碱中毒对烧结烟气SCR催化剂脱硝脱二噁英的影响

摘要：采用湿式浸渍法对商用V2O5-WO3/TiO2催化剂进行了碱金属硫酸盐（Na/K/Rb）中毒实验。在模拟铁矿烧结烟气条件下，对比了新鲜和中毒催化剂同时脱除NOx和二噁英的活性（以氯苯作为二噁英的模拟物），并通过N2吸脱附、XRD、NH3 TPD、H2 TPR和XPS等检测手段对催化剂进行了表征。结果表明：中毒催化剂的脱除NOx和催化降解氯苯活性明显降低，失活率顺序为K2SO4>Rb2SO4>Na2SO4。催化剂中毒后，碱金属离子可以占据催化剂表面化学吸附氧空位，导致表面化学吸附氧数量减少，物质的量之比n(V5+)/n(V4+)降低，V物种可还原性减弱。     

Promotional effects of cerium doping and NO_x on the catalytic soot combustion over MnMgAlO hydrotalcite-based mixed oxides

A series of MnMgAlO samples with different amounts of Ce doping were facilely prepared using coprecipitation method and their catalytic soot combustion activity was evaluated by temperature programmed oxidation reaction(TPO).The methods of X-ray diffraction(XRD),Brumauer-Emmett-Teller(BET),H2-TPR,NO-TPO and in situ IR were used to characterize the physiochemical properties of these samples.Dopant Ce improved the soot combustion performance of MnMgAlO catalyst due to the enhanced redox ability.Introduction of NOx led to the further increase of catalytic soot oxidation activity on these samples.Over Ce-containing samples,the catalytic activity was slightly decreased as the amount of dopant Ce increased in O2.Differently,in NO+O2,a certain amount of dopant Ce was much more favorable and excess amount of Ce resulted in a sharp drop of the catalytic soot combustion activity.Both NO2 and nitrates were found to have great contributions to the effects of NOx on the soot combustion activity of Ce-doped catalysts.More NO2 was generated as dopant Ce increased.When appropriate amount of Ce was introduced,the as-formed NO2 was stored as bridging bidentate nitrate on Mn-Ce site,which was confirmed to have higher reactivity with soot than nitrite or monodentate nitrate on Mn and/or Ce sites.Overall,Mn0.5Mg2.5Ce0.1Al0.9O was considered as the most potential catalyst for soot combustion.     

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).     

Simultaneous Desulfurization and Denitrification by Microwave Catalytic over FeCoCu/Zeolite 5A Catalyst

FeCoCu/zeolite 5A was used as a catalyst for microwave catalytic desulfurization and denitrification and for microwave catalytic reduction of SO2 and NOx with ammonium bicarbonate (NH4HCO3) as a reducing agent. Microwave catalytic desulfurization and denitrification efficiency attained 99.5 and 86.1%, respectively. The reaction efficiencies of microwave catalytic reduction of SO2 and NOx could be up to 95.8 and 95.1% separately; the optimal microwave power and empty bed residence time on microwave catalytic reduction of SO2 and NOx simultaneously are 280 W and 0.358 s, respectively. Microwave accentuates catalytic reduction treatment, and microwave addition can increase the SO2 and NOx removal efficiency. The microwave catalytic SO2 and NOx removal follows the Langmuir-Hinshelwood model.     

二氧化钛的水热制备及其催化性能评价

以工业钛液为原料,利用水热法制备二氧化钛催化剂。采用SEM、FT-IR、XPS、N2吸附脱附对样品进行表征,并对其催化性能进行考察。研究结果表明,试验所制二氧化钛具有较高的活性,对亚甲基蓝的光催化降解活性同P25接近;对NO的选择性还原反应随温度的升高,降解率呈现先增加后降低的趋势,其中450℃下的降解率最高,达到84.14%;其粒径分布为0.36~1.08μm,比表面90.47 m2/g。     

金纳米粒子的催化特性及其应用

金纳米粒子的特殊性质产生于其特殊结构及特殊效应。负载或非负载型Au纳米粒子表现出极高的化学活性和催化性能，使其在化学工业中得到了广泛应用。用沉积或共沉淀方式将Au纳米粒子负载到金属氧化物载体上，在室温催化氧化C0为C02的效率比其它贵金属催化剂高得多；Au／Ti02催化剂在气相中能够高效率地催化氧化丙稀为环氧丙烷，选择性高达90％；Au纳米粒子催化剂在不饱和碳氢化合物的部分氢化反应中表现出良好的选择性：非负载型和负载型Au纳米粒子在液相反应中表现出独特的催化特性;Au/Fe2O和Au/ZrO2等负载型催化剂在低温水气转换制备氢气的反应中催化活性很高，而且载体的结晶度越高，催化活性越高。中对近年来Au纳米粒子的上述催化特性和应用进行评述。     

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.     

新型CeO2-Fe2O3联合催化剂用于催化CO还原NO

采用3种不同的方法合成新型的以Fe₂O₃颗粒为载体的Ce-Fe复合氧化物催化剂,探究不同制备方式的复合氧化物催化剂的催化CO还原NO性能,并通过X射线衍射(XRD)、拉曼光谱(Raman)、氢气-程序升温还原(H2-TPR)、X射线光电子能谱(XPS)表征来对催化剂进行探究。结果证明Ce-Fe复合氧化物具有较高的催化活性,硝酸水热法Ce-Fe复合氧化物在900℃时脱硝率可达到99%以上。XRD中显示硝酸水热样品中CeO₂峰向高角度偏移,并且晶格常数变小。Raman结果说明硝酸水热样品CeO₂的振动峰向左大幅度偏移,结合XRD说明硝酸水热法可以形成Ce-O-Fe固溶体。H2-TPR说明氧化还原性:硝酸水热法>硝酸浸渍法>普通浸渍法。XPS结果说明硝酸水热法形成的Ce-O-Fe固溶体可以促进Fe³⁺向Fe²⁺、晶格氧向吸附氧的转换,这体现出复合催化剂Ce、Fe之间的联合作用。在整个反应过程中Fe₂O₃作为载体可以提供大量晶格氧,Ce-O-Fe固溶体的存在决定了复合催化剂的高催化活性。     

固定床内半焦燃烧释放HCN和NO_x的规律

采用立管炉及傅里叶红外光谱烟气分析仪研究反应温度、活性炭和添加剂对固定床内半焦燃烧时HCN和NO_x的排放特性的影响。实验结果表明,850~950℃范围内,温度升高,半焦燃料型N向HCN和NO_x的转化率降低,最大降幅分别为1.43%和8.67%;850~900℃和900~950℃范围内,半焦燃料型N向HCN和NO_x的转化率存在线性关系;活性炭促进半焦燃料型N向HCN和NO_x的转化,添加剂CaO和Al2O3减弱活性炭对半焦HCN和NO_x的释放,但对HCN向NO_x的转化没有太大影响。     

Rare earth containing catalysts for selective catalytic reduction of NO_x with ammonia:A Review

Increasingly stringent regulations in many countries require effective reduction and control of NOx emissions. To meet these limits, various methods have been exploited, among which the selective catalytic reduction of NOx using ammonia as the reductant(NH3-SCR) is the most favored technology. High catalytic activity, N2 selectivity and resistance to deactivation by sulfur, alkaline metals and hydrothermal conditions are the optimal properties of a successful SCR catalyst. Rare earth oxides, particularly CeO2, have been increasingly used to improve the catalytic activity and resistance to deactivation of deNOx catalysts, both modifying traditional vanadium catalysts, and also developing novel catalysts, especially for low temperature applications. This review summarized the open literature concerning recent research and development progresses in the application of rare earths for NH3-SCR of NOx. Additionally, the roles of rare earths in enhancing the performance of NH3-SCR catalyst were reviewed.     

含砷难处理金精矿的催化氧化酸浸（COAL）新工艺开发

介绍了催化氧化酸浸（COAL）新工艺开发及产业化的情况,该工艺可以在100 ℃及0.4 MPa氧分压条件下对含砷金矿进行处理,金和银的回收率都可达到92%～96%。较低的工业压力和温度使设备简单、易于开工,基建投资和维修操作费用均较传统加压浸出工艺明显降低。在小型试验基础上,开发出100 m3加压浸出反应釜,并在招远金矿建成了100 t/d的工业试验及生产厂,工业试验证实金和银回收率分别为 93%～95%和 92%～96%,与小型试验结果一致。在操作参数及设备形式调整后,本工艺亦可适用于高砷高碳金精矿的处理。     

烧结矿催化还原NO的实验研究

摘要：《钢铁企业超低排放改造工作方案（征求意见稿）》中，计划将烧结烟气中NOx排放质量浓度控制在50mg/m3以内，烧结烟气NOx减排势在必行。因此，旨在利用烧结矿本身作为脱硝催化剂，以烧结过程产生的还原性气体CO为还原剂，系统地研究了烧结矿粒径、焙烧温度、空速比、CO/NO物质的量之比和O2体积分数对烧结矿催化脱硝效果的影响。结果表明，O2体积分数对烧结矿催化还原NO的转化率影响较大，当CO体积分数为3%、O2体积分数为1.04%时，NO的转化率为68.83%；O2体积分数降低至0.90%以下时，NO的转化率可达95%以上。无O2条件下，烧结矿粒径为0.2～1.0mm、焙烧温度为500℃、空速比为3000h-1、CO/NO物质的量之比为6时，NO的转化率可达99.58%。以烧结矿为催化剂能有效地促进CO对NO的还原，具有十分重要的环保意义和经济应用前景。     

Corneal penetration of diclofenac from a fixed combination of diclofenac-gentamicin eyedrops

Recent studies suggest a dual role for nitric oxide (NO) in tumour biology. High concentrations of NO can mediate tumouricidal activity, whereas lower concentrations have been shown to promote tumour growth. In this study, NO synthase (NOS) activity was investigated in cells that were prepared from tissue from primary and metastatic sites and from malignant effusions in 41 cases of suspected ovarian cancer. NO biosynthesis, determined by nitrite + nitrate (NOx) accumulation in medium from cultured cells prepared from disaggregated tumours or effusions and indicative of the inducible NO synthase isoform, was detected in 37% of the cases investigated (range 10.2-114 microM). There was a significant relationship between NOx and tumour differentiation (P = 0.014), with NOx being significantly higher for the more differentiated tumours. NOS activity, determined by the conversion of radiolabelled L-arginine to citrulline by tissue or cell extracts, was detected in 29% of cases (range 0.9-6.9 pmol/min per mg of protein), with all samples tested being moderately or poorly differentiated. Seventy percent of this activity was calcium dependent, indicative of constitutive NOS isoforms. Morphological and immunohistochemical assessment of tumour samples indicated a significant relationship between high macrophage content and NOS activity (as NOx biosynthesis) (rs = 0.726, N = 16, P < 0.01). The relationship between NOS expression, immune response, and disease progression is complex and not simply dependent on the differentiation status of ovarian cancer.     

改善鞍钢烧结矿冶金性能的试验研究

以烧结矿碱度和w(FeO)为出发点,进行了鞍钢烧结矿冶金性能优化试验研究。结果表明:烧结矿碱度增加,低温还原粉化性和还原性得到改善;但碱度过高时,对低温还原粉化和还原性的影响不明显,鞍钢烧结矿适宜碱度为2.05~2.14。w(FeO)提高,烧结矿低温还原粉化性能得到明显改善,但烧结矿还原性变差,综合考虑烧结生产和烧结矿冶金性能,烧结矿适宜w(FeO)应控制在8%左右。     

Ceria modified three-dimensionally ordered macro-porous Pt/TiO2 catalysts for water-gas shift reaction

Three-dimensionally ordered macro-porous(3DOM) TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were pre-pared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy(SEM), X-ray dif-fractometer(XRD), high-resolution transmission electron microscopy(HRTEM) and texture programmed reduction(TPR) techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift (WGS) reaction in a wide temperature range macro-porous catalyst, owing to the macro-porous structure favoring mass uansfer. Addition of ceria into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the ceria modi-fied catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.     

Catalytic oxidation of CO on mesoporous codoped ceria catalysts:Insights into correlation of physicochemical property and catalytic activity

Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts. In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe_(1-x-y)O_2,Cu_xCe_(1-x)O_2,Mn_xCe_(1-x)O_2 and pure CeO_2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD, SEM, EDS, BET, Raman, H2-TPR, XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity. The doped samples maintain the cubic fluorite structure of CeO_2 with high crystallinity and small crystallite size, forming Ce-based solid solutions. The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm. The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids. The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies, pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst, thereby enhancing the catalytic activity for CO oxidation. Besides, the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.     

Effect of preparation method on the catalytic activity of Au/CeO2 for VOCs oxidation

The Au/CeO2 catalysts were synthesized by co-precipitation (CP), deposition-precipitation (DP) and metallic colloids deposition (MCD) method, and tested for oxidation of volatile organic compounds (VOCs). It was revealed that the Au/CeO2 catalyst prepared by DP method was the most efficient catalyst towards the total oxidation of toluene. The Au/CeO2 catalysts had obviously high catalytic activity, and the best results was obtained on 3 wt.% Au/CeO2 catalyst prepared by DP method. These catalysts were chara...     

含砷难浸金精矿柱浸生物氧化回收金

通过室内柱浸试验,对含砷难浸金精矿进行了生物氧化试验。样品经过制粒,用氧化亚铁硫杆菌,在15~28℃条件下分别进行了60 d1、32 d3、02 d的生物浸出,金的氰化浸出率最高达到88.66%,比常规氰化浸出率提高了50个百分点。结果显示,金的浸出率与砷的氧化率呈线性正相关关系;浸出液中Fe3+/Fe2+的氧化还原电位是该体系中的主控电位;细菌浸出液中全铁浓度增量和砷浓度增量呈现出了周期性的变化,这种变化反应了菌种活性的周期性变化,是氧化亚铁硫杆菌不断受到抑制、不断适应的表现。试验证明,用生物堆浸工艺处理含砷难浸金精矿具有一定的可行性,但如何缩短生物氧化时间还需要进一步研究。     

Preparation and characteristics of nano-crystalline Cu-Ce-Zr-O composite oxides via a green route: supercritical anti-solvent process

The nano-crystalline Cu-Ce-Zr-O composite oxides were successfully prepared by the supercritical anti-solvent (SAS) process. The physicochemical properties and catalytic performances were investigated by X-ray diffraction (XRD), Raman spectroscopy, H2 temperature-programmed reduction (H2 -TPR), oxygen storage capacity (OSC) measurement and catalytic activity evaluation. It was found that Cu2+ ions incorporated into CeO2 -ZrO2 lattice to form Cu-Ce-Zr-O solid solution associated with the formation of oxygen vacancies. The Cu-Ce-Zr-O catalysts prepared via the SAS process with the Cu content 2.63 mol.% showed the highest OSC index of 636.9 μmol/g. Compared with the samples prepared by impregnation method, Cu doping using SAS process could improve the dispersion of Cu2+ in the composite oxide, enhance the interaction between Cu2+ and CeO2-ZrO2 , improve the reducibility of catalyst, and thus improve the OSC performance and increase the catalytic activity for CO oxidation at low temperature.     

退火温度对0.2C-1.5Si-1.5Mn-(0.5Cu)TRIP 钢组织的影响

用彩色金相法、X 射线衍射、扫描电镜研究了成分(%)为 0.2C-1.5Si-1.5Mn和0.2C-1.5Si-1.5Mn-0.5Cu TRIP钢 750～780℃不同退火温度对组织的影响。结果表明,含0.5 %Cu TRIP钢750℃、760℃、780℃退火的残余奥氏体体积含量为15.2 %～17.2 % ,770℃退火为15.2 %～15.7% ;不含CuTRIP钢760℃和770℃退火的残余奥氏体体积含量分别为12.5 %～12.9%和14.6 %～15.1% ,低于750℃和780℃退火的奥氏体量分别为17.0 %～17.5%和16.0 %～16.4%。随退火温度由750℃提高至780℃ ,两种钢中的铁素体量由～70%降至～5 0% ,贝氏体量由～10%增至～30%