鋁鋯顆粒吸附材料去除水中氟、磷性能及機理研究
發(fā)布時間：2018-12-14 04:14
【摘要】：吸附法因其低廉、高效及操作方便等優(yōu)點而被廣泛用作深度凈水工藝,該技術(shù)的關(guān)鍵在于選取合適的吸附材料。針對水體中氟(F)、磷(P)污染物超標的問題,本研究研發(fā)出一種新型高效的吸附材料——顆粒型鋁鋯復合金屬氧化物(Aluminium Zirconium Granular Adsorbent,AZGA),通過熱失重、抗壓性實驗、XRD、BET、Zeta電位分析等表征手段研究了AZGA的表面物化特性和結(jié)構(gòu)特征;通過吸附動力學、吸附等溫線、pH影響和共存離子影響實驗來探討了該吸附劑對F、P的吸附特性及水質(zhì)因子影響規(guī)律;利用SEM-EDS、Mapping、FTIR、XPS、NMR、Raman等表征技術(shù)解釋了AZGA對F、P的吸附機理;通過解吸-再生實驗和動態(tài)小柱實驗評價了吸附劑動態(tài)除F/P效果及再生性能,主要研究成果如下:1.通過對比不同比例的鋁、鐵、鋯復合吸附劑對F、P的去除效果,確定了最佳吸附劑為Al:Zr=3:1的鋁鋯復合金屬氧化物,以聚乙烯醇(PVA)為粘合劑采用擠壓法制得粒徑為2~2.5mm的AZGA顆粒,并用多項表征技術(shù)對其表面特性進行研究后發(fā)現(xiàn):AZGA呈無晶型結(jié)構(gòu),最大機械載荷為34.21N,比表面積為29.55 m2/g,Zeta電位pHpzc=6.93,材料表面含有大量的羥基基團,主要元素有C、H、O、Al、Zr、S。2.AZGA除F、P的靜態(tài)實驗結(jié)果表明:AZGA除F的動力學特征符合擬二階模型、除P動力學特征符合Power模型,這說明F/P的吸附都在異構(gòu)表面發(fā)生,且以化學吸附為主;顆粒內(nèi)擴散模型擬合結(jié)果表明AZGA對F、P的吸附速率受到不止一個反應過程的影響。同時,AZGA對F/P吸附等溫線特征更符合Freundlich模型,這進一步驗證了吸附以化學作用為主,AZGA對F和P的最大吸附量分別是65.07mg/g和20.76mg/g,高于大多數(shù)的其他顆粒型吸附劑。3.AZGA熱力學參數(shù)分析表明其吸附為自發(fā)型吸熱反應;AZGA除F的最佳pH值為6.93,除P的最佳pH值為3;陰離子對AZGA除F除P均起抑制作用,其中PO43-對除F抑制最大,SiO32-對除P抑制最大,其干擾作用主要歸結(jié)于陰離子之間的競爭吸附作用;Ca、Mg等陽離子則均可通過架橋作用來促進F、P的吸附。4.AZGA除F的動態(tài)過柱及再生實驗表明:最佳再生濃度為0.3mol/LNaOH,循環(huán)五次后吸附效果仍可達到首次吸附的71.34%;當過柱體積達到808BV時,出水F-濃度為0.997mg/L,且再生過柱體積可達704BV,相比初次吸附,過柱體積降低了12.87%,吸附容量下降了16.6%。5.AZGA除P的動態(tài)過柱及再生實驗表明:最佳再生濃度為0.3mol/LNaOH,五次循環(huán)再生后吸附效果仍可達到首次吸附的77.8%;當過柱體積達到時,初次過柱吸附時出水P濃度超出國家一級A與一級B標準時的過柱體積分別為584BV、780BV,且動態(tài)再生后的過柱體積分別為504BV、636BV,對比再生過柱前后,過柱體積降低了18.5%,吸附容量下降了23.7%。6.對AZGA吸附F、P前后的樣品進行SEM-EDS、Mapping、FTIR、XPS、NMR、Raman等表征分析后發(fā)現(xiàn),AZGA主要通過表面豐富的羥基與F、P發(fā)生結(jié)合,少部分F、P還可與AZGA表面嵌入的SO42-發(fā)生離子交換反應。
[Abstract]:Adsorption method is widely used in deep water purification process because of its advantages of low cost, high efficiency and convenient operation. The key of this technology is to select suitable adsorption materials. Aiming at the problem of exceeding the standard of fluorine (F), phosphorus (P) pollutants in water, a new and high efficient adsorbent material, granular aluminum zirconium composite metal oxide (Aluminium Zirconium Granular Adsorbent,AZGA), was developed in this study. Through the experiments of thermogravimetric, compressive resistance, XRD,, The surface physicochemical and structural characteristics of AZGA were studied by means of BET,Zeta potential analysis. Adsorption kinetics, adsorption isotherm, influence of pH and coexisting ions were studied to study the adsorption characteristics and water quality factors of the adsorbent. The adsorption mechanism of AZGA on FNP was explained by means of SEM-EDS,Mapping,FTIR,XPS,NMR,Raman and other characterization techniques. Through desorption and regeneration experiments and dynamic column experiments, the dynamic removal of F / P and regeneration performance of adsorbent were evaluated. The main results are as follows: 1. By comparing the removal efficiency of aluminum, iron and zirconium composite adsorbents with different ratios, it was determined that the best adsorbent was the aluminum zirconium composite metal oxide with Al:Zr=3:1. AZGA particles with diameter of 2~2.5mm were prepared by extruding polyvinyl alcohol (PVA) as binder. The surface properties of AZGA particles were studied by multiple characterization techniques. It was found that AZGA had amorphous structure and the maximum mechanical load was 34.21N. There are many hydroxyl groups on the surface of pHpzc=6.93, material with a specific surface area of 29.55 m2 / g ~ (-1) G ~ (2 +). The static experimental results of P show that the kinetic characteristics of AZGA and P are in accordance with the quasi second order model and the Power model respectively, which indicates that the adsorption of F / P occurs on the isomerization surface and is mainly chemisorption. The fitting results of intraparticle diffusion model show that the adsorption rate of FNP by AZGA is affected by more than one reaction process. At the same time, the isotherm characteristics of F / P adsorption by AZGA are more in line with the Freundlich model, which further verifies that the adsorption is mainly chemical. The maximum adsorption capacity of F and P by AZGA is 65.07mg/g and 20.76 mg / g, respectively. Higher than most other granular adsorbents. 3.AZGA thermodynamic parameters analysis showed that the adsorption was self-generated endothermic reaction. The optimum pH value of AZGA divided by F was 6.93, and the best pH value of P was 3. The anion inhibited the removal of F and P by AZGA, especially by PO43- and SiO32-, which was mainly attributed to the competitive adsorption between anions. Ca,Mg and other cations can promote the adsorption of FNP by bridging. The dynamic column and regeneration experiments of 4.AZGA for removing F indicate that the optimum regeneration concentration is 0.3mol / L NaOH, and the optimum regeneration concentration is 0.3mol / L NaOH, and the optimum regeneration concentration is 0.3mol / L NaOH. After five cycles, the adsorption effect can still reach 71.34 of the first adsorption. When the column volume reaches 808BV, the effluent F- concentration is 0.997mg / L, and the regenerated column volume can reach 704BV, which is 12.87% lower than the initial adsorption. The adsorption capacity of 16.6%.5.AZGA decreased the dynamic column and regeneration experiments showed that the optimum regeneration concentration was 0.3 mol / L NaOH, and the adsorption effect was still 77.8% of the first adsorption after the fifth cycle regeneration. When the column volume is reached, when the effluent P concentration exceeds the national first class A and B standards, the column volume is 584 BV or 780 BV respectively, and the dynamic regenerated column volume is 504 BV or 636 BV, compared with that before and after regeneration. The volume of the column decreased by 18.5and the adsorption capacity decreased by 23.70.6. The samples before and after AZGA adsorption were characterized by SEM-EDS,Mapping,FTIR,XPS,NMR,Raman. It was found that AZGA binds to FNP mainly through the abundant hydroxyl groups on the surface. P can also exchange ions with SO42- embedded on the surface of AZGA.
【學位授予單位】：西北農(nóng)林科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X703;X52;O647.3
[Abstract]:Adsorption method is widely used in deep water purification process because of its advantages of low cost, high efficiency and convenient operation. The key of this technology is to select suitable adsorption materials. Aiming at the problem of exceeding the standard of fluorine (F), phosphorus (P) pollutants in water, a new and high efficient adsorbent material, granular aluminum zirconium composite metal oxide (Aluminium Zirconium Granular Adsorbent,AZGA), was developed in this study. Through the experiments of thermogravimetric, compressive resistance, XRD,, The surface physicochemical and structural characteristics of AZGA were studied by means of BET,Zeta potential analysis. Adsorption kinetics, adsorption isotherm, influence of pH and coexisting ions were studied to study the adsorption characteristics and water quality factors of the adsorbent. The adsorption mechanism of AZGA on FNP was explained by means of SEM-EDS,Mapping,FTIR,XPS,NMR,Raman and other characterization techniques. Through desorption and regeneration experiments and dynamic column experiments, the dynamic removal of F / P and regeneration performance of adsorbent were evaluated. The main results are as follows: 1. By comparing the removal efficiency of aluminum, iron and zirconium composite adsorbents with different ratios, it was determined that the best adsorbent was the aluminum zirconium composite metal oxide with Al:Zr=3:1. AZGA particles with diameter of 2~2.5mm were prepared by extruding polyvinyl alcohol (PVA) as binder. The surface properties of AZGA particles were studied by multiple characterization techniques. It was found that AZGA had amorphous structure and the maximum mechanical load was 34.21N. There are many hydroxyl groups on the surface of pHpzc=6.93, material with a specific surface area of 29.55 m2 / g ~ (-1) G ~ (2 +). The static experimental results of P show that the kinetic characteristics of AZGA and P are in accordance with the quasi second order model and the Power model respectively, which indicates that the adsorption of F / P occurs on the isomerization surface and is mainly chemisorption. The fitting results of intraparticle diffusion model show that the adsorption rate of FNP by AZGA is affected by more than one reaction process. At the same time, the isotherm characteristics of F / P adsorption by AZGA are more in line with the Freundlich model, which further verifies that the adsorption is mainly chemical. The maximum adsorption capacity of F and P by AZGA is 65.07mg/g and 20.76 mg / g, respectively. Higher than most other granular adsorbents. 3.AZGA thermodynamic parameters analysis showed that the adsorption was self-generated endothermic reaction. The optimum pH value of AZGA divided by F was 6.93, and the best pH value of P was 3. The anion inhibited the removal of F and P by AZGA, especially by PO43- and SiO32-, which was mainly attributed to the competitive adsorption between anions. Ca,Mg and other cations can promote the adsorption of FNP by bridging. The dynamic column and regeneration experiments of 4.AZGA for removing F indicate that the optimum regeneration concentration is 0.3mol / L NaOH, and the optimum regeneration concentration is 0.3mol / L NaOH, and the optimum regeneration concentration is 0.3mol / L NaOH. After five cycles, the adsorption effect can still reach 71.34 of the first adsorption. When the column volume reaches 808BV, the effluent F- concentration is 0.997mg / L, and the regenerated column volume can reach 704BV, which is 12.87% lower than the initial adsorption. The adsorption capacity of 16.6%.5.AZGA decreased the dynamic column and regeneration experiments showed that the optimum regeneration concentration was 0.3 mol / L NaOH, and the adsorption effect was still 77.8% of the first adsorption after the fifth cycle regeneration. When the column volume is reached, when the effluent P concentration exceeds the national first class A and B standards, the column volume is 584 BV or 780 BV respectively, and the dynamic regenerated column volume is 504 BV or 636 BV, compared with that before and after regeneration. The volume of the column decreased by 18.5and the adsorption capacity decreased by 23.70.6. The samples before and after AZGA adsorption were characterized by SEM-EDS,Mapping,FTIR,XPS,NMR,Raman. It was found that AZGA binds to FNP mainly through the abundant hydroxyl groups on the surface. P can also exchange ions with SO42- embedded on the surface of AZGA.
【學位授予單位】：西北農(nóng)林科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X703;X52;O647.3
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