Barium promoted manganese oxide catalysts in low-temperature methane catalytic combustion

In this study, a series of BaO-MnO_x mixed oxide catalysts were synthesized by the mechanochemical method and employed in lean methane catalytic combustion (MCC) at low temperatures. The synthesized catalysts were characterized by XRD, BET, TGA, FT-IR, H₂-TPR, O₂-TPD, and FESEM analyses. The results indicated that the 10 wt% BaO-MnO_x catalyst with a BET surface area of 25 m² g^?1 possessed the best catalytic performance. The higher activity of the 10 wt% BaO-MnO_x catalyst was due to the higher ability to supply oxygen through the components during the MCC process. The light-off temperature corresponding to 50% of the methane conversion was about 330 °C, which was about 50 °C lower than the pure MnO_x. Moreover, for the BaO(10)-MnO_x catalyst, the 10 and 90% of methane conversion temperatures were about 305 and 427 °C, respectively. Also, the 10 wt% BaO-MnO_x catalyst exhibited high catalytic stability under dry feed condition at 450 °C for 50 h. Furthermore, the influence of various parameters such as calcination temperature, feed ratio, GHSV, pretreatment condition, and presence of water vapor in the feedstock was studied on the catalytic performance.     

后处理料液中氨基羟基脲的分析方法研究

氨基羟基脲（HSC)是一种新型无盐试剂，可有效控制后处理料液中钚的价态，实现铀钚分离和钚的纯化，其含量是后处理工艺中的一项重要参数，需准确测定。本文根据HSC和对二甲氨基苯甲醛在酸性介质中发生显色反应，其产物在456 nm处有明显特征吸收的原理，建立了后处理料液中HSC的分析方法，并优化了分析条件。结果表明，HSC的最佳测量条件为测量波长456 nm、显色温度80～90 ℃（水浴）、显色时间45 min，NO^-₂、Fe³⁺、N₂H₄及其他共存组分对HSC的测定无明显影响。HSC含量在2.5～60.0 μmol/L范围内符合比耳定律，R²为0.999 9，测量精密度优于5.0%。在45 d内工作曲线重复性好，具有良好的长期稳定性。真实样品的测量结果显示，其重加回收率在99%～105%之间。     

乙二醇高温还原制备燃料电池核壳结构Cu@Pt-Pd电极的研究

通过对以碳为核心的燃料电池电催化剂Cu@Pt-Pd的制备方法的研究,以还原法成功将Cu、Pt、Pd还原到了靶核C上制备出了核壳结构电催化剂Cu@Pt-Pd。该催化剂以Cu为核来提升催化剂的表面积比,同时掺杂金属Pd,降低贵金属铂的使用量,在提高催化效率的同时可以降低成本。经过对所制备的催化剂的XRD和CV的测试与分析,探究出制备的成品具有一定的提升氧化还原反应的催化效率的能力,同时该制备方法简单易于操作,利于大量制备。     

催化共振光散射法测定空气中痕量甲醛的研究

吖啶橙分子聚集体微粒可在513nm波长处出现最大的共振光散射强度(RLS)。在稀硫酸介质中,甲醛能催化溴酸钾氧化吖啶橙的反应,促使其RLS强度减弱。在最佳实验条件下,甲醛质量浓度ρ在0.020～0.25μg/mL的范围内与△I值呈良好的线性关系,线性回归方程为△I=1113.99ρ+49.23,线性相关系数r为0.9986。本法与国标法进行对照,在置信度等于95%时,用Cochran检验,两种方法间不存在显著性差异,方法操作简单、灵敏度高,用于室内外空气中甲醛测定,结果满意。     

钼蓝分光光度法联合测定铁矿石中磷和二氧化硅

以往铁矿石中磷和二氧化硅含量的测定需要分别采用钼蓝分光光度法。在使用磷钼蓝分光光度法时,常会因钒、砷等的干扰使得磷测定结果不准确,需要将样品再处理后才能测定。实验采用石墨垫底铁坩埚,碳酸钠和硼酸混合熔剂高温熔融铁矿石,使铁矿石样品分解彻底,再分别采用铋磷钼蓝和硅钼蓝分光光度法测定磷和二氧化硅含量,从而实现了采用钼蓝分光光度法联合测定铁矿石中磷和二氧化硅。干扰试验表明,在高温熔融时,石墨可将钒(V)还原为钒(III),使样品中钒不干扰磷的测定;显色液中加入15mg硫代硫酸钠溶液可将砷(V)还原为砷(III),继而消除砷对磷测定的干扰。磷的质量浓度在0~3μg/mL范围内遵守比尔定律,校准曲线的线性相关系数为0.9999,表观摩尔吸光系数为2.242×10⁴ L·mol^-1·cm^-1;二氧化硅的质量浓度在0~5μg/mL范围内遵守比尔定律,校准曲线的线性相关系数为0.9995,表观摩尔吸光系数为9.342×10³ L·mol^-1·cm^-1。方法中磷和二氧化硅的检出限分别为0.0026μg/mL和0.0081μg/mL。按照实验方法测定6个铁矿石标准样品中磷和二氧化硅,磷测定结果的相对标准偏差(n=8)小于5%,相对误差小于2%;二氧化硅测定结果的相对标准偏差(n=8)小于2%,相对误差小于1.5%。按照实验方法测定5个铁矿石样品中磷和二氧化硅,磷测定结果的相对标准偏差(RSD,n=8)小于7%,二氧化硅测定结果的相对标准偏差(n=8)小于1%;磷和二氧化硅的测定值均与电感耦合等离子体原子发射光谱法的测定值相一致。     

分光光度法和光度滴定法联合测定湿法炼锌流程中钴渣浸出液中锌钴镍

湿法炼锌流程中钴渣浸出液中含有高浓度的Fe²⁺和Mn²⁺,用分光光度法测定Co²⁺和Ni²⁺时,Fe²⁺-EDTA会严重干扰Co²⁺和Ni²⁺的测定;在用光度滴定法测定Zn²⁺和Co²⁺合量时,Ni²⁺对二甲酚橙指示剂具有封闭作用,Mn²⁺亦与EDTA螯合,导致滴定结果偏高。为消除Fe²⁺和Mn²⁺对Zn²⁺、Co²⁺和Ni²⁺测定的干扰,实验进行氧化分离Fe²⁺和Mn²⁺预处理,在NaAc/Hac缓冲体系下,以EDTA作显色剂用分光光度法测定Co²⁺、Ni²⁺。在波长466nm处,Co²⁺的线性范围为50~500mg/L时与吸光度呈线性,相关系数R²为0.9992;在384nm处,Ni²⁺的线性范围为50~500mg/L时与吸光度呈线性,相关系数R²为0.9998。根据分光光度法测出Ni²⁺物质的量,加入1.1倍的丁二酮肟以除去Ni²⁺,用二甲酚橙为指示剂,EDTA鳌合-光度滴定法测定Zn²⁺、Co²⁺合量,扣减Co²⁺含量得出Zn²⁺含量。选取4个锌湿法炼锌流程中钴渣浸出液实际样品,按照实验方法中的分光光度法测定Co²⁺和Ni²⁺,光度滴定法测定Zn²⁺、Co²⁺合量,Zn²⁺、Co²⁺和Ni²⁺测定结果的相对标准偏差(RSD,n=6)均不大于0.70%,加标回收率分别为99.59%~100.41%、99.69%~100.64%、99.92%~100.08%。     

煤直接液化反应中分散相催化剂研究进展

煤直接液化工艺中催化剂作用十分重要,粒径小、分散性高的催化剂能够有效提升煤转化效率。将流动反应介质中小颗粒的固体催化剂命名为分散相催化剂,综述煤直接液化中常用的几种分散相催化剂,包括金属卤化物催化剂、过渡金属氧化物催化剂和铁系催化剂,提出可能的催化机理。     

炭化活化条件对Cu/AC表面Cu价态及其催化降解苯酚的影响

采用前体浸渍法研制了生物质基载铜活性炭催化剂（Cu/AC），利用N₂-吸附脱附、X射线光电子能谱等技术对Cu/AC性质进行了表征，在固定床反应器中研究了不同炭化活化条件所得Cu/AC催化湿式氧化降解苯酚性能。结果表明：Cu/AC表面Cu物种以Cu²⁺和（Cu⁺+Cu⁰）共存。随着制备Cu/AC炭化温度的升高，炭化过程中产生更多的挥发分，促进Cu²⁺还原为Cu⁺和Cu⁰，（Cu⁺+Cu⁰）含量增大，Cu/AC降解苯酚催化活性逐渐升高；随着炭化时间延长，（Cu⁺+Cu⁰）含量下降，Cu₂O、CuO较好地并入载体使晶格氧含量增加，催化活性先升高后下降；随着活化温度升高和活化时间延长，Cu/AC比表面积达到1096.1m²/g并有大量微孔生成，大量含氧官能团分解将炭化过程中还原生成的（Cu⁺+Cu⁰）氧化为Cu²⁺，晶格氧含量增加，催化活性随着活化温度的升高而升高，随着活化时间的延长先升高后下降。催化湿式氧化降解苯酚过程中，Cu/AC具有良好的稳定性和低的Cu离子浸出浓度。Cu/AC的最优制备条件为炭化温度800℃，炭化时间2h，活化温度880℃，活化时间为2h，所得Cu/AC在反应8.5h时实现98.5%的苯酚转化率和91.1%的COD转化率。     

Interactions of mixing and reaction kinetics of depolymerization of cellulose to renewable fuels

As the biofuel industry is heavily depend on technological advancement to remain competent, creation of new process techniques becomes inevitable to replace the existing under-performed operations. Mixing in the reactor requires enormous amount of energy to achieve required homogeneity. Reduction in the energy consumption and ultimately the cost of the product is possible by devising smart mixing strategies. In this review, interactions of mixing and reaction kinetics of enzymatic hydrolysis, fermentation, and cellulosic depolymerization in ionic solvents are discussed. When the processes are operated under various mixing conditions, changes in the reaction kinetics and dynamics of the processes occur. Therefore, analyzing the mixing effects at various levels (micro to macro) is crucial to decide best operating mixing conditions that drive the reaction kinetics toward the increased product yield. The review is helpful to identify a suitable mixing strategy that maximizes the production of biofuels—ethanol, 5-hydroxymethylfurfural, etc.     

Kinetic,thermodynamic parameters and in vitro digestion of tannase from Aspergillus tamarii URM 7115

Tannase is an enzyme used in various industries and produced by a large number of microorganisms. The aim of this study was to evaluate tannase production to determine the biochemical, kinetic, and thermodynamic properties and to simulate tannase in vitro digestion. The tannase-producing fungal strain was isolated from “jamun” leaves and identified as Aspergillus tamarii. Temperature at 26°C for 67?h was the best combination for maximum tannase activity (6.35-fold; initial activity in Plackett–Burman design—15.53?U/mL and average final activity in Doehlert design—98.68?U/mL). The crude extract of tannase was optimally active at 40°C, pH 5.5 and 6.5. Moreover, tannase was stimulated by Na⁺, Ca²⁺, Mg²⁺, and Mn²⁺. The half-life at 40°C lasted 247.55?min. The free energy of Gibbs, enthalpy, and entropy, at 40°C, was 81.47, 16.85, and ?0.21?kJ/mol?·?K, respectively. After total digestion, 123.95% of the original activity was retained. Results suggested that tannase from A. tamarii URM 7115 is an enzyme of interest for industrial applications, such as gallic acid production, additive for feed industry, and for beverage manufacturing, due to its catalytic and thermodynamic properties.