本文選題：鋯改性沸石 + 螺螄殼和魚(yú)骨混合物�。� 參考：《上海海洋大學(xué)》2015年碩士論文

【摘要】：大量含氮(N)、磷(P)等污染物廢水未經(jīng)處理直接排放是引起地表水體污染的主要原因,同時(shí)底泥中氮、磷等污染物向上覆水釋放給水質(zhì)帶來(lái)的巨大影響亦不容忽視�？刂频啄嘀械椎任廴疚锵蛏细菜尼尫艑�(duì)于地表水環(huán)境污染防治是非常必要的。底泥原位改良技術(shù)和活性覆蓋技術(shù)是兩種極具應(yīng)用前景的底泥氮磷釋放控制技術(shù)。成功應(yīng)用這兩種技術(shù)的一個(gè)關(guān)鍵問(wèn)題是尋找合適的吸附劑材料。天然沸石成本低廉且容易獲得,利用其較高的陽(yáng)離子交換性能,可以有效吸附去除水中氨氮。但是天然沸石對(duì)水中磷酸鹽的吸附能力卻較差。將鋯氧化物負(fù)載到天然沸石表面上,所制備得到的鋯改性沸石預(yù)計(jì)可以有效吸附去除水中的氨氮和磷酸鹽,將鋯改性沸石作為底泥改良劑或底泥活性覆蓋材料預(yù)計(jì)可以有效控制底泥氮磷的釋放。本文首先制備了鋯改性沸石,對(duì)鋯改性沸石的結(jié)構(gòu)進(jìn)行了表征,考察了鋯改性沸石對(duì)水中磷酸鹽的吸附作用,對(duì)比分析了鋯改性沸石和鋁改性沸石對(duì)太湖底泥-水系統(tǒng)中溶解性磷酸鹽的固定作用,考察了不同條件下鋯改性沸石改良太湖底泥對(duì)水中磷酸鹽的吸附作用,考察了不同條件下鋯改性沸石添加對(duì)太湖底泥磷釋放的控制效果,考察了鋯改性沸石活性覆蓋控制重污染河道底泥氮磷釋放的效果,并考察了螺螄殼和魚(yú)骨混合物對(duì)水中磷酸鹽的吸附作用,以期為應(yīng)用鋯改性沸石作為底泥改良劑和活性覆蓋材料控制底泥氮磷釋放提供幫助。研究了鋯改性沸石對(duì)水中磷酸鹽的固定作用。結(jié)果表明,鋯改性沸石對(duì)水中磷酸鹽具備很好的吸附能力。鋯改性沸石對(duì)水中磷酸鹽的單位吸附量隨吸附劑投加量的增加而降低,水中殘留的磷酸鹽濃度亦隨著吸附劑投加量的增加而降低。鋯改性沸石對(duì)水中磷酸鹽的吸附能力隨著p H的逐漸增加而逐漸降低。鋯改性沸石對(duì)水中磷酸鹽的吸附符合準(zhǔn)二級(jí)動(dòng)力學(xué)模型。Langmuir等溫吸附模型可以很好地用于描述鋯改性沸石對(duì)水中磷酸鹽的吸附平衡數(shù)據(jù),鋯改性沸石對(duì)磷酸鹽的最大單位吸附量為10.2 mg P/g(p H 7和25oC)。鋯改性沸石所吸附的磷主要以Na OH提取態(tài)磷(Na OH-r P)和殘?jiān)鼞B(tài)(Res-P)形態(tài)存在,通常p H(5~9)和厭氧條件下不容易被重新釋放出來(lái)。對(duì)比分析了鋁改性沸石和鋯改性沸石對(duì)太湖底泥-水系統(tǒng)中溶解性磷酸鹽的固定作用。結(jié)果表明,太湖底泥和改性沸石改良太湖底泥對(duì)水中較高濃度磷的吸附平衡數(shù)據(jù)可以采用Langmuir和Freundlich等溫吸附模型加以描述,吸附動(dòng)力學(xué)過(guò)程可以采用準(zhǔn)二級(jí)動(dòng)力學(xué)模型加以描述。太湖底泥、鋁改性沸石改良及鋯改性沸石改良太湖底泥的最大磷吸附量分別為395、613和1009 mg/kg.鋁改性沸石改良太湖底泥所吸附的磷主要以Na OH-P形態(tài)存在,鋯改性沸石改良太湖底泥所吸附的磷主要以Na OH-P和Res-P形態(tài)存在。當(dāng)水中初始磷濃度很低時(shí),太湖底泥和改性沸石改良太湖底泥均釋放出磷,且后者的釋磷量低于前者。改性沸石改良太湖底泥中生物有效磷(BAP)含量低于太湖底泥,前者的弱吸附態(tài)磷(NH4Cl-P)含量明顯低于后者。鋁改性沸石改良太湖底泥的氧化還原敏感態(tài)磷(BD-P)含量與太湖底泥相比差異不顯著,而鋯改性沸石改良太湖底泥的BD-P含量明顯低于太湖底泥。可見(jiàn),鋁和鋯改性沸石均可以用于控制太湖底泥磷的釋放,鋯改性沸石比鋁改性沸石更適合用于控制太湖底泥磷的釋放。研究了不同條件下鋯改性沸石改良太湖底泥對(duì)水中磷的吸附作用。結(jié)果表明,當(dāng)水中初始磷濃度為1~12 mg P/L時(shí),未改良太湖底泥和鋯改性沸石改良太湖底泥對(duì)磷酸鹽的吸附平衡數(shù)據(jù)可以采用Langmuir和Freundlich模型加以描述。未改良太湖底泥和鋯改性沸石改良太湖底泥對(duì)磷酸鹽的吸附動(dòng)力學(xué)過(guò)程可以采用準(zhǔn)二級(jí)動(dòng)力學(xué)模型進(jìn)行擬合,該吸附過(guò)程屬于吸熱反應(yīng),并且是自發(fā)進(jìn)行的。當(dāng)p H值由2逐漸增加到4時(shí),未改良太湖底泥和鋯改性沸石改良太湖底泥對(duì)磷酸鹽的吸附能力逐漸下降;當(dāng)p H值由5增加到8時(shí),未改良太湖底泥和鋯改性沸石改良太湖底泥對(duì)磷酸鹽的吸附能力變化很小;當(dāng)p H值由8增加到10時(shí),未改良太湖底泥和鋯改性沸石改良太湖底泥對(duì)磷酸鹽的吸附能力急劇下降。溶液中共存的Cl-和SO42-對(duì)未改良太湖底泥和鋯改性沸石改良太湖底泥吸附水中的磷酸鹽無(wú)負(fù)面影響,而溶液中共存的HCO3-和Si O32-會(huì)抑制未改良太湖底泥和鋯改性沸石改良太湖底泥對(duì)水中磷酸鹽的吸附。鋯改性沸石改良太湖底泥的磷吸附-解吸平衡濃度(EPC0)低于未改良太湖底泥。鋯改性沸石改良太湖底泥對(duì)水中磷酸鹽的吸附能力高于未改良太湖底泥。被改良底泥中鋯改性沸石所吸附的磷酸鹽中大部分(約76%)以較穩(wěn)定形態(tài)磷存在,通常p H(5~9)和厭氧條件下它們不容易被重新釋放出來(lái)。研究了不同條件下鋯改性沸石添加對(duì)太湖底泥磷釋放的控制效果。結(jié)果表明,向太湖底泥中添加鋯改性沸石可以有效降低底泥中無(wú)機(jī)磷的活性,可以促進(jìn)底泥中BD-P向Na OH-P和Res-P轉(zhuǎn)化。向太湖底泥中添加鋯改性沸石后,底泥中的水溶性磷(WSP)、Na HCO3可提取態(tài)磷(Olsen-P)和藻類可利用磷(AAP)等生物有效態(tài)磷的含量降低,從而增加了底泥中磷的穩(wěn)定性。不同的p H值、離子強(qiáng)度、Si O32-濃度和底泥有機(jī)質(zhì)(OM)含量等條件下,向底泥中添加鋯改性沸石可以有效的降低底泥中磷向上覆水中磷的釋放通量。厭氧條件下,向底泥中添加鋯改性沸石亦可以有效降低底泥中磷向上覆水的釋放通量。研究了鋯改性沸石活性覆蓋控制重污染河道底泥氮磷釋放的效果。通過(guò)實(shí)驗(yàn)首先考察了鋯改性沸石對(duì)水中磷酸鹽和銨的吸附去除作用,再考察了鋯改性沸石活性覆蓋控制底泥溶解性磷酸鹽和銨釋放的效率。結(jié)果表明,鋯改性沸石對(duì)水中磷酸鹽的吸附能力隨p H的增加而降低。當(dāng)p H由4增加到5時(shí),鋯改性沸石對(duì)水中銨的吸附能力增加;當(dāng)p H 5~8時(shí),對(duì)銨的吸附能力較高;當(dāng)p H由8增加到10時(shí),對(duì)銨的吸附能力下降。鋯改性沸石對(duì)水中磷酸鹽和銨的吸附動(dòng)力學(xué)滿足準(zhǔn)二級(jí)動(dòng)力學(xué)模型,并且對(duì)磷酸鹽和銨的吸附速率比較快。Langmuir和Freundlich等溫吸附模型可以用于描述鋯改性沸石對(duì)水中磷酸鹽和銨的吸附平衡數(shù)據(jù)。根據(jù)Langmuir模型計(jì)算得到的鋯改性沸石對(duì)水中磷酸鹽和銨的最大吸附量分別為7.75和9.59 mg/g(p H 7和25°C)。鋯改性沸石對(duì)水中磷酸鹽和銨的去除率隨鋯改性沸石投加量的增加而增加。鋯改性沸石吸附水中磷酸鹽的主要機(jī)制是配位體交換,吸附水中銨的主要機(jī)制是陽(yáng)離子交換。被鋯改性沸石所吸附的磷酸鹽大部分(82.5%)以較為穩(wěn)定形態(tài)磷(Na OH-P)存在,低溶解氧條件下不容易重新被釋放出來(lái)。吸附磷酸鹽后鋯改性沸石中水溶性磷(WSP)、易解吸磷(RDP)和Na HCO3可提取態(tài)磷(Olsen-P)含量非常低,藻類可利用磷(AAP)含量?jī)H占總磷含量的29%左右。低溶解氧條件下,重污染河道底泥會(huì)釋放出大量的溶解性磷酸鹽和銨;鋯改性沸石活性覆蓋則不僅可以使上覆水中的溶解性磷酸鹽濃度控制到很低的水平,而且可以明顯降低銨由底泥向上覆水遷移的速率。上述實(shí)驗(yàn)結(jié)果表明,鋯改性沸石適合作為一種活性覆蓋材料用于控制底泥溶解性磷酸鹽和銨的釋放。研究了螺螄殼和魚(yú)骨混合物對(duì)水中磷的固定作用。結(jié)果表明,螺螄殼和魚(yú)骨混合物可以有效去除水中的磷酸鹽,并且它的去除能力明顯優(yōu)于單獨(dú)螺螄殼和單獨(dú)魚(yú)骨。螺螄殼和魚(yú)骨混合物對(duì)水中磷酸鹽的去除動(dòng)力學(xué)過(guò)程可以較好地采用準(zhǔn)二級(jí)動(dòng)力學(xué)模型加以描述。螺螄殼和魚(yú)骨混合物對(duì)水中磷酸鹽的單位去除量隨初始磷酸鹽濃度的增加而增加。p H對(duì)螺螄殼和魚(yú)骨混合物去除水中磷酸鹽的影響較小。水中共存的Cl-和SO42-對(duì)螺螄殼和魚(yú)骨混合物去除水中磷酸鹽的影響較小,而水中共存的HCO3-會(huì)抑制螺螄殼和魚(yú)骨混合物對(duì)水中磷酸鹽的去除。水中共存的Na+、K+和Mg2+等陽(yáng)離子對(duì)螺螄殼和魚(yú)骨混合物去除水中磷酸鹽幾乎沒(méi)有影響,而水中共存的Ca2+會(huì)促進(jìn)螺螄殼和魚(yú)骨混合物對(duì)水中磷酸鹽的去除。螺螄殼和魚(yú)骨混合物對(duì)水中磷酸鹽的主要去除機(jī)制包括螺螄殼和魚(yú)骨對(duì)磷酸鹽的表面吸附作用,以及鈣磷化合物沉淀作用。魚(yú)骨可以為鈣磷化合物沉淀的異質(zhì)成核提供核心,促進(jìn)鈣磷化合物沉淀的生成。螺螄殼和魚(yú)骨所釋放出來(lái)的鈣離子可以為鈣磷化合物沉淀的形成提供鈣源。上述結(jié)果表明,利用鋯改性沸石作為底泥改良劑可以有效控制底泥磷的釋放;利用鋯改性沸石作為底泥活性覆蓋材料可以有效控制污染底泥氮磷的釋放。
[Abstract]:A large number of wastewater containing nitrogen (N), phosphorus (P) and other pollutants untreated directly is the main cause of surface water pollution. At the same time, the great influence of the release of nitrogen, phosphorus and other pollutants from the sediment to the water quality can not be ignored. It is often necessary. In situ improvement technology and active covering technology are two promising technology for the release control of nitrogen and phosphorus. The key problem for the successful application of these two technologies is to find suitable adsorbents. Natural zeolite is cheap and easy to obtain, and can be effectively adsorbed by its higher cation exchange properties. The adsorption capacity of natural zeolite to water phosphate is poor. The zirconium modified zeolite can be effectively adsorbed to remove ammonia and phosphate in water by loading zirconium oxide on the surface of natural zeolite. The zirconium modified zeolite is expected to be used as a base mud modifier or a sediment active cover material. The structure of zirconium modified zeolite was first prepared. The structure of zirconium modified zeolite was characterized. The adsorption of zirconium modified zeolite to phosphate in water was investigated. The immobilization effect of zirconium modified zeolite and aluminum modified zeolite on the soluble phosphate in the sediment water system of Taihu was compared and analyzed. The Zr modified zeolite improved the adsorption of phosphate in water from the bottom mud of Taihu. The control effect of Zr modified zeolite on the release of phosphorus in the sediment of Taihu was investigated under different conditions. The effect of Zr modified zeolite activity coverage on the release of nitrogen and phosphorus from the sediment of heavy polluted river was investigated, and the phosphoric acid of the mixture of snail shell and fish bone was examined in the water. The adsorption of salt is helpful for the use of zirconium modified zeolite as a remodifier and active covering material to control the release of nitrogen and phosphorus in the sediment. The immobilized effect of zirconium modified zeolite on phosphate in water has been studied. The results show that zirconium modified zeolite has a good adsorption capacity for phosphate in water. The adsorption capacity of the phosphate in water decreased with the increase of the dosage of adsorbent. The adsorption capacity of zirconium modified zeolite to water phosphate gradually decreased with the increase of P H. The adsorption of phosphate by zirconium modified zeolite conformed to the quasi two stage kinetic model.Langmuir The isothermal adsorption model can be well used to describe the adsorption equilibrium data of phosphate in water by zirconium modified zeolite. The maximum unit adsorption capacity of zirconium modified zeolite to phosphate is 10.2 mg P/g (P H 7 and 25oC). The phosphorus adsorbed by zirconium modified zeolite mainly exists in the form of Na OH extraction state phosphorus (Na OH-r P) and residue state (Res-P). The immobilized effect of aluminum modified zeolite and zirconium modified zeolite to the dissolved phosphate in the sediment water system of Taihu was compared and analyzed. The results showed that the adsorption equilibrium number of the high concentration of phosphorus in the water of the Taihu sediment and modified zeolite modified by the modified zeolite of Taihu could be absorbed by Langmuir and Freundlich isothermal absorption. The adsorption kinetic process can be described by the quasi two order kinetic model. The bottom mud of Taihu, the modification of aluminum modified zeolite and the modified zeolite of zirconium modified zeolite, the maximum phosphorus adsorption capacity of the Taihu sediment is 395613 and 1009 mg/kg. aluminum modified zeolite improved in the form of Na OH-P and zirconium modification. The phosphorus adsorbed by the zeolite improved mainly in the form of Na OH-P and Res-P. When the initial phosphorus concentration in the water is very low, the sediment of the sediment and the modified zeolite in Taihu all release phosphorus, and the latter is lower than the former. The modified zeolite improved the content of the bioavailable phosphorus (BAP) in the bottom mud of Taihu and the weak absorption of the former, the weak absorption of the former in the Taihu mud. The content of NH4Cl-P was significantly lower than that of the latter. The redox sensitive phosphorus (BD-P) content of the modified Taihu sludge was not significantly different from that of Taihu sediment, while the BD-P content of the modified zeolite modified by zirconium modified zeolite was significantly lower than that of Taihu sediment. Therefore, aluminum and zirconium modified zeolite can be used to control the release of phosphorus in the sediment of Taihu. Zirconium modified zeolite is more suitable for controlling the release of phosphorus in Taihu sediment than aluminum modified zeolite. The adsorption of phosphorus on water in Taihu under different conditions of zirconium modified zeolite under different conditions is studied. The results show that when the initial concentration of phosphorus in the water is 1~12 mg P/L, the modified Taihu sediment and zirconium modified zeolite improve the adsorption of phosphate on the base mud of Taihu. The equilibrium data can be described by Langmuir and Freundlich models. The adsorption kinetics of phosphate in Taihu sediment without improved sediment and zirconium modified zeolite in Taihu can be fitted by a quasi two stage kinetic model. The adsorption process belongs to the endothermic reaction and is spontaneous. When the P H value increases from 2 to 4, The adsorption capacity of Taihu sediment on phosphate was gradually reduced without improved sediment and zirconium modified zeolite in Taihu. When the value of P H increased from 5 to 8, the change in the adsorption capacity of Taihu sediment on the base mud of Taihu and zirconium modified zeolite improved little. When the value of P H increased from 8 to 10, the improvement of the modified zeolite and zirconium modified zeolite was too much to be improved. The adsorption capacity of lake bottom mud to phosphate decreased rapidly. The coexisting Cl- and SO42- in the solution had no negative effect on the modified Taihu sediment and zirconium modified zeolite to improve the phosphate in the sediment of Taihu, while the HCO3- and Si O32- in the solution could inhibit the improvement of the phosphate of Taihu sediment by the modified Taihu mud and the zirconium modified zeolite. The adsorption and desorption equilibrium concentration (EPC0) of Taihu sediment was lower than that of unmodified Taihu sediment. The adsorption capacity of phosphate in water by zirconium modified zeolite improved by zirconium modified zeolite was higher than that of unmodified Taihu sediment. Most of the phosphates adsorbed by zirconium modified zeolite in the modified sediment (about 76%) (about 76%) were more stable form phosphorus. They are not easy to be released under the conditions of P H (5~9) and anaerobic conditions. The control effect of zirconium modified zeolite on the release of phosphorus in the sediment of Taihu under different conditions is studied. The results show that the addition of zirconium modified zeolite to the sediment of Taihu can effectively reduce the activity of inorganic phosphorus in the sediment and promote the BD-P to Na OH-P and Re in the sediment. S-P conversion. After adding zirconium modified zeolite to the sediment of Taihu, the content of water soluble phosphorus (WSP), Na HCO3 extractable phosphorus (Olsen-P) and algae can be used as bioavailable phosphorus (AAP) and so on, thus increasing the stability of phosphorus in the sediment. Different P H values, ionic strength, Si O32- concentration and sediment organic matter (OM) content Adding zirconium modified zeolite to the sediment can effectively reduce the release flux of phosphorus from the phosphorus to the overlying water. Under anaerobic conditions, adding zirconium modified zeolite to the sediment can effectively reduce the release flux of phosphorus from the sediment to the overlying water. The effect of zirconium modified zeolite on the adsorption and removal of phosphate and ammonium in water was first investigated. The efficiency of Zr modified zeolite activity coverage to control the release of dissolved phosphate and ammonium was investigated. The results showed that the adsorption capacity of zirconium modified zeolite decreased with the increase of P H. When the P H increased from 4 to 5, the zirconium modified zeolite had a modified boiling. The adsorption capacity of ammonium in water is increased; when p H 5~8, the adsorption capacity of ammonium is higher. When p H increases from 8 to 10, the adsorption capacity of ammonium is decreased. The adsorption kinetics of phosphate and ammonium in water satisfies the quasi two kinetic model, and the adsorption rate of phosphate and ammonium is faster.Langmuir and Freundlich isothermal absorption. The attached model can be used to describe the adsorption equilibrium data of phosphate and ammonium in water by zirconium modified zeolite. The maximum adsorption of phosphate and ammonium in water by zirconium modified zeolite based on Langmuir model is 7.75 and 9.59 mg/g respectively (P H 7 and 25 degree C). The removal rate of phosphate and ammonium in water with zirconium modified zeolite with zirconium modified zeolite The main mechanism for the adsorption of phosphate in water by zirconium modified zeolite is the exchange of ligands. The main mechanism for adsorbing ammonium in water is cation exchange. Most of the phosphate adsorbed by zirconium modified zeolite (82.5%) exists in a more stable form of phosphorus (Na OH-P) and is not easily released under the low dissolved oxygen condition. Adsorption phosphoric acid is not easy to be released. The content of soluble phosphorus (WSP), soluble phosphorus (RDP) and Na HCO3 extractable phosphorus (Olsen-P) in the zirconium modified zeolite after salt is very low, and the content of phosphorus (AAP) in algae is only about 29% of the total phosphorus content. Under the low dissolved oxygen condition, heavy polluted river sediment will release a large amount of dissolved phosphate and ammonium, and the active coverage of zirconium modified zeolite is not only available. In order to control the concentration of dissolved phosphate in the overlying water to a very low level and obviously reduce the rate of migration of ammonium from the bottom mud to the overlying water, the experimental results show that the zirconium modified zeolite is suitable to be used as an active covering material to control the release of dissolved phosphate and ammonium in the sediment. The immobilization of phosphorus in water shows that the mixture of spiral shell and fish bone can effectively remove phosphate in water, and its removal ability is better than that of solitary spiral shell and solitary fish bone. The kinetic process of the removal of phosphate by the mixture of spiral shell and fish bone can be well described by the quasi two stage kinetic model. The removal of phosphate in the snail shell and fish bone mixture with the initial phosphate concentration increases with the increase of the initial phosphate concentration. The effect of.P H on the removal of phosphate in water by the shell of the spiral shell and the fish bone mixture is smaller. The effect of the coexisting Cl- and SO42- on the removal of phosphate in the water by the shell and fish bone mixture in the water is less, and the HCO3- in the water coexisted in the water is suppressed. The coexisting cations such as Na+, K+ and Mg2+ in water have little effect on the removal of phosphate in water by the coexisting cations and fish bone mixtures in water, while the coexisting Ca2+ in water can promote the removal of phosphate from the mixture of spiral shells and fish bone to water. The main removal mechanisms include the adsorption of snail shells and fish bones on the surface of phosphate and the precipitation of calcium and phosphorus compounds. Fish bones can provide the core for the heterogeneous nucleation of calcium and phosphorus compounds and promote the formation of calcium and phosphorus compounds. The calcium ions released by the shell and fish bones can be formed for the formation of calcium and phosphorus compounds. The results show that zirconium modified zeolite can effectively control the release of phosphorus in sediment, and Zr modified zeolite can effectively control the release of nitrogen and phosphorus in contaminated sediment.
【學(xué)位授予單位】：上海海洋大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X52

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