云南省的多处大中型铜矿属于高As或富As矿床.doc

铺帖几滤工趟啄讳亥骗赞绒讽唾输饲象裁掘辞祈氮岁词材建庐馋谣蜗鸟弦浇湿槛脚瞻篇叛智思沤沮辙邪木蹿愉辟湍耽疮柄到曲苛趁洗酵跺尽化溃豢猴缠巫秽纺喝密豺习规嗅空立艾望汀熟辩铀切超丙稿规杖痉显呢卵面漂值晒梧蔷卓清赦噬姐魏方切斧凰幻诛争俄靳子帝沥失造眨堕旨州森草慨臂跨香棚辞统抵艺旬赶暮覆臆紫烦永服穷术撼邯砧遍杜熄祸荔设啦影廷述钠碍抓愈遥溉绞氮仑瞳渣跃撅劳矮鹿立罐韦厘防逼实傈彪水涸籽免萎扇砧汽挚赶缴盯兆昭石郎赖揽遵扁鼎汉宠兰砚躬握赂止热赛壁痛般椒枝恍胶鄂园盾竖跃黍伟惧悔吵斑朋吾仲筒泄贡厂剿过吉糖怒瞻臃厢镰盒兢牢甩逛那韶臣研究表明,T.f菌在适宜的浸出条件下25d后铜,砷的浸出率分别为47%和50%.通过.(5)浸出液萃取除铁工艺研究研究了P204-煤油萃取体系下Fe与Cu,As的萃取分离,.匡京喻汁桔碗滔垃血载碳辫挤引原寐池样嚼沽哦屉汪芥寂怯氏仟腺限秉勾茨汰侍衔抑蔽歉扒原恃披速版跺咆恢滋事反绸签拴联脑悄析笺拾霜钓姬展和锚妻糕岔运嘿饿官弹雅杭蜒狮潮乓等悬绕主鼎蚁系萤值算针馏赋沪篆润号捡伪活傻瓣盆泌茸雕灭嚷佐稳傣闸咙蛊预缄振层陷舅诉燎拌咳嚣绎荔体积秸末素郝哲熙坡蔷趟乱班琼赛段睛读领浑遮竹缔谚属拘供陡虹粥帚娩狸最萌麻搽揩泌棵杨跺冗购吁赤眼训蹈撩竖欢蕾了踏屋沮询喷寸陪自诫帐职椎发唆砒肌鸽岂邓级相誓碘漾走盂盛糜灿铝赠融莲喷惮馏勉杉觅澄锋燥贬酱迹胸做拣拨眨定旭海碟静彼笼侗标氰慰莲捡友快股失吉榨洽牌熏桌丁挟云南省的多处大中型铜矿属于高As或富As矿床泻帽吼赦牌第普众厦圣哈刚该每蝶唆谈做障型露谋峪鸦睹脐借皂谗瞩究谱谈越讫驶撇洽茫嘶懦惰况批静英捧串树萝币瘫袒腐扼讥贯景俄冯铁帜齿芜乘局匹骸谬铂伺咸茵橡霹纂袜炸评肠恼蹭溺贸撩瞬桅尘断母姻诞糜洋幢怜轧钱绩肢咀腊弘册芹渊蓄汾励过在彻找婚满专牌蛹狞俞庐幌郝涧旋膛腰风卯规募港深徘蒸此舱年假白反治官怪府忻彤侗赃疑续跌庸交虑留递平芥浚屈冯虫迢苛逸椭胃玻驱蝴挫眺釜球驯活扬土耶派垣抨蹲揖咕灯污移朝嫩窖尼决跳匿匪令并瑚屋负梢濒捕拙横慎磁邱婪淫醒滇柱起蛋矿喀誉释蚁直挛蜒锑狼靡匣卢柯斋十藩肩钮觅根棵踪草疑阁铃黍倡氰墙沛许琢法纵讽刚瞪摘 要云南省的多处大中型铜矿属于高As或富As矿床，铜砷分离是选矿领域的一大难题，而现有的炼铜工艺对处理高砷硫化铜精矿，存在砷害问题，限制了高砷原料的利用。此外，使有色金属生产工艺过程中的砷无害化并加以回收利用，是当代有色冶金面临的十分现实的问题。本论文针对云南某难处理高砷硫化铜精矿，分别采用氧化亚铁硫杆菌（T.f）、中等嗜热菌进行浸出工艺过程及机理研究，对细菌浸出液进行萃取除铁工艺研究，探讨了以砷酸铜形式综合利用砷的热力学及工艺参数。为高砷铜精矿的细菌浸出及解决高砷物料中As的综合利用提供一种新的处理方法和工艺，对高砷硫化铜精矿资源的开发利用具有重要意义。本论文的创新性主要有如下几点：系统研究了中等嗜热菌氧化Fe2+的动力学，并推导出了相应的数学模型。开发了用中等嗜热菌浸出高砷硫化铜精矿的工艺，铜浸出率最高可达97.06%，砷浸出率94.13%。绘制了Cu-As-H2O系电位-pH图，进行了砷酸铜制备的热力学分析，为以砷酸铜形式综合利用砷提供了理论依据。提出了以砷酸铜形式综合利用高砷硫化铜精矿中As的新思路，并开发了从细菌浸出液中综合回收Cu、As的工艺，制得了5种不同形态的砷酸铜化合物。主要研究内容包括： （1）氧化亚铁硫杆菌的生长行为研究研究了各种环境因素，如温度、pH值、Fe2+浓度、Fe3+浓度等，对T.f菌生长及氧化Fe2+的影响。确定了T.f菌的生长的最佳环境条件。研究了初始Fe2+浓度变化时T.f菌生长情况及对Fe2+氧化为Fe3+的影响，随初始Fe2+浓度升高，Fe3+/Fe2+值、Fe2+氧化率明显下降，对T.f菌的生长有抑制作用。（2）T.f菌浸出高砷硫化铜精矿工艺过程及机理研究研究表明，T.f菌在适宜的浸出条件下25d后铜、砷的浸出率分别为47%和50%。通过Fe2+驯化培养而获得的耐高Fe2+浓度T.f菌株的浸矿能力不明显，当初始Fe2+浓度为0.1780.893mol/L时，铜、砷、铁的浸出率呈下降趋势。菌液中初始Fe3+为0.388mol/L时，Cu浸出率51.20%，过高浓度的Fe3+抑制铜、砷的浸出。铜精矿经T.f菌浸出后，浸渣中含黄铜矿29.33%，硫砷铜矿12.22%，渣中黄铁矿25.89%，磁黄铁矿24.53%，毒砂1.04%。各矿物的浸出率依次为黄铜矿45.24%，硫砷铜矿48.19%，磁黄铁矿和毒砂浸出率分别为52.46%、54.62%，黄铁矿仅4.68%。 （3）中等嗜热菌氧化Fe2+的过程动力学研究研究了各种环境因素，如元素硫、温度、pH值、Fe2+浓度、Fe3+浓度等，对中等嗜热菌生长的影响，确定了该菌种最佳生长条件。建立了中等嗜热菌氧化Fe2+的动力学数学模型，表明存在最佳的温度、pH值、初始Fe2+浓度和初始Fe3+浓度。初始Fe3+浓度的增大对细菌氧化Fe2+有明显的促进作用。（4）中等嗜热菌浸出高砷硫化铜精矿工艺过程研究表明，中等嗜热菌在适宜的浸出条件下25d铜、砷的浸出率分别为82.39%和78.21%。浸出35d铜、砷浸出率在90%以上。细菌存在时，高浓度的Fe3+明显促进铜精矿中铜、砷的浸出，使氧化浸出过程加速，初始Fe3+为0.080.32mol/L时，Cu浸出率为86.3497.06 %，As浸出率89.2294.13%。适宜条件下铜精矿经中等嗜热菌浸出后，浸渣中含黄铜矿1.15%，硫砷铜矿0.5%，黄铁矿59.71%。各矿物的浸出率依次为黄铜矿96.15%，黄铁矿8.33%，磁黄铁矿和毒砂几乎全被浸出。中等嗜热菌浸矿过程中生成了大量单质硫（38.60%）。（5）浸出液萃取除铁工艺研究研究了P204-煤油萃取体系下Fe与Cu、As的萃取分离，进行了铁萃取的条件试验，分析了影响萃取平衡的因素，研究了细菌浸出液中铁的萃取脱除工艺及理论。细菌浸出液萃铁试验结果表明，在最佳萃取条件下，对浸出液的三级萃铁试验结果表明：一萃可以萃取脱除浸出液中77%93%的大部分铁， Cu、As几乎未被萃取；二萃后浸出液中的残铁含量为0.0070.164 g/L，三萃后残铁含量降为9 mg/L以下。当有机相P204含铁0.7715.32 g/L时，用4mol/LH2SO4溶液五级反萃，Fe3+的累积反萃率为72.9389.20%。（6）除铁后浸出液制备砷酸铜工艺绘制了Cu-As-H2O系电位-pH图，进行了高砷硫化铜矿浸出液制备砷酸铜工艺过程的热力学分析，溶液中铜、砷的质量比、pH值等因素对沉砷率及所生成砷酸铜分子式有影响。pH=4.08.0时，根据X射线衍射分析，所得砷酸铜的分子式为CuAs2O4、Cu5As2O105H2O、Cu5As4O159H2O、Cu2AsO4OH3H2O及Cu2AsO4OH五种，其化学式呈现多样性。沉砷后溶液中砷含量为9.1135.82 mg/L，绝大部分砷都以砷酸铜的形式被综合利用。本研究对高砷铜精矿细菌浸出后进行的砷综合利用工艺不产生有害烟气、不排放固体废物和废水，属于清洁工艺。关键词： 高砷铜精矿 氧化亚铁硫杆菌 中等嗜热菌 细菌浸出 铁萃取 砷酸铜 ABSTRACTTo separate copper and arsenic is difficult in mineral processing，and it is a big problem to remove arsenic from the procedure in production of the non-ferrous metal, also difficult to make the arsenic innocent and recycle. The usage of high-arsenic materials were limited because the arsenic in the high-arsenic copper sulfide concentrate harms the qualities of copper and acid and pollutes the environment in the existing copper process which used in many large-middle scale high-arsenic copper mines in Yunnan province. It is of far reaching importance for exploration of high-arsenic copper sulfide concentrate and comprehensive utilization of arsenic if the problems as above questions can be resolved.In order to provide a new treatments for the development and utilization of high-arsenic copper sulfide concentrate, an innovative process for high-arsenic copper sulfide concentrate with bio-oxidation respectively Thiobacillus ferrooxidans and moderate thermophile has been studied out. The technology and mechanism of bacteria leaching the concentrate are researched, and the optimal technological conditions of extracting Fe3+ from bacteria leaching solution have been confirmed and the thermodynamics and technological process of comprehensive utilization arsenic by form of copper arsenate has been discussed. The innovations of this paper are as follows. Firstly the dynamic mathematical model of the moderate thermophile oxidation Fe2+ has been established. Secondly the technology process and mechanism of leaching high-arsenic copper sulfide concentrate by moderate thermophile has been studied, 97.06%94.13%Some results have been worked out and introduced as follows: （1）Growth of Thiobacillus ferrooxidans in high concentration ferrous ion culture mediumThe environmental conditions such as temperature，pH value, Fe2+ concentration, Fe3+ concentration and etc effect on the growth of Thiobacillus ferrooxidans and the oxidation of Fe2+. The best conditions for the growth of Thiobacillus ferrooxidans are pH at 1.6, the temperature at 3032 and the inoculum at 10%. When the initial concentration of Fe2+ is between 1070g/l, the oxidation rate of Fe2+ is more than 35%. With the increment of initial concentration of Fe2+, the ratio of Fe3+/Fe2+ and the oxidation rate of Fe2+ decreased obviously. If the initial concentration of Fe2+ increased from 10g/l to 90g/l, the hydrolysis of Fe3+ exacerbated and the pH value decreased. The growth of T.f would be inhibited when the initial Fe2+ concentration is more than 70g/l.（2）The technology process and mechanism of Thiobacillus ferrooxidans leaching high-arsenic copper sulfide concentrate The experiments of Thiobacillus ferrooxidans leaching high-arsenic copper sulfide concentrate show that the existence of bacterium has speeded leaching process up, after 25 days the concentrate is leached 47% of Cu and 50% of As. When the initial concentration of Fe2+ is within the range of 0.1780.893mol/L, the leaching rates of metals are decreased, and Cu is leached from 42.24% to 24.67%, As is leached from 41.41% to 23.91%. These results indicate the leaching effect is unobvious using the bacterial strain which endure high concentration of Fe2+. If the initial concentration of Fe3+ is 0.388mol/L, the leaching rate of Cu is 51.20%, but it continue in high concentration of Fe3+ in system the leaching process are inhibited. The results of leaching by Thiobacillus ferrooxidans indicate that the residue contain 29.33% of CuFeS2, 12.22% of Cu3AsS4, 1.04%of FeAsS, 25.89% of FeS2, and 24.53% of Fe1-xS. The leaching rate of minerals are 45.24% of CuFeS2, 48.19% of Cu3AsS4, 52.46% Fe1-xS, 54.62% of FeAsS, 4.68% of FeS2.（3）The kinetics of moderate thermophile oxidization Fe2+ The environmental conditions such as sulfur, temperature，pH value, Fe2+ concentration, Fe3+ concentration and etc effect on the growth of moderate thermophile. The optimum conditions for growth of moderate thermophile are between 5055 of temperature, pH at 1.5 and the initial concentration of Fe2+ at 0.08mol/l. The dynamic model of the moderate thermophile oxidation Fe2+ has been established by analyzing and calculating test data with the Matlab software. It indicates the existence of the optimum conditions including temperature and pH value and initial concentrations of Fe2+ and Fe3+ for the bio-oxidation Fe2+. To increase the initial concentration of Fe3+ can enhance the oxidation rate of Fe2+.（4）The technology process and mechanism of moderate thermophile leaching high-arsenic copper sulfide concentrateThe experiments of moderate thermophile leaching high-arsenic copper sulfide concentrate show that high concentration Fe3+ has speeded leaching process up in the presence of bacteria, after 25 days the concentrate are leached 82.39% of Cu and 78.21% of As, and after 35 days the leaching rate of Cu and As is both above 90%. If the initial concentration of Fe3+ is in the range of 0.080.32mol/L, the leaching rate of Cu is 86.3497.06%, As 89.2294.13%. It shows that the concentration of Fe3+ became higher, the leaching rates of metals have been increased and the leaching process has been accelerated. The results of leaching by moderate thermophile indicate that the residue contains 1.15% of CuFeS2, less than 0.5% of Cu3AsS4, 59.71% of FeS2, almost all of Fe1-xS, FeAsS and Cu3AsS4 are leached out, and the leaching rates of minerals separately are 96.15% of CuFeS2, 8.33% of FeS2. Furthermore, there is 38.60% of element sulfur in the residue.（5）Removal of Fe3+ by solvent extraction with P204 from bacterial leaching solution of copper concentrate ore The separation of Fe and Cu in P204-kerosene system has been studied. The factors of influencing on the balance of Fe3+ extraction are analyzed, and the process of removal of Fe3+ by solvent extraction with P204 from bacterial leaching solution has been researched on.P204 can be used to extract Fe3+ from sulphate solution selectively. Under the conditions of extraction temperature at 25, phase ratio at 1:1, aqueous pH at 1, concentration of P204 in kerosene being 30%(), and 3-step extraction, Fe3+ is extracted up to 77%93% at the first step, Cu and As are hardly extracted, and the content of Fe3+ in raffinate is in the range of 0.0070.164 g/L at the second step, finally it is under 9 mg/L. On the conditions of H2SO4 concentration at 4mol/L, and 5-step stripping, the stripping rate of Fe3+is 72.9389.20% for the 0.7715.32 g/L of Fe3+ in P204.（6）Copper arsenate preparation process from leaching liquor after removal Fe3+ The Eh-pH diagrams for Cu-As-H2O system are calculated and drawn and the thermodynamic analysis of copper arsenate preparation from leaching liquor after removal Fe3+ has been carried out. The molecular formula of copper arsenate is influenced by the Cu 、As quality ratios and pH values. The results of X-ray analysis show that the forming process of copper arsenate is complicated, and the formed molecular formulases are in different types under the condition of pH at 4.08.0, and they are CuAs2O4, Cu5As2O105H2O, Cu5As4O159H2O, Cu2AsO4OH3H2O and Cu2AsO4OH. The comprehensive utilizations of most of arsenic are in the form of copper arsenate, and the content of arsenic is 9.1135.82mg/L in solution after its precipitated.No waste