针对含砷硫酸烧渣酸浸液的铁盐沉淀固砷

为考察含砷硫酸烧渣中酸浸脱砷效果和铁盐沉淀固砷行为,采用常温常压酸浸法脱除硫酸烧渣中的砷,并对进入浸出液中的砷以铁盐沉淀的形式脱除,进而对沉淀渣的浸出毒性进行研究。同时,研究了磨矿细度、酸浓度、固液比、浸出时间对硫酸烧渣中砷脱除效率的影响。结果表明,通过控制浸出参数可以将硫酸烧渣中砷的质量分数降低到0.2%以下,通过调节浸出液的pH和Fe/As摩尔比将其中的砷以沉淀的形式脱除。当Fe/As 2、pH=4～6时,溶液中砷浓度降到了0.5 mg·L~(-1)以下。沉淀砷渣主要是以非晶态的形式存在,提高铁砷比有利于提高砷渣稳定性,从而降低浸出毒性。在Fe/As=3、pH=6.04～6.22的条件下,得到的沉淀渣的浸出毒性为0.711 mg·L~(-1)。因此,通过酸浸脱除硫酸烧渣中的砷,进而采用铁盐沉淀的方法能够实现硫酸烧渣中砷的安全处置。     

二段铁盐沉淀深度脱除高浓度含砷废水中的砷

探索高浓度含砷废水中砷的深度脱除方法及脱除机理。采用预氧化-二段铁盐沉淀的方法脱除炼铅烟尘浸出液中的砷,研究影响砷脱除效率的控制条件和因素,砷脱除机理。结果表明,用双氧水氧化原料液中的低价铁和砷,加Fe Cl3调节铁砷比=1,在p H=4~5、T=60~70℃反应60 min,砷的脱除率达到99.95%,XRD分析结果表明,沉淀物为非晶态砷酸铁形态;在二段除砷中,控制铁砷比=5、p H=7~8,除砷后液中的砷含量小于0.014 mg/L,远低于允许的排放限值。采用二段铁盐脱砷工艺可以将高砷溶液中的砷深度脱除。     

非晶态磷酸锡去除高盐介质中Cu2+的研究

利用合成的非晶态磷酸锡作为吸附剂,研究了多种因素(pH、吸附时间、初始浓度、温度、离子强度)对吸附剂吸附水溶液中Cu2+的影响.结果表明,非晶态磷酸锡对Cu2+的吸附量随着pH(3.00～6.50)的增大、吸附时间的延长而增加.用Freundlich、Langmuir方程对等温吸附数据进行处理,Langmuir方程拟合...     

高砷烧渣酸浸-深度还原-磁选提铁除杂

对云南某高砷烧渣进行了酸浸-深度还原-磁选实验研究,采用HSC、SEM-EDS、XRD等检测技术分析了提铁脱杂的机理。研究结果表明,原料中Fe品位为57.35%,含As高达2.78%,As主要以金属砷酸盐形式赋存,Cu和Zn的品位分别为0.52%和0.57%。在浸出温度60℃,硫酸质量分数25%的条件下,浸出作业As脱除率为86.43%。浸出渣碳热深度还原最佳实验条件为:还原温度1 050℃,还原时间120 min,煤粉质量分数30%,砷的作业挥发率78.23%。焙烧样品经磁选后,最终获得铁品位71.19%,总回收率约92%,含As 0.08%,含Cu 0.29%,含Zn 0.10%的铁精矿。基础理论分析及样品特性研究结果表明,酸浸促使难溶性金属砷酸盐中As转变为易溶性的H_3AsO_4,碳热深度还原实现了氧化铁矿物向金属铁相的转变以及As的进一步脱除。研究为类似硫酸烧渣的综合利用提供了一定的理论基础和技术支撑。     

螯合沉淀联合微滤法脱除电镀废水中的低浓度络合金属

针对电镀废水中络合金属采用常规硫化钠沉淀法难以脱除问题,选用螯合沉淀-微滤法对实际电镀废水中低浓度络合Fe、Cu、Zn和Cr进行深度脱除。重点考察了pH值,重金属捕集剂EDTC投加量,EDTC反应时间,絮凝剂PAC投加量及其共存金属等因素对Fe、Cu、Zn和Cr去除效果的影响,并对EDTC去除各金属的反应机制进行了对比研究。结果表明,在pH为7,EDTC为60 mg·L~(-1),反应时间为1 min,PAC为20 mg·L~(-1),反应时间为2 min,PAM为2.5 mg·L~(-1),反应时间为2 min条件下,经微滤作用后,出水Cu 0.020 mg·L~(-1)(0.3 mg·L~(-1)),Fe 0.43 mg·L~(-1)(2.0 mg·L~(-1)),Zn 0.37mg·L~(-1)(1.0 mg·L~(-1)),Cr 0.45 mg·L~(-1)(0.5 mg·L~(-1)),均低于《电镀污染物排放标准(GB21900-2008)》中的特别限值。Fe、Cu、Zn和Cr之间存在抢夺EDTC的竞争关系,而Fe、Zn对Cr的去除又具有一定促进作用。红外光谱图表明,EDTC脱除金属Fe、Cu、Zn和Cr的反应机制是一致的,EDTC与金属发生螯合反应,EDTC巯基中硫原子捕捉金属阳离子,生成难溶的螯合产物,从而有效地去除废水中金属。     

含铁材料对污染水稻土中砷的稳定化效果

通过化学实验方法,向砷污染水稻土中添加4种含铁材料(FeCl3、FeCl2、Fe0和Fe2O3),分析稳定后土壤中pH、砷形态及砷毒性浸出量的变化,研究4种含铁材料对污染水稻土中砷的稳定化效果。结果表明,FeCl3和FeCl2处理降低了土壤pH,Fe0和Fe2O3处理对土壤pH影响不大。4种含铁材料均明显降低了土壤中易溶态砷(WE-As)和毒性浸出砷含量。在最大添加量为8.00 g/kg时,FeCl3、FeCl2、Fe0和Fe2O3分别使易溶态砷比对照降低了86.4%、63.6%、77.3%和36.4%,使毒性浸出砷比对照降低了96.3%、88.9%、70.4%和30.4%。4种含铁材料均对水稻土壤中砷具有较好的稳定化效果,且能力大小依次为:FeCl3FeCl2、Fe0Fe2O3。Fe0和Fe2O3处理使WE-As、铝型砷(Al-As)、铁型砷(Fe-As)向钙型砷(Ca-As)和残渣态砷(RS-As)转化;FeCl3处理使土壤WE-As、Al-As向Fe-As、Ca-As和RS-As转化;FeCl2处理使土壤WE-As、Ca-As向Al-As、Fe-As转化,对RS-As影响不明显。说明Fe0固砷的机理与Fe2O3相似,与FeCl3有一定差异,与FeCl2的差异可能更大。     

氧化亚铁硫杆菌菌液脱除SO_2的实验研究

对比了酸性水溶液、酸性Fe3+溶液、含Fe3+的氧化亚铁硫杆菌菌液的SO2脱除效果,分析了氧化亚铁硫杆菌在SO2脱除过程中的主要作用。结果表明:(1)在实验的进气SO2浓度范围内,酸性水溶液对SO2的吸收仅为物理吸收,反应进行到60min时,SO2脱除率均降至15%以下,溶液不再具有SO2脱除能力。(2)对酸性水溶液、酸性Fe3+溶液和含Fe3+的氧化亚铁硫杆菌菌液3种吸收液而言,在实验的进气SO2浓度范围内,进气SO2浓度越高,SO2脱除率越低;Fe3+初始质量浓度为4.44g/L时,SO2脱除效果较好。(3)氧化亚铁硫杆菌在SO2脱除过程中,直接氧化作用不明显,其主要作用是将Fe2+氧化为Fe3+,维持溶液中Fe3+的浓度,这种间接氧化的作用对SO2的有效脱除非常重要。     

改性MIL-101(Fe)非均相芬顿反应降解罗丹明B

金属有机骨架材料MIL-101(Fe)具有一定的催化活性,为进一步提升其催化性能,利用金属掺杂和柠檬酸调节对其进行改性,制备得到Cu/Ce-MIL-101(Fe)和Cu/Ce-MIL-101(Fe)-N两种改性材料。通过X射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、场发射扫描电镜(SEM)、氮气吸附脱附测试及X射线光电子能谱(XPS)对材料进行表征。结果显示,改性后催化剂具有相似的骨架结构和化学键组成,活性位点的结合能减少0.2～0.3 eV。金属掺杂和柠檬酸调节改性后Cu/Ce-MIL-101(Fe)-N平均孔径增大至14.932 nm。采用非均相芬顿反应研究降解时间和pH对罗丹明B降解性能的影响,结果表明,在温度为25℃,罗丹明B初始质量浓度为24 mg/L,溶液pH为4且Cu/Ce-MIL-101(Fe)-N投加量为0.2 g/L,3%(体积分数) H₂O₂投加量为60 mL/L,反应60 min时,罗丹明B降解率高达98%。改性前后催化剂降解过程均更符合准一级动力学模型。其中,Cu/Ce-MIL-101(Fe)-N能够在60...     

磁性纳米吸附剂Fe3O4·ZrO(OH)2的合成及对水中氟和砷的吸附性能

用共沉淀法将ZrOCl2·8H2O包裹在磁性纳米Fe3O4表面,合成了一种针对高浓度含砷含氟废水的高效新型磁性纳米吸附剂Fe3O4·ZrO(OH)2.研究考察了吸附剂对氟和砷的吸附容量、反应平衡时间以及pH对吸附效果的影响.实验表明,磁性纳米Fe3O4·ZrO(OH)2吸附剂对水中F-和As(Ⅲ/Ⅴ)等温吸附模型符合Langmuir和Freundlich模型.对溶液中总氟和总砷的吸附容量分别可达70.42 mg/g和133.33 mg/g.通过拟二级动力学方程可得知吸附过程在20 min左右即可达到平衡.随着pH的不断增加,吸附剂对氟的吸附容量逐渐降低,而对砷的吸附量则是先增加后减少.     

生物滴滤法净化低浓度磷化氢及其微生物群落分析

采用生物滴滤法净化低浓度磷化氢气体,探讨填料种类、进气量、氧浓度、进气磷化氢浓度等因素对净化过程的影响。复合填料能促进气态磷化氢的吸附,但微生物对磷化氢的净化起决定性作用。进气负荷高于300 mL·min~(-1)(空间速度为8.2 h~(-1))时,滴滤塔内磷化氢去除率下降明显;进气中氧含量不足时,生物氧化进程受到抑制,磷化氢净化效果变差。在进气流量200 mL·min~(-1)、氧体积分数8.2%、磷化氢入口浓度20 mg·m~(-3)条件下,磷化氢脱除率可高达76.8%,定期废弃的吸收液中总磷含量均低于1.0 mg·L~(-1)。生物滴滤塔内具有较高的微生物种群多样性,细菌以变形菌门(Proteobacteria)最为丰富,主要的细菌种属有:鞘氨醇单胞菌(Sphingomonas)、甲醇杆菌(Methylobacterium)、嗜甲基菌(Methylophilus)及伯克氏菌(Burkholderia)。     

A novel application of H2O2-Fe(II) process for arsenate removal from synthetic acid mine drainage (AMD) water

Batch experiments were carried out to investigate the influences of H₂O₂/Fe(II) molar ratio, pH, sequence of pH adjustment, initial As(V) concentration, and interfering ions on As(V) removal in H₂O₂-Fe(II) process from synthetic acid mine drainage (AMD). The optimum H₂O₂/Fe(II) molar ratio was one for arsenate removal over the pH range of 4-7. Arsenate removal at pH 3 was poor even at high Fe(II) dosage due to the high solubility of Fe(III) formed in situ. With the increase of Fe(II) dosage, arsenate removal increased progressively before a plateau was reached at pH 5 as arsenate concentration varied from 0.05 to 2.0 mg L⁻¹. However, arsenate removal was negligible at Fe/As molar ratio <3 and then experienced a striking increase before a plateau was reached at pH 7 and arsenate concentration ≥1.0 mg L⁻¹. The co-occurring ions exerted no significant effect on arsenate removal at pH 5. The experimental results with synthetic AMD revealed that this method is highly selective for arsenate removal and the co-occurring ions either improved arsenate removal or slightly depressed arsenate removal at pH 5-7. The extended X-ray absorption fine structure (EXAFS) derived As-Fe length, 3.27-3.30 Å, indicated that arsenate was removed by forming bidentate-binuclear complexes with FeO(OH) octahydra. The economic analysis revealed that the cost of the H₂O₂-Fe(II) process was only 17-32% of that of conventional Fe(III) coagulation process to achieve arsenate concentration below 10 μg L⁻¹ in treated solution. The results suggested that the H₂O₂-Fe(II) process is an efficient, economical, selective and practical method for arsenate removal from AMD.     

Copper distribution in surface and subsurface soil horizons

The horizons of four natural soils were treated with Cu²⁺ in an acid medium to study the retention capacity of Cu. The possible mineralogical changes arising because of the treatment were also studied. The soil properties and characteristics with the greatest influence on the metal retention and its distribution among the different soil fractions were determined. Crystalline phases of each horizon were determined by X-ray diffraction (XDR). The morphology, structural distribution and particle chemical composition of soil samples were investigated using field emission scanning electron microscopy. Cu distribution in the different geochemical phases of the soil was studied using a sequential extraction. The treatment led to an increase in the amorphous phases and the formation of new crystalline phases, such as rouaite (Cu₂(NO₃)(OH)₃) and nitratine (NaNO₃). Cu was also found superficially sorbed on amorphous hydroxy compounds of Fe that interact with albite, muscovite and gibbsite, and also on spherical and curved particles of aluminium clays. The largest amount of Cu retained was in an exchangeable form, and the smallest amount associated with the crystalline Fe oxides and residual fraction. In the surface horizons, the predominant Cu retention process is complexation in organomineral associations, while in the subsurface horizons it is adsorption.     

电镀污泥回收重金属的新工艺

合理、经济地处理混合电镀污泥,回收其中有价值的金属具有重要意义。以不同的酸作为浸出剂对电镀污泥中的金属进行了浸出效果实验。结果表明,在相同条件下,各酸的浸出效果顺序为:硫酸>盐酸>王水>硝酸;液体水与固体电镀污泥比为3,干污泥为5 g,硫酸加入量为15 mL,时间1 h条件下,混合电镀污泥中金属铜锌的浸出率最大,达到97.38%。分别采用铁和铁锰合金还原剂常温还原低熔点重金属离子铜、锌,浸出液中99%以上含量的铜、锌沉淀,使低熔点重金属与黑色金属铁、锰、铬有效分离。低熔点混合重金属可以用来做铜合金添加剂使用,最后沉淀的混合黑色金属氢氧化物处理后可以用来做炼钢合金添加剂使用。     

电化学脱硝过程参数的响应曲面优化研究

以Ti/IrO2-TiO2-RuO2为阳极,Cu/Zn合金电极为阴极,在无隔膜电解池中对这一新构造电极对的脱硝氮性能进行了研究。为了有效结合阴极硝氮还原能力和阳极氧化能力,采用响应曲面法中的Box-Behnken设计优化了对电化学脱硝过程有显著影响的4个重要因素:氯化钠含量、电流密度、pH和初始硝氮浓度。优化结果表明,相对于pH和初始硝氮浓度,氯化钠含量和电流密度对脱硝性能影响更大,而阴极硝氮还原性能主要受初始硝氮浓度、pH的影响。以6 h内电极对脱氮百分率为响应量,优化得最佳电化学脱硝过程参数为:氯化钠含量,1 g/L;电流密度,24.99 mA/cm2;pH,1.81;初始硝氮浓度100 mg/L。在此实验条件下,6 h内电极对脱氮百分率预测值为99.84%。通过3次重复验证实验,确认实际6 h内电极对脱氮百分率为91.34%。预测值与实测值两者相差不大,由此可知,Box-Behnken设计是一种优化电化学脱氮实验参数的有效方法,经过优化后的电极对具有较佳的脱氮效率。     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.     

铜铈掺杂六铝酸盐的脱硝性能

用共沉淀法制备用于脱除NO的六铝酸盐催化剂LaMxAl12-xO19(M =Cu,Ce,CuCe).用XRD、H2-TPR和BET对催化剂进行了结构和物性表征.用微型催化反应装置考察了催化剂在CO选择性催化还原NO中的活性.结果表明,Cu离子易于进入六铝酸盐晶格内,形成完整的六铝酸盐结构.Ce离子不易于进入六铝酸盐晶格内,主要以CeO2的形式存在.在CO+ NO条件下,3种催化剂都表现出较好的脱硝活性,LaCuCeAl10O19中由于Cu离子与Ce离子间产生协同作用,该催化剂的脱硝活性有所增加.加入SO2后,3种催化剂都有不同程度的失活现象发生,其中LaCuAl11O19催化剂受SO2中毒影响最严重,LaCuCeAl10O19催化剂的脱硝活性在三者中最好.     

Discoloration of methylene blue and wastewater from a plant by a Fe/Cu bimetallic system

Using a Fe/Cu bimetallic system (Fe/Cu system), the discoloration of both methylene blue in aqueous solution and the colored wastewater from a plant was investigated under the anaerobic condition in batch or continuous reactors. Results show that the Fe/Cu system effectively removed the color with over 88% of color removal efficiency for both methylene blue solution and the wastewater from the plant in batch test. Color removal efficiencies increased rapidly with Fe/Cu dosage and reaction time, respectively, at initial time and slowly to stable values. Optimum pH was neutral range. In addition, in continuous test it also removed the color of the wastewater from the plant with 63% of discoloring efficiency under the condition of 2 h of hydraulic retention time and neutral range of pH (7.0-8.3). High discoloring efficiencies with low chemical oxygen demand removal efficiencies were found in all experiments. The reduction of chromophores in pollutants was the main mechanism of the discoloration in the Fe/Cu system.     

Phenol electrooxidation on Fe-Co3O4 thin film electrodes in alkaline medium

Fe-Co₃O₄ thin film with different amounts of Fe have been used for the electro-oxidation of phenol in alkaline medium at room temperature. The electrodes were prepared by coating stainless steel supports with successive layers of the oxides, obtained by thermal decomposition at 673 K. The electrolysis was carried out at constant potential and the phenol disappearance, during the electrolysis, was monitored by UV-Vis absorbance measurements between 250 and 500 nm. After 3 h of electrolysis, the intermediates were identified by comparing the HPLC data and UV-Vis spectra to those from pure standards. The results indicate that the same oxidation products are formed on the different prepared electrodes, namely the decomposition products of phenol such as benzoquinone, hydroquinone and cathecol in basic medium. Simulated results show clearly the decrease of the amount of phenolic species with the electrolysis time. An enhancement of the phenol removal is observed with the presence of iron in the oxide. Under the operating conditions, around 30% of the initial phenol has been removed at ca. 3 h and the complete degradation is obtained after 54 h of electrolysis, when Fe-Co₃O₄ thin film with 10% of Fe is used as anode.     

Appraisal of measurement methods, chemical composition and sources of fine atmospheric particles over six different areas of Northern Belgium

Daily and seasonal variation in the total elemental, organic carbon (OC) and elemental carbon (EC) content and mass of PM_2.5 were studied at industrial, urban, suburban and agricultural/rural areas. Continuous (optical Dustscan, standard tapered element oscillating micro-balance (TEOM), TEOM with filter dynamics measurement system), semi-continuous (Partisol filter-sampling) and non-continuous (Dekati-impactor sampling and gravimetry) methods of PM_2.5 mass monitoring were critically evaluated. The average elemental fraction accounted for 2-6% of the PM_2.5 mass measured by gravimetry. Metals, like K, Mn, Fe, Cu, Zn and Pb were strongly inter-correlated, also frequently with non-metallic elements (P, S, Cl and/or Br) and EC/OC. A high OC/EC ratio (2-9) was generally observed. The total carbon content of PM_2.5 ranged between 3 and 77% (averages: 12-32%), peaking near industrial/heavy trafficked sites. Principal component analysis identified heavy oil burning, ferrous/non-ferrous industry and vehicular emissions as the main sources of metal pollution.     

Sorption of pentachlorophenol on surficial sediments: the roles of metal oxides and organic materials with co-existed copper present

The sorption characteristics of pentachlorophenol (PCP) in the surficial sediments were investigated using a selective extraction procedure. The results show that the Gamma(max) of PCP sorption decreased from 1.60mumolg(-1) to 0.69mumolg(-1) by approximately 60% after selective removal of organic materials from the sediments. The sorption of PCP in the sediments after selective removal of Mn oxides increased nearly up to 600% (from 1.60mumolg(-1) to 11.11mumolg(-1)) and, to a less degree, the PCP sorption in the sediments after simultaneous removal of Fe/Mn oxides (Gamma(max)=3.53mumolg(-1)). The analysis of the data using an additional model indicates that the contribution of Mn oxides to PCP sorption was negative, and Fe oxides and organic materials both have greater potential for sorption of PCP with less contribution from residues including Mn and Fe oxides in the residual fractions determined by a sequential extraction procedure and clay and silicate minerals. The differences in the decreased degrees of PCP sorption with increasing of Cu suggest that competition between Cu and PCP for sorption sites mainly takes place on Fe oxides.