还原焙烧电镀污泥中的金属形态和浸出性

分别以煤粉和稻杆为还原剂对电镀污泥进行还原焙烧,并通过酸浸回收焙烧渣中的金属。研究了焙烧温度、焙烧时间和还原剂投加量对目标金属Cu浸出率的影响以及主要杂质金属的浸出性,并采用BCR逐级提取法分析了焙烧前后污泥中的金属形态分布。结果表明,当在电镀污泥中投加30％的煤粉在600℃下焙烧1h后Cu的浸出率达到97．78％,当投加50％的稻杆时浸出率为89．47％,而氧化焙烧后浸出率仅为37．71％;并且还原焙烧渣中多数杂质金属的浸出率较低,从而可以实现Cu与杂质金属的初步分离。氧化焙烧容易导致金属从易浸出的非残渣态向难浸出的残渣态转化,而还原焙烧则能抑制这种转化过程,金属形态是决定其浸出性的重要因素。     

电镀污泥的还原焙烧-酸浸

将电镀污泥作为一种重要的重金属资源加以回收利用,逐渐成为了国内外研究的重点。以电镀污泥为研究对象,在不同的温度及不同的焙烧时间下进行直接焙烧和还原焙烧,并对焙烧底渣进行酸浸,分别研究了污泥减量率以及Cu、Ni、Zn和Cr 4种重金属的含量和浸出率,并探索了还原剂(煤粉)和催化剂(CaCO3)投加量的影响。实验结果表明,原始电镀污泥中,Cu含量最高,达到10.05%,因此,电镀污泥中Cu具有回收价值;焙烧后电镀污泥得到了减量化,同时污泥中的金属得到了富集;还原焙烧比直接焙烧更有利于Cu的选择性浸出,当煤粉投加量为10%,CaCO3投加量为0.5%,在700℃下焙烧20 min时,Cu的浸出率达到98.73%,Cu的含量达到15.07%。     

还原焙烧-酸浸回收电镀污泥中的铜

采用还原焙烧—酸浸工艺处理电镀污泥,可以实现对铜的选择性回收.研究了不同焙烧条件下,电镀污泥的失重率和金属含量,并探索了焙烧温度、焙烧时间、煤粉用量、CaCO3投加量对金属浸出率的影响.结果表明,还原焙烧有利于污泥减量和金属富集;并且经还原焙烧污泥中金属的浸出效果明显优于直接焙烧;在电镀污泥中添加10％(质量分数)的煤...     

电镀污泥钠钙化焙烧过程金属的矿相转化及平衡分布

电镀污泥钠化焙烧过程,由于Al、Cr和Zn的氧化物易与Fe2O3反应生成铁酸盐及其他复杂含铁盐类,导致灰渣水浸过程浸其出率较低。在添加剂CaO作用下,采用FactSage软件模拟污泥焙烧过程金属的矿相转化规律,找到提高Cr、Al和Zn浸出率的方法。研究结果表明,污泥钠化焙烧过程,添加剂CaO易与Fe2O3反应生成2CaO·Fe2O3,阻止Fe2O3与Cr、Al和Zn的氧化物反应生成铁酸盐及其他复杂盐类,一定程度上提高了Cr、Al和Zn的浸出率。但高温下,Al2O3也易与Cr、Al和Zn的氧化物反应生成难溶性铝酸盐,所以浸出率提高幅度不大。可采用稀碱先脱除污泥中的铝,铝的浸出率达95%以上,脱铝渣再拌苏打和CaO焙烧,灰渣水浸脱铬率达95%以上。通过分析可知,污泥在焙烧之前脱铝和在焙烧过程铁转化成2CaO·Fe2O3,阻止了难溶性铝酸盐、铁酸盐以及其他复杂盐类的生成,同时Cr和Al得到分离,且灰渣中铜、镍和锌以游离氧化物和极少部分结合氧化物形式存在,有利于后续金属的浸出和分离。     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

电镀污泥中无定型铝的选择性浸出

针对电镀污泥加碱、石灰焙烧灰渣水浸过程铝浸出率较低的问题,在分析电镀废水处理工艺的基础上,根据污泥中铝、铬、锌、铜等金属的存在相态以及焚烧过程所发生的化学反应,拟采用低浓度氢氧化钠溶液先选择性浸出污泥中的铝。研究了稀氢氧化钠溶液浸出铝的工艺条件,结果表明,电镀污泥用2 mol·L-1氢氧化钠在90 ℃浸出60 min,铝的浸出率可达95%以上,而铬、锌和铜等金属则大部分进入浸出渣,基本上达到铝与其他金属的初步分离的目的。研究结果为混合电镀污泥中铝的回收以及铝及其他金属的选择性分步分离工艺流程的选择提供理论与技术支持。     

基于响应曲面法的钠化焙烧-水浸法回收废加氢催化剂中有价金属工艺优化

为提高废加氢催化剂钠化焙烧-水浸分离工艺回收有价金属的效率,采用响应面法优化了废加氢催化剂钠化焙烧-水浸工艺条件,探讨了焙烧温度、焙烧时间、碳酸钠添加量、浸出温度和液固比对Mo、Al浸出率的影响,并确定了最优工艺条件;同时,采用热重-差示扫描量热法 (TG-DSC) 和X射线衍射法 (XRD) 分析了废催化剂预处理与钠化焙烧过程的物相变化。结果表明：适宜的预处理温度为400~500 ℃。随着预处理温度的升高,钼与铝结合生成Al₂(MoO₄)₃;Al₂(MoO₄)₃可参与钠化反应。在钠化焙烧温度为950 ℃、焙烧时间为2 h、碳酸钠与废加氢催化剂质量比为1.1∶1、浸出液固比为6：1、浸出温度为70 ℃的条件下,Mo的浸出率可达98%以上、Al的浸出率可达94%以上。当碳酸钠添加量较少时,未参与钠化反应的Mo和Al会结合生成Al₂(MoO₄)₃,从而造成Mo、Al浸出率降低。Mo、Al发生钠化反应的温度在700~1000 ℃之间;当焙烧温度为700 ℃时,钠化反应未大量发生;随着反应温度的提高,钠化反应大量发生,至950 ℃时钠化反应最充分。本研究结果可为废加氢催化剂钠化焙烧-水浸分离回收有价金属提供参考。     

钢铁厂冷轧废水污泥中铬回收实验研究

钢铁厂冷轧废水污泥中含有10%以上的铬、20%以上的铁和1.5%以上的锌(均以质量分数计).为了从污泥中回收铬,首先研究了污泥中铬的形态,确定为Cr(Ⅲ);然后以碳酸钠为氧化助剂,将污泥与碳酸钠按一定比例混合后焙烧,再用水浸取.研究了碳酸钠的添加量、焙烧温度和时间、浸取时间和浸取方式对铬回收率的影响.研究表明,每克干污泥中添加0.6 g或以上碳酸钠,在固定床上700 ℃焙烧4 h以上,可实现60%以上的总铬浸出率,残渣为Fe2O3基脱硫剂原料.     

嗜酸硫杆菌和黑曲霉对电镀污泥重金属浸出效果

电镀污泥重金属浸出对电镀污泥资源化利用具有重要意义。为了降低处置成本,采用嗜酸硫杆菌与黑曲霉对电镀污泥重金属浸出效果进行了研究。结果表明,采用嗜酸性氧化硫硫杆菌和氧化亚铁硫杆菌混合菌种对含固率为3%的电镀污泥进行为期15 d（培养驯化后）的处理后,污泥中Ni、Cr与Cu的浸出率虽分别高达92.8%、85.0%和96.8%,但耗时久,无法大规模地实际应用。利用黑曲霉对电镀污泥进行为期6 d的处理,Ni、Cr和Cu的浸出率分别达到92.0%、74.4%和55.3%。若采用黑曲霉培养15 d后产生的生物有机酸和同pH的柠檬酸处理电镀污泥4 h后,两者对Ni、Cr和Cu的浸出率分别为：85.0%与94.2%、63.8%与73.7%、57.9%与99.6%。可见,利用黑曲霉发酵菌液浸出电镀污泥中重金属有一定的实际应用价值。     

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。     

Heavy metals removal from anaerobically digested sludge by chemical and microbiological methods

The metal removal from anaerobically digested sludge was studied by chemical treatment and microbial leaching processes in laboratory reactors. The removal of metals increased with decreased sludge solid concentration and pH. In the acid treatment process, a pH of 1.5 was required to reduce the copper concentration in the sludge to an acceptable level. In the microbial processes mixed culture gave 10% better solubilisation of metals than in single culture. The acid requirement was lower for the microbial process. The cost of sludge treatment in terms of chemicals was found to be decreased by 80% in microbial leaching.     

Fractionation and leachability of Fe,Zn, Cu and Ni in the sludge from a sulphate-reducing bioreactor treating metal-bearing wastewater

This work presents and discusses experimental results on the characterisation and metal leaching potential of a biogenic, metal-rich sulphidic sludge, generated in a sulphate-reducing bioreactor, operated to treat acidic synthetic solutions bearing Fe, Zn, Ni and Cu. The sustainability of the metal removal bioprocess strongly depends on the fate of the sludge. To propose appropriate management practices, a detailed characterisation of the sludge is necessary. The granulometry, chemical composition and mineralogy of the sludge were initially determined. The mobility of the metals was assessed via a modified Tessier experimental procedure. The leachability of the sludge metal content was determined via a standard compliance method (EN 12457-2) and experiments designed to evaluate the effect of pH and time on metal leaching from the sludge. The sludge metal content sums up to 69.5% dw, namely iron (14.8%), zinc (18.7%), nickel (17.7%) and copper (18.2%) and, based on the criteria set by European Union, the sludge is characterised as hazardous and inappropriate for landfilling without any pretreatment. The sludge consists mainly of very fine poorly crystalline aggregates of Fe, Zn, Cu and Ni sulphides. The fine grain size, the poorly crystalline structure and the oxidation of sulphide upon exposure to water/air render the high metal content of the sludge recoverable.     

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。     

Effect of solids concentration on bacterial leaching of heavy metals from sewage sludge

Microbial metal leaching from sewage sludge (2-9% w/v) was carried out with the iron-oxidizing bacterium Thiobacillus ferrooxidans. Measurements of pH, oxidation-reduction potential, and concentration of Fe2+ indicated that T. ferrooxidans was effective in removing metals from an incubation bath containing less than 5% sludge solids concentration. Specifically, Cu leaching was completely suppressed at a high solids concentration of 9% (w/v). Results indicated that the deactivation of T. ferrooxidans at a high sludge content was mainly due to the presence of inhibiting materials such as organic matter. A mixed culture of sulfur-oxidizing bacteria was obtained by enrichment from anaerobically digested sewage sludge to enhance the efficiency of the microbial leaching process. These bacteria were much more effective in metal leaching than was iron-oxidizing T. ferrooxidans. At 9% (w/v) solids concentration, the leaching efficiencies of Zn and Cu were 78% (2.66 g/kg dry sludge) and 59% (1.36 g/kg dry sludge), respectively. Therefore, when removing heavy metals from the anaerobically digested sewage sludge, the indigenous sulfur-oxidizing bacteria isolated in the current study were more efficient than T. ferrooxidans, especially at high sludge solids concentrations.     

Stabilization of heavy metals in municipal sewage sludge by freeze–thaw treatment with a blend of diatomite,FeSO4, and Ca(OH)2

In this work, the effects of diatomite with 15% FeSO₄?7H₂O and 7.5% Ca(OH)₂ on sludge stabilization were investigated using batch leaching tests. The influence of cell rupture caused by freezing and thawing on stabilization was also evaluated. The results indicated that the optimal diatomite percentage was 2%. Cell rupture by freezing and thawing reduced heavy metal leachability, followed by cell death and decrease of organic groups. The concentration of heavy metals in sludge leachate increased after cell rupture, indicating that the heavy metal leachability was reduced after freezing and thawings. Moreover, the stabilization effects were generally improved after freezing and thawing. As compared with the stabilization of the original sludge, the unstable fractions decreased and the residual fractions of the heavy metals increased in the stabilized sludge after cell rupture.

Implications: This study developed a method to stabilize heavy metals in municipal sewage sludge. Diatomite combined with FeSO₄·7H₂O and Ca(OH)₂ improved the treatment of sewage sludge contaminated by heavy metals. Cell lysis by freeze–thaw treatment reduced the risk of leaching heavy metals caused by cell death and decreased major organic groups in the sludge.     

含重金属水处理污泥的固化和浸出毒性研究

工业危险固体废物在进行安全填埋前需要进行固化稳定处理。针对电镀厂和皮革厂含重金属的水处理污泥 ,用不同比例的水泥、粉煤灰进行固化稳定处理。考虑酸雨环境 ,浸出实验采用TCLP标准。电镀厂污泥单独固化时 ,其浸出液中铜离子浓度由 78 0mg/L下降到 1 5mg/L ;镍离子浓度由 2 2 4 5mg/L下降到 2 2 2mg/L ,高于危险废物允许进入填埋区 15mg/L的控制限值。电镀厂污泥与皮革厂污泥混合后固化 ,浸出液毒性明显降低。铜离子的浸出浓度降低到1 98mg/L ,镍离子降低到 4 10mg/L ,总铬降低到 0 4 0mg/L ,各项指标均低于国家危险废物允许进入填埋区的控制限值 ,可安全填埋。     

矿区炼金废渣的固化/稳定化处理

通过对金矿矿区炼金废渣的酸中和能力、净产酸量及浸出毒性实验,测定了废渣的产酸潜力及重金属砷、镉、铅、锌的总量和它们的浸出量。为了合理处置矿区炼金废渣,并为矿区重金属污染土壤的修复提供技术支持,采用石灰、粉煤灰、堆肥化污泥作为添加剂对废渣进行固化/稳定化处理;通过浸出毒性实验对固化/稳定化处理效果进行综合分析,试图寻求一种最佳的稳定剂。结果表明,无论是单独添加石灰、粉煤灰或者堆肥化污泥还是两两组合混合添加,样品浸出液的pH都有升高,As、Cd的浸出浓度都有明显下降,而且两两组合添加比单独添加的固化/稳定化处理效果更好。在两两组合添加中,粉煤灰混合堆肥化污泥的处理效果最好,浸出液的pH值达到7.82,As、Cd的浸出率分别下降72.0%和72.2%。说明粉煤灰混合堆肥化污泥处理炼金废渣效果最佳,同时具有以废治污的资源化生态效能。