本文選題：黃鐵礦　切入點：輝銅礦　出處：《北京有色金屬研究總院》2017年博士論文　論文類型：學(xué)位論文

【摘要】：隨著礦產(chǎn)資源的不斷開發(fā),有價金屬品位不斷降低,共伴生程度日益復(fù)雜,浸出過程中有價有害元素同步溶解,后續(xù)溶液分離難度大,實現(xiàn)有價金屬選擇性浸出是濕法冶金未來發(fā)展的趨勢。紫金山銅礦是我國大型斑巖型次生硫化銅礦,銅品位低,黃鐵礦含量高,生物浸出中出現(xiàn)酸過剩、鐵累積現(xiàn)象,對環(huán)境影響大,并導(dǎo)致生產(chǎn)成本升高,是制約銅金屬高效回收的瓶頸技術(shù)難題。本論文以福建紫金山銅礦為研究對象,針對主要礦物黃鐵礦、輝銅礦和銅藍(lán),采用MLA礦物組成分析法、模擬計算和高通量測序法等現(xiàn)代研究手段,通過電子結(jié)構(gòu)特性、電化學(xué)、動力學(xué)、微生物學(xué)等研究探討了選擇性浸出機(jī)理,揭示不同硫化礦物溶解差異性,并確立合理的調(diào)控手段,為低品位硫化銅礦選擇性浸出提供了新的研究思路和理論指導(dǎo)。通過采用基于密度泛函理論的第一性原理方法,從分子和原子水平研究了黃鐵礦、輝銅礦和銅藍(lán)三種硫化物電子結(jié)構(gòu)及性質(zhì),在微觀本質(zhì)上揭示了三種硫化礦物溶解差異性。研究表明,從黃鐵礦、銅藍(lán)到輝銅礦,能帶寬度依次變窄,穩(wěn)定性逐漸減弱,溶解反應(yīng)難度依次降低,黃鐵礦的氧化性最強(qiáng),更易得到電子,而輝銅礦的還原性最強(qiáng),更易失去電子。三種硫化礦物晶體結(jié)構(gòu)不同,決定了溶解性存在較大差異,為實現(xiàn)選擇性浸出奠定了理論基礎(chǔ)�；诳s核模型,得到細(xì)菌接種濃度、Fe3+濃度、pH值、溫度等因素與硫化溶解速率之間的關(guān)聯(lián)指數(shù),建立了硫化礦溶解半經(jīng)驗動力學(xué)模型。升高溫度是促進(jìn)黃鐵礦、輝銅礦和銅藍(lán)溶解的關(guān)鍵因素,其中銅藍(lán)活化能(84.97kJ/mol)最高,對溫度最敏感,而細(xì)菌接種濃度、Fe3+濃度、pH值與溶解速率關(guān)聯(lián)指數(shù)較低,對浸出過程影響較小。氧化還原電位對輝銅礦和銅藍(lán)浸出影響較小,在低電位下,浸出速率也較快。而黃鐵礦的浸出與電位呈強(qiáng)相關(guān)性,當(dāng)電位低于760mV時,黃鐵礦浸出速率很慢,浸出20天,鐵浸出率不足20%。低溫、低電位下,黃鐵礦與輝銅礦和銅藍(lán)溶解差異性顯著。揭示了礦物種類、電位與優(yōu)勢菌群組成之間的關(guān)聯(lián)規(guī)律,建立以硫氧化菌為優(yōu)勢菌的浸出體系,是實現(xiàn)選擇性浸出的必要條件。不同類型硫化礦,對細(xì)菌組成有一定影響,黃鐵礦與輝銅礦和銅藍(lán)性質(zhì)存在差異,對細(xì)菌的影響不同。黃鐵礦浸出過程中優(yōu)勢菌主要以鐵氧化菌Leptospirillum為主,隨著浸出過程的進(jìn)行,Acidithiobacillus和Sulfobacillus菌數(shù)量和占比大幅降低。而銅藍(lán)和輝銅礦浸出過程中,優(yōu)勢菌主要為Acidithiobacillus和Sulfobacills,其中Sulfobacilus菌屬占比較高。當(dāng)氧化還原電位較高時,浸出體系優(yōu)勢菌主要以Leptospirillum為主,隨著氧化還原電位的降低,占比逐漸降低,當(dāng)電位低于700mV以下時,Leptospirillum菌占比基本降為零,而氧化還原電位對Acidithiobacillus菌的影響較小,不同電位下都可成為優(yōu)勢菌。低溫(≤45℃)、低電位(≤760mV)和硫氧化菌占絕對優(yōu)勢的浸出體系下,黃鐵礦與輝銅礦和銅藍(lán)硫化礦物溶解差異性最大,能確保實現(xiàn)輝銅礦和銅藍(lán)的高效浸出,并可有效抑制黃鐵礦的浸出。
[Abstract]:With the continuous development of mineral resources, valuable metal grade decreased and the associated degree is more complicated, the leaching process of valuable harmful elements simultaneously dissolved, subsequent solution separation is difficult to achieve selective leaching of valuable metals is the future development trend of hydrometallurgy. Zijinshan Copper Mine is a large porphyry type secondary copper sulfide, copper low grade, high pyrite content, acid excess bioleaching, the accumulation of iron, a large impact on the environment, and lead to increased production costs, is a bottleneck problem efficient recovery of copper metal. This paper takes Fujian Zijinshan Copper Mine as the research object, the main mineral pyrite, chalcocite and covellite, using MLA mineral composition analysis, simulation and research methods of modern high-throughput sequencing method, the electronic structure characteristics, electrochemical kinetics, microbiology research on selective leaching machine Daniel, reveal the different sulfide mineral dissolution differences, and establish reasonable regulation and control means, to provide new research ideas and theoretical guidance for the selective leaching of low grade copper sulfide. By using the first principle method based on density functional theory, from the molecular and atomic level of pyrite, chalcocite and covellite three sulfide electronic structure in the micro essence and nature, reveals three differences in dissolved sulfide minerals. The results show that from pyrite, covelline to chalcocite, band width are narrow, stability gradually weakened, difficult dissolution reaction reduces in turn, the strongest oxidizing pyrite, more electronic, and the reduction of the strongest chalcocite, more easily lose electrons. Three sulfide mineral crystal structure, determines the difference of solubility, provides a theoretical basis for the realization of selective leaching. The shrinking core model based on the obtained bacteria Inoculum concentration, Fe3+ concentration, pH value, temperature and other factors and the correlation index between sulfide dissolution rate, a semi empirical kinetic model of dissolved sulfide. Temperature is the key factor to promote the pyrite, chalcocite and covellite dissolved, the activation energy of ceruloplasmin (84.97kJ/mol) the highest, most sensitive to temperature, and the bacterial concentration. Fe3+ concentration, pH value and the dissolution rate of correlation index is low and has little effect on the leaching process. The redox potential has little effect on the leaching of chalcocite and covellite, at low potential, the leaching rate is higher. And the leaching and potential of pyrite showed strong correlation, when the potential is lower than 760mV, the leaching rate of pyrite leaching is very slow, 20 day, iron leaching rate of less than 20%. at low temperature, low potential, pyrite and chalcocite and covellite dissolution reveals significant differences. Mineral species, association rules and potential advantages of flora between the establishment of The leaching system of sulfur oxidizing bacteria were the dominant bacteria, is a necessary condition to achieve the selective leaching of sulfide minerals. Different types of bacteria, which have a certain influence, there are differences of pyrite and chalcocite and covellite properties, effects on bacterial leaching process. The advantages of different pyrite bacteria are mainly iron oxidizing bacteria Leptospirillum, with the leaching process Acidithiobacillus and Sulfobacillus, the number of bacteria and accounted for a substantial decrease. And the leaching process and chalcocite covellite, dominant bacteria were Acidithiobacillus and Sulfobacills, of which Sulfobacilus bacteria accounted for the higher. When the redox potential is higher, the leaching system of dominant bacteria is dominated by Leptospirillum, with the redox potential decreased and the proportion gradually decreased when the potential is less than 700mV, Leptospirillum bacteria accounted for basic zero, and the redox potential of Acidithiobacillus bacteria The effect under different potentials can become dominant. Low temperature (less than or equal to 45 DEG C), low potential (760mV) leaching system and sulfur oxidizing bacteria dominated by pyrite and sulfide chalcocite and covellite mineral dissolution of greatest difference, to ensure the efficient implementation of leaching of chalcocite and covellite, leaching and effectively the suppression of pyrite.

【學(xué)位授予單位】：北京有色金屬研究總院
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TF811

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