本文關(guān)鍵詞： 絮凝劑 復(fù)合材料 磁性 絮凝機(jī)理 分形模型　出處：《中國礦業(yè)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：絮凝劑是水處理過程中最常使用的藥劑之一,其種類繁多、應(yīng)用廣泛。絮凝劑去除水中懸浮顆粒的作用機(jī)理主要包括吸附電中和作用、靜電簇作用、吸附架橋作用以及網(wǎng)捕卷掃作用等。水中的懸浮顆粒物在絮凝劑的作用下首先逐步形成較大的絮團(tuán),所形成的絮團(tuán)在后續(xù)的氣浮或沉淀工藝中從水中分離出來,達(dá)到凈化水質(zhì)的目的。凈化的效率與絮凝劑的絮凝性能緊密相關(guān),在實(shí)際使用過程中為了提高凈化效果,往往將兩種不同類型的絮凝劑配合投加。隨著材料科學(xué)技術(shù)的發(fā)展,有機(jī)-無機(jī)復(fù)合材料不斷地推陳出新,在追求穩(wěn)定絮凝性能的同時(shí)可以將一些特殊功能材料與傳統(tǒng)絮凝劑復(fù)合在一起形成具有特殊功能的復(fù)合絮凝劑。本研究采用納米Fe_3O_4顆粒作為磁性材料制備合成了環(huán)境友好的PAM基復(fù)合磁性絮凝劑,并表征了其結(jié)構(gòu)與性質(zhì);通過混凝實(shí)驗(yàn),探討各型磁性復(fù)合絮凝劑的絮凝效果及絮凝機(jī)理;利用分形理論,研究使用各型絮凝劑形成絮體的分形維數(shù),揭示絮體分形特征與混凝效果之間的關(guān)系,建立了數(shù)學(xué)模型。本研究基于Fe_3O_4所具有穩(wěn)定的晶體結(jié)構(gòu)和很強(qiáng)的鐵磁性,利用油酸將其納米顆粒表面進(jìn)行化學(xué)修飾,然后與丙烯酰胺(AM)單體和二甲基二烯丙基氯化銨(DMDAAC)單體、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)單體等在有機(jī)-無機(jī)雙引發(fā)體系下進(jìn)行水溶液聚合反應(yīng),合成制備了一系列磁性復(fù)合絮凝劑,即陽離子型磁性復(fù)合絮凝劑CMF1、CMF2和CMF3,陰離子型磁性復(fù)合絮凝劑AMF1、AMF2和AMF3,以及兩性型磁性復(fù)合絮凝劑ACMF1、ACMF2和ACMF3。通過FTIR、TG、XRD、SEM、EDX、粒度、磁化率、特性粘度和zeta電位等分析方法,對(duì)磁性復(fù)合絮凝劑的結(jié)構(gòu)和性質(zhì)進(jìn)行了全面地表征,結(jié)果表明:Fe_3O_4被成功引入到復(fù)合絮凝劑的分子鏈上,使復(fù)合絮凝劑帶有磁性,在外磁場(chǎng)的作用下這一特性有利于縮短絮凝后續(xù)工藝泥水分離所需要的時(shí)間,從而能夠減小絮凝后續(xù)氣浮池或沉淀池的容積、減少占地面積、降低投資和運(yùn)行成本。隨著共聚單體種類的變化,磁性復(fù)合絮凝劑具有明顯的帶電性質(zhì),通過對(duì)單體比例的調(diào)節(jié),制備得到一種分子鏈上帶有正負(fù)電荷數(shù)相當(dāng)?shù)膬尚孕痛判詮?fù)合絮凝劑ACMF2。制備的系列磁性復(fù)合絮凝劑具有較好的熱穩(wěn)定性、水溶性,且粒度較小、分散均勻、分子量較高。通過對(duì)熱重曲線的分析,判斷CMF系列磁性復(fù)合絮凝劑及ACMF1、ACMF3為接枝共聚物,分子鏈上存在有雜環(huán),需與其他絮凝劑配合使用,AMF系列磁性復(fù)合絮凝劑及ACMF2為嵌段共聚物,分子鏈呈長直線性,可單獨(dú)使用。將CMF系列磁性復(fù)合絮凝劑、AMF系列磁性復(fù)合絮凝劑和ACMF2分別在高嶺土模擬廢水、Fe(OH)_3膠體溶液模擬廢水和皂土模擬廢水中進(jìn)行系統(tǒng)地混凝實(shí)驗(yàn)研究�？疾炝思铀幜�、pH、攪拌轉(zhuǎn)速和攪拌時(shí)間等因素對(duì)絮凝性能的影響,并結(jié)合混凝反應(yīng)后廢水上清液中的zeta電位和形成絮體的形貌特征分析判斷絮凝劑的作用機(jī)理。結(jié)果表明:除CMF3外,該類絮凝劑均具有良好的絮凝性能,絮體團(tuán)塊狀特征明顯,尺寸較大,易于快速分離,在最佳混凝實(shí)驗(yàn)條件下對(duì)濁度或總鐵含量的去除率均大于90%,有些甚至達(dá)到了99%以上。其中AMF3在混凝過程中隨著GT值的增加經(jīng)歷了絮體形成—破碎—再凝聚—再破碎的復(fù)雜過程。CMF1、AMF2和ACMF2的混凝作用機(jī)理主要是靜電簇作用和磁凝聚作用,伴隨著吸附架橋作用和網(wǎng)捕卷掃作用;CMF2、AMF1和AMF3的混凝作用機(jī)理主要是吸附電中和作用和磁凝聚作用,伴隨著吸附架橋作用和網(wǎng)捕卷掃作用;CMF3的混凝作用機(jī)理主要是吸附電中和作用和磁凝聚作用,存在一定程度的吸附架橋作用,無網(wǎng)捕卷掃作用。其中,磁凝聚作用是該類絮凝劑所特有的機(jī)理,是對(duì)復(fù)雜的混凝作用機(jī)理的補(bǔ)充。利用平面圖形分析技術(shù)對(duì)混凝實(shí)驗(yàn)形成的絮體的分形特征進(jìn)行了統(tǒng)計(jì)計(jì)算,得出混凝實(shí)驗(yàn)條件下絮體的二維分形維數(shù)。在最佳混凝實(shí)驗(yàn)條件下形成的絮體的二維分形維數(shù)都高度接近于2,說明在靜電引力、磁耦合力及范德華引力等結(jié)合力的綜合作用下該類絮凝劑形成的絮體結(jié)構(gòu)緊密,具有自相似性和標(biāo)度不變性分形特征。實(shí)驗(yàn)針對(duì)在各種條件下得到的去除率和絮體的二維分形維數(shù)之間的相關(guān)性,建立了數(shù)學(xué)模型(?),并統(tǒng)計(jì)分析出各因素對(duì)數(shù)學(xué)模型中的α值和β值的影響變化情況,為衡量絮凝劑的性能及混凝效果提供了新的研究方法。
[Abstract]:Is one of the most commonly used chemical flocculants in water treatment, its variety, a wide range of applications. The mechanism of flocculant to remove suspended particles including neutralization, electrostatic adsorption bridging and cluster effect, sweep function. Suspended particles in the water under the action of flocculant first and gradually form a large the floc, the floc flotation or sedimentation process in the separated from the water, achieve the purpose of purifying water quality. The purification efficiency and flocculant flocculation performance are closely related, in the actual use of the process in order to improve the purification effect, often will be two kinds of different types of complex flocculant dosage. With the development of technology materials science, organic inorganic composite materials constantly at the same time, the pursuit of stable flocculation performance can be some special functional materials with traditional flocculants The composite flocculant has special function together to form. This study is the preparation of magnetic material synthesized PAM composite magnetic flocculant using environmental friendly nano Fe_3O_4 particles, and characterized its structure and properties; through coagulation experiments, investigate the flocculation effect and flocculation mechanism of the magnetic composite flocculant; the use of fractal theory, research the formation of flocculant floc fractal dimension, reveal the relationship between fractal characteristics of flocs and the coagulation effect, a mathematical model is established. Based on the Fe_3O_4 has a stable crystal structure and strong ferromagnetism, the chemical modified by oleic acid to the surface of nano particles, and acrylamide (AM) monomers and two dimethyl diallyl ammonium chloride (DMDAAC) monomer, 2- acrylamido -2- methylpropanesulfonic acid (AMPS) monomer in organic - inorganic dual initiator system of aqueous solution polymerization, A series of magnetic composite flocculants were synthesized, the cationic magnetic composite flocculant CMF1, CMF2 and CMF3, anionic magnetic composite flocculant AMF1, AMF2 and AMF3, as well as the amphoteric magnetic composite flocculant ACMF1, ACMF2 and ACMF3. by FTIR, TG, XRD, SEM, EDX, particle size, magnetic susceptibility, intrinsic viscosity and Zeta potential analysis method, structure and properties of magnetic composite flocculant were comprehensively characterized, the results showed that Fe_3O_4 was successfully introduced into the molecular chain of composite flocculant, the composite flocculant with magnetic, the external magnetic field under the action of this characteristic is beneficial to shorten the follow-up process Xu Ning separation time required to volume Xu Ning can reduce the subsequent flotation tank or tank, reduce the area, reducing the investment and running cost. With the change of comonomer type, magnetic composite agent has obvious nature of the charged Xu Ning, By adjusting the monomer ratio, was prepared by a molecular chain with a series of magnetic amphoteric magnetic composite flocculant ACMF2. prepared composite flocculant charge very good thermal stability, water solubility, and smaller particle size, uniform dispersion, high molecular weight. Through the analysis of the thermogravimetric curves. CMF series of magnetic composite flocculant and ACMF1 ACMF3 graft copolymer, the molecular chain there are heterocyclic compounds, to be used in conjunction with other flocculants, AMF series magnetic composite flocculant and ACMF2 block copolymer molecular chain is linear, can be used alone. The CMF series of magnetic composite flocculant, magnetic composite flocculant and AMF series ACMF2 wastewater in kaolin respectively, Fe (OH) _3 colloidal solution of simulated wastewater and bentonite simulated systematically experimental study on coagulation in wastewater was studied. The dosage, pH, stirring speed and stirring time The influence factors on the flocculation performance, and with the zeta potential wastewater in the supernatant and floc morphology analysis of the coagulation reaction after the judgment mechanism of flocculant. The results showed that except CMF3, the flocculant has good flocculation, floc mass characteristics, large size, easy fast separation and in the best coagulation conditions on the turbidity and total iron content removal rate was more than 90%, some even reached more than 99%. The AMF3 in the coagulation process with the increase of GT value after floc formation - crushing - condensed -.CMF1 complex process of crushing, coagulation mechanism and AMF2 ACMF2 is the main function of electrostatic and magnetic cluster agglomeration, along with the network and bridging sweep function; CMF2, coagulation mechanism of AMF1 and AMF3 are mainly the neutralization and magnetic coagulation, adsorption with frame The role of bridge and sweep coagulation; coagulation mechanism of CMF3 is mainly neutralization and magnetic flocculation, adsorption bridging action to a certain extent, no sweep. The magnetic coagulation mechanism is peculiar to the flocculant, is a supplement to the coagulation mechanism of complex. Analysis of fractal characteristics of flocs formed by coagulation technology are calculated using plane graphics, draw mixed fractal dimension of floc coagulation under the experimental conditions. The fractal dimension of flocs formed in the optimum coagulation experimental conditions are highly close to 2, in the electrostatic attraction of flocs the structure of the formation of this type of magnetic coupling force and Fan Dehua force flocculant node force under the comprehensive action closely, with self similarity and scale invariant fractal characteristics. Experiments on two dimensional and removal rate of flocs obtained under various conditions The correlation between fractal dimensions is established, and the influence of various factors on the change of the alpha and beta values in mathematical models is statistically analyzed. It provides a new research method for measuring the performance and coagulation effect of flocculants.

【學(xué)位授予單位】：中國礦業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703

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