嗜酸硫氧化细菌作用下元素硫化学形态的研究进展

嗜酸硫氧化细菌是生物冶金过程中研究最为广泛的细菌,广泛分布在含硫和硫化物丰富的环境中。嗜酸硫氧化细菌作用下,单质硫及其它还原型硫化物（包括金属硫化矿）经过一系列形态转换使得硫在其细胞体内、体外和环境沉积物中存在着不同形态分布。单质硫经细菌细胞活化后在细胞体内以硫球形式积累;还原型硫化物可被细菌氧化至硫酸盐,其氧化中间态多为单质硫或连多硫酸盐等。有关嗜酸硫氧化细菌作用下硫的形态研究十分缺乏,进一步开展嗜酸硫氧化细菌作用下元素硫化学形态的研究可以为这类细菌的硫氧化机制及对硫化矿的浸出机理的阐明提供理论依据。     

含铜金矿的压力氧化浸出及其机理

含铜金矿在氧气分压为o.45 MPa、温度约为110℃条件下于高压釜中氧化一定时间,浸出铜后,渣氰化浸金,获得的铜、金浸出率分别为90.3%和96.55%.通过分析X射线衍射谱及CuFeS2-H2SO4-NaCl-H2O体系在25℃下的ψ-pH图,确定了载金矿物的氧化机理,分析了浸出体系的酸度、温度及氯化钠浓度对含铜金矿预氧化及浸出过程的影响规律.结果表明:硫化矿的氧化溶解首先是磁黄铁矿,其次是铜的次生硫化矿,再次是黄铜矿,最后是黄铁矿;载金黄铜矿的氧化首先是铁从黄铜矿的晶格中氧化溶解出来,生成中间产物CuS2和CuS;较高的酸度和氯化钠浓度有利于单质硫的生成、三价铁的水解和铜的浸出,进而有利于金浸出率的提高.     

硫铜钴矿生物浸出过程中细菌的作用及其溶解反应途径

研究硫铜钴矿生物浸出过程中细菌的作用及其溶解反应途径。结果表明,间接作用机制和接触作用机制均对硫铜钴矿生物浸出过程产生影响。当细菌吸附到矿物表面时,矿物溶解速率显著加快,说明浸出过程中接触作用机制对硫铜钴矿的溶解有重要影响。浸出过程中硫元素氧化价态的变化顺序为S?2→S0→S+4→S+6,并有单质硫沉淀在矿物表面,说明硫铜钴矿生物浸出过程按照多硫化物途径进行。硫铜钴矿表面被细菌严重腐蚀,出现许多大小不一的腐蚀坑洞,并有单质硫、硫酸盐及亚硫酸盐生成。这些氧化产物在矿物表面形成一层钝化层。     

原电池效应对混合硫化矿细菌浸出的影响

研究了黄铜矿与黄铁矿混合矿细菌浸出过程的原电池效应，提出了原电池效应模型。研究结果表明：当黄铜矿细菌浸出过程中加入黄铁矿及C时，浸出率大大提高，黄铜矿浸出30d，Cu浸出率可达40％；单一黄铁矿细菌浸出时，黄铁矿会被大量氧化分解，而当与黄铜矿混合浸出时，黄铜矿氧化加快，黄铁矿氧化速率降低；加入C及黄铁矿与黄铜矿混合时，由于接触电位的影响，黄铜矿氧化反应电流增大、反应起始电位负移，反应加尉，而黄铁矿的氧化反应受到抑制；混合矿浸出过程中，黄铜矿表面Cu含量较单一矿浸出时低得多，说明混合效应对浸出具有强化作用；黄铜矿中Cu浸出愈多，表面生成的元素硫愈多，黄铁矿细菌浸出时，表面不会有元素硫产生。     

硫铜钴矿生物浸出过程中细菌的作用及其溶解反应途径（英文）

研究硫铜钴矿生物浸出过程中细菌的作用及其溶解反应途径。结果表明,间接作用机制和接触作用机制均对硫铜钴矿生物浸出过程产生影响。当细菌吸附到矿物表面时,矿物溶解速率显著加快,说明浸出过程中接触作用机制对硫铜钴矿的溶解有重要影响。浸出过程中硫元素氧化价态的变化顺序为S-2→S0→S+4→S+6,并有单质硫沉淀在矿物表面,说明硫铜钴矿生物浸出过程按照多硫化物途径进行。硫铜钴矿表面被细菌严重腐蚀,出现许多大小不一的腐蚀坑洞,并有单质硫、硫酸盐及亚硫酸盐生成。这些氧化产物在矿物表面形成一层钝化层。     

Acidianus manzaensis浸出黄铁矿过程中铁L边和硫K边XANES光谱学分析（英文）

基于同步辐射技术对Acidianus manzaensis(A.manzaensis)浸出黄铁矿过程中铁L边XANES和硫K边XANES进行光谱学分析。浸出实验表明,A.manzaensis能加速黄铁矿的氧化。随着浸出时间的增加,浸出液的pH值逐渐降低;氧化还原电位值在第0~3天快速增加,然后缓慢增加。SEM结果表明,黄铁矿表面被A.manzaensis逐渐腐蚀;XRD结果表明,浸出残渣包含新组分黄钾铁矾和单质硫。铁L边XANES光谱学分析表明,黄铁矿生物氧化过程中铁形态逐渐转变为含Fe(Ⅲ)物质。硫K边XANES光谱学分析表明,在黄铁矿生物浸出过程中产生元素硫且其质量比维持在3.2%~5.9%。硫代硫酸盐在第2~4天也被检测出来,这表明黄铁矿生物浸出过程中存在硫代硫酸盐。     

黄铜矿表面生物氧化膜的形成过程

在细菌浸出黄铜矿的过程中,浸出速率缓慢的原因是矿物表面会形成一层阻碍矿物与浸出液之间物质交换的钝化膜,这层膜的组成会随着浸出的进行而变化.利用SEM,EDS,XRD和XPS等对细菌浸出黄铜矿的过程中,矿物表面的形貌、组成及物相变化进行了研究.结果表明,黄铜矿在细菌浸出过程中依次形成了缺铁铜硫化物Cu_1-xFe_1-yS_z（x0.氧化铁,羟基氧化铁和黄钾铁矾.由于浸矿混合细菌ASH-07对硫的氧化作用.硫化物层和单质硫层都是氧化膜形成过程中的中间产物,致密的黄钾铁矾层则对黄铜矿的浸出产生钝化作用.     

卡林型金矿的HClO4-FeCl3浸出及正交试验研究

采用HClO4预氧化、FeCl3进一步氧化络合方法联合浸出品位低、成分杂的卡林型金矿中的金。机理分析认为，在浸出前期加入HClO4将金属硫化物中的硫以高价态硫酸根离子、硫酸氢根离子等形式进入溶液而脱除，减少单质硫形成钝化膜包裹从而阻碍金属硫化物的解离，同时保证体系中一定初始浓度的[Fe³⁺]、[Cl^-]，有利于后续FeCl3浸金。正交试验研究表明，选定的4个因素对金浸出率的影响顺序为HClO4体积分数＞FeCl3浓度＞浸出温度＞HClO4预氧化时间，得到的较优浸出条件为HClO4体积分数6%、预氧化时间1 h、FeCl3浓度1.8 mol/L、40℃浸出5 h，在该条件下卡林型金矿金的浸出率为71.02%。     

元素硫对黄铜矿生物浸出行为及群落结构的影响(英文)

研究3种典型铁/硫代谢菌—Acidithiobacillus ferrooxidans,Leptospirillum ferriphilum及Acidithiobacillus thiooxidans混合浸出黄铜矿过程中铁/硫氧化活性、群落结构(PCR-RFLP)的变化,以及不同浓度的元素硫对其影响。结果发现,加入3.193g/L元素硫能促进细菌的表观硫氧化活性,改变浸矿体系的群落结构,并进一步影响钝化层的形成、金属离子的溶出,其浸出率(71%)较未添加硫的(67%)有一定程度的提高。而过量的元素硫会抑制铜的浸出(浸出率44%)。     

古菌生物浸出黄铜矿过程中的表观硫氧化活性表征

对4株纯的极端嗜热古菌及它们的混合菌在生物浸出黄铜矿过程中的硫氧化活性进行对比研究。结果表明,混合菌比纯菌拥有更高的硫氧化活性,它大幅度促进黄铜矿浸出率的提高。表征嗜热古菌硫氧化活性的参数值通常受很多因素的影响,以致在不同的硫氧化菌和不同的条件下生物浸出黄铜矿时,这些参数很难准确地反映出相应的硫氧化活性。因此,期待找到一种能有效表征浸矿菌硫氧化活性的方法。     

Gold leaching with elemental sulfur in alkaline solutions under oxygen pressure

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Mechanism of electro-generating leaching of chalcopyrite-MnO_2 in presence of Acidithiobacillus thiooxidans

A dual cell system with chalcopyrite anode and MnO_2 cathode was used to study the relations between time and such data as the electric quantity and the dissolution rates of the two minerals in the electro-generating leaching(EGL)and the bio-electro-generating leaching(BEGL),respectively.The results showed that the dissolution rates for Cu~(2+)and Fe~(2+)in BEGL were almost 2 times faster than those in EGL,and nearly 3 times for Mn~(2+);the electric output increased nearly by 3 times.The oxidation residu...     

Effect of initial pH on chalcopyrite oxidation dissolution in the presence of extreme thermophile Acidianus manzaensis

The influence of initial pH on the chalcopyrite oxidation dissolution at 65 °C was investigated by bioleaching and cyclic voltammetry experiments, and the oxidation products were investigated by XRD and Raman spectroscopy. Bioleaching results show that chalcopyrite dissolution rate increases with the decrease of the initial pH in chemical leaching, while the influence of initial pH on bioleaching is on the contrary. The presence of Acidianus manzaensis does not promote chalcopyrite dissolution under initial pH 1.0, which mainly results from serious inhibition of high acidity to the growth of Acidianus manzaensis. Electrochemical experiments results show that anodic oxidation currents of electrolyte with or without Acidianus manzaensis both increase with the increase of initial pH, and covellite and sulfur are detected on the electrode surface. The results confirm that chalcopyrite dissolution in chemical leaching is under the combined action of oxidation and non-oxidation of proton, with conversion of chalcopyrite to covellite and elemental sulfur.     

Selective removal of As from arsenic-bearing dust rich in Pb and Sb

The selective removal of arsenic from arsenic-bearing dust containing Pb and Sb in alkaline solution was studied. The influence of NaOH concentration, temperature, leaching time, liquid to solid ratio, and the presence of elemental sulfur on the dissolution of As, Sb and Pb in NaOH solution was investigated. The results indicate that the presence of elemental sulfur can effectively prevent leaching of lead and antimony from arsenic. The Sb₂O₃, As₂O₃ and Pb₅(AsO₄)₃OH in the raw material convert to NaSb(OH)₆ and PbS in the leaching residue, while arsenic is leached out as As(III) or As(V) ions in the leaching solution. Arsenic leaching efficiency of 99.84% can be achieved under the optimized conditions, while 97.82% of Sb and 99.97% of Pb remain in the leach residue with the arsenic concentration of less than 0.1%. A novel route is presented for the selective removal of arsenic and potential recycle of lead and antimony from the arsenic-bearing dust leached by NaOH solutions with the addition of elemental sulfur.     

Single and cooperative bioleaching of sphalerite by two kinds of bacteria —— Acidithiobacillus ferriooxidans and Acidithiobacillus thiooxidans

A cooperative bioleaching （Acidithiobacillus ferriooxidans and Acidithiobacillus thiooxidans） and single bioleaching （Acidithiobacillus ferriooxidans or Acidithiobacillus thiooxidans） of sphalerite were investigated by X-ray diffractometry, energy dispersive spectrography and scanning electron microscopy. The experimental results show that the leaching rate of zinc in the mixed culture is higher than that in pure culture and the sterile control. In these processes, two kinds of bacteria perform different functions and play a cooperative role during leaching of sphalerite. The bioleaching action carded out by Acidithiobacillus ferriooxidans （.4. ferriooxidans） is not directly performed through Fe^2＋ but Fe^3＋, and its role is to oxidize Fe^2＋ to Fe ^3＋ and maintain a high redox potential. Moreover, the addition of an appropriate concentration of ferric iron to the leaching systems is beneficial to zinc dissolution. In the leaching systems without Acidithiobacillus thiooxidans （.A. thiooxidans）, elemental sulfur layers are formed on mineral surface during the dissolution of zinc and block continuous leaching. Acidithiobacillus thiooxidans, however, eliminate the passivation and cause the bioleaching process to continue in the leaching systems. At the same time, protons from the bacterial oxidization of the elemental sulfur layers also accelerate the leaching of zinc.     

Mechanism of electro-generating leaching of chalcopyrite-MnO2 in presence of Acidithiobacillus thiooxidans

A dual cell system with chalcopyrite anode and MnO2 cathode was used to study the relations between time and such data as the electric quantity and the dissolution rates of the two minerals in the electro-generating leaching（EGL） and the bio-electro-generating leaching（BEGL）, respectively. The results showed that the dissolution rates for Cu^2＋ and Fe^2＋ in BEGL were almost 2 times faster than those in EGL, and nearly 3 times for Mn^2＋; the electric output increased nearly by 3 times. The oxidation residue of chalcopyrite was represented by TEM and XRD, whose pattern was similar to that of the raw ore in EGL. The mechanism for leaching of CuFeS2-MnO2 in the presence of Acidithiobacillus thiooxidans was proposed as a successive reaction of two independent sub-processes for the anode. The first stage, common to both processes, is dissolution of chalcopyrite to produce Cu^2＋, Fe^2＋ and sulfur. The second stage is subsequent oxidization of sulfur only in BEGL, which is the controlling step of the process. However, the dissolution of MnO2 lasts until the reaction of chalcopyrite stops or the ores exhaust in two types of leaching.     

Relatedness between catalytic effect of activated carbon and passivation phenomenon during chalcopyrite bioleaching by mixed thermophilic Archaea culture at 65 °C

The relatedness between catalytic effect of activated carbon and passivation phenomenon during chalcopyrite bioleaching by mixed thermophilic Archaea culture (Acidianus brierleyi, Metallosphaera sedula, Acidianus manzaensis and Sulfolobus metallicus) at 65 °C was studied. Leaching experiments showed that the addition of activated carbon could significantly promote the dissolution of chalcopyrite for both bioleaching and chemical leaching. The results of synchrotron-based X-ray diffraction, iron L-edge and sulfur K-edge X-ray absorption near edge structure spectroscopy indicated that activated carbon could change the transition path of electrons through galvanic interactions to form more readily dissolved secondary mineral chalcocite at a low redox potential (<400 mV) and then enhanced the copper dissolution. Jarosite accumulated immediately in the initial stage of bioleaching with activated carbon but copper dissolution was not hindered. However, much jarosite precipitated on the surface of chalcopyrite in the late stage of bioleaching, which might account for the decrease of copper dissolution rate. More elemental sulfur (S⁰) was also detected with additional activated carbon but the mixed thermophilic Archaea culture had a great sulfur oxidation activity, thus S⁰ was eliminated and seemed to have no significant influence on the dissolution of chalcopyrite.     

线切割加工硬质合金模具的WC浸出机理及抑制研究

快走丝线切割工作液组成包括水、基础油、表面活性剂、爆炸剂、防锈剂、缓蚀剂、极压剂、防腐剂等,而碳酸钠是一种常用的防锈剂。本文采用实验研究与理论分析相结合的方法,通过硬质合金的浸泡实验与实际切割实验,借助扫描电子显微镜(SEM)、X射线能谱仪(EDX)等设备,研究了碳酸钠对硬质合金中WC浸出的影响。研究结果表明:在硬质合金的线切割加工过程中,由于高温的作用,硬质合金表面的WC会由于氧化作用而生成三氧化钨,加入碳酸钠后,溶液为碱性环境,易生成钨酸根离子,三氧化钨的氧化溶解程度加剧。三氧化钨脱落之后,内层的WC继续氧化溶解促使了W的浸出,从而降低了硬质合金的硬度、耐磨性和使用寿命。在工作液中添加硼砂、油酸三乙醇胺和苯并三氮唑能够有效抑制WC的氧化溶解,减少W的浸出。     

铜阳极泥处理过程中中和渣中碲的提取与制备

采用硫酸浸出二氧化硫还原方法从中和渣中制取单质碲。研究表明:采用硫酸浸出中和渣,当反应温度为30℃、反应时间为0.5 h、硫酸浓度为53.9 g/L、硫酸用量为理论用量的1.5倍时,碲浸出率为99.99%;采用亚硫酸钠还原酸浸液中碲时,碲(Ⅳ)发生水解生成二氧化碲;采用二氧化硫还原酸浸液中碲时,当反应温度为75℃、反应时间为2 h、盐酸浓度为3.2 mol/L、二氧化硫流量为0.4 L/min时,碲回收率达到99.84%。X射线衍射(XRD)分析表明二氧化硫还原得到的产物为单质碲,电感耦合等离子体发射光谱(ICP)分析表明,碲粉中碲含量为98.27%。扫描电子显微系统(SEM)分析表明,碲粉的形态为针形。     

Bioleaching of marmatite flotation concentrate by Acidithiobacillus ferrooxidans and Leptospirillum f errooxidans

Bioleaching of marmatite flotation concentrate by Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans was investigated at 35℃, the initial pH value of 2.0 on an orbital shaker with 160 min^-1 over a period of 10 days. Experimental results indicate that the adapted strains increase markedly the dissolution rate and the leac-hing ratio of marmatite. Pulp density also affects the bioleaching of marmatite. Massive elemental sulfur and jarosite form during the leaching process in the systems inoculating the adapted strains in pure and mixed cultures;and acid product is enhanced, which decreases the pH below to 2.0 in latter leaching period. Marmatite preferentially dis-solves during the bacterial leaching of complex sulfides. Compared with the pure cultures of original and adapted strains, the adapted strains of Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans in mixed cultures are more efficient in the oxidation of marmatite.