再生水中水質(zhì)因子對(duì)不銹鋼管材的腐蝕影響及控制研究
發(fā)布時(shí)間：2018-11-11 15:52
【摘要】：本課題以熱電廠循環(huán)冷卻水系統(tǒng)為研究背景,以316L不銹鋼(Stainless steel 316L,SS316L)為研究材質(zhì),以取自北京高碑店再生水廠的二級(jí)出水的再生水作為研究介質(zhì),以硫酸鹽還原菌(Sulfate Reducing Bacteria,SRB)為研究菌種,采用水分析化學(xué)、生物化學(xué)、電化學(xué)和表面分析等方法,對(duì)北方4個(gè)代表性電廠(A、B、C、D)的再生水進(jìn)行水質(zhì)分析和評(píng)估;研究了濃縮3倍循環(huán)水中Cl-、氨氮、SO42-對(duì)SS316L電化學(xué)腐蝕影響;研究了 4種阻垢緩蝕劑之間的協(xié)同效應(yīng)以及對(duì)SS316L的緩蝕效果;分別研究了殺菌劑和阻垢緩蝕劑對(duì)SS316L表面SRB生物膜化學(xué)組分及腐蝕行為的影響,從生物膜特性及膜下腐蝕的角度判斷了藥劑緩蝕性能的優(yōu)劣。通過以上研究,本課題可以為熱電廠防腐防垢的藥劑選擇提供一定的理論和數(shù)據(jù)支持。研究取得了如下成果:(1)水質(zhì)分析評(píng)估表明,北方4個(gè)電廠的再生水中存在結(jié)垢問題,主要是CaCO3、BaSO4和Ca3(PO4)2等鹽類的結(jié)垢;SO42-存在超標(biāo)的問題,Cl-引起較大的腐蝕傾向;有機(jī)物含量較為豐富、含氮量超標(biāo),有利于微生物的滋生。(2)電化學(xué)研究表明,當(dāng)濃縮3倍循環(huán)水中Cl-濃度超過380mg/L,Cl-對(duì)SS316L鈍化膜的侵蝕作用明顯加劇,表現(xiàn)為陽極溶解電流密度顯著增加,最大達(dá)到2.11μA/cm2;當(dāng)氨氮濃度超過15mg/L,氨氮對(duì)SS316L鈍化膜的侵蝕作用明顯加劇,最大陽極溶解電流密度達(dá)到1.01 μA/cm2;S042-與水中Cl-在SS316L表面存在競(jìng)爭(zhēng)吸附,當(dāng)SO42-濃度達(dá)到520mg/L時(shí),此時(shí)[Cl-]/[SO42-]的值為0.54,濃縮3倍循環(huán)水對(duì)SS316L鈍化膜的侵蝕被有效緩解,陽極溶解電流密度最大降幅達(dá)到59.0%,但隨著浸泡時(shí)間的延長(zhǎng),腐蝕依舊有所加劇。(3)阻垢緩蝕劑復(fù)配研究發(fā)現(xiàn),4種阻垢緩蝕劑的阻鈣垢性能排序?yàn)?PESAPBTCAPASPHEDP,4種阻垢緩蝕劑對(duì)SS316L的緩蝕性能排序?yàn)?PBTCAPASPHEDPPESA;由于PESA與PBTCA能夠增加羧酸基、磷酸基、羥基的數(shù)量,并且改變CaCO3晶體的結(jié)垢類型,二者同時(shí)具有最佳的阻垢和緩蝕協(xié)同效應(yīng),濃度比為1:3時(shí),阻垢率達(dá)到最大,為97.8%;濃度比為1:1時(shí),緩蝕率達(dá)到最大,為81.2%。(4)阻垢緩蝕劑和殺菌劑對(duì)SRB生物膜組分影響研究表明,PBTCA和PESA分別使得SS316L表面EPS含量增加了 1.4%和5.8%;由于不同的殺菌機(jī)理,異噻唑啉酮、NaClO和1227對(duì)EPS含量的削減率分別達(dá)到了 62.5%、70.3%和80.6%,其中,NaClO對(duì)蛋白質(zhì)的削減能力最大,削減率為70.4%,1227對(duì)多糖的削減能力最大,削減率為84.0%,三種殺菌劑均能有效地抑制SRB及其生物膜在不銹鋼表面的粘附。(5)阻垢緩蝕劑和殺菌劑均能改變SS316L表面生物膜形貌;X射線光電子能譜結(jié)果顯示,添加NaClO后,SS316L表面-NH2的含量最低,從基團(tuán)角度印證了 NaClO對(duì)蛋白質(zhì)較強(qiáng)的削減能力,同時(shí),檢測(cè)到的FeCl2,表明NaClO對(duì)SS316L鈍化膜產(chǎn)生了一定的侵蝕;1227能夠大幅度改變SS316L表面膜中C:O比值,影響了以多糖為主的碳氧化合物的結(jié)構(gòu)。(6)阻垢緩蝕劑和殺菌劑對(duì)SRB生物膜下SS316L腐蝕行為影響研究表明,PBTCA能夠降低陽極溶解電流密度,而PESA可以微弱地促進(jìn)微生物腐蝕;異噻唑啉酮、NaClO和1227均能有效抑制微生物腐蝕,但是,由于還原生成Cl-,NaClO急劇增大陽極溶解電流密度,降低擊穿電位,侵蝕SS316L鈍化膜;1227具有成膜性,使得擊穿電位達(dá)到最大值1.19V,有助于鈍化保護(hù)。交流阻抗圖譜(EIS)表明,PBTCA和PESA能增加生物膜厚度;3種殺菌劑均能削減生物膜厚度,降低表面膜阻抗,NaClO使得SS316L表面膜阻抗降至最低,增大腐蝕風(fēng)險(xiǎn),而1227條件下,膜阻抗值較高。本研究最終確定了最優(yōu)復(fù)配阻垢緩蝕劑方案為PBTCA:PESA=1:1;最佳殺菌劑為1227,具有最優(yōu)的殺菌和緩蝕性能。
[Abstract]:Taking the circulating cooling water system of the thermal power plant as the research background, taking 316L stainless steel (Sainless steel 316L, SS316L) as the research medium, as the research medium, the sulfate-reducing bacteria (SRB) was used as the research medium. The water quality of four representative power plants (A, B, C, D) in the north was analyzed and evaluated by water analytical chemistry, biochemistry, electrochemical and surface analysis. The effects of Cl-, ammonia nitrogen and SO42-on the electrochemical corrosion of SS316L were studied. The effect of corrosion inhibitor on the chemical composition and corrosion behavior of SRB biofilm on SS316L surface was studied. The effect of the corrosion inhibitor and the corrosion inhibitor on the chemical composition and corrosion behavior of SS316L surface was studied. Through the above research, this project can provide some theoretical and data support for the selection of anti-fouling agent for thermal power plant. The results are as follows: (1) The water quality analysis and evaluation show that the problem of scaling in the regeneration water of the four power plants in the north is mainly the scaling of the salts such as CaCO3, BaSO4 and Ca3 (PO4) 2; the problem that the SO42-is in excess of the standard, Cl-causes a large corrosion tendency; the organic content is rich, The nitrogen content exceeds the standard, which is beneficial to the breeding of microorganisms. (2) The electrochemical study shows that when the concentration of Cl-in the 3-fold circulating water exceeds 380mg/ L, the etching effect of the Cl-to the SS316L passivation film is obviously increased, and the dissolution current density of the anode is obviously increased, and the maximum reaches 2.11. mu. A/ cm2; when the concentration of the ammonia nitrogen exceeds 15mg/ L, The effect of ammonia nitrogen on the passivation film of SS316L is obviously increased, the maximum anodic dissolution current density is 1. 01.mu. A/ cm2, S042-and Cl-in the water are competitive adsorption on the surface of SS316L, when the SO42-concentration reaches 520mg/ L, the value of[Cl-]/[SO42-] is 0.54, The effect of 3-fold concentration of circulating water on the passivation film of SS316L is effectively relieved, the maximum reduction of the current density of the anode is 59. 0%, but with the extension of the soaking time, the corrosion is still increasing. (3) The anti-scale corrosion inhibitor compound study found that the corrosion resistance of four corrosion-resistant corrosion inhibitors was ordered to be: PESAPBTCAPASPHEDP, and the corrosion resistance of four kinds of scale inhibitor to SS316L was ordered as: PBTCAPASPHEEDPPESA; because of the addition of PESA and PBTCA to increase the number of acid-based, phosphoric and hydroxyl groups, and to change the scale type of CaCO3 crystals, When the concentration ratio is 1: 3, the corrosion resistance rate reaches the maximum, which is 97.8%, the concentration ratio is 1: 1, and the corrosion rate reaches the maximum of 81.2%. (4) The effect of the corrosion inhibitor and the bactericide on the composition of the SRB biofilm shows that the EPS content of the SS316L surface is increased by 1. 4% and 5. 8%, respectively, and the reduction rate of the EPS content is 62.5%, 70.3% and 80.6%, respectively, due to different sterilization mechanisms. Among them, the reduction ability of NaClO to the protein is the most, the reduction rate is 70.4%, the reduction capacity of 1227 to the polysaccharide is the most, the reduction rate is 84.0%, and the three fungicides can effectively inhibit the adhesion of the SRB and the biofilm to the surface of the stainless steel. The results of X-ray photoelectron spectroscopy show that after addition of NaClO, the content of SS316L surface-NH2 is the lowest, and the ability of NaClO to reduce the protein is confirmed from the group angle, meanwhile, FeCl2 is detected, The results show that NaClO has a certain erosion on the SS316L passivation film, and 1227 can greatly change the C: O ratio in the surface film of SS316L. The structure of the carbon-oxygen compound with the main polysaccharide is affected. (6) The study of the effect of the corrosion inhibitor and the bactericide on the corrosion behavior of SS316L in the SRB biofilm shows that the PBTCA can reduce the current density of the anode, and the PESA can effectively promote the corrosion of the microorganism. The reduction of Cl-, NaClO dramatically increases the anodic dissolution current density, decreases the breakdown potential and erodes the SS316L passivation film; 1227 has a film-forming property so that the breakdown potential reaches a maximum value of 1.19V, which contributes to the passivation protection. The exchange impedance map (EIS) shows that PBTCA and PESA can increase the thickness of the biofilm; 3 fungicides can reduce the film thickness, reduce the surface membrane impedance, and NaClO makes the surface film impedance of the SS316L surface drop to the lowest, increasing the corrosion risk, and under the 1227 condition, the membrane impedance value is high. The optimum anti-scaling inhibitor scheme is PBTCA: PESA = 1: 1, and the optimal bactericide is 1227, which has the best bactericidal and corrosion-resistant properties.
【學(xué)位授予單位】：北京交通大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM621
本文編號(hào)：2325347
[Abstract]:Taking the circulating cooling water system of the thermal power plant as the research background, taking 316L stainless steel (Sainless steel 316L, SS316L) as the research medium, as the research medium, the sulfate-reducing bacteria (SRB) was used as the research medium. The water quality of four representative power plants (A, B, C, D) in the north was analyzed and evaluated by water analytical chemistry, biochemistry, electrochemical and surface analysis. The effects of Cl-, ammonia nitrogen and SO42-on the electrochemical corrosion of SS316L were studied. The effect of corrosion inhibitor on the chemical composition and corrosion behavior of SRB biofilm on SS316L surface was studied. The effect of the corrosion inhibitor and the corrosion inhibitor on the chemical composition and corrosion behavior of SS316L surface was studied. Through the above research, this project can provide some theoretical and data support for the selection of anti-fouling agent for thermal power plant. The results are as follows: (1) The water quality analysis and evaluation show that the problem of scaling in the regeneration water of the four power plants in the north is mainly the scaling of the salts such as CaCO3, BaSO4 and Ca3 (PO4) 2; the problem that the SO42-is in excess of the standard, Cl-causes a large corrosion tendency; the organic content is rich, The nitrogen content exceeds the standard, which is beneficial to the breeding of microorganisms. (2) The electrochemical study shows that when the concentration of Cl-in the 3-fold circulating water exceeds 380mg/ L, the etching effect of the Cl-to the SS316L passivation film is obviously increased, and the dissolution current density of the anode is obviously increased, and the maximum reaches 2.11. mu. A/ cm2; when the concentration of the ammonia nitrogen exceeds 15mg/ L, The effect of ammonia nitrogen on the passivation film of SS316L is obviously increased, the maximum anodic dissolution current density is 1. 01.mu. A/ cm2, S042-and Cl-in the water are competitive adsorption on the surface of SS316L, when the SO42-concentration reaches 520mg/ L, the value of[Cl-]/[SO42-] is 0.54, The effect of 3-fold concentration of circulating water on the passivation film of SS316L is effectively relieved, the maximum reduction of the current density of the anode is 59. 0%, but with the extension of the soaking time, the corrosion is still increasing. (3) The anti-scale corrosion inhibitor compound study found that the corrosion resistance of four corrosion-resistant corrosion inhibitors was ordered to be: PESAPBTCAPASPHEDP, and the corrosion resistance of four kinds of scale inhibitor to SS316L was ordered as: PBTCAPASPHEEDPPESA; because of the addition of PESA and PBTCA to increase the number of acid-based, phosphoric and hydroxyl groups, and to change the scale type of CaCO3 crystals, When the concentration ratio is 1: 3, the corrosion resistance rate reaches the maximum, which is 97.8%, the concentration ratio is 1: 1, and the corrosion rate reaches the maximum of 81.2%. (4) The effect of the corrosion inhibitor and the bactericide on the composition of the SRB biofilm shows that the EPS content of the SS316L surface is increased by 1. 4% and 5. 8%, respectively, and the reduction rate of the EPS content is 62.5%, 70.3% and 80.6%, respectively, due to different sterilization mechanisms. Among them, the reduction ability of NaClO to the protein is the most, the reduction rate is 70.4%, the reduction capacity of 1227 to the polysaccharide is the most, the reduction rate is 84.0%, and the three fungicides can effectively inhibit the adhesion of the SRB and the biofilm to the surface of the stainless steel. The results of X-ray photoelectron spectroscopy show that after addition of NaClO, the content of SS316L surface-NH2 is the lowest, and the ability of NaClO to reduce the protein is confirmed from the group angle, meanwhile, FeCl2 is detected, The results show that NaClO has a certain erosion on the SS316L passivation film, and 1227 can greatly change the C: O ratio in the surface film of SS316L. The structure of the carbon-oxygen compound with the main polysaccharide is affected. (6) The study of the effect of the corrosion inhibitor and the bactericide on the corrosion behavior of SS316L in the SRB biofilm shows that the PBTCA can reduce the current density of the anode, and the PESA can effectively promote the corrosion of the microorganism. The reduction of Cl-, NaClO dramatically increases the anodic dissolution current density, decreases the breakdown potential and erodes the SS316L passivation film; 1227 has a film-forming property so that the breakdown potential reaches a maximum value of 1.19V, which contributes to the passivation protection. The exchange impedance map (EIS) shows that PBTCA and PESA can increase the thickness of the biofilm; 3 fungicides can reduce the film thickness, reduce the surface membrane impedance, and NaClO makes the surface film impedance of the SS316L surface drop to the lowest, increasing the corrosion risk, and under the 1227 condition, the membrane impedance value is high. The optimum anti-scaling inhibitor scheme is PBTCA: PESA = 1: 1, and the optimal bactericide is 1227, which has the best bactericidal and corrosion-resistant properties.
【學(xué)位授予單位】：北京交通大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM621
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