本文關(guān)鍵詞： 高氟地下水 水化學(xué)性質(zhì) 吸附材料 除氟效果 競爭吸附 適應(yīng)性　出處：《中國水利水電科學(xué)研究院》2015年博士論文　論文類型：學(xué)位論文

【摘要】：我國高氟地下水分布廣泛,且呈區(qū)域性存在的特點,很多地區(qū)往往沒有可選擇優(yōu)質(zhì)水源,除氟技術(shù)是解決高氟水地區(qū)居民飲用水問題的有效途徑。本文通過總結(jié)除氟技術(shù)發(fā)展現(xiàn)狀以及前期工程調(diào)研,確定吸附法除氟技術(shù)作為本文開展除氟技術(shù)研究的方向。結(jié)合目前吸附法除氟技術(shù)所面臨的應(yīng)用難點,以目前最急需解決的應(yīng)用問題展開實驗研究,以闡述高氟地下水的關(guān)鍵水化學(xué)特征為基礎(chǔ),以提高吸附材料與高氟地下水的關(guān)聯(lián)性為核心,以闡述吸附材料除氟效果對水化學(xué)性質(zhì)的響應(yīng)機制和適應(yīng)性為最終目標(biāo)。通過研究,得到的主要結(jié)論如下：(1)研究尺度上,基于渤海灣、皖北以及山東、內(nèi)蒙、吉林、陜西等地區(qū)水文地質(zhì)調(diào)查,遵循水化學(xué)性質(zhì)分析和多元統(tǒng)計分析相結(jié)合的原則,描述不同地區(qū)高氟地下水的水化學(xué)性質(zhì)和關(guān)鍵水化學(xué)特征。結(jié)果表明不同地區(qū)高氟地下水水化學(xué)性質(zhì)有差異,但具有共性水化學(xué)特征,主要體現(xiàn)在pH值大于7.5(p=0.95),水化學(xué)類型以Na-HCO3型為主,pH值、總堿度、HCO3-、Na+、剩余堿度等指標(biāo)與F-密切相關(guān),是影響高氟地下水形成的關(guān)鍵水化學(xué)因素。高氟地下水的形成是長期水-巖相互作用下的陽離子交換以及氟礦物的溶解。此外,Mg2+、Ca2+含量決定高氟地下水中氟化物其他賦存形態(tài)的含量。(2)充分利用高氟地下水的陰陽離子分布狀況,克服地下水對吸附材料的挑戰(zhàn),制備了取材簡單、方便易得的無定形氫氧化鋁和MgO等兩種吸附材料。其中無定形氫氧化鋁吸附材料的制備采用共沉淀法并控制反應(yīng)過程中pH值,MgO吸附材料的制備采用水熱法并煅燒前驅(qū)體的方法。所制備的吸附材料均具有良好的吸附性能,在pH值為7.0的條件下,Langmuir最大吸附容量分別為166.67mg/g和125mg/g,可以重復(fù)利用5個周期,提高了適應(yīng)地下水pH值的能力以及與天然高氟地下水的關(guān)聯(lián)性。(3)結(jié)合高氟地下水水化學(xué)性質(zhì)以及離子組分分布狀況,基于模擬含氟水試驗,無定形氫氧化鋁和MgO吸附材料的除氟效果對地下水中pH值、HCO3-、SO42-、Cl-、P043-等指標(biāo)產(chǎn)生不同程度的響應(yīng),均會隨著溶液中的pH值、HCO3-、 SO42-、Cl-、PO43-等指標(biāo)值(含量)的升高而降低,其中pH值和HC03-尤為突出,屬于倍數(shù)級和差量級競爭吸附。吸附材料對地下水中HC03-和S042-的吸附過程符合Freundlich吸附等溫模型,且屬于優(yōu)惠型吸附,吸附容量均大于31mg/g和14mg/g。陰離子競爭吸附導(dǎo)致吸附材料對F’的吸附速率減緩、親和力下降。(4)通過非高氟地下水和天然高氟地下水的吸附材料吸附試驗,從首次吸附的除氟效果角度而言,無定形氫氧化鋁和MgO吸附材料均對天然高氟地下水具有適應(yīng)性,在投加量為0.5-1.0g/L的基礎(chǔ)上,將氟化物濃度降至1.0 mg/L以下。吸附材料在吸附氟的同時也吸附了大量共存陰離子,特別是HCO3-,吸附量大于10mg/g,但所吸附的差量級共存陰離子均對首次吸附過程的除氟效果沒有顯著影響。(5)與純水配水試驗相比,在天然高氟地下水試驗條件下(F=1.72 mg/L)吸附材料的可重復(fù)利用性能顯著降低。無定形氫氧化鋁和MgO吸附材料運行至第4個周期時,無法將初始溶液中氟化物濃度降至1.0 mg/L以下。基于純水配制高氟水試驗條件下的再生手段滿足不了實際高氟水再生手段的需求,再生手段不僅僅需考慮脫附F-,更應(yīng)全面考慮如何脫附HCO3-、SO42-和C1-等陰離子從而釋放更多的吸附位點。多孔鋁鎂氧化物除氟效果對地下水水化學(xué)性質(zhì)的響應(yīng)機制及適應(yīng)性這一基礎(chǔ)研究,描述了我國不同地區(qū)高氟地下水的水化學(xué)性質(zhì)和關(guān)鍵水化學(xué)特征,明確了制約多孔鋁鎂氧化物除氟效果的關(guān)鍵因素,解釋了共存陰離子與F-的競爭吸附機理,闡述了多孔鋁鎂氧化物除氟效果對水化學(xué)性質(zhì)的響應(yīng)機制和適應(yīng)性,為吸附法除氟技術(shù)的發(fā)展和應(yīng)用提供了新的方向,為高氟地下水地區(qū)飲用水問題的解決奠定基礎(chǔ)。
[Abstract]:The distribution of groundwater with high fluorine extensively in our country, and a regional characteristics exist in many areas, often have no choice of high-quality water, fluoride removal technology is an effective way to solve the problem of drinking water in residential areas of high fluoride water. In this paper, through summarizing the current situation of the development in technology and Engineering Research of fluorine, determination of fluoride adsorption technology is carried out in this paper study on fluorine removing technology. Combining the adsorption method in addition to the application of difficulties to the current application of fluoride, the need to resolve the issue of study, the key characteristics of water chemistry on high fluorine groundwater as the basis, to improve the relevance of adsorption materials and high fluorine groundwater as the core, to explain the adsorption material in addition to the response mechanism and adaptability of the chemical properties of water fluoride effect as the ultimate goal. Through the research, the main conclusions are as follows: (1) research scale, based on the Gulf of Bohai, North Shandong, Anhui Inner Mongolia, Jilin, Shaanxi and other regions, hydrogeological investigation, follow water chemistry analysis and multivariate statistical analysis of the principle of combining the description of water chemistry and key hydrochemical characteristics of groundwater with high fluorine in different regions. The results show that different areas of high fluoride groundwater chemical properties are different, but with common hydrochemical characteristics, mainly reflected in the pH value greater than 7.5 (p=0.95), water chemistry type Na-HCO3, pH, HCO3-, Na+, total alkalinity, residual alkalinity index is closely related with F-, is a key factor affecting the formation of high fluoride groundwater water chemistry factors. The formation of high fluoride groundwater is cation exchange long-term water rock interaction and the dissolved fluorine minerals. In addition, Mg2+, Ca2+ content in determining high fluoride fluoride in ground water and other forms. (2) make full use of ions distribution of fluoride in groundwater, groundwater to overcome adsorption material The challenge was prepared from simple, easy to obtain amorphous aluminium hydroxide and MgO two adsorption materials. The amorphous aluminum hydroxide adsorption materials were prepared by co precipitation method and control the reaction process of pH, MgO adsorption materials were prepared by hydrothermal method and calcination method. The precursor the adsorption material prepared has good adsorption properties, the pH value is 7, the maximum adsorption capacity of Langmuir were 166.67mg/g and 125mg/g, can be reused for 5 cycles, improve the ability to adapt to the pH value of groundwater and the related natural fluoride in groundwater. (3) with high fluorine water chemistry groundwater and ion component distribution, simulation of fluoride test based on amorphous aluminum hydroxide and MgO adsorbent fluoride effect on groundwater in pH, HCO3-, SO42-, Cl-, P043- and other indicators of different levels of response, both with A solution of pH, HCO3-, SO42-, Cl-, PO43- and other indicators of value (content) increased, the pH value and HC03- is particularly prominent, belongs to the multiple level and poor level of competitive adsorption. Adsorption process of adsorption of HC03- and S042- in underground water with the Freundlich adsorption isotherm model, and belongs to the preferential adsorption the adsorption capacity was more than 31mg/g, and the 14mg/g. anion adsorption leads to competitive adsorption materials on the adsorption rate slowed down, F 'affinity decreased. (4) through the adsorbent non high fluoride groundwater and natural fluoride in groundwater from the first test, the adsorption of fluoride removal effect perspective, amorphous aluminum hydroxide and MgO adsorption on natural materials the high fluoride groundwater adaptability in the dosage of 0.5-1.0g/L based on the fluoride concentration is below 1 mg/L. At the same time, adsorbent in the adsorption of fluoride is the large amount of adsorbed CO existing anions, especially HC O3-, the adsorption amount is greater than 10mg/g, but the difference in magnitude of adsorbed anions on the first adsorption process of fluoride removal had no significant effect. (5) compared with the pure water test in natural high fluoride groundwater conditions (F=1.72 mg/L) adsorption material can be reused can significantly reduce the amorphous aluminum hydroxide. And MgO adsorption materials run to fourth cycles, the initial fluoride concentration in solution cannot be reduced to below 1 mg/L. Water recycled means high fluorine water under the experimental conditions can not meet the actual demand of high fluoride water regeneration method based on the students not only need to consider the means to the desorption of F-, it should comprehensively consider how the desorption of HCO3-, SO42- C1- and anion releasing more adsorption sites. This is the foundation of study on the response mechanism of the effect of fluoride on water chemistry of groundwater and adaptability in porous aluminum magnesium oxide, described our country different Water chemistry and water chemical characteristics of key area of high fluorine groundwater, the key factor restricting the porous aluminum magnesium oxide fluoride removal effect, explained the mechanism of competitive adsorption of anions and F-, expounds the porous aluminum magnesium oxide fluoride effect on water chemistry response mechanism and adaptability, provides a new direction for the development and application of fluoride removal by adsorption, which lays the foundation for solving the problem of drinking water with high fluoride groundwater area.

【學(xué)位授予單位】：中國水利水電科學(xué)研究院
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TU991.266

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