Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

长庆油田水处理新技术研究

长庆油房庄油田水经过处理后仍具有较高的矿化度、较多的悬浮物及残留油,同时其SRB严重超标。现场处理水质不稳定,在进行回注时与地层的配伍性较差。针对这些情况,研究了一种新型的水处理工艺技术。对成垢离子调整剂、水质净化剂和成垢离子钝化剂进行了筛选,并对含油污水的成垢离子含量及比例进行了调整。运用这种技术,使油房庄油田水经处理后达到回注水的标准,且提高了与地层的配伍性。同时提出了新型水处理技术的工艺流程。     

农用改性硝酸铵拒爆机理及工业化可行性研究

对农用硝铵作改性处理,通过筛选和优化实验确定了改性硝酸铵配方。结果表明,当硝酸铵中添加3%的改性剂GXJ1,10%的改性剂GXJ2时,产品在1mm铁皮管约束下的雷管感度试验条件下具有拒爆特性。改性硝酸铵总养分与普通硝酸铵相当,并且颗粒强度高,不易粉化、结块和吸潮,具有优良的肥料品质。同时还利用X射线衍射分析、扫描电子显微镜分析对改性硝铵的拒爆机理作初步探讨。最终,建立了改性硝酸铵的脱水性能、流动性能、凝固性能、颗粒强度的评价方法,并进行了工业化可行性研究。     

微生物燃料电池改性阳极处理PTA废水

探讨了不同改性阳极对微生物燃料电池(microbial fuel cell,MFC)产电性能及其对MFC处理难降解废水能力的影响.以单室空气阴极为基础,利用0.1 g电气石、质量分数75%二氧化锰/埃洛石纳米管(manganese bioxide/halloysite nanotube,MnO_2/HNT)和多壁碳纳米管-羧基(multi-walled carbon nanotube-carboxyl,MWCNT-COOH)对MFC阳极进行修饰.结果表明,不同改性阳极的MFC对含精对苯二甲酸(purified terephthalic acid,PTA)废水的去除率均高于70%,且化学需氧量(chemical oxygen demand,COD)去除率在79%以上.相较于其他几种改性阳极,以MWCNT-COOH改性材料作阳极的MFC产生的最大输出电压最高,获得的最大功率密度最高,分别为529 mV和252.73 mW·m~(-2).     

La3+掺杂对吸附相反应制备TiO2复合催化剂的结晶过程及弱紫外光下活性的影响

利用吸附相反应技术制备弱紫外光响应的高效催化剂,并通过XRD、XPS以及HRTEM探索了不同焙烧温度下La3+掺杂量对TiO2结晶过程的影响.结合弱紫外光下甲基橙的降解反应,深入研究催化剂结晶过程的变化对弱紫外光下催化剂活性的影响.结果表明,La3+掺杂会抑制TiO2的结晶过程.当焙烧温度或者掺杂量较低时,La3+不能进入TiO2的晶格结构但会轻微地抑制TiO2的结晶过程;未进入晶格结构的La3+存在会引入光生载流子的浅能级捕获中心,在弱光体系中极大提升了催化剂的活性.当La3+的掺杂量为0.05%(原子分数)时,经过900℃焙烧后催化剂降解能力最高,其活性超过商用P25的2倍多.在较高La3+掺杂量(超过0.20%)时,900℃焙烧后一定量La3+进入TiO2的晶格结构而大大抑制了TiO2结晶;这种强烈的抑制作用使得催化剂中存在大量无定形结构TiO2,无定形TiO2甚至多于700℃焙烧后的催化剂,反而大大抑制了弱光体系中催化剂活性.     

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.     

T型氧化沟工艺处理低碳源生活污水的效果研究

详细介绍了T型氧化沟工艺的特征,并考察研究了该工艺处理低碳源生活污水的长期运行效果。研究结果表明,工艺出水COD、BOD5、NH3-N、TN和TP年平均浓度分别为13.9、3.8、0.91、18.80和1.67 mg/L,去除率分别为88.99%、94.37%、96.74%、37.57%和41.58%,均能达到相应的排放标准。由于T型氧化沟中以好氧环境为主,缺乏厌氧和缺氧环境以及进水的BOD5/TN值低,工艺对有机物及NH3-N的去除效果较好,但TN和TP去除效果较低。提出了加强工艺脱氮除磷的措施,为同类型污水处理厂改造提供参考。     

有机化改性海泡石对六六六吸附性能的探讨

分别采用阴阳离子表面活性剂对海泡石进行有机化改性处理,并对改性海泡石进行了吸附六六六实验.结果表明,未经有机化改性的海泡石对六六六各异构体去除能力由小到大依次为:γ-六六六(12.66%)、δ-六六六(12.79%)、α六六六(17.35%)、β-六六六(33.57%).经DOSO3Na有机化改性的海泡石对六六六各异构体的去除能力由小到大依次为:β-六六六、γ δ-六六六、α-六六六.经CTMAB有机化改性的海泡石对六六六各异构体的去除能力由小到大依次为:β-六六六、α-六六六、γ δ-六六六.有机化改性海泡石使体系中β-六六六大幅度增加,可能为有机化海泡石催化α、γ、δ各异构体向β异构体转化.     

有机改性膨润土在印染废水处理中的应用

膨润土是一种非常有用的非金属矿物原料,其有机改性得到的有机改性膨润土可以较好地去除印染废水中的有机污染物和色度。本文综述了有机改性膨润土的制备方法及其在印染废水处理中的应用现状。     

Removal of polycyclic aromatic hydrocarbons from aqueous solution by raw and modified plant residue materials as biosorbents

Removal of polycyclic aromatic hydrocarbons （PAHs）, e.g., naphthalene, acenaphthene, phenanthrene and pyrene, from aqueous solution by raw and modified plant residues was investigated to develop low cost biosorbents for organic pollutant abatement. Bamboo wood, pine wood, pine needles and pine bark were selected as plant residues, and acid hydrolysis was used as an easily modification method. The raw and modified biosorbents were characterized by elemental analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The sorption isotherms of PAHs to raw biosorbents were apparently linear, and were dominated by a partitioning process. In comparison, the isotherms of the hydrolyzed biosorbents displayed nonlinearity, which was controlled by partitioning and the specific interaction mechanism. The sorpfion kinetic curves of PAHs to the raw and modified plant residues fit well with the pseudo second-order kinetics model. The sorption rates were faster for the raw biosorbents than the corresponding hydrolyzed biosorbents, which was attributed to the latter having more condensed domains （i.e., exposed aromatic core）. By the consumption of the amorphous cellulose component under acid hydrolysis, the sorption capability of the hydrolyzed biosorbents was notably enhanced, i.e., 6-18 fold for phenanthrene, 6-8 fold for naphthalene and pyrene and 5-8 fold for acenaphthene. The sorpfion coefficients （Kd） were negatively correlated with the polarity index [（O＋N）/C], and positively correlated with the aromaticity of the biosorbents. For a given biosorbent, a positive linear correlation between logKoc and logKow for different PAHs was observed. Interestingly, the linear plots of logKoc-logKow were parallel for different biosorbents. These observations suggest that the raw and modified plant residues have great potential as biosorbents to remove PAHs from wastewater.