【摘要】：堿渣是氨堿法制純堿排出的廢渣,其堆存和排放已造成嚴(yán)重的環(huán)境問題,堿渣治理已成為世界性難題。由于堿渣難以處理,發(fā)達(dá)國(guó)家大多已摒棄氨堿法而尋求新的制堿工藝。我國(guó)是發(fā)展中國(guó)家,工業(yè)發(fā)展水平相對(duì)落后,舍棄氨堿法不符合現(xiàn)有國(guó)情,故堿渣治理只能走綜合利用之路,以期變廢為寶,化解其資源和環(huán)境問題。目前,堿渣綜合利用已在農(nóng)業(yè)、化工、建筑材料等諸多領(lǐng)域進(jìn)行研究,并取得一定成果,但堿渣利用率低是目前應(yīng)用的主要問題。2013年,我國(guó)堿渣綜合利用率不到16%。究其原因,則是農(nóng)業(yè)、化工等領(lǐng)域本來需量較少,而建材領(lǐng)域雖需求量大,但堿渣氯離子含量太高,會(huì)嚴(yán)重威脅建筑物耐久性,因此阻礙了其大量應(yīng)用。針對(duì)以上問題,本文首先研究了堿渣的物相組成及微觀結(jié)構(gòu),在此基礎(chǔ)上采用浸泡、粉磨、水洗、電滲等方法研究了堿渣的氯離子溶出特性。進(jìn)而研究了堿渣作為礦物摻合料對(duì)砂漿和混凝土性能的影響,得到了堿渣用作礦物摻合料的適宜處理方法及應(yīng)用方式。本文主要研究?jī)?nèi)容和研究結(jié)論如下：(1)通過X-射線熒光光譜、XRD析、差熱分析等方法研究了堿渣化學(xué)組成及物相組成,結(jié)果表明堿渣主要物相為碳酸鈣、二水石膏、氯化鈣。通過掃描電鏡、激光粒度儀、壓汞、氮吸附等方法研究了堿渣的微觀結(jié)構(gòu)構(gòu)成,結(jié)果表明堿渣微觀結(jié)構(gòu)是：由納米碳酸鈣通過結(jié)合和搭接形成2-5umm的團(tuán)聚體顆粒,團(tuán)聚體顆粒間結(jié)合形成10-74um的聚集體顆粒,聚集體顆粒和二水石膏通過堆積、搭接構(gòu)成堿渣土的宏觀形貌。堿渣土具有發(fā)達(dá)的孔隙結(jié)構(gòu),包括：聚集體顆粒間的空隙、聚集體內(nèi)部的微米級(jí)孔隙結(jié)構(gòu)、團(tuán)聚體顆粒上的納米級(jí)微孔。(2)通過浸泡試驗(yàn)研究了堿渣聚集體顆粒加水分散后空隙中氯離子的溶出特性；通過粉磨試驗(yàn)研究了破壞堿渣聚集體內(nèi)部微米級(jí)孔隙后的氯離子溶出特性；通過高水固比條件下的多次水洗試驗(yàn)研究了聚集體內(nèi)部微米級(jí)孔隙中氯離子的擴(kuò)散溶出特性；通過電滲試驗(yàn)研究了團(tuán)聚體內(nèi)部納米級(jí)孔隙中氯離子在電場(chǎng)作用下的進(jìn)一步溶出。結(jié)果表明,堿渣氯離子主要存在于聚集體顆粒間的空隙中,部分存在于聚集體內(nèi)部團(tuán)聚體顆粒間的微米級(jí)孔隙中,團(tuán)聚體上納米級(jí)微孔中氯離子含量極低。堿渣中氯離子的分布約為：空隙水中含73%、微米級(jí)孔隙水中含20%、納米級(jí)微孔水中含7%。堿渣氯離子主要為可溶性氯離子,可通過水洗去除。(3)通過正交試驗(yàn)研究了摻加堿渣的優(yōu)化砂漿膠凝材料組成；采用優(yōu)化的膠凝材料組成,研究了原狀堿渣、水洗堿渣、除氯堿渣對(duì)砂漿性能的影響及除氯堿渣用作砂漿保水劑的可行性。結(jié)果表明：氯離子含量低于0.30%的除氯堿渣可作為礦物摻合料應(yīng)用于砂漿。除氯堿渣、粉煤灰、礦粉的較佳摻量組合為：堿渣10%-15%、粉煤灰10%-20%、礦粉10%。除氯堿渣取代15%粉煤灰時(shí),砂漿28d抗壓強(qiáng)度可提高74%,膠凝材料可溶氯含量低于鋼筋混凝土環(huán)境的限值(0.1%),可滿足耐久性要求,砂漿可溶性氯離子浸出含量遠(yuǎn)低于地下水排放限值,不會(huì)造成地下水源污染。除氯堿渣用作砂漿保水劑時(shí),摻加減水劑保持水膠比不變時(shí),砂漿保水性能和干縮性能優(yōu)于傳統(tǒng)有機(jī)保水劑,可單獨(dú)作為砂漿保水劑使用。(4)通過堿渣單摻和復(fù)摻試驗(yàn)研究了較優(yōu)的混凝土膠凝材料組成；采用優(yōu)化的膠凝材料組成,研究了原狀堿渣、水洗堿渣、除氯堿渣對(duì)混凝土力學(xué)性能、耐久性及環(huán)境的影響。結(jié)果表明,堿渣、粉煤灰、礦粉的適宜摻量分別為10%、10%-20%、10-20%。摻加減水劑保持水膠比不變時(shí),以堿渣取代10%的粉煤灰或水泥后混凝土強(qiáng)度均略有增大。但摻入原狀堿渣和水洗一次堿渣均會(huì)造成鋼筋銹蝕,不能滿足耐久性要求。而摻入氯離子含量低于0.30%的除氯堿渣不會(huì)造成鋼筋銹蝕,其半電池電位測(cè)定值遠(yuǎn)低于鋼筋銹蝕電位臨界值,且和未摻堿渣的空白組十分接近,可滿足耐久性要求。氯離子含量低于0.30%的除氯堿渣可作為混凝土礦物摻合料使用,無需摻阻銹劑即可使用。
[Abstract]:Alkali residue is a kind of waste residue discharged from ammonia-alkali soda process. Its storage and discharge have caused serious environmental problems. The treatment of alkali residue has become a worldwide difficult problem. At present, the comprehensive utilization of alkali residue has been studied in many fields, such as agriculture, chemical industry, building materials and so on. However, the low utilization rate of alkali residue is the main problem of its application. In 2013, the comprehensive utilization of alkali residue in China was carried out. The rate is less than 16%. The reason is that the demand in agriculture, chemical industry and other fields is small, but the demand in building materials is large, but the chloride ion content of alkali residue is too high, which will seriously threaten the durability of buildings, thus hindering its extensive application. The chloride ion dissolution characteristics of alkali slag were studied by soaking, grinding, washing and electroosmosis. The effect of alkali slag as mineral admixture on the properties of mortar and concrete was studied. The suitable treatment methods and application methods of alkali slag as mineral admixture were obtained. The chemical composition and phase composition of alkali residue were studied by means of spectroscopy, XRD and differential thermal analysis. The results showed that the main phase of alkali residue was calcium carbonate, dihydrate gypsum and calcium chloride. The agglomerate particles of 2-5 umm are formed by bonding and lapping, and the agglomerate particles of 10-74 umm are formed by bonding. The agglomerate particles and dihydrate gypsum are stacked together to form the macroscopic morphology of alkali slag soil. (2) The leaching characteristics of chloride ions in the pores of alkali residue aggregates dispersed by adding water were studied by immersion test; the leaching characteristics of chloride ions after destroying the micro-pores of alkali residue aggregates were studied by grinding test; and the leaching characteristics of chloride ions were studied by multiple washing tests under high water-solid ratio. The diffusion and dissolution characteristics of chloride ions in the micron-sized pores in the aggregates were studied by electroosmosis experiment, and the further dissolution of chloride ions in the nano-sized pores in the aggregates under electric field was studied. Chloride ion content in nano-pore of aggregate is very low in meter-scale pore. The distribution of chloride ion in alkali slag is about 73% in pore water, 20% in micro-pore water and 7% in nano-pore water. Chloride ion in alkali slag is mainly soluble chloride ion and can be removed by water washing. (3) The optimized sand with alkali slag was studied by orthogonal test. The effect of original alkali slag, washing alkali slag, removing chlor-alkali slag on the properties of mortar and the feasibility of using chlorine-alkali slag as water-retaining agent for mortar were studied by using optimized cementitious material composition. The optimum content of slag is 10%-15%, fly ash 10%-20% and slag 10%. When the slag is used to replace 15% fly ash, the compressive strength of mortar can be increased by 74%. The soluble chlorine content of cementitious material is lower than the limit value of reinforced concrete environment (0.1%). It can meet the durability requirement. The leaching content of soluble chloride ion of mortar is far lower than that of groundwater discharge. When dechlorinated alkali slag is used as water-retaining agent for mortar, the water-retaining performance and dry shrinkage performance of mortar are better than those of traditional organic water-retaining agent when water-reducing agent is added to keep water-binder ratio unchanged, and can be used as water-retaining agent for mortar alone. (4) Optimum composition of concrete cementing material is studied by mixing alkali slag with single and compound. The effects of original alkali slag, washing alkali slag and removing chlor-alkali slag on the mechanical properties, durability and environment of concrete were studied by using the optimized cementitious material composition. The results show that the suitable dosage of alkali slag, fly ash and mineral powder are 10%, 10% - 20% and 10 - 20% respectively. The strength of the solidified soil increases slightly, but the corrosion of the reinforcing steel bar will be caused by mixing the undisturbed alkali slag with the first washing alkali slag, which can not meet the durability requirements. The slag containing less than 0.30% chloride ion can be used as concrete mineral admixture without any rust inhibitor.
【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TU528

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本文編號(hào)：2214687