Heavy metal removal from aqueous solution using carbonaceous K2S-impregnated adsorbent

A novel carbonaceous adsorbent for heavy metal removal was prepared from raw coal by one-step simple sulfur impregnation using K2S. Raw coal was mixed with K2S powder and then heated at 800°C for 30 min in nitrogen to produce K2S char. The sulfur content and form in K2S char were determined, and the ability of K2S char to adsorb Zn2+, Cd2+ and Pb2+ was examined. The K2S impregnation was e ective at impregnating sulfur into coal, especially in the form of elemental, thiophenic and sulfatic sulfur. The sulfur content of K2S char was higher than those of raw coal and pyrolysis char. The Zn2+ removal in 2.4 mmol/L of Zn2+ solution by K2S char was higher than raw coal with the removal rate of 100%. K2S char adsorbed Pb2+ and Cd2+ in 24 mmol/L of Pb2+ and Cd2+ solution with the removal rate of 97% and 35%, respectively. The elution extents of adsorbed Pb2+ and Cd2+ were zero in distilled water and 27% in 0.1 mol/L HCl solution. These results indicated that an e ective adsorbent for heavy metal ions was prepared from coal using K2S sulfur impregnation, and that the adsorbed metals were strongly retained in K2S char.     

Chemodynamics of heavy metals in long-term contaminated soils：Metal speciation in soil solution

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations (Cd2+, Cu2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%–52%) and Zn2+ (11%–72%) in soil solutions were generally higher than those of Cu2+ (0.2%–30%) and Pb2+ (0.6%–10%). Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients (Kp) and dissolved organic carbon did not show any significant influence on Kp.     

重金属在松花江沉积物中的竞争吸附行为及pH的影响

研究了复合污染的重金属体系(多元体系)中松花江沉积物吸附Hg2+,Cu2+,Pb2+,Zn2+和Cd2+的热力学和动力学特征,以及pH对重金属吸附量的影响. 结果表明:Langmuir吸附等温线可以很好地描述多元体系中沉积物吸附重金属的热力学过程,沉积物吸附5种重金属离子能力的顺序为Hg2+>Cu2+>Pb2+>>Zn2+> Cd2+. 在相同的条件下,与单一体系相比,多元体系中Pb2+,Zn2+和Cd2+吸附量减小的程度远远大于Hg2+和Cu2+,Pb2+,Zn2+和Cd2+的吸附量分别减少了31.9%,32.1%和68.1%. 一级动力学方程和Langmuir动力学方程可以较好地描述沉积物吸附Hg2+,Cu2+,Pb2+,Zn2+和Cd2+的动力学过程. 沉积物对5种重金属的吸附速率为Cd2+>Zn2+>Pb2+>Cu2+>Hg2+. 沉积物对Cu2+,Pb2+,Zn2+和Cd2+的吸附能力随pH的降低而减小,pH的降低造成锰氧化物的溶解,可能在一定程度上影响沉积物对重金属的吸附能力.      

电炉钢渣对水中Cu2+、Cd2+和Pb2+的去除作用

以宝钢电炉钢渣为研究对象,考察了钢渣对溶液中重金属离子Cu2+、Cd2+、Pb2+的吸附动力学、吸附等温线、吸附热力学特征,借助多种分析手段(XRD、BET比表面分析、SEM/EDS等)对钢渣进行了理化性能测试和表征.结果表明,电炉钢渣对重金属离子的吸附速率较快,吸附速率顺序为Cd2+>Pb2+>Cu2+,吸附过程符合一级动力学模型(R2>0.99).吸附等温实验结果表明,Langmuir模型较为适合重金属离子在钢渣上的吸附,实验条件下对Cu2+、Cd2+、Pb2+离子的最大吸附容量分别为0.101、0.058、0.120 mmol.g-1.3种重金属离子在钢渣上的吸附是一个吸热(ΔH0<0)、熵值增大(ΔS0>0)的自发反应过程(ΔG0<0),熵效应是吸附反应自发进行的主要驱动力.SEM/EDS分析结果揭示了吸附前后钢渣表面形貌和化学成分的变化.电炉钢渣以其低价、高效性在重金属废水处理中具有广阔的应用前景.     

电解法回收胶团强化超滤(MEUF)浓缩液中的Cd2+

胶团强化超滤是基于表面活性剂的双亲分子结构特性去除水中金属离子的新方法.重金属离子废水经胶团强化超滤处理后的浓缩液中含有高浓度的重金属离子,需进一步处理.采用电解法回收胶团强化超滤浓缩液中的Cd2+,考察了电极种类、电压、电解时间、pH、SDS与Cd2+浓度比等5个条件对电解效率的影响.研究发现,表面活性剂对电解有一定的阻化作用.实验得到最佳条件为:不锈钢(阳极)-石墨(阴极),U为2.8 V,电解时间为100 min,pH为4,[SDS]/[Cd2+]=5([SDS]=8.5 mmol/L恒定).在此条件下,浓缩液中的Cd2+的回收率达到了50.26%.     

灰分对高硫煤热解部分气化硫变迁的影响

采用分步脱除矿物质方法,对义马原煤及HCl,HCl-HF,HCl-HNO₃处理后煤样,分别在固定床反应器中考察了热解部分气化下硫的脱除规律.结果表明:一方面在热解过程中原煤及酸处理煤样H₂S和COS的析出均呈双峰趋势,其析出值主要受温度、原煤中灰分和HNO₃氧化作用;另一方面,在部分气化和酸处理后煤样热解半焦在600℃～900℃范围内硫脱除率可达50%～80%,800℃时,无机硫可完全脱除.而原煤热解半焦总硫,无机硫的脱除率在700℃时最大.气化温度的升高,加强了碱性矿物质的固硫作用,其结果是900℃气化时,总硫和无机硫脱除率降低.酸处理后有机硫含量基本保持不变,其噻吩结构只随碳骨架的气化而析出.     

固定化活性污泥吸附重金属离子的试验研究

讨论了固定化活性污泥对重金属离子的吸附。在实验条件下 ,温度对固定化活性吸附金属的影响并不显著 ,而体系pH值和底物浓度的影响较为重要 ,固定化活性污泥对Cu2 + 的吸附符合Langmuir模型。研究了固定化细胞填充柱对各种金属离子的吸附特性和选择性 ,固定化活性污泥对Cu2 + 离子的吸附性能明显高于Cd2 + 和Zn2 + 。     

一株苯并[a]芘高效降解真菌的筛选与降解特性

从长期受多环芳烃(PAHs)污染的土壤中分离出一株能够降解苯并[a]芘(B[a]P)的真菌,经鉴定为绿色木霉(Trichoderma viride)(命名为BF-1),并对其以B[a]P为唯一碳源进行反复驯化,考察了B[a]P浓度、不同重金属和培养基对其降解能力的影响.结果表明,菌株BF-1在B[a]P浓度为5mg.L-1,32℃振荡培养约6d的条件下,降解速度最快,B[a]P的降解率达68.28%.BF-1在B[a]P浓度分别为10与25mg.L-1,32℃振荡培养6d的条件下,B[a]P的降解率分别为73.29%与87.36%.Cu2+(50mg.L-1)基本不影响BF-1对B[a]P的降解率;Cd2+(100mg.L-1)、Pb2+(300mg.L-1)对BF-1降解B[a]P有一定影响,但仍表现出较高的耐受能力;而Zn2+(200mg.L-1)对BF-1有明显的抑制作用.选用含5mg.L-1B[a]P的土豆葡萄糖液体培养基,6d后B[a]P的降解率为71.31%.对比前述实验结果表明,培养基对B[a]P降解率的影响并不明显.因此,BF-1的应用价值较高.     

垃圾渗滤液水溶性有机物对土壤吸附重金属Cd2+、Pb2+的影响

采用序批次吸附试验,研究了不同填埋年限(0、4～5、12a)垃圾渗滤液中的DOM对土壤吸持重金属Cd2 、Pb2 的影响.结果表明,垃圾渗滤液中的DOM能促进土壤对重金属Cd2 、Pb2 的吸附.在有垃圾渗滤液DOM存在的条件下,Cd2 、Pb2 的吸附等温线可用Freundlich方程拟合(R2＞0.94),土壤对Cd2 、Pb2 的吸附量比对照处理(无垃圾渗滤液DOM)分别高1.13～1.42倍和1.09～1.84倍,填埋年限长的垃圾渗滤液较之填埋年限短的渗滤液对土壤吸附Cd2 、Pb2 的影响强烈.在Cd2 、Pb2 初始浓度相同时,潮土较红壤具有更高的吸持能力,并且随体系pH的增高,其吸持量增加.     

锌对磷酸铵镁和磷酸钙结晶回收磷的影响

以模拟废水为对象,研究了pH及Zn2+浓度对磷酸铵镁(MAP)和羟基磷灰石(HAP)法除磷率的影响,并对不同Zn:P摩尔比条件下除磷所得产物进行了XRD物相分析。结果表明,锌磷共存条件下进行MAP和HAP法除磷,当pH在7.4～8.0时,Zn2+浓度越大,除磷率越高,随着pH继续增加,Zn2+浓度越大,除磷率反而越小。当pH为9.5时,Zn2+浓度从0增加到25mg/L时,MAP法的除磷率从91%下降到82%;而HAP法的除磷率从95%下降到92%,受Zn2+浓度影响较MAP法小。锌磷共存条件下的除磷产物中均含有Zn(3PO4)2,随着溶液中Zn:P增加,产物中Zn(3PO4)2含量越来越多,且HAP法除磷产物纯度受Zn2+浓度影响较MAP法大。     

Coordination geometry of Zn~(2+) on hexagonal turbostratic birnessites with different Mn average oxidation states and its stability under acid dissolution

Hexagonal turbostratic birnessite,with the characteristics of high contents of vacancies,varying amounts of structural and adsorbed Mn~(3+),and small particle size,undergoes strong adsorption reactions with trace metal(TM)contaminants.While the interactions of TM,i.e.,Zn~(2+),with birnessite are well understood,the effect of birnessite structural characteristics on the coordination and stability of Zn~(2+)on the mineral surfaces under proton attack is as yet unclear.In the present study,the effects of a series of synthesized hexagonal turbostratic birnessites with different Mn average oxide states(AOSs)on the coordination geometry of adsorbed Zn~(2+)and its stability under acidic conditions were investigated.With decreasing Mn AOS,birnessite exhibits smaller particle sizes and thus larger specific surface area,higher amounts of layer Mn~(3+)and thus longer distances for the first Mn\O and Mn\Mn shells,but a low quantity of available vacancies and thus low adsorption capacity for Zn~(2+).Zn K-edge EXAFS spectroscopy demonstrates that birnessite with low Mn AOS has smaller adsorption capacity but more tetrahedral Zn(~(IV)Zn)complexes on vacancies than octahedral(~(VI)Zn)complexes,and Zn~(2+)is more unstable under acidic conditions than that adsorbed on birnessite with high Mn AOS.High Zn~(2+)loading favors the formation of~(VI)Zn complexes over~(IV)Zn complexes,and the release of Zn~(2+)is faster than at low loading.These results will deepen our understanding of the interaction mechanisms of various TMs with natural birnessites,and the stability and thus the potential toxicity of heavy metal pollutants sequestered by engineered nano-sized metal oxide materials.     

Effects of Cd2+ and Pb2+ on the substrate biofilms in the integrated vertical-flow constructed wetland

The effects of single Cd~(2+)and Pb~(2+),and combined Cd~(2+)and Pb~(2+)on dehydrogenase activity and polysaccharide content of the substrate biofilms in the integrated vertical-flow constructed wetland(IVCW)were studied.Dehydrogenase activities decreased linearly with the increasing concentrations of Cd~(2+)and Pb~(2+)at different times(6,24,72,and 120 h).The activities at both 6 and 24 h were significantly higher than that at 72 and 120 h in the case of single and combined treatments.The single Cd~(2+)...     

V2O5-WO3/TiO2系SCR催化剂的钾中毒及再生方法

以钾为代表的碱金属元素会引发严重的SCR催化剂中毒现象.通过浸渍法和干混法使催化剂钾中毒,比较不同K₂O负载量下催化剂脱硝活性的变化.结果表明,采用浸渍法使K₂O的负载量达到1%时,催化剂的最大脱硝效率由100%下降到30%左右;而干混法负载1% K₂O的催化剂样品的脱硝活性变化较小.对浸渍法负载1% K₂O的催化剂样品的再生试验表明,水洗可以使中毒后催化剂的脱硝活性由30%升至70%以上;而使用1%的H₂SO₄溶液酸洗,则可以使350～500 ℃催化剂的脱硝活性高于中毒前.通过扫描电镜和抗压强度的对比分析发现,中毒与再生前后催化剂的微观形貌和机械性能均未发生很大改变.      

Using a novel adsorbent macrocyclic compound cucurbit[8]uril for Pb~(2+) removal from aqueous solution

In this study, cucurbit[8]uril(CB[8]) was utilized as a kind of new adsorbent to remove Pb~(2+) ions from aqueous solution. With the solution p H increased from 2 to 6, the removal efficiency of adsorption increased from 55.6% to 74.5%correspondingly. The uptake of Pb~(2+) increased rapidly in the initial 30 min, and then the adsorption rate became slower. The Pseudo-second order model could be used to interpret the adsorption kinetics satisfactorily;and the rate determining step in Pb~(2+) adsorption onto CB[8] was the external mass transfer step. Equilibrium isotherm study reveals that the Langmuir model gave a better fitting result than Freundlich model. The maximum adsorption capacity calculated by the Langmuir model was 152.67 mg/g for 298 K, 149.70 mg/g for 313 K and 136.42 mg/g for 323 K, respectively.The adsorption is a spontaneous process of exothermic nature. The effect of the adsorbent dosage and the influences of solution p H and co-existing cations were also investigated.The CB[8] was synthesized and characterized by ~(1)H NMR, IR, ESI-MS spectra, SEM-EDAX,Zeta-potential and BET-analysis. The adsorption mechanism was due to the coordination between CB[8] molecule and Pb~(2+) ions.     

离子交换树脂吸附Cd(Ⅱ)和Pb(Ⅱ)的研究

采用静态法和动态法对阳离子交换树脂吸附Cd(Ⅱ)、Pb(Ⅱ)的行为进行了研究。考察了pH值、流速、吸附时间等条件对吸附效果的影响,优化了树脂洗脱再生的最佳条件。实验结果表明,732型强酸阳离子交换树脂能够有效地吸附废水中的Cd(Ⅱ)和Pb(Ⅱ)。对比两种交换方式,动态法具有操作简单、效率高、可连续运行等特点,具有较高的实用价值。     

烟曲霉胞外聚合物对Pb2+的吸附特性

采用阳离子交换树脂(CER)法提取了烟曲霉胞外聚合物（EPS）,并分析了其生物化学成分.同时,考察了烟曲霉EPS对重金属离子Pb2+的去除效果,探讨了其生物吸附机理和动力学特性.结果表明,CER法提取的烟曲霉EPS多糖含量较高,对细胞破坏程度较小.烟曲霉EPS吸附Pb2+的平衡时间约为3h,最佳吸附pH为6.5,吸附平衡时 Pb2+去除率为73.48%.烟曲霉EPS对Pb2+的吸附平衡均能较好地用Langmuir模型和Freundlich模型来描述,而且更适用Langmuir模型,最大吸附量qm为32.22mg·g -1.烟曲霉EPS的FTIR分析结果表明,多聚糖中的羟基、羧基和C—O—C等是与Pb2+发生了作用的基团,而其中蛋白质的作用不明显.     

高硫煤热解部分气化过程中硫的变迁行为

针对3种不同煤阶的高硫煤,分别在固定床反应器中考察其固定升温速率下原煤热解和半焦在不同温度下的水蒸气部分气化过程中的硫变迁行为.研究过程分为热解和部分气化2个子过程.结果表明,热解过程中大同、义马和西山煤总脱硫率分别为41%、42.5%和23.1%,其过程中FeS₂完全转化为FeS,不稳定的有机硫部分析出,硫从固相中的脱除大于碳的转化,硫在气相中得到富集;在部分气化过程中,对于大同和西山煤,半焦中硫含量可有效降低,脱硫率分别提高26.47%和19.37%,其中无机硫化物(FeS)易于气化析出,其析出程度随温度升高而增大.但对义马煤焦部分气化结果证实:在700℃气化时,总脱硫率可提高24.60%,在高于700℃气化时,有利于碱土金属与H₂S反应进行,同时由于碳骨架的气化速度加快,降低了其有机质对灰分固硫行为的传质阻力,所以灰分中碱土金属的固硫作用增强,使得半焦中硫含量增加,脱硫率与碳转化率的差值下降,不利于硫的脱除.     

Cu~(2+)和Zn~(2+)对日本新糠虾生长、蛋白含量和体内磷酸酶活性的影响

观察了不同浓度(10、20、40和80 μg/L)重金属离子Cu~(2+)和Zn~(2+)对日本新糠虾存活、蜕皮、蛋白含量和体内磷酸酶(碱性磷酸酶和酸性磷酸酶)活性的慢性(30 d)影响.结果显示:(1)Cu~(2+)和Zn~(2+)能明显降低糠虾存活率,金属离子浓度增高,存活率降低,其中Cu~(2+)引起的存活率降低更为明显,在最高浓度(80 μg/ L)Cu~(2+)组中糠虾的存活率仅为同浓度Zn~(2+)组的1/3,两组均明显低于对照组(P<0.05);Cu~(2+)和Zn~(2+)能明显降低糠虾蜕皮次数,最高浓度(80 μg/ L)Cu~(2+)和Zn~(2+)中糠虾的蜕皮数分别为11.00±1.73(次)和11.33±0.58(次),分别约为对照组的55.92%和57.6%.(2)Cu~(2+)和Zn~(2+)均能明显影响糠虾蛋白含量,其中Cu~(2+)的影响力更强,最高浓度(80 μg/ L)Cu~(2+)组糠虾体内蛋白白含量占湿重比为9.78%,仅约为对照组的1/2.(3)Cu~(2+)和Zn~(2+)能明显抑制糠虾体内两种磷酸酶的活力,碱性磷酸酶和酸性磷酸酶活力能作为糠虾监测环境重金属污染(Cu~(2+)和Zn~(2+))的检测指标.     

白腐菌处理铅污染废弃稻草的动态变化研究

通过研究铅污染废弃稻草基质,探讨了不同w(Pb2+)条件下白腐菌对半纤维素、纤维素和木质素的降解性能以及发酵基质总重、腐殖酸碳的变化规律,并在降解半纤维素、纤维素和木质素的同时,研究了白腐菌对发酵基质中重金属的钝化作用.结果表明:在w(Pb2+)为200 mg/kg条件下,白腐菌对半纤维素、纤维素和木质素等较难降解的有机物表现出最好的降解性能,且对Pb2+的钝化作用很明显,对半纤维素、纤维素和木质素的降解率分别为52.36%,32.29%和44.16%;发酵基质总失重率最高达29.89%;w(腐殖酸碳)达142.01 mg/g.      

锰离子催化臭氧液相烟气脱硫实验研究

对Mn2+催化臭氧(O3)液相氧化脱除二氧化硫(SO2)进行了实验研究,以揭示Mn2+对臭氧液相氧化SO2的影响.采用标准碘量法测定了O3浓度曲线.实验比较了添加Mn2+前后吸收液对SO2的脱除效率,并研究了O3与SO2摩尔比([O3]/[SO2])、Mn2+浓度对SO2脱除效率的影响.在[O3]/[SO2]=0.5、未添加Mn2+时O3对SO2的氧化效率为35%,而添加Mn2+后的氧化效率达到70%.随着[O3]/[SO2]的增大,SO2脱除效率逐渐增加,而且脱除效率也随Mn2+浓度的增加而增加,合适的Mn2+浓度范围为1.2×10-2~1.2×10-1mol/L.