本文選題：二氧化氯　切入點(diǎn)：消毒副產(chǎn)物　出處：《哈爾濱工業(yè)大學(xué)》2016年博士論文　論文類型：學(xué)位論文

【摘要】：我國《生活飲用水衛(wèi)生標(biāo)準(zhǔn)》GB5749-2006規(guī)定二氧化氯可作為飲用水消毒劑,但其在消毒過程中所產(chǎn)生的無機(jī)消毒副產(chǎn)物,對人類健康存在潛在的危害。在二氧化氯消毒劑的使用過程中,確保其消毒效果,保證消毒副產(chǎn)物不超標(biāo)是目前水廠關(guān)注的重點(diǎn)。而在飲用水輸送過程中,管網(wǎng)對水質(zhì)產(chǎn)生影響因素眾多,系統(tǒng)分析飲用水流經(jīng)管網(wǎng)過程中消毒副產(chǎn)物的濃度變化及相關(guān)影響因素與機(jī)制,進(jìn)而幫助二氧化氯投加量的精確調(diào)控是本文的研究目的。通過評估水中含氯化合物的檢測技術(shù),闡明了顯色劑DPD的動(dòng)力學(xué)的區(qū)分效果最好,響應(yīng)時(shí)間為30s,加標(biāo)回收率98.5%;掩蔽劑EDTA的響應(yīng)時(shí)間最短(50s),標(biāo)準(zhǔn)偏差0.02mg/L。采用上述檢測方法,分析了實(shí)際水廠的二氧化氯及其消毒副產(chǎn)物分布特征。認(rèn)為高純二氧化氯消毒的供水管網(wǎng)中產(chǎn)生的主要副產(chǎn)物是亞氯酸鹽,不同季節(jié)的管網(wǎng)中二氧化氯和亞氯酸鹽的濃度都呈現(xiàn)轉(zhuǎn)化趨勢,且管網(wǎng)中的管垢存積會(huì)對亞氯酸鹽產(chǎn)生影響。對實(shí)際管網(wǎng)水中消毒副產(chǎn)物濃度進(jìn)行分析,得到亞氯酸鹽轉(zhuǎn)化率為22.6%。在此發(fā)現(xiàn)基礎(chǔ)上,為了闡明基于高純二氧化氯消毒的供水管網(wǎng)中亞氯酸鹽轉(zhuǎn)化的原因,通過研究二氧化氯衰減的影響因素,發(fā)現(xiàn)二氧化氯的衰減速率在鑄鐵管網(wǎng)中最高,PVC管最低;二氧化氯初始濃度與其衰減速率呈負(fù)相關(guān)趨勢;溫度和水流速度與二氧化氯衰減速率呈正相關(guān)趨勢;二氧化氯的衰減符合一級反應(yīng)動(dòng)力學(xué)。通過分析供水管網(wǎng)中水相因素對消毒副產(chǎn)物轉(zhuǎn)化的作用,表明二氧化氯的主要消毒副產(chǎn)物,亞氯酸鹽的轉(zhuǎn)化受游離二氧化氯濃度、管網(wǎng)材質(zhì)、亞鐵離子和零價(jià)鐵濃度的影響。分析亞氯酸鹽轉(zhuǎn)化的關(guān)鍵影響因素,結(jié)果表明0.05mg/L Fe2+、0.3mg/L Fe0、0.5mg/L Cl O2、p H 7.0、20℃的條件最符合實(shí)際管網(wǎng)轉(zhuǎn)化環(huán)境,轉(zhuǎn)化率為1.2%。為了分析供水管網(wǎng)中固相因素對亞氯酸鹽轉(zhuǎn)化的作用,探討了管垢吸附消毒副產(chǎn)物的影響因素。采用吸附動(dòng)力學(xué)二級模型、顆粒內(nèi)擴(kuò)散模型和吸附熱力學(xué)Freundlich模型擬合分析,說明管垢吸附是以化學(xué)吸附為主,其中顆粒內(nèi)擴(kuò)散是影響吸附速率的限速步驟之一。通過熱力學(xué)平衡分析,闡明了管垢吸附Δ?00,是自發(fā)進(jìn)行的吸附。同時(shí),采用X熒光光譜分析(WDXRF)、X射線衍射分析(XRD)、X射線光電子能譜分析(XPS)等分析儀器對管垢吸附亞氯酸鹽前后的組分進(jìn)行分析,結(jié)果表明管垢吸附后增加的氯元素價(jià)態(tài)主要為-1價(jià),從理論與實(shí)驗(yàn)兩個(gè)水平上解釋了管垢吸附消毒副產(chǎn)物的影響因素及吸附行為。最后在以上研究基礎(chǔ)上,構(gòu)建了消毒副產(chǎn)物的吸附模型,并運(yùn)用響應(yīng)曲面分析技術(shù)進(jìn)行優(yōu)化。建立了亞氯酸鹽的管垢吸附模型為η=212.40+37.35C_o-48.23pH+2.75T-6.00C_opH~2-0.07T~2。運(yùn)用模型及優(yōu)化條件預(yù)測了管垢吸附亞氯酸鹽的轉(zhuǎn)化率,為16.8%。結(jié)合化學(xué)轉(zhuǎn)化率1.2%,預(yù)測管網(wǎng)中亞氯酸鹽的總轉(zhuǎn)化率為18.0%,與管網(wǎng)調(diào)查中獲得的轉(zhuǎn)化率22.6%接近。參照我國《生活飲用水衛(wèi)生標(biāo)準(zhǔn)》,按照理論轉(zhuǎn)化率95-98%計(jì)算,二氧化氯的最大實(shí)際投加量為1.14-1.18 mg/L�；诟呒兌趸认镜牡叵滤�,按照國際上最嚴(yán)格的標(biāo)準(zhǔn),亞氯酸鹽允許濃度不超過0.2mg/L,計(jì)算得到二氧化氯的理論投加量增加0.04mg/L時(shí)仍然符合標(biāo)準(zhǔn);按照我國的標(biāo)準(zhǔn),亞氯酸鹽允許濃度不超過0.7mg/L,計(jì)算得到二氧化氯的理論投加量增加0.18mg/L時(shí)仍然符合國家標(biāo)準(zhǔn)。綜上所述,本論文通過研究高純二氧化氯消毒的給水管網(wǎng)中消毒副產(chǎn)物亞氯酸鹽的轉(zhuǎn)化機(jī)制,對實(shí)際使用中二氧化氯投加量的精確調(diào)控提供了幫助與理論依據(jù),有助于實(shí)現(xiàn)從安全用水到健康用水的新局面。
[Abstract]:>GB5749-2006 sanitary standard for drinking water in China "can be used as drinking water regulations of chlorine dioxide disinfectant, but inorganic disinfection by-products generated in the process of disinfection, the potential harm to human health. In the process of using chlorine dioxide disinfectant, ensure the disinfection effect, ensure the disinfection by-products does not exceed the standard is the focus of attention in current while drinking water. In the transport process, the pipeline network to quality factors, system factors and mechanism analysis of concentration of disinfection by-products in drinking water management process and related effects, precise control and help of chlorine dioxide dosage is the purpose of this study. By evaluating the water detection technology of chlorinated compounds that illustrates the dynamics of chromogenic agent DPD to distinguish the best effect, the response time is 30s, the recovery rate of 98.5%; the response time of the masking agent EDTA (50s), marking the shortest The standard deviation of the 0.02mg/L. detection method, analyzed the distribution characteristics of disinfection by-products of chlorine dioxide and its actual water. That the main by-product of high purity chlorine dioxide in the water supply network is chlorite, the concentration of network in different seasons of chlorine dioxide and chlorite are transformation trend, and pipe scale in the network storage product will have an impact on chlorite. The actual pipe network water disinfection by-products concentration analysis, get the chlorite conversion rate is 22.6%. on the basis of this, in order to clarify the reason of high purity chlorine dioxide disinfection of water supply network based on the transformation of the chlorite, factors according to the influence of chlorine dioxide decay, found the highest rate in the cast iron pipe in the decay of chlorine dioxide, PVC minimum; chlorine dioxide concentration and initial decay rate was negatively correlated; temperature and flow rate and two The oxidation of chlorine decay rate was positively correlated; the decay of chlorine dioxide followed first-order kinetics. Through the analysis of water supply networks of water phase factors on Transformation of disinfection by-products of chlorine dioxide disinfection, showed that the main by-products, conversion of chlorite by free chlorine dioxide, pipeline material, effects of ferrous ion and zero valent iron concentration. Analysis of key factors influencing chlorite conversion, the results show that 0.05mg/L Fe2+, 0.3mg/L Fe0,0.5mg/L Cl O2, P H 7.0,20 DEG C is the most realistic network environment for the transformation, the conversion rate of 1.2%. in order to analyze the factors of water supply network in solid phase transformation of chlorite, and discusses the factors affecting the adsorption pipe scale disinfection by-products. The adsorption kinetics of two level model, analysis model and the adsorption thermodynamics of Freundlich particle diffusion model fitting, illustrate the pipe scale adsorption is mainly chemical adsorption, the In the intra particle diffusion is one of the rate limiting step of the adsorption rate. The thermodynamic equilibrium analysis, the pipe scale is 00, the adsorption was spontaneous? Adsorption. At the same time, the analysis of fluorescence spectra of X (WDXRF), X ray diffraction (XRD), X ray photoelectron spectroscopy (XPS) analysis instrument the pipe scale before and after adsorption of chlorite were analyzed, results showed that chlorine pipe scale after adsorption increased valence is mainly -1 price, explains the factors and influence the adsorption behavior of pipe scale adsorption disinfection by-products from the two levels of theory and experiment. Finally based on the above research, the construction of adsorption the model of disinfection by-products, and the use of response surface analysis techniques were optimized. A pipe scale adsorption model of chlorite as the model and the optimization conditions of =212.40+37.35C_o-48.23pH+2.75T-6.00C_opH~2-0.07T~2. by ETA predicted chlorite adsorption pipe scale Salt conversion rate, 16.8%. combined with chemical conversion rate of 1.2%, the total conversion prediction network chlorite rate was 18%, 22.6% and close to the conversion rate of the network investigation. According to "our drinking water health standards", in accordance with the theory of computing the conversion rate of 95-98%, the actual chlorine dioxide dosage is 1.14-1.18 mg/L. underground water of high purity chlorine dioxide disinfection based on in accordance with the most stringent standards, chlorite allowable concentration is less than 0.2mg/L, calculated by the theory of chlorine dioxide dosage still conforms to the standard of 0.04mg/L increase; in accordance with the standard of our country, the chlorite allowable concentration does not exceed 0.7mg/L, calculated by the theory of adding chlorine dioxide increase the amount of 0.18mg/L is still in line with national standards. In summary, this paper through the transformation mechanism of water supply pipe network of high purity chlorine dioxide disinfection disinfection by-products in the chlorite, on The accurate control of the dosage of chlorine dioxide in actual use provides a help and theoretical basis, and helps to realize a new situation from safe water to healthy water.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：R123.6

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本文編號：1625887