【摘要】：近年來,水資源危機(jī)日益嚴(yán)重,工業(yè)循環(huán)冷卻水系統(tǒng)補(bǔ)給水的水源逐步被再生水替代,該措施在一定程度上緩解了用水緊缺狀況,但再生水引起的循環(huán)冷卻系統(tǒng)結(jié)垢問題,以及污水外排造成了環(huán)境污染問題日趨嚴(yán)重。因此,需要合成一種高效且環(huán)境友好的水處理藥劑。本文在聚天冬氨酸改性的基礎(chǔ)上研發(fā)出了一種新型的水處理藥劑,用于解決系統(tǒng)中存在的問題。首先,以天冬氨酸和蘋果酸為原料,采用微波加熱的方式,合成了天冬氨酸-蘋果酸共聚物(PAMA)。研究了原料配比、微波功率、微波時(shí)間等對(duì)共聚物的絡(luò)合性能及產(chǎn)率的影響,得到了最優(yōu)合成工藝條件:以KH2PO4為催化劑,N-N二甲基甲酰胺(DMF)為有機(jī)溶劑,當(dāng)n(Asp)/n(Asp+MA)=0.5,n(Cat)/n(Asp+MA)=0.10,V(DMF)=6mL,微波功率為1000W,微波時(shí)間3.5min時(shí),合成的共聚物產(chǎn)率達(dá)到98.91%,絡(luò)合量達(dá)到500mg/g。利用紅外光譜和核磁共振表征了天冬氨酸-蘋果酸共聚物的結(jié)構(gòu)。其次,對(duì)天冬氨酸-蘋果酸共聚物的可生物降解性進(jìn)行了研究,結(jié)果表明:PAMA是一種易生物降解的藥劑;在一定范圍內(nèi),分子量越小,蘋果酸含量越高,PAMA可生物降解性越好;蘋果酸和天冬氨酸的可生物降解性能接近,而PAMA的降解效果較其兩個(gè)單體差一些;加入Al~(3+)和Mn~(2+)對(duì)PAMA的可生物降解性能沒有產(chǎn)生負(fù)面影響,甚至在Mn~(2+)的存在下,PAMA的可生物降解性能有所提升;而加入Zn~(2+)和Cu~(2+)對(duì)PAMA的可生物降解性能均產(chǎn)生了負(fù)面影響,并且Cu~(2+)的負(fù)面影響最嚴(yán)重;PAMA的降解效果優(yōu)于ATMP和HEDP,但是較PASP和PBTCA的效果要差一些。之后,對(duì)天冬氨酸-蘋果酸共聚物的絡(luò)合性能進(jìn)行研究,針對(duì)CaCO_3和CaSO4兩種垢型,考察了阻垢劑投加量、pH值、金屬離子濃度、恒溫溫度、恒溫時(shí)間不同時(shí),PAMA對(duì)二者Ca~(2+)的絡(luò)合性能的影響,結(jié)果表明:PAMA適用于溫度較高,水力停留時(shí)間較長的循環(huán)冷卻水系統(tǒng);溶液中加入金屬離子后,PAMA的絡(luò)合性能降低,在金屬離子超過一定濃度以后,絡(luò)合性能幾乎完全喪失。因此,在循環(huán)冷卻系統(tǒng)中應(yīng)嚴(yán)格控制金屬離子的含量。最后,利用XRD和SEM對(duì)天冬氨酸-蘋果酸共聚物的絡(luò)合機(jī)理進(jìn)行探討,結(jié)果表明:加入PAMA后,晶體結(jié)構(gòu)由方解石轉(zhuǎn)變?yōu)榍蝣笔?晶型由規(guī)則堅(jiān)硬的六面體變?yōu)椴灰?guī)則結(jié)構(gòu)松散的體形。
[Abstract]:In recent years, the crisis of water resources is becoming more and more serious, the source of recharge water of industrial circulating cooling water system is replaced by reclaimed water gradually, this measure alleviates the shortage of water to some extent, but the scale problem of circulating cooling system caused by reclaimed water. The problem of environmental pollution caused by sewage efflux is becoming more and more serious. Therefore, it is necessary to synthesize an efficient and environmentally friendly water treatment agent. Based on the modification of polyaspartic acid, a new water treatment agent was developed to solve the problems in the system. Firstly, aspartic acid-malic acid copolymer (PAMA). Was synthesized by microwave heating using aspartic acid and malic acid as raw materials. The effects of raw material ratio, microwave power and microwave time on the complexation properties and yield of copolymers were studied. The optimum synthetic conditions were obtained as follows: using KH2PO4 as catalyst and N-N dimethylformamide (DMF) as organic solvent. When n (Asp) / n (Asp MA) 0.5n (Cat) / n (Asp MA) 0.10V (DMF) 6mL, microwave power 1000W, microwave time 3.5min, the yield of the synthesized copolymers is 98.91 and the complexation amount is 500mg / g. The structure of aspartic acid-malic acid copolymer was characterized by IR and NMR. Secondly, the biodegradability of aspartic acid-malic acid copolymers was studied. The results showed that: (1) PAMA is a biodegradable agent, and the lower the molecular weight is, the higher the malic acid content is, the better the biodegradability of PAMA is. The biodegradability of malic acid and aspartic acid was similar, but the degradation effect of PAMA was worse than that of its two monomers, and the addition of Al3 and Mn2 had no negative effect on the biodegradability of PAMA. Even in the presence of Mn2, the biodegradability of PAMA was improved, but the addition of Zn2 and Cu2 had a negative effect on the biodegradability of PAMA. The degradation effect of Cu2 was more serious than that of ATMP and PBTCA, but it was worse than that of PASP and PBTCA. After that, the complexing properties of aspartic acid-malic acid copolymer were studied. The pH value, concentration of metal ions, constant temperature of scale inhibitor were investigated for two kinds of scale types: CaCO_3 and CaSO4. The effect of PAMA on the complexation property of Ca2 was studied at different time of constant temperature. The results showed that the ratio of PAMA to PAMA was suitable for circulating cooling water system with high temperature and long HRT, and the complexation property of PAMA was decreased when metal ions were added into the solution. When metal ions exceed a certain concentration, the complexation property is almost completely lost. Therefore, the content of metal ions should be strictly controlled in the circulating cooling system. Finally, the complexation mechanism of aspartic acid-malic acid copolymers was investigated by XRD and SEM. The results showed that the crystal structure of the copolymers changed from calcite to vermicelli after the addition of PAMA. The crystal form changes from the regular hard hexahedron to the irregular structure loose body shape.
【學(xué)位授予單位】：華北電力大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.3;X703

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