎施以不同成熟温度的釉料分别进行氧化气氛和还原气氛烧制实验，观察烧成时的外观性状，找出铁胎中Fe₂O₃氧化分解和还原反应产生气体的规律，从而为解决铁胎青瓷由于Fe₂O₃引起的起泡和孔洞问题而提供理论依据。     

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_...     

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。     

Fe/γ-Al2O3催化剂上CO同时还原NO和SO2研究

研究了不同载体(γ-Al₂O₃、HZSM-5、TiO₂、SiO₂和MgO)负载Fe催化剂上CO还原NO反应及CO同时还原NO和SO₂反应。结果表明,Fe/γ-Al₂O₃催化剂对CO与NO反应具有良好的催化活性,但随着反应时间的延长,催化剂很快失活;在CO和NO反应中加入SO₂,可以明显改善Fe/γ-Al₂O₃催化剂对CO还原NO反应的活性稳定性;O₂和H₂O对催化剂活性的影响较大,CO₂对催化剂的影响较小。XRD结果表明,FeS₂是催化剂的活性中心,在CO与NO反应后,FeS₂转变为催化惰性的Fe₇S₈而导致催化剂活性下降;在CO与NO及SO₂反应体系中引入O₂后,Fe/γ-Al₂O₃催化剂上的活性组分FeS2被氧化为Fe₂O₃,导致催化剂失活。     

化学链干重整联合制氢热力学分析及实验

提出了一种化学链甲烷干重整联合制氢工艺。该工艺由还原反应器、干重整反应器、蒸汽反应器和空气反应器组成，在实现制氢的同时获得可变H₂/CO比的合成气。借助ASPEN plus软件和小型流化床实验台，在等温条件下，温度900℃，采用Fe₂O₃/Al₂O₃载氧体，对该工艺进行热力学分析和实验验证。结果显示，当铁氧化物被还原至FeO/Fe时，干重整反应器内甲烷转化率可以达到98%，CO产率可以达到94%。干重整反应器中同时发生甲烷干重整和部分氧化反应，载氧体内部晶格氧可以有效降低积炭并提高合成气H₂/CO比。积炭发生于晶格氧消耗殆尽时。积炭进入蒸汽反应器，发生气化反应，降低氢气纯度。     

Co-Fe2O3[104]铁基载氧体优化体系作用下褐煤化学链燃烧特性

前期研究发现高弥勒指数晶面载氧体Fe₂O₃[104]具有高的化学链燃烧反应特性,且Co对煤及其热解中间产物具有催化气化和催化转化作用。通过正交实验优化制备Co-Fe₂O₃[104]/Al₂O₃载氧体体系结构,开展Co-Fe₂O₃[104]/Al₂O₃与褐煤的化学链燃烧,揭示载氧体与褐煤发生化学链燃烧的特性。结果表明:形貌控制制备的高弥勒指数晶面铁基载氧体Co-Fe₂O₃[104]/Al₂O₃(质量分数10%)促进了褐煤化学链燃烧过程中氧的迁移速率以及载氧体的还原程度,进而显著提高了载氧体与褐煤化学链燃烧的反应速率及反应效率。进一步通过CO多循环化学链燃烧反应、XRD和TEM表征了Co-Fe₂O₃[104]/Al₂O₃(10%)的可再生性及反应稳定性。     

稻壳白炭黑负载Fe2O3的气相芬顿反应NO预氧化

以稻壳为硅源,采用直接煅烧法制备白炭黑,以其为载体,采用共浸渍法制备Fe₂O₃/SiO₂催化剂;并采用同样方法以商用二氧化硅为载体制备Fe₂O₃/C-SiO₂催化剂,将二者用于催化H₂O₂预氧化NO的实验。探究不同工况（负载量、催化温度、H₂O₂汽化温度、H₂O₂流量和水汽浓度）对NO预氧化的影响,并对催化剂进行表征,分析其物理化学性质对催化性能的影响。结果表明,在负载量为50%、催化温度为140℃、H₂O₂汽化温度为120℃、H₂O₂流量为2.5mL/h时,达到最佳工况,NO氧化度能达到73%;在相同实验条件下Fe₂O₃/SiO₂催化剂的预氧化效果要比Fe₂O₃/C-SiO₂催化剂高20%左右。TPR结果表明载体可以降低活性组分的还原温度,减少活性组分的团聚;催化剂的晶相结构稳定,机械强度及热稳定性良好;ESR和XPS结果显示Fe₂O₃/SiO₂催化剂的催化性能优于Fe₂O₃/C-SiO₂催化剂,能够更好地催化分解H₂O₂产生·OH。     

硅质耐火材料中矿化剂氮化硅铁和碳酸钙的作用机理

硅砖使用石灰土加铁鳞的组合矿化剂是早期国内生产条件限制下的无奈选择，随着生产条件的提升，探寻新型矿化剂以实现硅砖性能的进一步突破是切实可行且十分必要的。本工作分别以氮化硅铁和碳酸钙替代传统石灰乳加铁鳞的复合矿化剂制备硅砖。制备的新型硅砖性能良好，添加2%(质量分数)氮化硅铁和碳酸钙的硅砖中鳞石英含量分别达到62%和65%。结果表明：以氮化硅铁作为矿化剂的硅砖内，海胆结构氮化硅铁中柱状Si₃N₄相互交织构成的Si₃N₄网络，通过自身的氧化反应对其中心位置的Fe和Fe₃Si起到了保护作用，于高温下实现了FeO–Fe₂O₃–SiO₂三元系中更高的FeO/Fe₂O₃摩尔比，并同时降低了液相的生成温度。借由氮化硅铁中Fe、Fe₃Si、Si₃N₄的还原性，FeO–Fe₂O₃...     

巯基功能化镁层状硅酸盐复合材料的构筑及其催化还原性能研究

通过原位合成法将银纳米粒子和Fe₃O₄磁性纳米粒子负载于巯基功能化镁层状硅酸盐(MgSH)上,制备得到Fe₃O₄@MgSH/Ag纳米复合材料。通过SEM、XRD、FTIR等手段对复合材料进行了表征,并考察了Fe₃O₄@MgSH/Ag催化NaBH₄还原4-硝基苯酚(4-NP)的性能。研究结果表明,Fe₃O₄@MgSH/Ag保留了巯基黏土具有的疏松多孔结构,且银纳米粒子和Fe₃O₄纳米粒子均匀负载于MgSH表面。通过动力学分析可知,Fe₃O₄@MgSH/Ag催化NaBH₄还原4-NP的反应遵循准一级反应动力学规律,其表观速率常数k_app为0.160 8 min^-1,并可在10 min内使溶液中0.5 mmol/L4-NP的降解率达到98%以上,...     

模拟氢基竖炉工况条件下铝硅质耐火材料的结构与性能演变

基于H₂/CO混合气强还原服役环境,本工作模拟常压氢基竖炉服役工况,研究典型的铝硅质耐火材料经还原处理后性能变化规律及失稳机制。结果表明,在V(H₂)∶V(CO)=5∶2的条件下,热处理温度由450℃升高至950℃,混合气体对铝硅质耐火材料的还原能力逐渐增强。现有条件下,铝硅质耐火材料失稳的两个关键因素在于Fe₂O₃含量以及磷酸盐结合剂：1)当铝硅质耐火材料中Fe₂O₃含量较高时,在H₂/CO气氛下,Fe₂O₃极易被还原为单质铁。同时,这种情况会导致铝硅质耐火材料发生一定程度的体积变化和显著的力学性能下降。2)磷酸盐结合铝硅质耐火材料也面临磷酸盐挥发,导致显气孔率提高,结构稳定性降低。然而,研究还发现磷酸盐结合刚玉-莫来石砖中Fe₂O₃含量较低且伴生一定含量的TiO₂时,材料具有较好的抗H₂/CO气还原能...     

一种新γ相氧化铝负载的铁铝双金属催化剂用于反向水煤气转化反应(英文)

In reverse water gas shift (RWGS) reaction CO₂ is converted to CO which in turn can be used to produce beneficial chemicals such as methanol. In the present study, Mo/Al₂O₃, Fe/Al₂O₃ and Fe-Mo/Al₂O₃ catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H₂-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch reactor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/Al₂O₃ catalyst enhances its activity as compared to Fe/Al₂O₃. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/Al₂O₃ catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fe₂(MoO₄)₃ phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fe₂(MoO₄)₃ phase has low reducibility, therefore the Fe₂(MoO₄)₃ phase signifificantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al₂O₃ catalyst. Overall, this study introduces Fe-Mo/Al₂O₃ as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.     

Cu-based spinel catalysts CuB2O4 (B = Fe, Mn, Cr, Ga, Al, Fe0.75Mn0.25) for steam reforming of dimethyl ether

Cu-based spinel-oxides CuB₂O₄ (B = Fe, Mn, Cr, Ga, Al, or Fe_0.75Mn_0.25) were synthesized via a sol–gel method and subsequent solid-state reaction. The spinels mechanically mixed with γ-Al₂O₃ were evaluated for production of hydrogen from dimethyl ether steam reforming (DME SR). The reduction behavior and crystal property of these spinel-oxides, and the Cu oxidation state in spinel catalysts were investigated by temperature-programmed reduction, X-ray diffraction, and X-ray photoelectron spectroscopy techniques. The reduced phases of the Cu-based spinel catalysts that strongly affected the catalytic activity and durability were composed of metallic copper with metal oxides (MnO (B = Mn), Cr₂O₃ (B = Cr), and Al₂O₃ (B = Al)) or with spinels (CuGa₂O₄ (B = Ga), Fe₃O₄ (B = Fe), and MnFe₂O₄ (B = Fe_0.75Mn_0.25). The stability of B metal oxides and the interaction between copper species and B metal oxides significantly contributed to the reforming performance.     

Determination of the intrinsic kinetics of iron oxide reduced by carbon monoxide in an isothermal differential micro-packed bed☆

The intrinsic kinetics of iron oxide reduced by carbon monoxide is evaluated by a method of online measuring concentration of off-gas in an isothermal differential micro-packed bed. Under the condition of getting away from the influence of gas diffusion and gas–solid heat transfer and mass transfer, the reaction of Fe₂O₃ to Fe₃O₄, Fe₃O₄ to FeO and FeO to Fe in the process of single reaction can be clearly distinguished from each other, and the relevant activation energy is characterized to be 75.4, 74.4, and 84.0 kJ·mol^-1, respectively. Therefore, the change of surface area in the reaction process due to losing oxygen could be easily calculated by combining it with pre-exponential parameters of Arrhenius equations. In conclusion, these kinetic parameters are verified by the experimental data for the process of ore reduced by carbon monoxide in a packed bed.     

REDUCTION OF NO WITH NH3 ON Fe-Cr OXIDES CATALYST

A catalyst consisting of a mixture of Fe₂O₃ and Cr₂O₃ (5/1 atomic ratio of Fe:Cr) supported on alumina pellets was examined for the complete reduction of NO with NH₃ to N₂ in an isothermal flow reactor. The reduction of NO was determined at various inlet concentrations of NO (approximating utility boiler emissions) and NH₃, and catalyst bed temperatures. In the absence of O₂, NO reduced completely to N₂ without N₂O formation. Correlation of the kinetic data considering both external and internal reactant mass transfer provided the following rate expression for the reduction of NO, r = 7.71 × 10⁴ exp. ( - 12,300/RT) P^0.9_NO P^0.1_NH3, moles / g.cat-sec atm.     

氢氛还原法制备氧化铁/膨润土 复合材料及其表征研究

以膨润土和硝酸铁为原料,采用氢氛还原法制备Fe₃O₄/膨润土复合材料,并采用X射线衍射（XRD）、扫描电子显微镜（SEM）和电子能谱（EDS）做表征分析。通过实验得到最佳的工艺条件：n（OH^-）∶n（Fe³⁺）=1∶1、铁土比为10 mmol/g、还原温度为200 ℃、还原时间为30 min。制备的Fe₃O₄/膨润土具有良好的类Fenton催化性能、稳定性与磁分离性能。制备过程中铁元素化合物能够有效固载在膨润土上,并在氢气还原作用下转化为Fe3O4,所得Fe3O4/膨润土是结构分散、孔隙明显、物化形态优良的催化复合材料。     

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%。     

Influence of metal oxides on the catalytic behavior of Au/Al2O3 for the selective reduction of NOx by hydrocarbons

The reduction of NO by propene in the presence of excess oxygen over mechanical mixtures of Au/Al₂O₃ with a bulk oxide has been investigated. The oxides studied were: Co₃O₄, Mn₂O₃, Cr₂O₃, CuO, Fe₂O₃, NiO, CeO₂, SnO₂, ZnO and V₂O₅. Under lean C₃H₆-SCR conditions, these oxides (with the exception of SnO₂) convert selectively NO to NO₂. When mechanically mixed with Au/Al₂O₃, the Mn₂O₃ and Co₃O₄ oxides and, to a much greater extent, CeO₂ act synergistically with this catalyst greatly enhancing its SCR performance. It was found that their synergistic action is not straightforwardly related to their activity for NO oxidation to NO₂. The exhibited catalytic synergy may be due to the operation of either remote control or a bifunctional mechanism. In the later case, the key intermediate must be a short-lived compound and not the NO₂ molecule in gas-phase.     

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%。     

Combined plasma-catalytic processing of nitrous oxide

The gliding arc discharge, combined with a catalytic bed, has been applied for nitrous oxide processing in oxygen containing gases. It has been found that under conditions of the gliding arc, nitrous oxide in mixtures with oxygen or air not only decomposes to oxygen and nitrogen, but is also oxidised to nitric oxide. The overall conversion of nitrous oxide, as well as the degree of N₂O oxidation to NO were studied as a function of its initial concentration, flow rate, and discharge power. The overall N₂O conversion and degree of oxidation to NO decreased with increasing flow rate and initial N₂O concentration, and increased with increasing discharge power. The degree of N₂O oxidation to NO varied within 20–37%. The overall conversion and degree of N₂O oxidation increased when granular dielectric materials (TiO₂, SiO₂ (quartz glass), and γ-Al₂O₃) were introduced into the reaction zone. The energy efficiency and the overall conversion of N₂O were still further increased due to catalytic effects of a number of metal oxides (CuO, NiO, MnO₂, Fe₂O₃, Co₃O₄, ZrO₂) deposited on γ-Al₂O₃. The activity of the oxide catalysts within the active power range of 300–360 W decreased in the order: CuO>Fe₂O₃>NiO>MnO₂>Co₃O₄>ZrO₂. It has been concluded that the combined plasma-catalytic processing may be an efficient way for the reduction of N₂O emissions.