本文選題：含鐵錳礦 + 重金屬吸附��； 參考：《華中農(nóng)業(yè)大學(xué)》2017年碩士論文

【摘要】：重金屬吸附材料一直是環(huán)境科學(xué)的研究重點(diǎn),其中針對(duì)典型吸附材料鐵氧化物、錳氧化物的研究較多。天然含鐵錳礦集合了鐵氧化物、錳氧化物的特性,對(duì)重金屬具有很好的去除效果,且資源廣泛,具有非常好的應(yīng)用前景,但目前對(duì)含鐵錳礦性質(zhì)及對(duì)重金屬去除機(jī)理的研究較少。本文以天然含鐵錳礦、合成的鐵氧化物、錳氧化物及鐵錳二元復(fù)合氧化物作為研究對(duì)象,采用XRD、FTIR、TG、XPS、掃描電鏡等技術(shù)手段對(duì)材料進(jìn)行成分分析、礦物學(xué)及表面化學(xué)表征,并研究了材料對(duì)重金屬(鉛、鋅、鎘、鉻、砷)的吸附效果,分析了不同因素對(duì)含鐵錳礦吸附砷的影響,再結(jié)合對(duì)吸附砷前后材料的表征,探討了含鐵錳礦吸附砷的機(jī)理。主要結(jié)論如下:1.采用XRD、FTIR分析技術(shù)發(fā)現(xiàn),供試10種天然含鐵錳礦均含有軟錳礦、磁鐵礦、赤鐵礦、褐鐵礦,其中碳酸錳礦還含有特有物質(zhì)菱鐵礦和菱錳礦。通過(guò)掃描電鏡觀察材料形貌特征發(fā)現(xiàn),天然含鐵錳礦以塊狀形式存在為主,表面較光滑,吸附砷后有小顆粒吸附在塊狀表面;而合成礦物顆粒較小,排列疏松,比表面積相較于天然含鐵錳礦而言要大幅增加。2.采用TG分析技術(shù)發(fā)現(xiàn),10種天然含鐵錳礦及人工合成的鐵氧化物、錳氧化物在47℃、260℃、590℃時(shí)質(zhì)量減輕幅度較大,分別造成濕存水、結(jié)晶水、結(jié)構(gòu)水的損失,同時(shí)物質(zhì)結(jié)構(gòu)遭到破壞。而人工合成的鐵錳二元復(fù)合氧化物主要在300℃之前損失質(zhì)量。3.采用Tessier 5步順序提取法分析鐵、錳形態(tài)發(fā)現(xiàn),天然含鐵錳礦中Mn主要以可氧化態(tài)、可還原態(tài)和殘?jiān)鼞B(tài)的形式存在,含量分布分別是18%~20%、11%~21%和59%~68%;Fe主要以殘?jiān)鼞B(tài)的形式存在,含量約占95%,但殘?jiān)鼞B(tài)不具備氧化As的能力。因此,含鐵錳礦在對(duì)砷的吸附氧化過(guò)程中,Fe主要起吸附作用,而Mn則起到氧化作用。此外,在10種天然含鐵錳礦中,Ca、As含量與鐵、錳各形態(tài)含量顯著相關(guān),但與Fe、Mn含量無(wú)關(guān)。4.研究供試材料對(duì)5種重金屬的吸附實(shí)驗(yàn)發(fā)現(xiàn),10種天然含鐵錳礦對(duì)Pb的吸附能力最強(qiáng),平均去除率為92.17%,其次為As,平均去除率為61.60%,碳酸錳礦對(duì)As的吸附能力最弱,去除率僅有15.54%,但對(duì)Zn和Cd具有較好的吸附能力,其去除率分別為66.93%、42.62%。人工合成的鐵錳二元復(fù)合氧化物對(duì)Pb、Cr、As的吸附能力都很強(qiáng),平均去除率依次為97.25%、99.34%、99.98%,對(duì)Zn、Cd的吸附能力卻很弱,平均去除率依次為67.61%、53.85%。人工合成的鐵氧化物和錳氧化物對(duì)Pb、As的吸附量很高,對(duì)Zn、Cr、Cd的吸附量隨氧化物種類(lèi)不同而有較大差異,表現(xiàn)出選擇性吸附。含鐵錳礦對(duì)Cr的去除率與材料比表面積及Fe含量顯著正相關(guān),與錳的氧化度顯著負(fù)相關(guān);As去除率與材料比表面積及Fe含量顯著正相關(guān)。5.采用實(shí)驗(yàn)室批處理實(shí)驗(yàn)發(fā)現(xiàn),含鐵錳礦材料吸附砷符合Freundlich等溫吸附方程。吸附動(dòng)力學(xué)分析結(jié)果表明,前4h含鐵錳礦與砷溶液反應(yīng)迅速,至12h時(shí)反應(yīng)達(dá)到平衡。6.采用XRD、FTIR、XPS對(duì)吸附砷前后的礦物材料進(jìn)行分析,結(jié)果表明,在吸附過(guò)程中,Mn作為氧化劑將As(Ⅲ)氧化成As(Ⅴ),而Mn則由Mn(Ⅳ)還原成Mn(Ⅱ),反應(yīng)過(guò)程中Fe的價(jià)態(tài)并未發(fā)生變化,說(shuō)明在含鐵錳礦吸附As(Ⅲ)過(guò)程中Mn起到氧化還原的作用,而Fe僅參與吸附反應(yīng),促進(jìn)提高含鐵錳礦對(duì)As(Ⅲ)的去除。
[Abstract]:Heavy metal adsorption materials have always been the focus of environmental science. Among them, there are many studies on the typical adsorbents iron oxide and manganese oxide. The natural ferromanganese contains iron oxide, manganese oxide, and has a very good removal effect to heavy metals, and has a very good application prospect. But at present, iron and manganese containing iron and manganese are very good. The properties of ore and the mechanism of heavy metal removal are seldom studied. In this paper, the composition analysis, mineralogy and surface chemical characterization of XRD, FTIR, TG, XPS, and scanning electron microscope are used in the study of natural ferromanganese, synthetic iron oxides, manganese oxides and iron manganese two composite oxides. The effect of the adsorption of (lead, zinc, cadmium, chromium, arsenic) on the adsorption of arsenic in ferromanganese ore was analyzed. The mechanism of the adsorption of arsenic in manganese ore was discussed. The main conclusions were as follows: 1. using XRD and FTIR analysis technology, 10 kinds of natural ferromanganese ores were found to contain pyrolusite, magnetite and hematite. By scanning electron microscope, it is found that the natural ferromanganese deposits are mainly in the form of massive form, the surface is smooth, and the small particles are adsorbed on the massive surface after the adsorption of arsenic, while the synthetic ore particles are smaller and are loosely arranged and compared to the natural surface area. As for ferromanganese ore,.2. can be greatly increased by TG analysis technology, 10 kinds of natural iron containing manganese ore and synthetic iron oxide, manganese oxide at 47, 260 and 590 C, the quality is greatly reduced, resulting in the loss of wet storage water, crystalline water, loss of structure water and the destruction of the material structure, while the artificial synthetic iron and manganese compound is two. The oxide mainly lost mass.3. before 300 centigrade by Tessier 5 step sequential extraction method to analyze iron. The form of manganese in the natural iron containing manganese ore was found to be mainly oxidizable, reducible and residue, and the content distribution was 18%~20%, 11%~21% and 59%~68%, respectively, and the content of Fe was about 95% in the form of residue, but the residue was about 95%. The state does not have the ability to oxidize As. Therefore, during the adsorption and oxidation of arsenic by ferromanganese ore, Fe mainly plays an adsorption role, while Mn plays the role of oxidation. In addition, the content of Ca and As in 10 natural ferromanganese ores is significantly related to the content of iron and manganese, but the content of Fe and Mn is not related to the adsorption experiment of the 5 kinds of heavy metals by the.4. research materials. The 10 kinds of natural ferromanganese ores have the strongest adsorption capacity to Pb, the average removal rate is 92.17%, the second is As, the average removal rate is 61.60%, the adsorption ability of manganese carbonate to As is the weakest and the removal rate is only 15.54%. But the adsorption capacity of Zn and Cd is better, the removal rate is 66.93%, and 42.62%. synthetic iron manganese two compound oxide is on P. The adsorption capacity of B, Cr and As is very strong, the average removal rate is 97.25%, 99.34%, 99.98%. The adsorption capacity of Zn, Cd is very weak, the average removal rate is 67.61%. The adsorption capacity of 53.85%. synthetic iron oxide and manganese oxide on Pb, As is very high. The adsorption capacity of Zn, Cr, Cd is very different with the species of oxide, showing the choice of selection. The removal rate of Cr with ferromanganese has a significant positive correlation with the specific surface area and Fe content of the material, and a significant negative correlation with the oxidation degree of manganese; the removal rate of As and the specific surface area and Fe content of the materials are significantly positively correlated.5. using the laboratory batch experiment. The adsorption equation of the arsenic bearing Freundlich isothermal adsorption equation and the adsorption dynamic credits are found. The results show that the reaction of the former 4H iron manganese ore with the arsenic solution is rapid, and the reaction reaches the equilibrium.6. at the time of 12h. XRD, FTIR, XPS are used to analyze the mineral materials before and after the adsorption of arsenic. The results show that during the adsorption process, Mn is oxidized to As (V) as an oxidant, while Mn is reduced to Mn (II) by Mn (IV), and the valence state of the reaction does not occur during the reaction process. The result shows that Mn plays the role of redox in the process of adsorbing As (III) with ferromanganese, while Fe only participates in the adsorption reaction, which promotes the improvement of the removal of As (III) by ferromanganese.
【學(xué)位授予單位】：華中農(nóng)業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：P579;X703

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