在Pt／Al2O3催化剂上乙醇深度氧化的内扩散影响

用30—40目Pt/Al_2O_3催化剂时,乙醇深度氧化动力学可用乙醇,O_2及CO_2吸附L-H动力学方程描述。当催化剂粒度增大至4×2mm时,内扩散强烈地影响乙醇深度氧化速度。用动力学方法测定了O_2有效扩散系数。用Adams显示方法计算了在催化剂孔内O_2的压力分布。测定了乙醇深度氧化内扩散活化能,并将内扩散对活化能的影响用方程(10)解释。在动力学和内扩散区域,0_2的反应级数都接近一级。由实验测定的催化剂有效因子可用方程(11)估计。     

羊角月芽藻的生长与湖水中几种磷形态关系模型的建立

将湖水中的磷分成六种形态:总溶解磷(TSP)、溶解反应磷(SRP)、总反应磷(TRP)、溶解的水解性磷(SHP)、溶解的光解性磷(UVSRP)及颗粒磷(PP),研究其对羊角月芽藻的生物有效性.获得了各磷形态及总磷(TP)与藻生长的相关方程.并通过多元回归,建立了藻的生长量(Y)与多种磷形态的模型:Y=1.40×10~4C_(pp)+8.69×10~3C_(TSP)+1.02×10~4C_(SHP)(r=0.9811,n=19)及简便模型:Y=1.04×10~4C_(pp)+4.97×10~3C_(TSP)(r=0.9759,n=19)这两个模型在评价湖泊水体富营养化中,对预测藻的生长潜力将有很大的帮助作用.     

超临界水氧化去除含酚废水TOC的动力学研究

本文利用自行设计的一套连续式超临界水氧化实验装置,以过氧化氢为氧化剂,处理实验室模拟含酚废水。在超临界条件下(P=30MPa,T=400℃,440℃,480℃,520℃)进行超临界水氧化实验。结果表明,TOC去除速率在氧化剂过量10倍的情况下,对TOC是2.15级反应。速率常数与温度的关系符合阿仑尼乌斯公式。反应的实验活化能为171.7kJ/mol,前置因子A为2.99×1011。     

Pt/TiO2对水中黑索今的光催化降解

在模拟日光下利用Pt/TiO2光催化剂对水中黑索今进行了光催化降解,有催化剂存在时,黑索今(RDX)的转化降解遵循一级反应动力学,RDX分子上的氮部分转化为硝酸盐氮和亚硝酸盐氮,催化剂的存在没有加快黑索今的转化速率,但是大大加快了溶液COD和中间产物亚硝酸盐的氧化,对10mg·l-1亚硝酸盐的光催化降解显示,亚硝酸盐氮在有催化剂存在时被氧化的速率提高了16.8倍.     

Pt/SiO_2-Al_2O_3抗硫型柴油车尾气净化氧化催化剂的制备及性能

使用浸渍法制备了一系列SiO2含量不同的改性Al2O3材料,并以此为载体制得一系列Pt/SiO_2-Al_2O_3柴油车尾气净化氧化催化剂(DOC).N2吸附-脱附实验和扫描电子显微镜(SEM)检测证实,SiO_2以多孔形式均匀覆盖在Al2O3表面,没有明显影响Al2O3的织构性质.运用热重法对各催化剂的抗硫性进行了表征,结果证实,SiO_2的引入有效提高了Pt/Al_2O_3催化剂的抗硫性;经硫累积实验后,所制备的Pt/SiO_2-Al_2O_3系列催化剂硫酸盐累积量均小于1.0 wt.%,而Pt/Al_2O_3的硫酸盐累积量约为3.94 wt.%.催化剂活性检测结果表明,适量SiO_2的引入不会影响Pt/Al_2O_3催化剂的活性;当SiO_2引入量为18 wt.%时,Pt/SiO_2(18%)-Al_2O_3催化剂不仅抗硫性能优异而且具有更好的耐久性,模拟柴油车使用160000 km后,其催化活性未明显降低.因此,本研究认为SiO_2在Pt/Al_2O_3DOC催化体系中,可以起着抑制硫中毒及提高耐久性的作用.     

砷钼酸—结晶紫分光光度法测定水中微量砷

Ag—DDTC法广泛用于水及底泥中砷的测定。但该法在有机相显色,有机溶剂氯仿毒性大,污染环境,危害人体健康。此外该法灵敏度(ε=1.2×10~4)也不能满足10ppb以下砷的测定。近年来有人用砷钼兰—孔雀绿水相分光光度测定矿石中微量砷,摩尔吸光系数比Ag—DDTC法有所提高(ε=7.5×10~4)。A.K.等人曾提出用丙酮溶解砷钼酸—结晶紫色淀测定砷的可能性,但重现性差,要用环已酮—甲苯混合溶剂从过剩试剂     

Mnx/SEP(海泡石)催化剂低温NH_3-SCR脱硝性能

以Mn(CH_3COO)_2和KMnO_4为前驱体,采用原位生长法在海泡石(SEP)载体表面负载锰氧化物,制备Mnx/SEP催化剂应用于低温SCR脱硝反应.分别考察了制备工艺及反应条件等因素对Mnx/SEP催化剂低温NH_3-SCR脱硝活性的影响.采用BET、XRD、SEM、XPS等表征手段对催化剂的结构和形貌进行表征分析.结果表明,在锰负载量为8 wt%、n(Mn(CH_3COO)_2)/n(KMnO_4)为3∶2时所制备的催化剂具有较佳的NH_3-SCR低温脱硝活性.当空速为10000 h~(-1)、反应温度在100—250℃区间时,转化率为100%,表明该催化剂具有高空速适应性.锰氧化物活性组分在海泡石表面的均匀分布和高的分散性使催化剂具有较大的有效比表面积,有利于催化剂NH_3-SCR反应;此外n(Mn(AC)_2)/n(KMnO_4)对催化剂表面活性物种形态特别是表面Mn~(4+)/Mn~(3+)比具有显著影响,进而与催化剂的低温SCR脱硝活性紧密相关.     

高碘酸钾氧化甲基红催化光度法测定超痕量锰

拟定了测定超痕量锰的新催化光度法。方法基于存在氨三乙酸为活化剂,以高碘酸钾催化氧化甲基红。方法的检出限为4×10~(-11)g/ml,表观摩尔吸光系数为2×10~7L·mol~(-1)·cm~(-1),测定锰量的线性范围为2—28ng/25ml,可直接分析水样和谷物制品中锰。     

Pd-Fe/C催化氯酚还原脱氯-氧化联合降解

以Pd和Fe为活性金属组分通过沉积沉淀法制备了负载型Pd-Fe/C双金属催化剂,针对氯酚类污染物进行催化还原脱氯和催化氧化的连续降解处理.通过ICP-MS、XRD和TEM对催化剂进行表征,证实0.5%Pd-0.5%Fe/C催化剂中活性金属组分Pd和Fe在载体表面分散性最好,催化剂比表面积达到718.8 m~2·g~(-1).在温和条件下,以水作为反应介质,研究了负载型Pd-Fe/C催化剂对4-氯苯酚(4-CP)和2,4-二氯苯酚(2,4-DCP)的连续降解过程和反应条件,以及催化剂的重复使用情况.考察了Pd和Fe的负载量及p H值对催化剂活性的影响,得到了最佳反应条件,以0.5%Pd-0.5%Fe/C为催化剂,20 min内完成4-CP和2,4-DCP的催化还原脱氯,产物都为苯酚;之后加酸调节pH=5,并加入H2O2继续进行催化氧化,苯酚被彻底降解为H_2O和CO_2,而且转化率在60 min内可以达到97.5%以上,从而实现4-CP和2,4-DCP的彻底降解.     

小球藻对水中稀土元素的摄取

本文研究了小球藻对水体中轻、中和重稀土元素的摄取。结果表明:小球藻对水中可溶性稀土元素有高的富集能力。摄取动力学为首先迅速吸附在藻细胞表面,随后相对缓慢地扩散到细胞内部,动力学方程可近似表示为C_t=A(1—e~(-K_2t))。稀土元素在藻中的生物积累量与溶液中稀土元素浓度成正相关,藻对稀土元素摄取的BCF值分别为:La 2.44×10~4,Gd 2.47×10~4和Y 2.44×10~4。在试验条件下没有观察到混合稀土元素对藻的协同作用和拮抗作用。     

瞬态吸收光谱技术研究水体中亚硝酸-萘体系的微观反应机理

采用 35 5nm紫外光照射HNO2 萘 H2 O体系 .研究表明 ,光照后体系中间产物和最终产物的光反应过程是通过HNO2 激光光解产生OH自由基 ,OH自由基再与萘反应生成　 OH ,反应速率常数为 ( 1 1± 0 1 )× 1 0 1 0 M- 1 ·s- 1 .     

Chemical poison and regeneration of SCR catalysts for NOx removal from stationary sources

Selective catalytic reduction (SCR) of NO_x with NH₃ is an effective technique to remove NO_x from stationary sources, such as coal-fired power plant and industrial boilers. Some of elements in the fly ash deactivate the catalyst due to strong chemisorptions on the active sites. The poisons may act by simply blocking active sites or alter the adsorption behaviors of reactants and products by an electronic interaction. This review is mainly focused on the chemical poisoning on V₂O₅-based catalysts, environmental-benign catalysts and low temperature catalysts. Several common poisons including alkali/alkaline earth metals, SO₂ and heavy metals etc. are referred and their poisoning mechanisms on catalysts are discussed. The regeneration methods of poisoned catalysts and the development of poison-resistance catalysts are also compared and analyzed. Finally, future research directions in developing poisoning resistance catalysts and facile efficient regeneration methods for SCR catalysts are proposed.     

SO2-4/TiO2对SO2-C7H16-TiO2复相光化学反应的影响

研究了TiO2与SO2,C7H16复相光化学反应的光催化活性.在SO2-C7H16-O2-TiO2光催化反应过程中,TiO2表面可形成SO2-4/TiO2结构,它的存在可提高庚烷的光催化氧化速率,利用IR和XPS研究了反应过程中TiO2表面形成的SO2-4/TiO2结构.     

Cu/Cr co-stabilization mechanisms in a simulated Al2O3-Fe2O3-Cr2O3-CuO waste system

• Cu and Cr can be mostly incorporated into CuFe_xAl_yCr_2−x−yO₄ with a spinel structure. • Spinel phase is the most crucial structure for Cu and Cr co-stabilization. • Compared to Al, Fe and Cr are easier to be incorporated into the spinel structure. • ‘Waste-to-resource’ by thermal process at attainable temperatures can be achieved. Chromium slag usually contains various heavy metals, making its safe treatment difficult. Glass-ceramic sintering has been applied to resolve this issue and emerged as an effective method for metal immobilization by incorporating heavy metals into stable crystal structures. Currently, there is limited knowledge about the reaction pathways adopted by multiple heavy metals and the co-stabilization functions of the crystal structure. To study the Cu/Cr co-stabilization mechanisms during thermal treatment, a simulated system was prepared using a mixture with a molar ratio of Al₂O₃:Fe₂O₃:Cr₂O₃:CuO= 1:1:1:3. The samples were sintered at temperatures 600–1300°C followed by intensive analysis of phase constitutions and microstructure development. A spinel phase (CuFe_xAl_yCr_2−x−yO₄) started to generate at 700°C and the incorporation of Cu/Cr into the spinel largely complete at 900°C, although the spinel peak intensity continued increasing slightly at temperatures above 900°C. Fe₂O₃/Cr₂O₃ was more easily incorporated into the spinel at lower temperatures, while more Al₂O₃ was gradually incorporated into the spinel at higher temperatures. Additionally, sintered sample microstructures became more condensed and smoother with increased sintering temperature. Cu / Cr leachability substantially decreased after Cu/Cr incorporation into the spinel phase at elevated temperatures. At 600°C, the leached ratios for Cu and Cr were 6.28% and 0.65%, respectively. When sintering temperature was increased to 1300°C, the leached ratios for all metal components in the system were below 0.2%. This study proposes a sustainable method for managing Cu/Cr co-exist slag at reasonable temperatures.     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.     

KMnO4/H2SO4引发制备淀粉改性絮凝剂的研究

以高锰酸钾为引发剂,制备淀粉-丙烯酰胺接枝共聚物.研究酸浓度、引发剂浓度、单体浓度、温度和加料方式对接枝反应的影响.结果表明,少量KMnO4(0.45mmol·l-1)和H2SO4(0.8mmol·l-1)可有效引发淀粉-丙烯酰胺接枝共聚反应,接枝效率达到90%以上,分子量大大提高,对高岭土的絮凝效果较好.     

大气CO2、CH4、CO高精度观测混合标气配制方法

高精度、高准确度的大气CO2、CH4、CO浓度观测需使用以干洁大气为底气的标气.标气中水汽含量及CO2的δ13C对基于光学原理的观测系统有不可忽视的影响.本研究利用自组装的混合标气配制系统,以环境大气为底气,并通过添加高浓度气体或利用吸附剂吸附,调节目标物种浓度.CO2和CO吸附效率分别达99.7%和99.8%,标气水汽含量小于3.7×10-6(物质的量分数,下同),可配制不同浓度范围的CO2、CH4、CO混合标气.在青海瓦里关全球大气本底站配制环境大气浓度范围的标气,CO2、CH4、CO实际配制浓度同目标浓度的偏差小于10×10-6、30×10-9、30×10-9,CO2中δ13C同实际大气接近.本方法配制的标气已应用于我国本底站大气CO2、CH4、CO高精度观测,符合世界气象组织/全球大气观测(WMO/GAW)质量要求.     

食蚊鱼(Gambusia afinis)cat、gapdh和gst基因的克隆及其在生态毒理学中的应用

根据Ensembl、Genbank登录的鱼类cat、gapdh和gst基因的CDS序列设计普通PCR扩增引物,寻找食蚊鱼的cat、gapdh和gst基因的c DNA片段,并根据定量引物设计要求设计出相应的SYBR Green I荧光定量RT-q PCR引物,建立了食蚊鱼cat、gapdh和gst基因的SYBR Green I荧光定量RT-q PCR方法。该方法在104~108数量级范围内有良好线性关系(R=0.999~1.000);熔解曲线显示扩增产物特异性良好,均为单一峰值;质粒标准品最高浓度与最低浓度的批内试验变异系数与批间试验变异系数均低于2%。利用该方法监测和评价环境污染物对水生生物的影响,选择了水体中常见典型药物污染物——双氯芬酸,研究其对食蚊鱼抗氧化基因表达的影响。结果表明,雌性食蚊鱼暴露在不同浓度双氯芬酸钠(0.005、0.05、0.5和5 mg·L-1)24 h后,其肝脏cat、gapdh和gst的mRNA呈现显著变化,相对于对照组,在低浓度0.005 mg·L-1时,cat与gst mRNA的表达量均有极显著上升(p0.01),而其它浓度均极显著下降(p0.01)。试验表明该方法具有快速、精确、灵敏度高的优点,可为利用该类小型鱼类的原位污染物的生物监测和生态毒理评价提供有力的技术支持。     

六铝酸盐负载CuO催化还原NO性能

采用共沉淀法制备了LaAl12O19六铝酸盐载体,采用等体积浸渍法制备了不同负载量的CuO/LaAl12O19催化剂,并对其进行了XRD、H2-TPR和BET表征,考察了催化剂对CH4选择催化还原NO的性能.结果表明,CuO的负载并未改变六铝酸盐载体的结构,Cu在载体上以Cu2+的形式存在,活性组分CuO与载体LaAl12O19之间存在协同作用;CuO/LaAl12O19催化剂对CH4选择催化还原NO表现出良好活性,所制备的催化剂均能使NO的转化率达到99%;其中负载量为1.0 wt%的CuO/LaAl12O19催化剂的活性最好,完全反应温度T99%为560℃,且在80 h稳定性试验中表现出了良好的高温活性和热稳定性.     

Separation/degradation behavior and mechanism for cationic/anionic dyes by Ag-functionalized Fe3O4-PDA core-shell adsorbents

● PDA-Fe₃O₄-Ag was made by hydrothermal and oxidation self-polymerization method. ● PDA-Fe₃O₄-Ag had great magnetic separation performance. ● PDA-Fe₃O₄-Ag had good adsorption and degradation performance for ionic dyes. ● PDA-Fe₃O₄-Ag showed NR and MO degradation potential of 91.2% and 87.5%, respectively. High-performance adsorbents have been well-studied for the removal of organic dye pollutants to promote environment remediation. In this study, an Ag nanoparticle-functionalized Fe₃O₄-PDA nanocomposite adsorbent (PDA-Fe₃O₄-Ag) was synthesized, and the adsorption/separation performance of commonly used cationic and anionic organic dyes by the PDA-Fe₃O₄-Ag adsorbent were assessed. Overall, PDA-Fe₃O₄-Ag exhibited a significantly higher adsorption capacity for cationic dyes compared to anionic dyes, the highest of which was more than 110.0 mg/g (methylene blue (MB)), which was much higher than not only the adsorption capacities of the anionic dyes in this study but also other dye adsorption capacities reported in the literature. The dye adsorption kinetics data fitted well to both the pseudo second-order kinetics model and the Langmuir isotherm model, suggesting a monolayer-chemisorption-dominated adsorption mode. Thermodynamics analysis indicated that the adsorption process was both endothermic and spontaneous. Furthermore, the PDA-Fe₃O₄-Ag adsorbent achieved high photodegradation removal rates of the dyes, especially neutral red (NR) and methyl orange (MO), which were 91.2% and 87.5%, respectively. With the addition of PDA-Fe₃O₄-Ag, the degradation rate constants of NR and MO increased from 0.08 × 10⁻² and 0 min⁻¹ to 2.11 × 10⁻² and 1.73 × 10⁻² min⁻¹, respectively. The high adsorption and photocatalytic degradation performance of the PDA-Fe₃O₄-Ag adsorbent make it an excellent candidate for removing cationic and anionic dyes from the industrial effluents.