Preparation, characterization and application of CuCrO2/ZnO photocatalysts for the reduction of Cr(VI)

The delafossite CuCrO₂ elaborated by sol-gel from 40 nm diameter colloid is optically active in the visible region. It is characterized physically and photoelectrochemically. The microstructure is fairly homogenous with a mean crystallite size of ca. 2 μm. The optical gap (1.30 eV), determined from the diffuse reflectance, is well suited to the sunlight spectrum. The Mott Schottky plot is characteristic of P-type conductivity with a flat band potential of -0.26 V_SCE. As application, the photoreduction of chromate is successfully achieved in air-equilibrated suspension CuCrO₂/ZnO (1/1). CuCrO₂ is photoactivated by visible light and the electrons in the conduction band (-1.34 V_SCE) are injected to ZnO. In the presence of salicylic acid, a conversion of Cr(VI) to Cr(III) of 57% is obtained under optimal conditions (pH 3 at 25℃, 5×10^-4 mol/L) because of the HCrO₄^- dark adsorption onto ZnO (4HCrO₄^- + 3C₇H₆O₃ + 18O₂ + 16H⁺ → 4Cr³⁺ + 21CO₂ + 19H₂O, ΔG⁰ = -557 kcal/mol). Prolonged illumination is accompanied by a deceleration in the photoactivity owing to the competitive water reduction, an issue of energetic concern. The hetero-system exhibits self sensitization for hydrogen production with an evolution rate of 149 μmol/(hr·g).     

厌氧生物滴滤法脱除冷煤气中硫化氢的研究

水煤气中硫化氢在燃烧时会转变成二氧化硫,对环境产生污染。文章采用厌氧生物滴滤塔法对冷煤气进行脱硫处理。因煤气对氧的严格限制,通过设计生物滴滤塔,经挂膜驯化后在厌氧条件下对浓度在1~5 g/m3左右的硫化氢进行脱除处理,考察滴滤塔运行条件对脱除效果的影响。结果表明,生物挂膜25 d后,生物滴滤塔达到稳定,喷淋液pH值为2.23,ORP值为283 mV,溶解氧为0.4 mg/L,对溶液中硫离子氧化效率达到94%。滴滤塔在液气比0.15,空塔气速0.088 m/s,pH值5.0~7.0,填料高度为82 cm,塔温为25~30℃左右时,达到较优的运行条件,此时该滴滤塔对以CO、CO2、H2和1 940 mg/m3H2S组成的模拟水煤气的脱硫效率达91.2%。     

一种新型"Turn-on"荧光探针用于硫化氢可视化检测

硫化氢(H2S)是表征水体污染的重要参数之一,对其进行快速、有效地检测十分重要.荧光检测法由于具有不可比拟的优势得到了广泛的关注.以2-(2'-羟基苯基)苯并咪唑为荧光团,基于H2S的亲核性,设计合成了一种新型检测H2S的荧光探针.该探针与H2S作用后,荧光强度随H2S浓度的增加逐渐增强,颜色由淡黄色变成紫色,因此能够进行可视化检测,可视化检测限为3μmol·L-1.探针的最佳激发/发射波长为320/460 nm,对H2S表现出了良好的选择性和很快的响应速度(5 min),在较宽的p H(6~9)范围内,仍然表现出较好的荧光性能,荧光检测限为6μmol·L-1.该探针为H2S的检测提供了新方法.     

新型聚乙烯填料生物滴滤床净化硫化氢气体的启动研究

研究了新型高密度聚乙烯改良型拉西环填料生物滴滤床净化硫化氢气体的启动过程,重点比较了启动过程中不同的挂膜方式对启动时间及效能的影响.结果表明,采用液相连续流强化挂膜法成膜时间短,在环境温度20～28℃时7 d可以挂膜成功.在启动过程中,随着工艺参数的突然改变(GRT缩短)和入口浓度波动,液相连续流强化挂膜后反应器的硫化氢去除率更稳定.在进气浓度最高为343 mg/m³时硫化氢去除率稳定在95%以上.试验过程中还发现,将SO₄^2-浓度作为活性污泥驯化完成的监测指标、液相S^2-去除率作为挂膜完成的监测指标更合理.启动结束后,通过2种途径减去喷淋液中的碳源并未影响硫化氢的去除率,这进一步表明生物滴滤床中硫化氢的净化主要由自养菌完成.     

Fe和Fe2+对混合细菌产氢发酵的影响

在研究Fe粉剂量和Fe²⁺浓度对混合细菌产氢发酵的影响基础上,确定Fe和Fe²⁺促进混合细菌产氢能力的最佳阈值,并对乙醇型发酵菌群在不同Fe粉和Fe²⁺浓度下的产氢量和最大比产氢速率进行考察和对比.结果表明,Fe粉和Fe²⁺对乙醇型发酵菌群的产氢能力均有明显的促进作用.以葡萄糖为底物,投加Fe²⁺试验中,Fe²⁺浓度200mg/L获得最大产氢量143.7mL/g,较对照组提高32%;Fe²⁺浓度50mg/L获得单位VSS最大比产氢速率21.2 mL/(h·g),较对照组提高33%.投加单质Fe试验中,Fe粉剂量1000mg/L获得最大产氢量156.1mL/g,较对照组提高44%;Fe粉剂量500mg/L获得单位VSS最大比产氢速率23.5mL/(h·g),较对照组分别提高47%.单质Fe浓度高于50mg/L时,对发酵菌群产氢的促进作用要优于同浓度下的Fe²⁺.同时对混合细菌中铁的全量和形态分布进行了考察.     

阻挡放电联合金属氧化物催化降解H2S的研究

采用介质阻挡放电联合金属氧化物催化降解气态H2S,考察了单组分及复合金属氧化物催化剂、催化剂与低温等离子体结合方式对H2S及副产物O3去除性能的影响,分析了等离子体联合Mn复合金属氧化物催化降解H2S机理。结果表明,金属负载量相同条件下,电压低于22kV时,Mn复合金属氧化物对H2S的催化活性高于单组分Mn金属氧化物,催化活性及对O3的分解能力从大到小依次为:Ag+Mn、Cu+Mn、Fe+Mn、Mn。当电压为18 kV时,Ag+Mn、Cu+Mn、Fe+Mn复合催化剂分别比单组分Mn催化剂对H2S的去除效率提高了近10%、6%、4%。等离子体后催化区域中Mn催化剂催化氧化H2S的效率明显低于等离子体催化区域。Mn催化剂在等离子体后催化区域中能有效催化分解O3。随着电压的升高,Mn金属氧化物在等离子体后催化区域对H2S催化作用逐渐增强。在电压22 kV时,等离子体联合后催化比单独等离子体作用时,H2S去除效率提高了近11%。     

含硫天然气净化厂硫化氢泄漏分析及对策

以川东北某含硫天然气净化厂为对象,通过分析该净化厂的处理工艺及可能造成泄漏的各种原因,确定了硫化氢泄漏危险较高的生产单元。通过工艺压力、流量、物料组分的比对,选取了脱硫单元原料气和硫磺回收单元酸性气作为模拟泄漏物料。对该厂所在地的气象条件和厂区的地形地貌进行了调查,净化厂当地近5年风速、云量统计表明低风速和多云为主导天气,将D1.5m/s作为模拟硫化氢泄漏扩散的典型气象条件。采用了美国石油学会(API)推荐地面粗糙度长度。运用PHAST软件计算了在典型气象条件下通过3种不同孔径泄漏1 min,5min和30min,形成的立即危及生命或健康(IDLH)范围。在典型气象条件下IDLH的下风向边界距离在41m至1190m范围内,以硫磺回收单元的大孔径泄漏为最远。以小孔泄漏为例模拟并讨论了风速、大气稳定度对硫化氢扩散的影响。为降低H2S泄漏风险提出了在线监测及联锁系统设置的要求,对避免和减少硫化氢中毒伤亡事故具有指导意义。     

钻屑法测定煤层H_2S含量

为了测定煤层硫化氢(H2S)含量,防治矿井H2S涌出,提出一种通过钻屑法测定煤层H2S含量的方法。在未受采动影响的新鲜煤壁,采用钻屑法取样,通过测定煤样H2S解吸量、取样过程损失量和H2S残存量确定煤层H2S含量。根据溶于水中H2S的p H值和色谱分析解吸气体中H2S体积分数,确定H2S解吸量;根据煤样解吸规律和气样H2S体积分数,确定H2S损失量;根据色谱分析残存气体中H2S体积分数,确定其残存量。用此方法,对山西某矿H2S涌出煤层进行现场和实验室测定。研究表明,该矿H2S含量为(4.465~6.701)×10-3m3/t。钻屑法测定煤层H2S含量是可行的,可以为矿井H2S治理提供基础数据。     

Hybrid H2/Al dust explosions in Siwek sphere

Explosion indices and explosion behaviour of Al dust/H₂/air mixtures were studied using standard 20 l sphere. The study was motivated by an explosion hazard occurring at some accidental scenarios considered now in ITER design (International Thermonuclear Experimental Reactor). During Loss-of-Vacuum or Loss-of-Coolant Accidents (LOCA/LOVA) it is possible to form inside the ITER vacuum vessel an explosible atmosphere containing fine Be or W dusts and hydrogen. To approach the Be/H₂ explosion problem, Be dust is substituted in this study by aluminium, because of high toxicity of Be dusts. The tested dust concentrations were 100, 200, 400, 800, and 1200 g/m3; hydrogen concentrations varied from 8 to 20 vol. % with 2% step. The mixtures were ignited by a weak electric spark. Pressure evolutions were recorded during the mixture explosions. In addition, the gaseous compositions of the combustion products were measured by a quadruple mass-spectrometer. The dust was involved in the explosion process at all hydrogen and dust concentrations even at the combination ‘8%/100 g/m3’. In all the other tests the explosion overpressures and the pressure rise rates were noticeably higher than those relevant to pure H₂/air mixtures and pure Al dust/air mixtures. At lower hybrid fuel concentrations the mixture exploded in two steps: first hydrogen explosion followed by a clearly separated Al dust explosion. With rising concentrations, the two-phase explosion regime transits to a single-phase regime where the two fuel components exploded together as a single fuel. In this regime both the hybrid explosion pressures and pressure rise rates are higher than either H₂ or Al ones. The two fuels compete for the oxygen; the higher the dust concentration, the more part of O2 it consumes (and the more H₂ remains in the combustion products). The test results are used to support DUST3D CFD code developed at KIT to model LOCA or LOVA scenarios in ITER.     

Na_2CO_3/H_2O_2“稳定”的CO_2的型体研究(Ⅱ)——“稳定性二氧化氯”溶液的UV吸收光谱、纸层析特性、微观结构和离子色谱分析

本文对以稳定剂H_2O_2和Na_2CO_3与ClO_2制备的所谓"稳定性二氧化氯"溶液的UV吸收光谱、纸层析特性、微观结构及离子色谱进行了分析,并与纯NaClO_2及ClO_2溶液做了对比.结果表明,“稳定性二氧化氯” 与NaClO_2在UV吸收光谱、层析比移值、微观结构、离子色谱这几方面都具有很好或极其相似的一致性 表明“稳定性二氧化氮’与NaClO_2溶液中氯氧化物存在型体的一致性.因此,认为“稳定性二氧化氯“溶液中ClO_2是以亚氯酸盐ClO_2~-的型体存在的.