本文選題：高品位氧化鋅礦 + 氨溶蝕浸出��； 參考：《昆明理工大學(xué)》2015年碩士論文

【摘要】：本論文主要是針對(duì)復(fù)雜氨浸體系下高品位氧化鋅礦的浸出行為及其機(jī)理進(jìn)行初步研究。依托導(dǎo)師承擔(dān)的國(guó)家自然科學(xué)基金項(xiàng)目,前期已經(jīng)完成對(duì)低品位難處理氧化鋅礦的氨溶蝕浸出-浸渣浮選試驗(yàn)及相關(guān)機(jī)理研究,取得了相關(guān)成果。但在前期的研究過(guò)程中,時(shí)常會(huì)遇到含一定量硫化鋅礦的中高品位氧化鋅礦,為了探索該類礦的氨浸行為及其機(jī)理,同時(shí)也是作為對(duì)前期研究的有益補(bǔ)充,以較為全面的了解各品位段氧化鋅礦的氨浸行為及機(jī)理。本論文主要研究對(duì)象是含鋅40.61%、氧化率為78.72%的蘭坪氧化鋅礦,單從品位而言,該類礦可選擇的加工處理方法是比較多的,但從機(jī)理的探索而言,本論文具有一定的理論價(jià)值,可在一定程度上豐富氧化鋅礦氨溶蝕浸出的理論。在對(duì)高品位氧化鋅礦進(jìn)行氨溶蝕浸出試驗(yàn)的基礎(chǔ)上,對(duì)不同氨浸體系的浸出效果進(jìn)行了研究。首先分別進(jìn)行了低總氨濃度浸出和高總氨濃度浸出的試驗(yàn),選擇了其中浸出效果相對(duì)較好的三種不同的氨溶蝕浸出體系,即單一氨水浸出體系、氨水-氟化銨浸出體系和氨水-硫酸銨浸出體系。研究結(jié)果表明三種浸出體系的氨溶蝕浸出指標(biāo)的走勢(shì)規(guī)律大體一致,但浸出效果卻差異較大,與之前所述及的低品位氧化鋅礦的氨溶蝕浸出規(guī)律不盡相同。浸出效果最好的是單一氨水浸出體系,其對(duì)原礦鋅浸出率為39.42%,對(duì)可浸出相的鋅浸出率為73.47%；氨水-氟化銨浸出體系效果次之,高總氨濃度時(shí)與單一氨浸體系效果接近,對(duì)原礦鋅浸出率為39.33%,對(duì)可浸出相的鋅浸出率為73.29%；氨水-硫酸銨效果最差,對(duì)原礦鋅浸出率為30.88%,對(duì)可浸出相的鋅浸出率為57.55%。此外,通過(guò)對(duì)浸出體系的液固比、氨銨比、攪拌速度、浸出時(shí)間、浸出溫度、磨礦細(xì)度等因素的研究,得出對(duì)浸出效果影響最為顯著的是液固比和浸出溫度。通過(guò)采用XRD、SEM-EDS、XPS等分析測(cè)試手段,對(duì)不同浸出體系的浸出機(jī)理進(jìn)行了探討。XRD分析結(jié)果表明原礦及浸渣中的硅鋅礦和鋅鐵尖晶石均以無(wú)穩(wěn)定的晶體結(jié)構(gòu)的形式存在。在原礦的浸出過(guò)程中,硅酸鋅可與浸出劑反應(yīng)生成無(wú)定形二氧化硅,這種物質(zhì)在浸出體系中的存在形式十分復(fù)雜,對(duì)鋅的浸出效果有著顯著的影響。當(dāng)浸出體系為弱堿性時(shí),無(wú)定形二氧化硅以不溶物形式存在,當(dāng)浸出體系為強(qiáng)堿性時(shí),無(wú)定形二氧化硅以多核的穩(wěn)定物形式存在于浸出液中。由于原礦中鋅金屬含量高,推測(cè)無(wú)定形二氧化硅被溶解后浸渣表面電荷可能失衡,從而使已被溶出的硅重新變?yōu)闊o(wú)定形二氧化硅附著于礦粒表面并繼續(xù)與銨根離子及羥基反應(yīng)而被溶解,形成循環(huán),阻礙礦石中鋅的浸出。同時(shí)發(fā)現(xiàn)對(duì)單一氨水浸出體系,浸渣表面氨浸溶蝕痕跡明顯,出現(xiàn)定向排列的裂痕,呈現(xiàn)出光滑平整的晶面,推斷浸出是沿著某些晶面進(jìn)行；XPS分析結(jié)果表明原礦及浸渣表面的硅元素及碳元素的原子密度變化有一定規(guī)律性,鐵元素及硫元素的變化規(guī)律不明確,各元素的分峰擬合圖譜也顯示硅元素及鋅元素在進(jìn)出前后其結(jié)合能變化不大。研究得出無(wú)定形二氧化硅是浸出過(guò)程中的重要影響因素。溶液中總硅濃度([Si]T)濃度會(huì)隨著總氨濃度的增加而增加,且除H4SiO4的濃度不變之外,其余形態(tài)離子的濃度都將隨之增加,存在優(yōu)勢(shì)比較明顯的硅化合物離子可能是Si3O5(OH)53-、H3SiO4-、Si2O3(OH)42-。最后,論文對(duì)硅鋅礦及菱鋅礦在氨溶蝕浸出過(guò)程中的配位情況進(jìn)行了研究。菱鋅礦與硅鋅礦經(jīng)浸出處理后,體系中Zn2+的配合物主要存在的pH值范圍基本相同,只考慮對(duì)鋅離子的浸出時(shí),其浸出行為與礦物陰離子關(guān)系不大。其中,硅鋅礦在中性或偏酸性條件下主要以Zn2+及Zn(NH3)32+形式存在,當(dāng)pH升至9.246時(shí),Zn2+主要以高配位鋅配合物離子存在。由于試驗(yàn)所涉及的浸出體系總氨濃度較高,因此單一氨水浸出體系pH值高,根據(jù)熱力學(xué)計(jì)算結(jié)果,體系中Zn2+生成高配位的Zn(OH)64-,而氨水-氟化銨浸出體系實(shí)際為緩沖溶液,體系pH值較低且穩(wěn)定,Zn2+的配位反應(yīng)可能由氨基或氨基與羥基共同主導(dǎo)。
[Abstract]:This paper mainly studies the leaching behavior and its mechanism of high grade Zinc Oxide ore under the complex ammonia leaching system. Based on the National Natural Science Foundation project undertaken by the tutor, the ammonia dissolution leaching leaching residue flotation test and related mechanism of low grade refractory Zinc Oxide ore have been completed in the earlier period, and some related achievements have been obtained. In the early research process, the medium and high grade Zinc Oxide ore containing a certain amount of zinc sulfide ore is often encountered. In order to explore the ammonia leaching behavior and its mechanism of this kind of ore, it is also a useful supplement to the previous research, so as to understand the ammonia leaching behavior and mechanism of each grade of Zinc Oxide ore in a more comprehensive way. Zinc 40.61% and the oxidation rate of 78.72% in Lanping Zinc Oxide mine, the choice of processing methods for this kind of ore is more than the grade, but from the exploration of mechanism, this paper has a certain theoretical value, which can enrich the theory of ammonia dissolution leaching of Zinc Oxide ore to a certain extent. The leaching of ammonia in high grade Zinc Oxide ore is carried out in high grade Zinc Oxide ore. On the basis of the experiment, the leaching effect of different ammonia leaching systems was studied. First, the experiments of low total ammonia concentration leaching and high total ammonia concentration leaching were carried out respectively. Three different leaching leaching systems of ammonia leaching were selected, that is, single ammonia leaching system, ammonia water ammonium fluoride leaching system and ammonia water sulphur. The results show that the trend of the ammonia dissolution leaching indexes of the three leaching systems is generally the same, but the leaching effect is different, and the law of the ammonia dissolution and leaching of the low grade Zinc Oxide ore is not the same. The best leaching effect is the single ammonia water leaching system, and the leaching rate of zinc is 39.42%. The leaching rate of the leachable phase is 73.47%, the effect of ammonia water ammonium fluoride leaching system is second, the high total ammonia concentration is close to that of the single ammonia leaching system, the leaching rate of zinc is 39.33%, the leaching rate of zinc in the leachable phase is 73.29%, the effect of ammonia water ammonium sulfate is the worst, the leaching rate of zinc is 30.88%, and the leaching rate of the leachable phase is obtained. In addition, through the study of the liquid to solid ratio of the leaching system, the ratio of ammonia to ammonium, the stirring speed, the leaching time, the leaching temperature and the grinding fineness, the most significant effect on the leaching effect is the liquid to solid ratio and the leaching temperature. The leaching mechanism of different leaching systems is explored by means of XRD, SEM-EDS, and XPS. The results of.XRD analysis show that both the zine zinc ore and the zinc iron spinel in the raw ore and the leaching residue are all in the form of unstable crystal structure. In the leaching process of the original ore, zinc silicate can react with the leaching agent to produce amorphous silica. The existence of this substance in the leaching system is very complex, and the leaching effect of zinc is significant. When the leaching system is weak alkali, amorphous silica exists in the form of insoluble substances. When the leaching system is strong alkaline, amorphous silica is found in the leach solution in the form of polynuclear stabilizers. Due to the high content of zinc metal in the original ore, it is presumed that the surface charge of the impregnated silica may be unbalance after the amorphous silica is dissolved. The dissolved silicon is reformed into amorphous silica on the surface of the ore particles and continues to be dissolved in the reaction with the ammonium ion and hydroxyl group. It forms a cycle and hinders the leaching of zinc in the ore. At the same time, a single ammonia leaching system has been found, and the surface of the leaching residue is marked with obvious corrosion marks on the surface of ammonia leaching, showing a smooth and smooth crystal. The results of XPS analysis show that the change of the atomic density of silicon and carbon elements on the surface of the raw ore and the surface of the leaching residue has a certain regularity. The change law of iron and sulfur elements is not clear. The peak fitting Atlas of each element also shows that the binding energy of the elements and the elements of the silicon and zinc have little change. It is found that amorphous silica is an important factor in the leaching process. The concentration of total silicon ([Si]T) in the solution will increase with the increase of the concentration of the total ammonia. Besides the constant concentration of H4SiO4, the concentration of the other forms of ions will increase, and the presence of silicon compounds with obvious advantages may be Si3O5 (OH) 53-, H3SiO 4-, Si2O3 (OH) 42-. finally, the coordination of znite and znzite in the process of ammonia dissolution leaching is studied. After the leaching treatment of znzite and zine, the main pH range of Zn2+ complexes in the system of Zn2+ is basically the same, only when the leaching of zinc ions is considered, the leaching behavior has little relation with the mineral anions. In the form of Zn2+ and Zn (NH3) 32+ under neutral or partial acidic conditions, when pH rises to 9.246, Zn2+ mainly exists with high coordination zinc complex ions. Because the concentration of total ammonia in the leaching system is high, the pH value of the single ammonia leaching system is high. According to the thermodynamic calculation, the high coordination level of Zn2+ is generated in the system. Zn (OH) 64-, while ammonia water ammonium fluoride leaching system is actually a buffer solution, the system pH value is low and stable. The coordination reaction of Zn2+ may be dominated by the amino or amino group and the hydroxyl group.
【學(xué)位授予單位】：昆明理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TD952

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