改性镍铝催化剂氧化零价汞及抗氨干扰机理

采用尿素水解法制备NiAlO和NiAlMO(M=Zn、Ba、Mn、La、Cr)催化剂用于Hg0催化氧化研究.结果表明,在NH3存在时,NiAlZnO催化剂展现出最好的Hg0氧化活性,250℃时Hg0的转化率超过80％,并在350℃达到最高(90％).Raman和XPS结果显示,Zn掺杂构成Ni-O-Zn固溶体,引起Ni...     

Reuse of spent bleaching earth by polymerisation of residual organics

Spent bleaching earth (SBE) is a waste generated by the edible oil industry that currently has limited options for beneficial reuse. In excess of ～2 million tonnes per year of SBE is generated world-wide with major quantities available in the middle-east where significant volumes of edible oils are produced. Low pressure compaction followed by heat treatment at 150 °C causes polymerisation of the residual organic components in SBE and this produces monolithic samples with high unconfined compressive strengths (54 MPa). SBE can therefore be used to manufacture novel clay blocks for use in construction that are bonded by polymerised vegetable oil. This represents a new, innovative and resource efficient application for SBE. In this research, commercial SBE has been characterised and the effects of key processing variables (temperature and compaction pressure) on the compressive strength, porosity and density of the SBE clay blocks are reported and the mechanisms responsible for strength development are discussed.     

Dry reforming of methane over oil palm shell activated carbon and ZSM-5 supported cobalt catalysts

In this study, cobalt supported oil palm shell activated carbon (Co/OPS-AC) and ZSM-5 zeolite (Co/ZSM-5) catalysts have been prepared for dry reforming of methane. Cobalt ratios of 6.0 and 14.0 wt% were deposited via wet impregnation method to the OPS-AC and ZSM-5 catalysts. The catalysts were characterized by XRD, N₂ adsorption--desorption isotherms, BET surface area, SEM, FESEM-EDX, TPR-H₂, and TPD-NH₃. The dry reforming of methane was performed using a micro reactor system under the condition of 10,000 ml/h.g-cat, 3 atm, CH₄/CO₂ ratio of 1.2:1.0 and temperature range from 923 K to 1023 K. The gaseous products were analyzed by gas chromatography (GC) with thermal conductivity detector (TCD) and further quantified to determine the conversions of CH₄ and CO₂, and the yields of CO and H₂. Experimental results revealed both catalysts exhibited lower conversions of CO₂ and CH₄ with the increase in temperature from 923 K to 1023 K. The reduced conversions may be due to the formation of carboneous substance on the catalyst known as coking. Comparatively, Co/OPS-AC gave higher conversions of CO₂ and CH₄ as well as higher yields of H₂ and CO as it has a higher surface area than Co/ZSM-5 which subsequently rendered higher activity for the reforming of methane. With the increasing cobalt loadings and reaction temperature, OPS-AC(14) catalyst exhibited improved activity and H₂/CO ratio. Based on these results, cobalt supported OPS activated carbon catalyst was suggested to be more effective for CO₂ and CH₄ conversions.     

Characteristics of mercury emission from linear type of spent fluorescent lamp

In order to recycle the linear type of SFL (spent fluorescent lamp), mercury from SFL should be controlled to prevent leaking into the environment. For mercury emission from SFL, mercury concentration is estimated in the parts of SFL such as glass tube, phosphor powder, and base cap using the end-cutting unit. It is also evaluated mercury emission in the effluent gas in the end-cutting unit with changing flow rate. From the results of mercury emission from SFLs, phosphor powder has greater than 80% of mercury amount in SFL and about 15% of mercury amount contained in glass tube. The initial mercury concentration in vapor phase is almost decreased linearly with increasing airflow rate from 0.7 L/min to 1.3 L/min. It is desirable that airflow rate should be high until the concentration of mercury vapor will be stable because the stabilized concentration becomes to be low and the stabilized time goes to be short as increased airflow rate. From KET and TCLP results, finally, phosphor powder should be managed as a hazardous waste but base-cap and glass are not classified as hazardous wastes.     

中国报废汽车中铂族金属回收潜力估算

基于Gompertz模型预测中国2018~2050年民用汽车的社会保有量;在此基础上,采用物质流分析方法估算得出我国汽车高峰报废年限大约为9a.然后,通过市场供给A模型预测我国2018~2025年汽车报废量,结果显示,我国汽车报废量到2025年将达到2535.05万辆,并且地理空间分布极不均衡.基于上述汽车报废量的时空分布,测算不同技术发展情景下废汽车三元催化剂中的铂族金属回收潜力和需求量.结果显示：如果按照当前催化剂消耗水平,全国铂族金属的需求量均在2019年达到峰值,铂钯铑分别达到4.57,65.70,7.92t,有望实现行业内闭环供应;如果以欧盟汽车尾气治理标准为目标,而现有汽车技术不发生根本变化,需求量将大幅增加,铂钯铑分别在2020年达到峰值85.01,109.38,8.37t,存在严重的供需矛盾.为此,建议在汽车生产者责任延伸制度中,关注废催化剂的回收和再生利用,以促进前端生产环节在不同技术选择中考虑稀贵金属的供给限制.     

新型高效催化氧化技术的应用试验

采用新型高效催化氧化技术,在室内小试的基础上,将研究成果直接用于盘锦大兴化工有限公司高浓度COD的化工废水处理工程。     

Effects of synthesis methods on the performance of Pt + Rh/Ce0.6Zr0.4O2 three-way catalysts

The 0.7 wt% Pt + 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction(UAMR) co-precipitation, UAMR separation precipitation, co-impregnation, and sequential impregnation. The catalysts were physico-chemically characterized by N2 adsorption, XRD, TEM, and H2-TPR techniques, and evaluated for three-way catalytic activities with simulated automobile exhaust. UAMR co-precipitation- and UAMR separation precipitationprepared catalysts exhibited a high surface area and metal dispersion, wide λ window and excellent conversion for NOx reduction under lean conditions. Both fresh and aged catalysts from UAMRprecipitation showed the high surface areas of ca. 60–67 m2/g and 18–22 m2/g, respectively, high metal dispersion of 41%–55%, and small active particle diameters of 2.1–2.7 nm. When these catalysts were aged, the catalysts prepared by the UAMR method exhibited a wider working window(Δλ = 0.284–0.287) than impregnated ones(Δλ = 0.065–0.115) as well as excellent three-way catalytic performance, and showed lower T50(169.C) and T90(195.C) for NO reduction than the aged catalysts from impregnation processes, which were at 265 and 309.C, respectively. This implied that the UAMR-separation precipitation has important potential for industrial applications to improve catalytic performance and thermal stability. The fresh and aged 0.7 wt% Pt + 0.3 wt% Rh/Ce0:6Zr0:4O2 catalysts prepared by the UAMR-separation precipitation method exhibited better catalytic performance than the corresponding catalysts prepared by conventional impregnation routes.     

La0.8Ca0.2FeO3/MgAl2O4丝网整体催化剂用于低浓度甲烷催化燃烧

开发了涂覆在金属丝网基体上的La_(0.8)Ca_(0.2)FeO_3/MgAl_2O_4复合整体催化剂,用于低浓度甲烷(0.5%,体积分数)催化燃烧反应.首先用沉积-沉淀法制备了La_(0.8)Ca_(0.2)FO_3(LCF)钙钛矿与Mg Al_2O_4尖晶石复合的粉末催化剂LCF/Mg Al2O4,用程序升温微反应器(TPRS)测定了粉末活性,结合XRD、BET、SEM、TPR的表征结果,筛选出了最佳复合物质的量比和最适焙烧温度.当LCF与Mg Al_2O_4复合后,抗烧结能力增强,以拟一级反应速率常数(k,L·g~(-1)·s~(-1))计的活性提高了1倍左右.然后采用浆料涂覆法,在表面改性的金属丝网蜂窝基体上分层涂覆了作为第二载体的MgAl_2O_4和LCF/Mg Al_2O_4复合粉体涂层,考察了复合粉体球磨前焙烧的温度、第二载体及活性层涂覆量的影响.最后在空速GHSV=40000 h~(-1)条件下测试了甲烷催化燃烧反应的活性.与陶瓷基体相比,涂覆在金属丝网基体上的LCF/MgAl_2O_4活性在600℃时提升了48.1%.500 h长运转试验发现,催化剂活性在初期的200 h下降了20.3%,然后基本保持稳定.     

铁铜催化剂非均相Fenton降解苯酚及机制研究

通过浸渍法制备了负载于活性炭(AC)上的金属催化剂Fe/AC、Cu/AC和Fe-Cu/AC,并通过X射线衍射(XRD)、物理吸附仪及X射线光电子能谱(XPS)对其进行了表征.研究了非均相Fenton反应催化H2O2降解苯酚废水的工艺参数,并通过中间产物分析和电子自旋共振谱(ESR)探讨了过程反应机制.实验表明,Cu/AC催化剂中铜主要以CuO形式存在,Fe/AC中铁以多价态形式存在,以无定形形态分散于活性炭中.Fe/AC、Cu/AC和Fe-Cu/AC催化过氧化氢降解苯酚60 min内降解率分别达到96.7%、77.5%和99%;Cu/AC和Fe-Cu/AC催化剂中活性组分铜和铁有一定溶出,而Fe/AC中活性组分铁溶出很少,苯酚降解主要是以非均相催化为主,同时在三轮循环实验后的苯酚降解率仍然高达93%以上,显示了良好的催化稳定性.在优化条件pH=3、T=303 K及初始H2O2为4.38 mmol.L-1下,Fe/AC催化过氧化氢对苯酚和TOC去除率分别达到97%和53%,没有催化剂时苯酚几乎不降解.ESR结果表明Fe/AC催化过氧化氢产生了羟基自由基,证明苯酚降解是以羟基自由基氧化为主;通过高效液相色谱(HPLC)检测苯酚降解中间产物主要有邻苯二酚、对苯二酚和对苯醌,推测苯酚降解途径主要为邻位和对位的羟基取代反应.     

Catalytic activities of zeolite compounds for decomposing aqueous ozone

The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone.