【摘要】：改革開放以來,我國(guó)經(jīng)濟(jì)迅猛發(fā)展,工業(yè)化和城鎮(zhèn)化速度加快。與此同時(shí),產(chǎn)生了各種各樣的重金屬污染,嚴(yán)重威脅了人們的生存和健康。在各種重金屬廢水治理方法中,吸附法由于其處理效率高、吸附劑來源豐富、價(jià)格低廉、無二次污染而被廣泛應(yīng)用于對(duì)重金屬廢水的處理。本課題的研究目的是制備一種對(duì)水體中重金屬具有選擇性吸附和深度去除能力的新型吸附材料,為重金屬廢水治理研發(fā)新的材料。本文利用低溫輻射技術(shù),合成了共聚物水凝膠——聚(聚乙烯亞胺/2-丙烯酸羥乙酯)[p(PEI/HEA)],對(duì)制得的水凝膠進(jìn)行了銅離子印跡,得到銅離子印跡水凝膠Cu(Ⅱ)-p(PEI/HEA),通過一系列表征方法：SEM、EI、FTIR、TGA和XPS,對(duì)水凝膠微觀形貌、元素組成、基團(tuán)種類、熱穩(wěn)定性及元素形態(tài)進(jìn)行了分析,研究了p(PEI/HEA)和Cu(Ⅱ)-p(PEI/HEA)對(duì)Cu(Ⅱ)、Pb(Ⅱ)、Cd(Ⅱ)、Ni(Ⅱ)四種重金屬離子的吸附性能,探討了pH值、溫度、重金屬初始濃度、競(jìng)爭(zhēng)吸附等對(duì)吸附過程的影響,運(yùn)用TGA和XPS分析,解析了水凝膠對(duì)重金屬的吸附機(jī)理,并且探討了水凝膠的脫附再生特性,具體結(jié)論如下：1.在-78℃條件下,用60Co-γ射線對(duì)單體(PEI和HEA)進(jìn)行輻射,合成了聚合物水凝膠p(PEI/HEA)。在此基礎(chǔ)上,采用離子印跡技術(shù),對(duì)合成的水凝膠進(jìn)行銅離子印跡,制備了印跡水凝膠Cu(Ⅱ)-p(PEI/HEA);2.p(PEI/HEA)水凝膠具有多孔網(wǎng)狀結(jié)構(gòu),孔道不規(guī)格,孔徑范圍為10-20μm。銅離子印跡過程使水凝膠孔道尺寸略有增大,且表面粗糙度顯著增大；組分PEI穩(wěn)定存在于水凝膠網(wǎng)絡(luò)結(jié)構(gòu)中;p(PEI/HEA)和Cu(Ⅱ)-p(PEI/HEA)均是HEA和PEI的共聚產(chǎn)物,具有胺基和羥基；水凝膠p(PEI/HEA)和Cu(Ⅱ)-p(PEI/HEA)的熱穩(wěn)定性均高于純HEA單體但低于純PEI；水凝膠Cu(Ⅱ)-p(PEI/HEA)的各組成元素不是均勻分布在其表面及內(nèi)部的,銅離子可成功地被水凝膠吸附到其表面及內(nèi)部；3.不同單體配比的p(PEI/HEA)水凝膠的溶脹性能隨水體積分?jǐn)?shù)的增大以及PEI含量的增多而逐漸增大。溶脹率在2.7～3.4之間,當(dāng)PEI摩爾含量為25%,水所占體積為8/10時(shí),溶脹率達(dá)到最大；其對(duì)重金屬離子的吸附量隨著單體組分中PEI所占的摩爾分?jǐn)?shù)的增大以及體系水分的減少而顯著升高。PEI摩爾含量為25%,且水所占體積為6/10時(shí),對(duì)重金屬具有最優(yōu)的吸附效果；4.銅離子印跡后的水凝膠Cu(Ⅱ)-p(PEI/HEA)對(duì)銅離子的吸附量顯著提高,且遠(yuǎn)遠(yuǎn)高于未印跡的水凝膠p(PEI/HEA);5.水凝膠p(PEI/HEA)和Cu(Ⅱ)-p(PEI/HEA)的吸附量隨著體系pH值的逐漸升高而增大,在pH為5.5時(shí),達(dá)到最大；且均受溫度的影響,提高體系溫度,有利于吸附過程的進(jìn)行。吸附過程是自發(fā)的熵增過程,吸附反應(yīng)是吸熱反應(yīng)；6.水凝膠p(PEI/HEA)和Cu(Ⅱ)-p(PEI/HEA)的等溫吸附過程屬于Langmuir單分子層優(yōu)惠吸附；且其動(dòng)力學(xué)吸附過程符合準(zhǔn)二級(jí)動(dòng)力學(xué)方程,吸附限速步驟是化學(xué)吸附過程；7.Cu(Ⅱ)-p(PEI/HEA)對(duì)銅離子的吸附量受溶液中堿金屬含量的影響,但M/Cu摩爾比大于5之后,吸附量趨于平衡,不再降低；水凝膠Cu(Ⅱ)-p(PEI/HEA)對(duì)重金屬的競(jìng)爭(zhēng)優(yōu)先性為Cu(Ⅱ)Pb(Ⅱ)Cd(Ⅱ)Ni(Ⅱ),在Cu(Ⅱ)/Cd(Ⅱ)、Cu(Ⅱ)/Cd(Ⅱ)和Cu(Ⅱ)/Ni(Ⅱ)的混合溶液中,印跡凝膠對(duì)銅離子的選擇性系數(shù)分別為55.09、107.47、63.12,遠(yuǎn)高于未印跡凝膠,印跡作用提高了水凝膠對(duì)銅離子的選擇性；8.Cu(Ⅱ)-p(PEI/HEA)水凝膠通過化學(xué)吸附作用吸附水中銅離子,具體機(jī)理為含氮基團(tuán)(伯胺、仲胺、叔胺)和含氧基團(tuán)(羥基、羰基)與銅離子之間的絡(luò)合作用；9.最高的脫附效率在EDTA溶液濃度為0.1 mol/L時(shí)達(dá)到,為93.2%。水凝膠Cu(Ⅱ)-p(PEI/HEA)對(duì)銅離子的吸附量隨著吸附-脫附循環(huán)次數(shù)的增多而有所下降但經(jīng)過4次吸附-脫附循環(huán)之后對(duì)銅離子的吸附量仍保持在相對(duì)較高的水平,為初始吸附量的85%。
[Abstract]:Since the reform and opening up, China's economy has developed rapidly and industrialization and urbanization speed up. At the same time, a variety of heavy metal pollution has been produced, which seriously threaten people's survival and health. In the treatment of various heavy metal wastewater, adsorption method has high efficiency, rich adsorbents, low price, and no two pollution. It is widely used in the treatment of heavy metal wastewater. The purpose of this study is to prepare a new type of adsorbents for the selective adsorption and depth removal of heavy metals in the water body, and to develop new materials for the treatment of heavy metal wastewater. In this paper, a copolymer hydrogel, poly (polyethyleneimine /2-), is synthesized by using low temperature radiation technology. Hydroxyethyl acrylate) [p (PEI/HEA)], copper ion imprinting was carried out on the prepared hydrogels, and copper ion imprinted hydrogel Cu (II) -p (PEI/HEA) was obtained. Through a series of characterization methods, SEM, EI, FTIR, TGA and XPS, the micromorphology, element composition, group type, thermal stability and elemental morphology of the hydrogel were analyzed. P (PEI/HEA) and -p were studied. II) the adsorption properties of -p (PEI/HEA) on four kinds of heavy metal ions of Cu (II), Pb (II), Cd (II), Ni (II), and the influence of pH value, temperature, initial concentration of heavy metal and competitive adsorption on the adsorption process. The adsorption mechanism of hydrogels on heavy metals was analyzed by TGA and XPS analysis, and the desorption regeneration characteristics of hydrogels were discussed, and the specific conclusions were discussed. 1. under the condition of -78 C, the monomer (PEI and HEA) was irradiated with 60Co- gamma ray, and polymer hydrogel P (PEI/HEA) was synthesized. On this basis, the synthetic hydrogels were imprinted with copper ion imprinting by ion imprinting technology, and the imprinted hydrogel Cu (II) -p (PEI/HEA) was prepared. The 2.p (PEI/HEA) hydrogel had porous network structure and irregular channel. Lattice, the pore size of 10-20 M. copper ion imprinting process makes the pore size of the hydrogel slightly increased and the surface roughness increases significantly; the component PEI is stable in the hydrogel network structure; P (PEI/HEA) and Cu (II) -p (PEI/HEA) are all the copolymers of HEA and PEI, with the amino groups and hydroxyl groups; hydrogel P (PEI/HEA) and Cu (II) The thermal stability is higher than pure HEA monomer but lower than pure PEI; the composition elements of Cu (II) -p (PEI/HEA) of hydrogel are not evenly distributed on its surface and inside. Copper ions can be adsorbed on the surface and inside of the hydrogel successfully. 3. the swelling properties of P (PEI/HEA) water gel with different monomer ratio increase with the increase of water volume fraction and PEI content The swelling rate is between 2.7 and 3.4. When the PEI molar content is 25% and the volume of the water is 8/10, the swelling rate reaches the maximum. The adsorption capacity of the heavy metal ions increases with the increase of the molar fraction of PEI in the monomer component and the decrease of the system water, and the content of.PEI mole is 25%, and the water occupying body. When the product is 6/10, it has the best adsorption effect on heavy metals, and the adsorption capacity of Cu (II) -p (PEI/HEA) on copper ion after 4. copper ion imprinting is significantly higher than that of P (PEI/HEA), which is far higher than that of the non imprinted hydrogel. The adsorption capacity of the 5. hydrogel P (PEI/HEA) and Cu (II) -p (PEI /HEA) increases with the gradual increase of the system values, which is 5.5. The adsorption process is the spontaneous entropy increase process and the adsorption reaction is endothermic reaction; the isothermal adsorption process of 6. hydrogel P (PEI/HEA) and Cu (II) -p (PEI/HEA) belongs to the Langmuir single molecular layer preferential adsorption, and the kinetic adsorption process conforms to the adsorption process. The adsorption rate of 7.Cu (II) -p (PEI/HEA) is influenced by the content of alkali metals in the solution, but the adsorption amount of M/Cu (II) -p (II) -p (PEI/HEA) is Cu (II) Pb (II) Cd (II) Ni (II) Cd (II) Ni, but the adsorption amount of 7.Cu (II) -p (II) is affected by the alkali metal content in the solution, but after the molar ratio is greater than that of the -p (PEI/HEA). Second, in the mixed solution of Cu (II) /Cd (II), Cu (II) /Cd (II) and Cu (II) /Ni (II), the selectivity coefficient of the imprinted gel to copper ions is 55.09107.47,63.12, respectively, which is much higher than that of the non imprinted gel. The selectivity of the hydrogel improves the selectivity of the copper ion, and 8.Cu (II) -p (PEI/HEA) hydrogel adsorbs copper in water by chemical adsorption. The specific mechanism is the complexation of nitrogen groups (primary amines, secondary amines, tertiary amines) and oxygen containing groups (hydroxyl, carbonyl) and copper ions; 9. the highest desorption efficiency is reached when the concentration of EDTA solution is 0.1 mol/L, and the adsorption amount of Cu (II) -p (PEI/HEA) on the copper separation of 93.2%. hydrogel decreases with the increase of the number of adsorption desorption cycles. However, after 4 cycles of adsorption desorption, the adsorption capacity of copper ions is still relatively high, which is 85%. of initial adsorption capacity.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X703

【共引文獻(xiàn)】

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