Preparation of Au/CeO2 catalyst and its catalytic performance for HCHO oxidation

Aqueous precipitation and deposition-precipitation method were used to prepare CeO2 supports and Au/CeO2 catalysts, respectively. The effect of preparation condition of support on the catalyst activity was investigated. The catalytic combustion of HCHO was considered as the probe reaction for comparing the catalyst activity. The BET, X-ray diffraction, X-ray photoelectron spectroscopy （XPS）, and reduction （TPR） were carried out to analyze the influence factor on the catalysts activity. The results showed that the addition of dispersant and use of microwave in the support preparation procedure could be beneficial for enhancing the interaction of supports and gold species and thus improved the catalytic activity. The total conversion temperature for HCHO was 146 ℃ over AC400. With the modification during supports preparation process, the catalytic activity increased with total conversion temperature decreasing to 98 ℃. The results of XPS indicated that Au^0 and Au^＋1 species coexisted in these catalysts and the activity of catalyst correlated with Au^＋1/Au^0 ratio. Temperature-programmed reduction results demonstrated that the reduction peak appeared between 100-170 ℃ with the inducing of gold. The dependence of activity on the reduction peak temperature implied that ionic gold was catalytic activity component for HCHO oxidation.     

Construction of mesoporous ceria-supported gold catalysts with rich oxygen vacancies for efficient CO oxidation

Bearing unique redox nature and high oxygen storage capacity, ceria (CeO₂) has always been a promising CO oxidation catalyst support for gold (Au) catalysts and the like. Herein, a series of Au–CeO₂–P (P stands for pH value) samples was prepared by a co-precipitation method with the assistance of an alkaline environment and amino groups functionalized ordered mesoporous polymer (OMP-NH₂). Afterward, all samples described above were characterized that the Au–CeO₂–P catalysts are made of Au–Ce–O solid solution and Au nanoparticles (NPs) supported on CeO₂. It turns out that OMP-NH₂ is not just a simple sacrificial template for mesoporous structure, but also plays an important role as an amino source, explaining the presence of rich oxygen vacancies. Due to the concentration of oxygen vacancies in Au–Ce–O solid solution is the key factor for the oxygen mobility of CO oxidation, the catalytic results also demonstrate that the catalytic activity of Au–CeO₂–P catalysts is related to the concentration of their oxygen vacancies. Moreover, Au–CeO₂-9.6 with a highest concentration of oxygen vacancies (as high as 13.98%) in Au–CeO₂–P catalysts exhibits the best catalytic activity (complete conversion at 10 °C).     

从复杂银阳极泥中提取金、钯工艺优化与研究

复杂银阳极泥回收金工艺是通过对其水溶液氯化得到分金液,使用亚钠进行还原得到合格金粉,由于外购原料增多,经水溶液氯化得到的分金液含有铂钯,分金液亚钠还原效率仅能控制在65%左右,需二次亚钠还原回收金。然而,得到的二次金粉中钯含量超标,返工易富集循环,不利于钯回收。本研究改进了复杂银阳极泥氯化分金液在进行亚钠一次还原后提取金、钯的工艺,具体工艺流程：首先,通过小型试验对还原后液开展DBC萃金并提纯金工艺,萃余液在进行传统的提取钯工艺的基础上,采用水合肼还原二氯二氨络亚钯得到钯黑。之后,进行工业扩大试验,确定最佳工艺技术条件。整个工艺过程中,金和钯的直收率分别为99.52%和94.53%,技术指标良好。     

Catalytic Reduction of SO2 on CeO2-La2O3 Rare Earth Mixed Compounds

Adding rare earth oxide CeO2 with variable valences to La2O3 formed a mixture of rare earth oxides. By means of dipping CeO2, La2O3 and their mixture, whose carriers were all γ-Al2O3, were used as the catalyst for the reduction of SO2 by CO. The activation process of this catalyst and the impact of temperature and reactant concentration on the activation process were investigated. Using X-ray diffraction, the structure characteristics of catalyst before and after reaction were analyzed to reveal the change of phase structure. The result shows that the rare earth oxide mixtures composing of CeO2 and La2O3, as the catalyst for the reduction of SO2 by CO, diminish activation temperature 50～100℃ less and have higher activity than a single oxide CeO2 or La2O3. The reason possibl is that La2O3 goes into in the lattice of CeO2 to form solid phase complex CeO2-La2O3 and increases the capability of CeO2-La2O3/γ-Al2O3 catalyst to store oxygen, which supplies the redox of CeO2 reaction with a better condition. At the same time, elemental sulfur formed in the redox reaction impels La203 to be transformed to activation phase La2O2S in a lower temperature, which can be explained with the synergism between redox reaction and COS intermediate mechanism reaction.     

Reduction Kinetics of Vanadium Titano-Magnetite Carbon Composite Pellets Adding Catalysts Under High Temperature

Experiments were carried out by adding CaF2 and NaF as catalysts in an Ar atmosphere to study the isothermal reduction kinetics of vanadium titano-magnetite carbon composite pellets under high temperature in the range from 1 473 to 1 673 K. The scanning electron microscope (SEM) was used to characterize the microstructure of product. By analyzing reduction mechanism, it was found that the rate controlling step was gas diffusion, and the activation energy was 178.39 kJ/mol without adding any catalysts. Adding CaF2 or NaF of 3% to vanadium titano-magnetite carbon composite pellets can decrease the apparent activation energy of reduction, and the decrease extent was 14.95 and 15.79 kJ/mol, respectively. In addition, temperature was an important factor influencing on reaction rate.     

水合肼湿法还原金试验研究

选取水合肼作为还原剂还原王水溶金,考查了反应温度、时间、水合肼浓度配比、王水酸度、水合肼用量等因素对金泥杂质Cu+含量及含金废水金含量影响,获得了优化工艺条件。在优化工艺条件下开展了工业试验,并与常用的Na2SO3还原进行对比,结果表明,用水合肼还原王水溶金其杂质Cu、Ag含量分别为0.002 9%和0.012 4%,略高于Na2SO3还原,不会对金泥的品质造成影响。但其优势却颇为明显:无需加热,不会分解成SO2、不带入杂质、还原废水中金含量降低57%,且操作简单,劳动强度小。     

微型流化床中气氛对还原度的影响

为了过程优化和提高反应的还原度,设计了两步法试验。试验采用的是微型流化床反应器,能够确保反应器空间中的每一个颗粒都处于相同的温度和气体浓度。试验结果表明,预还原阶段形成的颗粒表观形貌对还原度有着重要的影响,终还原阶段中的CO在混合气体中所占的比例直接影响着还原速率的大小。合理的控制还原反应速率,延长反应时间,有利于还原度的提高。当CO在混合气体中所占的比例为83%时,巴西矿粉的还原度达到了88%。     

Valence State of Active Copper in CuOx/CeO2 Catalysts for CO Oxidation

CuOx/CeO2 catalysts were prepared by adsorption-impregnation method, CO conversion was tested over the catalysts pretreated under different conditions for preferential CO oxidation in H2, and the catalysts were characterized with X-ray photoelectron spectroscopy and temperature programmed reduction. Experimental results show that there are two kinds of copper, which are Cu^＋ and Cu^2＋ in calcined CuOx/CeO2, Among them, the Cu^＋ is the key active component for CO oxidation. The main reason is as follows： CO is activated by copper for CO oxidation over CuOx/CeO2, while CO can not be activated by Cu^2＋. Only when Cu^2＋ is reduced to Cu ^＋ or Cu^0, the copper may be active for CO oxidation, moreover, the experimental results show that the reduction of Cu^2＋ does not lead to an increase of catalytic activity. So the active species is Cu^＋ in CuOx/CeO2 catalysts.     

Influence of CeO_2 loading on structure and catalytic activity for NH_3-SCR over TiO_2-supported CeO_2

A series of supported CeO_2/TiO_2 catalysts were prepared to explore the influence of CeO_2 loading on these catalysts for the selective catalytic reduction of NO_3 by NH_3(NH_3-SCR).The catalysts were investigated in detail by means of XRD,Raman,H_2-TPR,NH_3-TPD,XPS,in situ DRIFTS,and NH3-SCR reaction.The activity of the catalyst is closely related to the content of CeO_2.When the loading of CeO_2 is near the dispersion capacity(1.16 mmol Ce~(4+)/100 m~2 TiO_2),the catalytic activity is better.This may be because that the dispersed CeO_2 is the active species and the catalyst has appropriate redox property,along with the larger amounts of surface Ce content and surface adsorbed oxygen species.Finally,a possible reaction mechanism via the Langmuir-Hinshelwood(L-H) mechanism is tentatively proposed to further understand the NH_3-SCR reaction.     

Influence of copper content on structural features and performance of pre-reduced LaMn_(1-x)Cu_xO_3 (0≤x<1) catalysts for methanol synthesis from CO_2/H_2

A series of pre-reduced LaMn1-xCuxO3 (0≤x<1) catalysts for methanol synthesis from CO2 hydrogenation were prepared by a sol-gel method. The catalytic performances were strongly dependent on the copper content. XRD investigation revealed that the single perovskite structure could be preserved after being reduced, when the substitution for Mn by Cu was less than 50%. The Cu-doped (x=0.5) LaMnO3 was much more active than the other catalysts for reaction, showing CO2 conversion up to 11.33% and methanol selecti...     

Structure and oxygen storage capacity of Pr-doped Ce_（0.26）Zr_（0.74）O_2 mixed oxides

Binary Ce-Zr(CZ),Pr-Zr(PZ) and ternary Ce-Zr-Pr(CZP) mixed oxides were prepared by an ammonia-aided co-precipitation method,and were aged in a steam/air flow at 1050 °C.X-ray diffraction(XRD),Raman spectra,X-photon spectra(XPS) and CO temperature programmed reduction(TPR) were carried out to characterize the micro-structure and reducibility of catalysts.The oxygen storage capacity(OSC) was evaluated with CO serving as probe gas.The results showed that a pseudo cubic structure was formed for the Zr-rich ceria-zirconia mixed oxides with Pr doping.The insertion of Pr prevented the phase segregation of the mixed oxides during the hydrothermal ageing.The Pr doped samples showed better redox performances in comparison with CZ,and the sample doped with 5 wt.% Pr showed the most remarkably promoted dynamic oxygen storage capacity.This phenomenon was closely related to both the reducibility and oxygen mobility of the mixed oxides.The introduction of praseodymium into ceria-zirconia could accelerate the oxygen migration by increasing the amount of oxygen vacancies,although it was difficult for Pr3+ ions themselves to participate in the oxygen exchange process.     

Temperature Programmed Reduction Studies on CeO2-Containing Catalysts

Temperature programmed reduction (TPR) study was carried out for CeO2/A12O3 and CeO2/ZrO2 catalysts to evaluate oxygen storage property induced by a facile redox cycling of Ce ion. The CeO2/ZrO2 catalyst possesses excellent oxygen storage activity at 373 K after reduction above 1173 K although the oxygen storage of CeO2/Al2O3 catalyst after reduction above 1173 K is poor because of the formation of CeAlO3. Consequently, the oxygen storage on the CeO2/ZrO2 catalyst smoothly occurs from low temperatures when the catalyst is reduced even at high temperatures.     

煅烧-还原一体化炼镁新技术研究进展

目前,世界85%以上的金属镁是在中国利用皮江法生产,尽管皮江法得到不断改进,仍属于高能耗、高排放的冶金工艺.针对皮江法的不足,东北大学提出集煅烧与还原于一体的炼镁方法,该方法采用预制球团为原料,煅烧和还原均在同一设备中完成的炼镁方法.新技术能够取消皮江法的回转窑煅烧工序,煅烧产生的CO2余热能够得到利用,且高浓度的CO2易于矿化捕集.本文汇总了该工艺的研究进展,包括球团预制、球团煅烧及球团的还原过程.实验结果表明:煅烧前后球团的抗压强度分别为76 N和55 N,在10 Pa真空条件下,1 400℃还原1 h,还原率为93.5%.     

添加剂作用下铁粉还原酸性硫 脲浸金液中的金

酸性硫脲浸金液由于H+、Fe3+和Cu2+等杂质离子的存在,直接采用金属置换法回收金会存在还原剂耗量大的问题.为降低杂质离子对金还原的影响,文中引入了添加剂X,通过添加剂X的使用优化铁粉置换硫脲金的过程.进行了在添加剂作用下铁粉还原酸性硫脲浸金液中金的试验研究,具体考察了添加剂X用量、反应时间、反应温度、搅拌转速及铁粉用量对金还原率的影响.试验结果表明:在添加剂用量为0.02 g/L,反应时间为90 min,反应温度35 ℃,搅拌转速为300 r/min,铁粉用量为0.2 g/L的较优条件下,金的还原率接近100 %.并进行了有无添加剂X的对比试验,验证了添加剂X的使用对铁粉还原酸性硫脲浸金液中的金有明显的促进效果.      

Mathematical Modelling and Experimental Investigation of Coke Reduction of FeO in Slag

Mathematic model development and experimental investigations were carried out for the reduction of FeO in slag by coke. Rate expressions for the reduction limited by the different steps and through different reaction routes were proposed. In the experimental investigation, the FeO reduction was found to be a first order and irreversible reaction; the reduction rate increased with increasing temperature and the FeO content in slag, and decreased with increasing ash content in the coke. Low CO₂/CO ratio in the product gas and preferential reduction of FeO over SiO₂ in slag were observed in the reaction system. The proposed reaction mechanisms were discussed with the observed kinetic phenomena. The reduction of FeO in slag by coke was found most likely to be jointly dominated by the mass transfer of FeO in slag and the chemical reactions at slag‐coke, slag‐gas or slag‐metal interfaces.     

Promotional effect of CO pretreatment on CuO/CeO2 catalyst for catalytic reduction of NO by CO

The CuO/CeO2 catalysts were investigated by means of X-ray diffraction(XRD),laser Raman spectroscopy(LRS),X-ray photoelectronic spectroscopy(XPS),temperature-programmed reduction(TPR),in situ Fourier transform infrared spectroscopy(FTIR) and NO+CO reaction.The results revealed that the low temperature(150 °C) catalytic performances were enhanced for CO pretreated samples.During CO pretreatment,the surface Cu+/Cu0 and oxygen vacancies on ceria surface were present.The low valence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation.These effects in turn led to higher activities of CuO/CeO2 for NO reduction.The current study provided helpful understandings of active sites and reaction mechanism in NO+CO reaction.     

Construction of bimetallic Pt-Pd/CeO2-ZrO2-La2O3 catalysts with different Pt/Pd ratios and its structure-activity correlations for three-way catalytic performance

A series of Pt-Pd bimetallic catalysts supported on CeO₂-ZrO₂-La₂O₃ mixed oxides were synthesized through the conventional impregnation method.Three-way catalytic performance evaluations along with detailed physio-chemical characterizations were carried out to establish possible structure-activity correlations.Results show that on the one hand,different Pt/Pd ratios can strongly affect the TWC behaviors of Pt-Pd/CZL catalysts by modulating the synergis...     

CO and C3H8 total oxidation over Pd/La-Al2O3 catalysts： Effect of calcination temperature and hydrothermal treatment

A series of Pd/La-Al2O3（PLA） catalysts with La-Al2O3（LA） support calcined at different temperatures（500, 700, 900 and 1050 oC） were prepared using an incipient wetness impregnation method. The activity of the fresh and hydrothermally aged PLA catalysts were tested for total oxidation of CO and C3H8. The activity of the fresh PLA catalysts for CO and C3H8 oxidation increased with increasing calcination temperature of the support, while the activities of the aged catalysts declined and became essentially the same. CO chemisorption results revealed that the suppressed activities of the aged catalysts were mainly due to the decline of palladium dispersion. The turnover frequency（TOF） of CO oxidation increased with increasing reduction ability of the catalysts, with a fresh catalyst calcined at 1050 oC having the highest value（0.048 s–1）. However, the TOF of C3H8 total oxidation was affected by not only the redox properties of catalysts but also the size of Pd particle, and large Pd particles possessed higher TOF value of C3H8 oxidation, with the highest value（0.125 s–1） being obtained on an aged catalyst calcined at 500 oC.     

Fe3O4内配石墨球团的还原动力学

开展了Fe3O4内配石墨球团还原试验,以考察球团的中温还原性。设定温度950～1 100℃,时间低于35min。并采用新建立的还原动力学方程(PKV方程)计算球团的动力学参数。结果表明,球团的还原能力随时间、温度的提高而增加,初始时间段及较低温度下增加幅度相对较大;温度对球团的还原影响很大。球团在19min前后的活化能分别为102.046kJ/mol和86.872kJ/mol。控制环节为界面化学反应,前19min为碳的气化反应,后19min为CO还原Fe3O4。     

旋转床CO还原澳大利亚PB粉特性及动力学研究

采用自主研制的小型旋转床反应器,结合化学分析和X射线衍射分析等技术对CO还原澳大利亚PB粉进行了直接还原实验研究。结果表明:CO流量为200 mL/min,矿粉粒径范围为0.044~0.089 mm,还原时间为60 min,还原温度为1 000℃时,还原产物还原度和金属化率达到最大值,分别为92.70%和86.28%;在700~1 000℃内基于收缩未反应核模型对澳大利亚PB粉还原反应进行动力学分析,得出反应前期(t30 min)还原过程由气体内扩散和界面化学反应混合控制;反应后期(t30 min)还原反应的限制性环节为气体内扩散,指前因子A为0.006 72 s~(-1),表观活化能E为10.043 kJ/mol。