本文關鍵詞： 腐殖酸 高嶺土 有機-礦質復合體 亞臨界水處理方法 吸附　出處：《中國地質大學(北京)》2017年碩士論文　論文類型：學位論文

【摘要】：為模擬地質吸附劑中的有機質礦化腐殖化及有機-礦質復合體的形成過程,探討其作用機制,采用亞臨界水處理技術,通過控制壓力反應釜的溫度、壓力和反應時間對商用腐殖酸、高嶺土及有機-礦質復合體進行處理,并通過比表面積全分析、傅里葉紅外光譜(FTIR)、特定波長可見吸光度比值(E4/E6)、X射線衍射(XRD)和13C核磁共振(13C-NMR)等表征手段及對典型疏水性有機污染物卡馬西平(CBZ)的吸附批實驗,探討了不同處理條件下有機質、粘土礦物及二者復合體的各自變化特征及吸附機制,并建立了概念模型。本研究主要得到以下結論:(1)比表面積全分析和E4/E6測定表明升溫增壓導致腐殖酸從“軟碳”向“硬碳”轉化。表現為比表面積顯著增加、分子量增大、以及芳化度增加;紅外光譜代表性基團的含量差異分析表明,其主要原因是游離羧基和鏈烴在升溫增壓條件下實現了成環(huán)、聚合過程,使其結構更加復雜,化學穩(wěn)定性提高。吸附批實驗顯示腐殖酸的吸附等溫線從非線性到線性,再到非線性轉變,是由于腐殖酸升溫增壓過程中,產生了從小球狀到鏈狀,再到團聚狀的結構改變,同時受水分子的競爭吸附作用和芳環(huán)的大π鍵之間的范德華力共同影響�；诒缺砻娣e變化的吸附位點計算進一步證實,腐殖酸處于小球狀和鏈狀時,吸附位點的多少控制吸附過程,當腐殖酸變?yōu)榫奂瘧B(tài)時,π鍵相互平衡使CBZ協(xié)同吸附在HA芳環(huán)結構上,進而控制吸附行為。(2) XRD衍射圖和四種高嶺土的紅外光譜代表性基團差異表明,高嶺土在升溫增壓的過程中脫水,架構起結晶更完整的有序結構。高嶺土吸附CBZ前后的紅外光譜的差異表明,常溫常壓下CBZ分子在KL表面填充空隙達到飽和后進入層間;升溫增壓前期高嶺土層間距減小,層狀結構被壓縮導致CBZ分子進入困難,引起了升溫增壓初期Kd銳減;后期高溫高壓的處理加劇了 Al-OH消耗,其釋放的OH-與CBZ分子C=O中O孤對電子的排斥作用削減,使得高溫高壓的后期KL對CBZ的吸附能力在保持平穩(wěn)態(tài)勢的前提下略有增強。(3)復合體實際吸附量和理論疊加吸附量的差值△Q表明,有機-礦質復合體的宏觀吸附并非腐殖酸和高嶺土吸附的簡單疊加。XRD圖譜顯示,升溫增壓初期,復合體相對于腐殖酸的芳香度變化存在滯后,表明腐殖酸的部分芳香組分插入高嶺土層間而免受高溫高壓的影響;同時復合體的芳化度與其非線性程度對應性表明,芳香化誘導力使靠近高嶺土表面的腐殖酸排列緊密;后期逐步升溫增壓的處理使得未被保護的腐殖酸成鏈成環(huán),致密的交界面上的變化共同導致有機-礦質復合體吸附介質的非均質性,也控制了吸附曲線的走向。此外,吸附量差值△Q與其脂肪度的變化具有一致性,表明復合體外空間可能存在依靠分子間作用力連接的脂肪性腐殖酸,且對CBZ分子的吸附有貢獻。
[Abstract]:In order to simulate the process of organic matter mineralization humification and the formation of organic-mineral complex in geological adsorbent, the mechanism of its action was discussed. The subcritical water treatment technology was used to control the temperature of pressure reactor. The commercial humic acid, kaolin and organo-mineral complex were treated by pressure and reaction time. Specific wavelength visible absorbance ratio E4 / E6). X-ray diffraction (XRD) and 13C NMR (13C-NMRs) and adsorption batch experiments on typical hydrophobic organic pollutant carbamazepine (CBZ). The characteristics and adsorption mechanism of organic matter, clay minerals and their complexes under different treatment conditions were discussed. The main conclusions of this study are as follows: 1). The total surface area analysis and E4 / E6 measurement showed that heating and pressurization resulted in the transformation of humic acid from "soft carbon" to "hard carbon", which was characterized by a marked increase in specific surface area. The molecular weight increased and the degree of aromatization increased; The analysis of the content difference of representative groups in infrared spectrum shows that the main reason is that the free carboxyl group and the chain hydrocarbon can be formed and polymerized under the condition of temperature and pressure, which makes the structure more complex. The adsorption batch experiment showed that the adsorption isotherm of humic acid changed from nonlinear to linear and then to nonlinear because of the small globular to chain shape in the process of heating and pressurizing humic acid. At the same time, it is affected by the competitive adsorption of water molecules and the van der Waals force between the large 蟺 bonds of aromatic rings. The calculation of adsorption sites based on the change of specific surface area further proves that. When humic acid is in small globular and chain shape, the number of adsorption sites controls the adsorption process. When humic acid becomes aggregated, 蟺 -bond equilibrium makes CBZ synergistically adsorbed on HA aromatic ring structure. The difference of IR groups between the XRD diffraction pattern and the four kaolinites shows that the kaolin dehydrates in the process of heating and increasing pressure. The IR spectra of kaolin before and after adsorption of CBZ indicate that the CBZ molecules enter the interlayer after filling the pores on the KL surface at room temperature and atmospheric pressure. In the early stage of heating and pressurizing, the interlayer spacing of kaolin decreases, and the lamellar structure is compressed, which makes it difficult for CBZ molecules to enter, which results in a sharp decrease of KD in the early stage of heating and pressurizing. The high temperature and high pressure treatment increased the consumption of Al-OH, which reduced the repulsion of OH- and O solitary electrons in CBZ molecule Con O. The difference Q between the actual adsorption capacity of KL and the theoretical superposition adsorption capacity of KL on CBZ at the later stage of high temperature and high pressure is slightly enhanced on the premise of maintaining a steady state. The macroscopical adsorption of organic-mineral complex is not a simple superposition of humic acid and kaolin adsorption. XRD spectra show that the aromaticity of the complex relative to humic acid lags at the initial stage of heating and pressurization. It is shown that some aromatic components of humic acid are inserted into the interlayer of kaolin to avoid the influence of high temperature and high pressure. At the same time, the degree of aromatization of the complex corresponds to its nonlinear degree, which indicates that aromatization induces the arrangement of humic acids near the surface of kaolin. In the later stage, the unprotected humic acid was chained into a ring, and the change of the dense interface resulted in the heterogeneity of the adsorptive medium of the organic-mineral complex. In addition, the difference of adsorption quantity Q is consistent with the change of fat degree, which indicates that there may be fatty humic acid connected by intermolecular force in the complex space in vitro. In addition, the adsorption of CBZ molecules has a contribution.
【學位授予單位】：中國地質大學(北京)
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X52;O647.3

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