本文選題：介孔硅酸鈣 + 復(fù)合材料　； 參考：《湖南科技大學(xué)》2017年碩士論文

【摘要】：重金屬廢水和有機(jī)染料廢水已成為目前水體污染的兩大難題。與傳統(tǒng)處理方法相比,吸附法操作簡(jiǎn)單,成本較低,適于各類廢水處理,在實(shí)際應(yīng)用中具有巨大潛力。而選擇一種性能優(yōu)良的高效吸附劑是采用該方法取得良好處理效果和經(jīng)濟(jì)效益的關(guān)鍵。本文以介孔硅酸鈣為研究對(duì)象,采用模板法和水解法制備介孔硅酸鈣,再由介孔硅酸鈣分別負(fù)載氧化石墨烯和納米零價(jià)鐵制備成復(fù)合材料,考察了介孔硅酸鈣負(fù)載氧化石墨烯復(fù)合材料對(duì)重金屬離子的吸附性能,探討吸附作用機(jī)理;同時(shí)考察了介孔硅酸鈣負(fù)載納米零價(jià)鐵復(fù)合材料對(duì)重金屬和有機(jī)染料甲基橙的去除效果。(1)以四水硝酸鈣和九水硅酸鈉為原料,十六烷基三甲溴化銨為模板劑,采用模板法制備介孔硅酸鈣,考察了模板劑的去除方法對(duì)其結(jié)構(gòu)、形貌等的影響,并用紅外光譜、X射線衍射、掃描電鏡和BET表面分析等對(duì)其結(jié)構(gòu)進(jìn)行了表征。結(jié)果表明,采用水洗法去除模板劑所制備的介孔硅酸鈣比表面積較大,為244.32 m~2/g,且孔道豐富、清晰,但水洗過程較為繁瑣,燒制法去除模板劑會(huì)影響其孔道結(jié)構(gòu),生成大孔,且比表面積僅為7.31 m~2/g。以正硅酸乙酯和四水硝酸鈣為原料,采用水解法制備介孔硅酸鈣。該方法操作簡(jiǎn)單,制備出的介孔硅酸鈣比表面積較大,為206.17 m~2/g,且表面孔道豐富呈現(xiàn)花狀。兩種硅酸鈣晶型均為水化硅酸鈣。(2)考察了上述兩種方法制備的介孔硅酸鈣對(duì)Cu~(2+)、Zn~(2+)、Cd~(2+)、Mn~(2+)和Ni~(2+)等5種重金屬離子的等溫吸附、熱力學(xué)和動(dòng)力學(xué)特征,探討了吸附劑對(duì)重金屬離子的吸附機(jī)理以及吸附劑的選擇性吸附和再生性能。結(jié)果表明,水解法制備的介孔硅酸鈣對(duì)Cu~(2+)、Zn~(2+)和Cd~(2+)的吸附符合Langmuir模型,是較為理想的單分子層化學(xué)吸附,吸附容量大小為Cu~(2+)Cd~(2+)Zn~(2+);而模板法制備的介孔硅酸鈣對(duì)Mn~(2+)和Ni~(2+)的吸附更符合Freundlich模型,為非均勻表面吸附,吸附容量大小為Ni~(2+)Mn~(2+)。動(dòng)力學(xué)研究表明,兩種介孔硅酸鈣對(duì)重金屬離子的吸附情況均更符合準(zhǔn)二級(jí)吸附動(dòng)力學(xué)模型,升高溫度有利于反應(yīng)進(jìn)行;一般均能在75 min內(nèi)對(duì)重金屬離子達(dá)到吸附平衡。熱力學(xué)研究表明,上述幾種重金屬離子的吸附過程△H0、△G0,為吸熱反應(yīng),自發(fā)進(jìn)行的過程,主要為“熵推動(dòng)”效應(yīng)。水解法介孔硅酸鈣的吸附機(jī)理研究表明,當(dāng)p H為6時(shí)對(duì)Cu~(2+)、Zn~(2+)和Cd~(2+)的吸附效果最好;酸性會(huì)影響吸附劑的孔道結(jié)構(gòu),堿性條件會(huì)使金屬離子水解沉淀;吸附過程中存在金屬離子與鈣離子的交換作用,且鈣離子的交換量與吸附劑對(duì)重金屬離子的吸附能力大小成正比。介孔硅酸鈣對(duì)Cu~(2+)、Cd~(2+)、Zn~(2+)的吸附存在一定的選擇性,選擇性強(qiáng)弱為:Cu~(2+)Cd~(2+)Zn~(2+),與吸附容量大小一致,說明吸附容量的大小可在一定程度上反映吸附選擇性的強(qiáng)弱。兩種材料均具有優(yōu)良的再生性能。(3)以水解法介孔硅酸鈣為載體,與氧化石墨烯復(fù)合制備復(fù)合吸附材料,考察了對(duì)Cu~(2+)的吸附性能。經(jīng)紅外、X射線衍射、掃描電鏡和BET表征,氧化石墨烯不均勻穿插在介孔硅酸鈣孔道中,孔徑均主要分布為10-30 nm,屬介孔材料,相比于原始硅酸鈣比表面積有所降低。復(fù)合材料對(duì)Cu~(2+)的吸附在293 K的條件下,添加量為0.01 g、0.02g和0.03 g的GO與介孔硅酸鈣復(fù)合材料的平衡吸附量依次為7.03 mmol/g、7.11 mmol/g和6.91 mmol/g。在此溫度下的平衡吸附量均高于原始硅酸鈣的6.81 mmol/g,且隨著GO添加量的增多,對(duì)Cu~(2+)的吸附量先增加后減少,最適添加量為0.02 g。吸附過程以化學(xué)吸附為主,吸附過程是比較理想的單層吸附,符合Langmuir模型。其吸附動(dòng)力學(xué)研究表明,準(zhǔn)二級(jí)吸附動(dòng)力學(xué)模型更適于描述介孔吸附劑對(duì)重金屬離子的吸附情況,且升高溫度有助于吸附速率的提高。較原始硅酸鈣能更快達(dá)到平衡,為60 min。復(fù)合材料對(duì)Cu~(2+)的吸附熱力學(xué)研究則表明吸附過程為吸熱反應(yīng),是熵增自發(fā)進(jìn)行的過程。復(fù)合材料的再生性能較強(qiáng),經(jīng)過6次的洗脫循環(huán),去除率僅下降了6.8%。(5)以硫酸鐵為原料,用Na BH_4還原制備納米零價(jià)鐵,再負(fù)載到介孔硅酸鈣上,制備成復(fù)合材料,經(jīng)X射線衍射和掃描電鏡和透射電鏡等表征,所制備的納米零價(jià)鐵成功負(fù)載到介孔硅酸鈣上,且能均勻分散在載體的孔道上。從經(jīng)濟(jì)和效果兩種因素分析,介孔硅酸鈣負(fù)載納米零價(jià)鐵要優(yōu)于納米零價(jià)鐵和介孔硅酸鈣,零價(jià)鐵與硅酸鈣的最佳質(zhì)量比為1:10,反應(yīng)溫度為293 K和p H為中性時(shí)對(duì)甲基橙的去除效果較好。此種比例的復(fù)合材料在處理銅和甲基橙及鋅和甲基橙復(fù)合污染時(shí),不僅效果優(yōu)于原始硅酸鈣對(duì)單一重金屬離子的吸附效果,還能保持良好甲基橙的去除效果。本課題著重于吸附材料對(duì)重金屬和有機(jī)染料的吸附性能研究,制備出具有優(yōu)良效果的吸附劑,為材料的實(shí)際應(yīng)用提供了大量的基礎(chǔ)數(shù)據(jù),是一類極具開發(fā)價(jià)值的新型吸附劑。
[Abstract]:Heavy metal wastewater and organic dye wastewater have become the two problem of water pollution at present. Compared with the traditional treatment methods, the adsorption method is easy to operate and is low in cost. It is suitable for all kinds of wastewater treatment, and has great potential in practical application. In this paper, mesoporous calcium silicate was used as the research object. Mesoporous calcium silicate was prepared by template method and hydrolysis method, and then the mesoporous calcium silicate loaded graphene oxide and nano zero valent iron were prepared. The adsorption properties of mesoporous calcium silicate loaded graphene oxide composite on heavy metal ions were investigated. At the same time, the removal effect of mesoporous calcium silicate loaded nano Zero Valent Iron Composites on heavy metals and organic dye methyl orange was investigated. (1) four calcium nitrate and nine sodium silicate were used as the raw material and sixteen alkyl trimethyl ammonium bromide as a template. The template method was used to prepare mesoporous calcium silicate, and the structure of the template was investigated. The structure was characterized by infrared spectroscopy, X ray diffraction, scanning electron microscopy and BET surface analysis. The results showed that the surface area of mesoporous calcium silicate prepared by water washing method was 244.32 m~2/g, and the pore was rich and clear, but the process of water washing was more complicated. The pore structure is influenced by the formation of a large pore, and the mesoporous calcium silicate is prepared by hydrolysis of ethyl orthosilicate and four calcium nitrate. The method is easy to operate, the surface area of the mesoporous calcium silicate is larger, the surface area is 206.17 m~2/g, and the surface pore is rich in flower shape. Two kinds of calcium silicate crystals are all water. Calcium silicate. (2) the isothermal adsorption of 5 heavy metal ions, such as Cu~ (2+), Zn~ (2+), Cd~ (2+), Mn~ (2+) and Ni~ (2+), prepared by the two methods, were investigated. The mechanism of adsorption and adsorption of adsorbents on heavy metal ions and the selective adsorption and regeneration of adsorbents were investigated. The results showed that the hydrolysis method was used. The adsorption of mesoporous calcium silicate on the adsorption of Cu~ (2+), Zn~ (2+) and Cd~ (2+) conforms to the Langmuir model. It is an ideal single molecular layer chemical adsorption. The adsorption capacity is Cu~ (2+) Cd~ (2+) Zn~ (2+) Zn~. It is Ni~ (2+) Mn~ (2+). The kinetic study shows that the adsorption of heavy metal ions by two mesoporous calcium silicate is more in line with the quasi two stage adsorption kinetic model, and the increase of temperature is beneficial to the reaction. The adsorption equilibrium of heavy metal ions can be reached within 75 min. Thermodynamic study shows the adsorption process of the heavy metal ions above Delta H0, Delta G0, which is a spontaneous process for endothermic reaction, is mainly a "entropy driven" effect. The adsorption mechanism of calcium silicate by hydrolysis method shows that when p H is 6, the adsorption effect of Cu~ (2+), Zn~ (2+) and Cd~ (2+) is the best. Acidity will affect the pore structure of adsorbents, alkaline conditions will make metal ions hydrolyze and precipitate; and the adsorption process is stored. The exchange of metal ions with calcium ions is proportional to the adsorption capacity of the adsorbents on heavy metal ions. The adsorption of Cu~ (2+), Cd~ (2+) and Zn~ (2+) on the adsorption of mesoporous calcium silicate is selective. The selectivity is: Cu~ (2+) Cd~ (2+) Zn~ (2+), which is consistent with the size of adsorption capacity, indicating the size of adsorption capacity. To a certain extent, it can reflect the strength of adsorption selectivity. The two materials have excellent regeneration properties. (3) the composite adsorbents were prepared by the hydrolysis of mesoporous calcium silicate and the compound of graphene oxide. The adsorption properties of Cu~ (2+) were investigated by infrared, X ray diffraction, scanning electron microscopy and BET, and the unevenly interspersed of graphene oxide. In the mesoporous calcium silicate channel, the pore size is mainly distributed at 10-30 nm, which is a mesoporous material, and the specific surface area of the calcium silicate is lower than that of the original calcium silicate. The adsorption amount of the composite material to Cu~ (2+) is 0.01 g, and the equilibrium adsorption capacity of GO and mesoporous Calcium Silicate Composites of 0.02g and 0.03 G is 7.03 mmol/g, 7.11 mmol/g and 7.11 mmol/g. The equilibrium adsorption capacity of 6.91 mmol/g. at this temperature is higher than that of 6.81 mmol/g of the original calcium silicate, and with the increase of GO addition, the adsorption amount of Cu~ (2+) is increased first and then decreased, and the optimum addition amount is 0.02 g. adsorption process mainly by chemical adsorption. The adsorption process is an ideal monolayer adsorption, which is in accordance with the Langmuir model. The adsorption kinetics study The study shows that the quasi two stage adsorption kinetic model is more suitable for describing the adsorption of heavy metal ions by mesoporous adsorbents, and the increase of temperature is helpful to increase the adsorption rate. The adsorption process is faster than that of the original calcium silicate. The adsorption thermodynamics of the 60 min. composite material to Cu~ (2+) shows that the adsorption process is an endothermic reaction, which is entropy increasing spontaneously. The regeneration performance of the composite is strong. After 6 times of elution cycle, the removal rate is only reduced by 6.8%. (5) with ferric sulfate as raw material. The nano zero valent iron is prepared by Na BH_4 reduction and then loaded onto the mesoporous calcium silicate, and the composite is prepared by X ray diffraction and scanning electron microscope and transmission electron microscope. Iron is successfully loaded on the mesoporous calcium silicate and can be evenly distributed on the channel of the carrier. From two factors of economic and effect, the mesoporous calcium silicate loaded nano zero valent iron is superior to nano zero valent iron and mesoporous calcium silicate. The optimum mass ratio of zero valent iron to calcium silicate is 1:10, and the reaction temperature is 293 K and P H is neutral to methyl orange. The effect of the composite is better than that of copper and methyl orange and zinc and methyl orange. The effect is better than the adsorption effect of the original calcium silicate on the single heavy metal ion, but also the removal effect of the good methyl orange. The research focuses on the adsorption properties of adsorbents on heavy metals and organic dyes. The adsorbent with excellent effect provides a lot of basic data for the practical application of materials, and is a new type of adsorbent with great development value.

【學(xué)位授予單位】：湖南科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB33;O647.3

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 劉榆;傅瑞琪;樓子墨;方文哲;王卓行;徐新華;;功能化碳質(zhì)材料的制備及其對(duì)水中重金屬的去除[J];化學(xué)進(jìn)展;2015年11期

2 秦澤敏;董黎明;賴花;周戀彤;;硅酸鈣負(fù)載零價(jià)納米鐵吸附去除水中六價(jià)鉻[J];硅酸鹽通報(bào);2015年08期

3 田延威;沙德宏;高峰;洪建華;嚴(yán)群;;改性硅酸鈣用于養(yǎng)殖廢水厭氧處理過程中除磷研究[J];工業(yè)水處理;2015年05期

4 馮冬燕;孫怡然;于飛;李晨璐;李強(qiáng);郭永福;白仁碧;馬杰;;石墨烯及其復(fù)合材料對(duì)水中重金屬離子的吸附性能研究[J];功能材料;2015年03期

5 馬自偉;葛華才;;氧化石墨烯/殼聚糖復(fù)合材料的制備及吸附研究進(jìn)展[J];材料導(dǎo)報(bào);2014年S1期

6 劉立華;曹菁;李艷紅;劉星;李波;唐安平;;聚(氯化二烯丙基銨)基二硫代氨基甲酸鈉的合成及其對(duì)Cu(Ⅱ)的去除性能[J];環(huán)境化學(xué);2013年09期

7 劉培;陳晨;;螯合沉淀法處理含鉻電鍍廢水[J];電鍍與涂飾;2013年05期

8 王興慧;朱桂茹;高從X&;;短孔道介孔二氧化硅SBA-15對(duì)鈾的吸附性能[J];化工學(xué)報(bào);2013年07期

9 付新;;有序介孔材料的合成及應(yīng)用研究進(jìn)展[J];化學(xué)與生物工程;2012年08期

10 劉立華;李鑫;曾榮今;令玉林;曹菁;李波;;乙二胺多(二硫代甲酸鈉)的合成及對(duì)含銅廢水的去除性能[J];湖南科技大學(xué)學(xué)報(bào)(自然科學(xué)版);2012年02期

相關(guān)博士學(xué)位論文 前2條

1 高軍凱;新型吸附材料的制備及其對(duì)溶液中鈾的凈化研究[D];天津大學(xué);2015年

2 劉立華;新型聚季銨鹽與聚合硫酸鐵復(fù)合絮凝劑合成及其基礎(chǔ)理論與應(yīng)用研究[D];中南大學(xué);2004年

相關(guān)碩士學(xué)位論文 前5條

1 汪翔宇;油頁巖灰渣基類水滑石吸附材料的制備及其對(duì)重金屬離子去除性能的研究[D];吉林大學(xué);2016年

2 楊剛剛;介孔硅酸鈣的合成、改性及其對(duì)重金屬離子的吸附性能[D];湖南科技大學(xué);2016年

3 華婷婷;殼聚糖納米材料的制備及其在重金屬廢水處理中的應(yīng)用[D];華南理工大學(xué);2016年

4 梁海歐;多孔硅酸鈣載銀系摻雜二氧化鈦光催化劑的制備及性能研究[D];內(nèi)蒙古工業(yè)大學(xué);2014年

5 晉瑞杰;電化學(xué)聯(lián)合工藝實(shí)現(xiàn)含鎳廢水的資源化研究[D];中國(guó)海洋大學(xué);2013年

，

本文編號(hào)：1844724