苯醌对聚合硅酸铁多相UV-Fenton体系的增效机制

通过构建苯醌增效聚合硅酸铁多相UV-Fenton体系,讨论了体系中橙Ⅱ的脱色和降解途径.在研究苯醌浓度对聚合硅酸铁铁离子的释放、Fe²⁺与Fe³⁺之间的转化、H₂O₂分解和·OH生成影响的基础上,提出了苯醌对聚合硅酸铁多相UV-Fenton体系的增效机制.结果表明,随苯醌浓度的增加,其紫外光下光解还原聚合硅酸铁并释放Fe²⁺的程度增大、H₂O₂分解速度加快、产生·OH浓度峰值增高且出现的时间提前;苯醌增效体系释放于溶液中的Fe²⁺可以通过Fenton反应转化成Fe³⁺,反应结束后聚合硅酸铁能重新吸附Fe³⁺并使其浓度降低,避免了增效体系铁离子的二次污染.本研究将为多相催化剂催化过程的调控提供新的视角,为多相光助-芬顿反应在有机废水资源化中的应用提供理论依据和技术支持.     

Effects of calcination temperature on physicochemical property and activity of CuSO4/TiO2 ammonia-selective catalytic reduction catalysts

CuSO_4/TiO_2 catalysts with high catalytic activity and excellent resistant to SO_2 and H_2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH_3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO_4/TiO_2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH_3,temperature-programmed reduction of H_2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO_4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO_4 changed surface reducibility of the catalyst and favored the process of NH_3 oxidation to nitrogen oxides(NO_x).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃) decreased largely.     

新型Fe3O4@α-MnO2活化过一硫酸盐降解水中偶氮染料

采用两步水热法制备了新型磁性纳米Fe₃O₄@α-MnO₂复合材料作为催化剂,用于活化过一硫酸盐（PMS）产生强氧化性的硫酸根自由基（SO₄^-·）氧化降解偶氮染料活性黑5（RBK5）.采用透射电子显微镜（TEM）,X射线粉末衍射仪（XRD）和振动样品磁强计（VSM）对制备的催化剂进行表征,证明成功合成了纳米α-MnO₂包覆Fe₃O₄形态的Fe₃O₄@α-MnO₂催化剂,催化剂的饱和磁化强度为39.89emu/g.Fe₃O₄@α-MnO₂催化剂活化PMS与单一的Fe₃O₄和α-MnO₂活化PMS相比,具有更高的催化效率,说明铁锰双金属存在协同作用.同时研究了催化剂的投加量、PMS的浓度和初始pH值等各种因素对RBK5的降解效率以及反应动力学的影响.实验结果表明,Fe₃O₄@α-MnO₂催化剂活化PMS降解RBK5的过程符合准一级反应动力学,在催化剂投加量为1.2g/L,PMS的浓度为4mmol/L,初始pH值为7.0,反应时间为60min的情况下,浓度为30mg/L的RBK5的降解效率可达到91%,此时RBK5的降解速率常数也达到最高值0.023min^-1.此外,通过加入自由基淬灭剂甲醇、叔丁醇和硝基苯判断了Fe₃O₄@α-MnO₂/PMS体系中起主要氧化降解作用的活性物种为SO₄^-·.     

Seasonal variation and size distribution of biogenic secondary organic aerosols at urban and continental background sites of China

Size-resolved biogenic secondary organic aerosols(BSOA) derived from isoprene and monoterpene photooxidation in Qinghai Lake, Tibetan Plateau(a continental background site) and five cities of China were measured using gas chromatography/mass spectrometry(GC/MS). Concentrations of the determined BSOA are higher in the cities than in the background and are also higher in summer than in winter. Moreover, strong positive correlations(R2= 0.44–0.90) between BSOA and sulfate were found at the six sites,suggesting that anthropogenic pollution(i.e., sulfate) could enhance SOA formation,because sulfate provides a surface favorable for acid-catalyzed formation of BSOA. Size distribution measurements showed that most of the determined SOA tracers are enriched in the fine mode( 3.3 μm) except for cis-pinic and cis-pinonic acids, both presented a comparable mass in the fine and coarse( 3.3 μm) modes, respectively. Mass ratio of oxidation products derived from isoprene to those from monoterpene in the five urban regions during summer are much less than those in Qinghai Lake region. In addition, in the five urban regions relative abundances of monoterpene oxidation products to SOA are much higher than those of isoprene. Such phenomena suggest that BSOA derived from monoterpenes are more abundant than those from isoprene in Chinese urban areas.     

水解酸化—厌氧工艺处理高浓度抗生素废水研究

研究了水解酸化与厌氧消化组合工艺处理高浓度抗生素废水,结果表明,水解酸化反应器最大CODcr容积负荷达到 16.84kg/m3·d,复合厌氧反应器CODcr容积负荷达到8.57kg/m3·d;系统进水SO42-浓度为1325mg/L,CODcr/SO42-值最低达到 3;CODCr与SO42-总去除率分别为75.5％和95.2％,对各种抑制物质和冲击负荷表现出很好的适应性。     

Enhanced removal of high-As(Ⅲ) from Cl(-Ⅰ)-diluted SO4(-Ⅱ)-rich wastewater at pH 2.3 via mixed tooeleite and(Cl(-Ⅰ)-free) ferric arsenite hydroxychloride formation

An advanced cost-saving method of removal of high-As(Ⅲ) from SO₄(-Ⅱ)-rich metallurgi cal wastewater has been developed by diluting the SO₄(-Ⅱ) content with As(Ⅲ)-Cl(-Ⅰ)-rich metallurgical wastewater and then by the direct precipitation of As(Ⅲ) with Fe(Ⅲ) at pH2.3.As(Ⅲ) removal at various SO₄(-Ⅱ)/Cl(-Ⅰ) molar ratios and temperatures was investigated The results showed that 65.2–98.2%of As(III) immobilization into solids occurred at the SO₄(Ⅱ)/Cl(-Ⅰ) mo...     

硝酸银滴定法与硫氰酸汞分光光度法测定水中氯化物（Cl^-）的方法比对

用硝酸银滴定法、硫氰酸汞分光光度法分别测定高浓度的考核已知样及低浓度的考核未知样，均合格。说明两种方法都能满足水和废水中氯化物（Cl^-）测定的需要。     

电晕氧化结合化学吸收脱除烟气中NO2实验研究

实验研究了直流电晕湿空气自由基簇射结合25%的NaOH溶液吸收的NOx脱除过程．结果表明：通过调节流过喷嘴电极中的空气流量,可以得到稳定的流光电晕;空气中水蒸汽对NOx脱除效率有影响;在反应器内同时有HNO2和HNO3生成;实验工况下,反应器NOx转化率45％以上,经吸收液吸收后系统总脱氮效率可达70％．     

强氧化自由基杀灭压载水微生物的模拟试验研究

在强电离电场作用下,H2O、O2分子发生电离、分解电离和电荷交换反应,在分子层次上加工成高浓度羟基溶液。试验是在每小时处理2t压载水的试验系统进行的。把羟基溶液加入压载水输送管道内,仅距加入点4m长度地方取样检测,当压载水的羟基比值浓度达到0 63mg/L时,原生动物、单胞藻、细菌浓度分别从4 4×104/mL、6 0×104/mL、1 9×105/mL均减少到低于检测方法的最低限;剩余羟基药剂分解成H2O、O2等。从试验数据表明,羟基溶液是治理压载水有效、廉价、无残留物的创新方法。     

Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical

Sulfamethoxypyridazine(SMP) is one of the commonly used sulfonamide antibiotics(SAs).SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants.In this work,SMP was selected as a representative of SAs.We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter,i.e.,anions(Br~-,Cl~-,and NO~-_3) and cations ions(Ca~(2+),Mg~(2+),and Zn~(2+)) on SMP photodegradation mechanism by quantum chemical methods.In addition,the degradation mechanisms of SMP by hydroxyl radical(OH·) were also investigated.The creation of SO_2 extrusion product was accessed with two different energy pathways(pathway-1 and pathway-2) by following two steps(step-I and step-II) in the tripletsensitized photodegradation of SMP.Due to low activation energy,the pathway-1 was considered as the main pathway to obtain SO_2 extrusion product.Step-II of pathway-1 was measured to be the rate-limiting step(RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step.All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1.The estimated low activation energies of different degradation pathways of SMP with OH·radical indicate that OH·radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring.