Bioleaching of heavy metals from dewatered sludge by Acidithiobacillus ferrooxidans

The feasibility of bioleaching for removal of heavy metals from dewatered sewage sludge using an iron‐oxidizing bacterium Acidithiobacillus ferrooxidans was investigated. The influence of seven process parameters including cell adaptation, total amount and particle size of the sludge, initial concentrations of Fe²⁺ and At ferrooxidans, and addition of inorganic nutrients and sulfur were evaluated in terms of the solubilization of Zn, Cu and Cr. When sludge‐adapted cells, addition of inorganic nutrients and lower sludge content were involved, higher yields of metal extraction were obtained. However, higher initial concentrations of At ferrooxidans and Fe²⁺, fine particle size of the sludge and S addition did not improve the metals' solubilization during an experimental period of 7 days. As a result of a long‐term (40 days) bioleaching experiment, 42% of Zn (1300–1648 mg kg^?1), 39% of Cu (613–774 mg kg^?1) and 10% of Cr (37–44 mg kg^?1) in the sludge were leached into the solution. The results indicate that a bioleaching process conducted under operationally optimal conditions can be effectively employed for the removal of heavy metals from sewage sludge before land application. Copyright © 2005 Society of Chemical Industry     

Bioleaching of molybdenum from coal liquefaction catalyst residues

It has been shown that the bacterium Thiobacillus ferrooxidans can solubilize MoS₂ from coal liquefaction catalyst residues. The MoS₂ is formed during the liquefaction process from a molybdenum catalyst precursor. MoS₂ is insoluble; in order to be recovered and reused, it must be converted to a soluble form. T. ferrooxidans can oxidatively solubilize the molybdenum in MoS₂ to molybdate, in which form it can be recovered as a soluble or HCl extractable material. Bioleaching experiments show that with a starting cell concentration of 1.0 × 10⁷ cells ml⁻¹, or greater, a significant amount of the molybdenum in the residue was solubilized. These experiments indicate that the amount of molybdenum biologically solubilized from the liquefaction residues is dependent on inoculum size, with all strains of T. ferrooxidans tested having equal ability, and on the particle size of the residue. An important factor in the solubilization of MoS₂ by T. ferrooxidans is the inhibitory effect of molybdate. Literature reports that as little as 10 ppm molybdate is inhibitory to growth or ferrous iron oxidation. However, leachates containing in excess of 70 ppm molybdenum (equivalent to 116 ppm molybdate) were generated as a result of bioleaching of the liquefaction residue. When cells from previous leaching experiments were used to inoculate flasks containing fresh media and additional liquefaction residue, the bacteria were able to bioleach the fresh residue. Recent experiments have focused on the ability of T. ferrooxidans to produce protective agents in the leachate that minimize the inhibitory effects of molybdate. We found that production of the protective factor(s) did not depend on previous exposure of the cells to molybdenum or liquefaction residue.     

电解锰渣基沸石对锰离子的吸附性能研究

电解锰渣是电解锰行业露天堆存的大宗固体废弃物,在堆存过程中将产生毒性污染物锰离子。为有效利用电解锰渣的同时消除锰离子对环境的危害,以电解锰渣为原料采用微波碱熔活化法制备沸石,并用于吸附锰离子。考察了溶液初始锰离子质量浓度、溶液pH、吸附温度和吸附时间等因素对锰离子吸附效果的影响。结果表明:在溶液初始锰离子质量浓度为500 mg/L、溶液pH为6、吸附时间为2 h、吸附温度为50 ℃条件下,电解锰渣基沸石对锰离子具有较好的吸附能力,最大吸附量高达79.18 mg/g。探究了电解锰渣基沸石对锰离子的吸附行为。结果表明,锰离子在沸石表面的吸附符合准二级动力学模型,Langmuir等温吸附模型比Freundlich模型更适合于描述电解锰渣基沸石去除锰离子的等温吸附过程。电解锰渣基沸石循环使用性能良好,在重金属废水处理方面具有潜在的应用前景。     

硫酸锰为原料沉淀-氧化法制备四氧化三锰的研究

以硫酸锰、氨水为原料,空气和硝酸铵为氧化剂,通过沉淀-氧化路线制备四氧化三锰粉体。采用X射线衍射（XRD）、红外光谱（FT-IR）、扫描电镜（SEM）等手段对产物的物相、形貌特征、平均粒径进行表征。研究了硫酸锰在氨水中的水解沉淀过程以及氢氧化锰液相氧化为四氧化三锰的过程,主要研究了液相氧化过程中氧化温度、氧化时间以及随后的干燥过程对氧化的影响。实验结果表明,将硫酸锰溶液反加到氨水中的加料方式可以避免正加料方式（氨水加入到硫酸锰溶液中）形成碱式硫酸锰而造成产品中含硫量高的问题;在通空气液相氧化氢氧化锰过程中添加液相氧化剂硝酸铵可以提高氧化速率。当硝酸铵用量为3 g（硝酸铵与硫酸锰的质量比约为1∶7.5）、液相氧化温度为70 ℃、氧化时间为4 h、随后在空气中于120 ℃干燥4 h的条件下,制备的四氧化三锰产物物相纯,粒度细,硫含量低,达到电子级原料标准。     

利用电解锰渣制备As(Ⅲ)吸附材料及其性能研究

通过对工业废弃物电解锰渣(electrolytic manganese residues, EMRs)进行改性制备As(Ⅲ)吸附材料（改性EMRs），探究了NaOH用量、超声及微波对其表面结构及吸附性能的影响。结果表明：该工业废渣在固液比M(EMRs)∶V(NaOH, aq) = 1∶10(C _NaOH，aq = 2.0 mol·L^-1)条件下，经超声反应（200 W）2 h脱除大部分Si、S、Ca后，再微波（700 W）反应5 min以使Fe、Mn等活性吸附基团在其表面沉积，最后经105℃烘干制得改性EMRs。SEM结果表明，EMRs改性后表面形成片层纳米结构，对砷具有良好的吸附性能，可将初始As(Ⅲ)浓度为50 mg·L^-1废水出水中砷降至0.042 mg·L^-1，符合国家地表水环境质量标准Ⅰ类水质量要求(GB 3838—2002)；同时，经3% NaOH溶液再生处理后可继续使用。XPS结果表明，改性EMRs吸附砷性能与其表面Fe₃O₄、FeOOH、MnO₂等对As(Ⅲ)具有吸附作用或氧化作用的活性物种的增多密切相关。     

电解锰渣中锰组分的粉磨浸取工艺研究

为促进电解锰渣的资源化综合利用,减少锰资源的浪费,以电解锰渣为原料,深入研究粉磨浸取工艺条件对锰元素浸取效率的影响。采用XRD、SEM、XRF以及AAS等手段检测分析样品的物相、成分、锰含量等属性。结果表明：二次粉磨可显著提高锰渣粉体中细粉的含量以及细粉中锰的含量。锰渣粉体细度和表面积的增加,加快了锰渣中锰矿颗粒的浸取反应速度,提高了锰的浸取率。浸取时间和浸取温度均显著影响了锰的浸取率,其中温度的影响更为重要。适宜的浸取反应温度为70~85 ℃。当反应温度为85 ℃、反应时间为1 h时,锰的浸取率可达97.15%。     

氧化亚铁硫杆菌与中度嗜热铁氧化菌浸出铁闪锌矿的比较

考察了采用氧化亚铁硫杆菌和中度嗜热铁氧化菌浸出铁闪锌矿浮选精矿的浸出效果. 结果表明,两种细菌的驯化菌株都可以显著提高铁闪锌矿的溶解速率,且接种中度嗜热铁氧化菌时浸出效果更好. 扫描电镜、X射线粉晶衍射和能谱分析等表明,接种不同菌种浸出铁闪锌矿时所产浸渣具有类似的表面形貌特征和矿物组成. 可以证明,采用中度嗜热铁氧化菌浸出铁闪锌矿浮选精矿可以在较高的温度和酸度下进行且具有更好的浸出效果,比氧化亚铁硫杆菌具有更好的工业应用前景.     

电解金属锰中微量铅镉的极谱法连续测定

在氨基乙酸-氯化铵-盐酸羟胺底液中,Pb(Ⅱ)于-0.55 V(vs,SCE),Cd(Ⅱ)(vs,SCE)于-0.74 V产生一个灵敏的导数极谱波,铅的浓度在0.02~10μg/mL、镉的浓度在0.01~5μg/mL范围内与波高呈线性关系,大量的Mn2+使铅镉的波高下降,通过分离锰后可消除干扰。电解金属锰试样经硝酸分解后,利用高氯酸在加热至冒烟时的强氧化性,将锰离子氧化为MnO2予以分离后,可直接在上述条件下进行测定,铅标准回收率94.80%~102.20%,相对标准偏差0.43%~0.86%;镉标准回收率96.60%~101.80%,相对标准偏差2.37%~4.62%。     

Catalytic mechanism of manganese ions and visible light on chalcopyrite bioleaching in the presence of Acidithiobacillus ferrooxidans

The bioleaching of chalcopyrite is low cost and environmentally friendly,but the leaching rate is low.To explore the mechanism of chalcopyrite bioleaching and improve its leaching rate,the effect and mechanism of manganese ions(Mn²⁺) and visible light on chalcopyrite mediated by Acidithiobacillus ferrooxidans(A.ferrooxidans) were discussed.Bioleaching experiments showed that when both Mn²⁺ and visible light were present,the copper extraction was 14.38% higher than that of t...     

Enhanced Mn2+ solidification and NH4+-N removal from electrolytic manganese metal residue via surfactants

Electrolytic manganese metal residue (EMMR) harmless treatment has always lacked a low-cost and quick processing technology. In this study, surfactants, namely tetradecyl trimethylammonium chloride (TTC), sodium dodecyl benzene sulfonate (SDBS), sodium lignin sulfonate (SLS), and octadecyl trimethylammonium chloride (OTC), were used in the solidification of Mn²⁺ and removal of NH₄⁺-N from EMMR. The Mn²⁺ and NH₄⁺-N concentrations under different reaction conditions, Mn²⁺ solidification and NH₄⁺-N removal mechanisms, and leaching behavior were studied. The results revealed that the surfactants could enhance the Mn²⁺ solidification and NH₄⁺-N removal from EMMR, and the order of enhancement was as follows: TTC > SDBS > OTC > SLS. The NH₄⁺-N and Mn²⁺ concentrations were 12.3 and 0.05 mg·L^-1 with the use of 60.0 mg·kg^-1 TTC under optimum conditions (solid–liquid ratio of 1.5:1, EMMR to BRM mass ratio of 100:8, temperature of 20 ℃, and reaction duration of 12 h), which met the integrated wastewater discharge standard (GB8978-1996). Mn²⁺ was mainly solidified as Mn(OH)₂, MnOOH and MnSiO₃, and NH₄⁺-N in EMMR was mostly removed in the form of ammonia. The results of this study could provide a new idea for cost-effective EMMR harmless treatment.     

电解锰渣浆液烟气脱硫性能及机制

电解锰渣是电解锰生产过程中产生的锰矿石酸浸渣,富含锰、铁等活性组分,理论上可催化氧化SO₂实现烟气脱硫,同时脱硫后的电解锰渣可资源化利用,然而目前尚未见电解锰渣矿浆脱硫的研究报道。本文研究了工艺参数对电解锰渣浆液脱除SO₂性能的影响,探究了电解锰渣浆液烟气脱硫的过程机制。结果表明：锰渣粒径为200目（<75μm）、锰渣浆液初始浓度5000mg/L、气体流量400mL/min、进口SO₂体积分数0.20％、反应温度50℃、反应时间180min的条件下,电解锰渣浆液脱硫率最高可达93.87%。脱硫前后电解锰渣XRD、SEM、XPS表征结果表明,MnO₂、MnO、Fe₂O₃等活性组分参与SO₂反应,且浆液中的Mn²⁺、Fe³⁺等过渡金属离子液相催化氧化SO₂生成H₂SO₄,实现烟气脱硫。     

生物淋滤去除污泥中重金属铬的试验研究

比较研究了皮革废水处理厂的剩余污泥在生物淋滤除铬过程中,由于添加辅助基质的种类、浓度及反应温度不同,重金属铬溶出效果的差异。结果表明:与对照相比,添加单质硫或硫酸亚铁作辅助基质可明显提高重金属铬的溶出效果;添加七水硫酸亚铁比添加单质硫的效果更好;其它反应条件相同,中温(35℃)条件下重金属铬的溶出效果比常温(25℃)和高温(45℃)都要好。控制反应温度可明显提高铬的溶出效果。     

中贫品位软锰矿直接还原为硫酸锰工艺研究

将生产硫酸锰传统法中的炭还原－硫酸提取工序合二为一,使二氧化锰直接转化为稳定的硫酸锰,重金属盐及可溶性硅酸盐转化为水难溶氧化物,提高了锰的利用率,水浸取硫酸锰的一次性收率可达90％左右,硫酸锰的纯度达到98．5％以上。     

电解锰渣盐酸浸取钙的动力学研究

以电解锰加工过程中产生的酸性废渣为原料,以盐酸为浸取剂,对电解锰渣中的钙进行浸取实验研究。结果表明：盐酸浓度为3 mol/L、液固体积质量比为6 mL/g、反应温度为80 ℃、反应时间为60 min的条件下,钙的浸取率为94.2%。酸浸过程的动力学分析表明,锰渣中钙的酸浸反应过程符合收缩核模型,受化学反应控制,其反应的表观活化能Ea为43.96 kJ/mol,反应级数为0.872 5。     

惰性气氛下电解锰渣高温还原焙烧脱硫

电解锰渣的化学成分与水泥的组成符合,但高含硫量限制了其在水泥生产中的掺量。本研究采用高温还原焙烧法脱除电解锰渣中的硫,以焦炭为还原剂,在氮气气氛中以不同条件对电解锰渣进行热分解生成SO₂。用扫描电镜（SEM）和X射线衍射（XRD）分析固体产物,气体分析仪分析SO₂的释放,高温还原焙烧法脱除电解锰渣中的硫,探究焙烧温度和焦炭添加量对焙烧产物的物相和硫含量的影响。实验结果表明,生成SO₂的最佳条件为焦炭添加量4％、分解温度1000℃。在最佳条件下,SO₂的最大浓度为3513mg/m³,可用于生产硫酸。焙烧固体产物在温度为900℃、焦炭添加量为4%添加时,SO₃含量可以降低到2.17％。根据GB175—2007《通用硅酸盐水泥》中规定,满足水泥中SO₃含量须低于3.5%的要求,电解锰渣还原焙烧产品可以作为水泥原料,为电解锰渣的资源化综合利用提供理论依据和技术参考。     

电解锰渣改良基质对牧草生长及锰、镉淋溶迁移的影响

在盆栽条件下采用生物质炭、熟石灰、生物质炭与熟石灰混合改良剂对电解锰渣进行改良,在改良后的基质上种植黑麦草和白三叶两种牧草,研究不同改良剂改良的基质对牧草生长的影响以及镉、锰在植物和环境中的迁移情况。研究结果表明：3种改良剂改良的基质不同程度地降低了两种草种的出苗率,但是可显著增加牧草的株高和生物量,特别是生物质炭与熟石灰混合改良剂;3种改良剂改良的基质均能降低牧草中的锰、镉含量,其中生物质炭的改良效果最好;在3种改良剂改良的基质上种植牧草,均有效降低了锰和镉的淋溶迁移,其中生物质炭和熟石灰混合改良剂最能有效减少锰和镉的溶出。     

硫酸锰室温固相球磨制备四氧化三锰

利用软锰矿吸收硫酸镁热解尾气二氧化硫制得硫酸锰,再与碳酸氢铵室温下固相球磨反应,制备出前躯体碳酸锰,经热分解获得四氧化三锰。分别考察了物料比、球磨时间、球料比等因素对硫酸锰转化率的影响,采用XRD对产物进行了分析。结果表明,在n（碳酸氢铵）∶n（硫酸锰）=3.5∶1、球磨时间为40 min、球料质量比为5∶1时,硫酸锰的转化率可达99.8%,将固相产物在1 000 ℃热解1 h后所制备的四氧化三锰纯度为99.9%。该工艺操作简单,产品纯度高,成本低,为硫酸锰制备四氧化三锰提供了新的途径。