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FeCl3调节铁砷比=1,在pH=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、pH=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 °C,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 °C,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H3AsO4,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。     

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...     

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)。     

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.     

天然有机物对零价铁去除水体中砷的影响研究

在研究零价铁对水体中砷去除动力学的基础上,着重探讨了天然有机物腐殖酸对零价铁除砷的影响.并对零价铁的腐蚀产物进行了分析.结果表明,水体中的砷可以通过在零价铁腐蚀产物上的吸附得到快速去除.腐殖酸显著降低了砷的去除率,这归因于腐殖酸与零价铁腐蚀产生的铁离子形成络合物,阻止了Fe(OH)3(或Fe(OH)2)沉淀的产生.腐殖酸浓度越高.砷的去除率越低.1.00 mg腐殖酸最多可以络合约0.75 mg铁离子.当铁离子与腐殖酸的络合达到饱和后,零价铁进一步腐蚀产生的铁离子可形成Fe(OH)3(或Fe(OH)2)沉淀,这些沉淀物可吸附水体中的腐殖酸和砷,从而加速砷的去除.冷冻干燥后的零价铁腐蚀产物的结构以无定型为主,含有少量的结晶化合物,包括γ-Fe2O3、γ-FeO(OH)和Fe3O4等.腐殖酸的存在可进一步增加腐蚀产物中的无定型成分.光电能谱(XPS)分析结果显示,吸附在腐蚀产物上的砷为5价,没有发现5价砷被还原成3价砷.在应用零价铁修复砷污染水体时,应考虑腐殖酸的影响.     

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.     

氧气促进纳米零价铁除砷效果及其作用机制

为了探究氧气对纳米零价铁(nZVI)除砷的影响,考察了不同的氧含量(厌氧、低氧、中氧和高氧)条件下nZVI对As(Ⅲ)/As(V)的去除效果,并结合表征结果分析了氧气对nZVI除砷的影响机制。结果表明：氧气存在会显著促进nZVI对As(Ⅲ)/As(Ⅴ)的去除,但不同氧含量对nZVI除砷的促进程度有所不同;随着氧含量的增加,As(Ⅲ)/As(Ⅴ)的去除率呈现先增大后减小然后再增大的趋势。在初始砷浓度为50 mg·L⁻¹、nZVI投加量为200 mg·L⁻¹、O₂/nZVI摩尔比等于0.5时,砷的去除率达到最大,As(Ⅲ)和As(Ⅴ)体系中砷的去除率分别为96.27%和51.75%。固相表征结果表明：氧气对nZVI的氧化程度及除砷效果具有较大的影响,在低氧条件下,nZVI被少量氧化为无定型铁矿物进而提高除砷效果;在中氧条件下,nZVI被氧化为大量的溶解态Fe(Ⅱ)/Fe(Ⅲ),溶解态铁对砷没有去除效果,从而导致砷的去除率降低;在高氧条件下,nZVI被大量氧化,溶解态Fe(Ⅱ)/Fe(Ⅲ)进一步被氧化形成新的无定型铁矿物,可增强除砷效果。以上结果可为评估不同氧含量条件下纳米零价铁除砷效果以及人为强化纳米零价铁除砷效果提供参考。     

多孔Fe-Si电极电催化还原硝酸根离子

水体硝酸盐污染已成为一个日益严重的问题。以多孔Fe和Fe-Si合金为阴极,Ti/IrO2为阳极构建电解系统,对模拟废水(100 mg·L-1NO3--N + 500 mg·L-1 NaCl + 500 mg·L-1 Na2SO4)进行电解以去除其中的硝酸根离子,并研究了多孔Fe-Si合金在电解过程中的稳定性。实验结果表明,增大电流密度有利于提高NO3--N和总氮的去除效率。当电流密度为40 mA·cm-2时,以多孔Fe为阴极,几乎无副产物产生,NO3--N和总氮去除率均为94.3%,但电解完成之后Fe电极腐蚀严重,溶液中铁离子浓度达1 418 mg·L-1。而以多孔Fe-Si为阴极时,随合金中硅含量增加,NO3--N和总氮去除率均呈下降趋势,但电极稳定性显著提高,电解完成之后溶液中Fe离子浓度显著下降。当Fe-Si合金中硅原子百分比为50%时,NO3--N和总氮去除率均为78.8%,此时溶液中Fe离子浓度仅为41 mg·L-1。多孔Fe-Si合金作为阴极还原硝酸根离子时,具有较高的硝酸根去除率和良好的稳定性,应用前景较好。     

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.     

Correlations among atmospheric elements,airborne particulate matter,benzene extracts,benzo(a)pyrene,NO, NO2 and so2 concentrations in Japan

Concentration levels of elements, airborne particulate matter, benzene extracts, benzo(a)pyrene B(a)P, NO, NO₂ and SO₂ in five residential areas were seasonally determined from May 1979 to January 1980. These air pollutants exhibited higher concentration in autumn and winter than in spring and summer. These were correlations among Pb, Cu, Ni, V and Se, among Si, Fe, Al and Ti and among NO, NO₂, B(a)P, benzene extracts and airborne particulate matter. NO, NO₂, B(a)P, benzene extracts and airborne particulate matter were correlated with Pb, Cu, Ni, V and Se, but not appreciably with Si, Fe, Al and Ti. On the basis of correlations between various air pollutants, the emitting source of the air pollutants and the health hazard by combined air pollution were discussed.