Effect of transition metal doping under reducing calcination atmosphere on photocatalytic property of TiO2 immobilized on SiO2 beads

TiO₂ immobilized on SiO₂ (TiO₂/SiO₂) have been prepared by sol-gel method and various ions of transition metals (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) were doped on the photocatalyst using wet impregnation method under reducing calcination atmosphere. The photocatalytic activity of metal doped TiO₂/SiO₂ towards phenol degradation under black light irradiation were investigated and compared with undoped TiO₂/SiO₂. The results showed that the photoresponse of Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂ were larger than undoped TiO₂/SiO₂, indicating that the photogenerated carriers were separated more efficiently in Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂. The reactivity was in the order of Cu²⁺ > Zn²⁺ > Ni²⁺ > Cr³⁺ > Co²⁺. The different photoreactivity was ascribed to combine effect of the different ionic radii and photocorrison tendency of the dopants. The sample was also characterized by surface analytical methods such as X-ray diffraction, scanning electron micrograph/electron dispersive X-ray analyzer and UV-Vis absorption spectrum.     

溴酸钾对二茂铁(Fc)非均相Fenton效能的影响

研究了KBrO3对二茂铁(Fc)非均相Fenton效能的影响,深入考察了KBrO3对体系中Fc溶解、H2O2分解和羟基自由基(·OH)生成的影响。结果表明,KBrO3的加入对不同反应阶段Fc/Fenton体系的效能均有明显的促进作用,初始阶段主要是由于KBrO3对·OH产生的促进作用所致,后期主要是由于KBrO3促进了体系中Fc的溶解,使得体系中溶解态的Fc催化的均相Fenton反应的比例增加,体系中H2O2的分解加快,·OH的表观生成率增加,进而促进了反应的进行。无KBrO3添加,pH=4,MB初始浓度为10 mg/L,Fc的量为1.6×10-3mol/L,[H2O2]/[MB]=3.14时,45 min时,MB的剩余率为9.1%,105 min时为0。当KBrO3的用量为3×10-4mol/L时,反应45 min后MB的去除率即可达到100%。随着KBrO3浓度的增加,其对Fc/Fenton效能的促进作用增强。     

微波诱导AC/Cu、AC/Fe催化非均相Fenton 反应催化降解垃圾渗滤液

采用活性炭载体负载Cu、Fe为催化剂,在微波诱导作用下,对垃圾渗滤液污染物进行降解。实验结果表明,活性炭负载金属前经适当浓度硝酸浸泡处理后,催化剂对COD去除率提高可超过15%,过高硝酸盐浓度对COD去除有不利影响;催化剂对COD去除率随Cu、Fe金属负载量增加呈先增加后降低的趋势,催化剂对Cu、Fe的最佳负载量分别为质量百分比2.11%和1.12%。对于AC-Cu体系,在初始pH=3,H2O2投加量为4.98×103mg/L,催化剂用量为5.0×103mg/L,420 W功率下微波辐射10 min时,垃圾渗滤液COD去除率可达到84.13%;对于AC-Fe体系,当H2O2投加量为0.33×103mg/L,催化剂AC-Fe用量为2.0×104mg/L,420 W功率下微波作用10 min时,垃圾渗滤液COD去除率为60.16%。分析2种催化剂对COD去除差异的原因,可能是催化剂AC-Cu表面单分子分布的阈值比AC-Fe高。降解液的pH值对AC-Cu体系、AC-Fe体系COD去除影响存在拐点,最高COD去除率点对应的降解液pH值为3。微波辐射功率较低时,体系COD去除率随辐射功率增加而增加;辐射功率较高时,高温下垃圾渗滤液中有机硫化物分解成小分子硫化物,对催化剂活性存在一定抑制作用。     

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

炮采放顶煤采空区自然发火的数值模拟应用

针对炮采放顶煤开采采空区容易发生自燃问题，基于漏风渗流方程、气体渗流一扩散-氧消耗方程，建立了采空区自然发火非稳定数值模型，采空区按非均质考虑，耗氧汇按煤矸氧化和瓦斯涌出稀释两方面综合考虑，用有限元数值方法联立求解模型。结合羊草沟矿实例，通过该矿自然发火后来的测试区的现场实测结果，拟合反演得到采空区煤的耗氧速度、瓦斯涌出强度和渗透特征参数，用确定的模型分析了前段出现自然发火的原因；描绘了炮采放顶煤开采时采空区冷却带、自燃带和窒息带等三带的形状，指出冒落压实的不均衡的非均质采空区，自燃点在偏人风一侧。用三带划分理论讨论了工作面参数（风量、推进度、控顶距）同自燃的量化关系，提出了从根本上预防采空区自然发火的途径与方法。     

Ozone facilitated degradation of caffeine using Ce-TiO2 catalyst

The ozone initiated oxidation of 1,3,7-trimethylxanthine (caffeine), commonly found in wastewaters as model compound is reported using cerium (Ce)/titanium dioxide (TiO₂) as catalyst. The effect of pH and loading of ceria on titania were investigated. Effect of reaction conditions on degradation of caffeine based on their pseudo first-order rate constants were compared. The combination of catalyst Ce-TiO₂ and ozone aeration significantly enhanced the degradation of caffeine compared to uncatalysed ozonation. The oxidation of caffeine ensued via the free radical mechanism, through enhanced ozone decomposition into OH radicals. Ce/TiO₂(0.5?wt%) showed good activity in degradation of caffeine at pH 6, in both natural stream and river water samples showing about 60% total organic carbon removal in 2?h ozonation period. Using liquid chromatography-mass spectroscopy, degradation products were analysed. A reaction intermediate and one final product were positively identified. Nano-catalysts with different loadings of Ce on TiO₂ synthesized by sol-gel route were characterized by scanning electron microscope, transmission electron microscopy, BET and powder X-ray diffraction spectrum techniques. The results showed that the material retained a highly ordered mesoporous structure and possessed large surface area.     

非均相催化湿式氧化法活性炭再生

使用浸渍法制备的CuO Al2 O3催化剂对吸附苯酚饱和的活性炭进行非均相催化湿式氧化再生研究 ,考察了反应温度、反应时间、催化剂投加量、反应氧分压、投炭量、蒸馏水量对非均相催化湿式氧化再生活性炭的影响结果 ,同时在该实验中得到非均相CuO Al2 O3催化湿式氧化再生活性炭的最佳条件。对催化剂进行了X衍射分析 ,并通过对催化剂的稳定性进行实验 ,得出该催化剂在进行催化湿式氧化再生活性炭的过程中具有较好的稳定性     

多相催化臭氧氧化技术处理染料废水生化出水

采用多相催化臭氧氧化技术对某染料废水一级好氧生化出水进行系统实验研究,考察该技术对废水COD、色度的去除能力,并探讨其提高废水可生化性的能力。结果表明：在最佳操作条件下,即臭氧投加量200 mg·L-1,接触时间20 min时,COD平均从647 mg·L-1降低到440 mg·L-1,臭氧化指数约等于1;进水色度2 000倍左右,色度去除率达95%以上;SOUR值平均提高至原水的4倍;毒性由65%左右降低至0%;GC-MS结果显示废水中苯胺类、挥发酚类和硝基苯类等有毒污染物几乎全部被去除。另外,对实验所用的自制催化剂（连续使用90 d）进行ICP、BET、SEM、EDS分析,其有效成分锰、铈基本无损耗,催化剂性能稳定。研究表明在废水处理一级生化阶段后增加多相催化臭氧技术,不仅能够进一步去除COD,还可以明显提高二级好氧生化脱氮能力,对于污水处理的升级改造具有重要意义。     

可见光/H2 O2/海藻酸铁非均相催化降解吖啶橙的研究

由海藻酸钠和氯化铁反应制备了海藻酸铁凝胶小球催化剂,考察了该催化剂的吸附和可见光下催化降解吖啶橙的性能.结果表明催化剂的吸附能力随pH升高而提高,且催化剂用量为40个凝胶小球时,可见光下吖啶橙能够在较宽pH值范围内脱色,脱色速率随H2O2的用量增加而增加,该反应符合Arrhenius规律,其表观活化能为49.6 kJ/mol.自由基清除剂的加入不会降低脱色速率,表明催化反应不是羟基自由基的机理,而与高活性的类{ Fe(Ⅳ)=O}高价铁中间产物有关.     

微波促进含Cr(VI)-H2O2体系降解甲基橙溶液的研究

研究了微波辐射下Cr(VI)－H₂O₂催化降解甲基橙溶液的行为，探索了微波功率、微波辐射时间、pH值、H₂O₂浓度、Cr(VI)等对甲基橙溶液脱色率和COD去除率的影响。研究结果表明，Cr(VI)-H₂O₂能形成类Fenton体系；微波辐射可提高H₂O₂产生羟基自由基(·OH)的效率。1000 mg/L的甲基橙溶液，在Cr(VI)浓度为10.0 mmol/L、pH值为2.5、H₂O₂浓度为20.0 mmol/L、微波功率为700W下加热2 min，甲基橙溶液的脱色率为99.2%，COD去除率为82.8%。