Q235B钢在船舶尾气脱硫液中的腐蚀行为
|
摘要
碱液脱硫是当前尾气处理领域的研究热点,产生的脱硫液是一个新的腐蚀体系。为了探究船舶尾气脱硫液对Q235B钢的腐蚀影响,通过浸泡试验并结合失重法,研究了Q235B钢在船舶尾气脱硫液中的腐蚀行为,并利用SEM、EDS、EPMA和XRD对浸泡后样品的锈层结构、组成、元素分布以及表面形貌进行分析。结果表明:腐蚀初期,碳钢表面沉积一层墨绿色絮状腐蚀产物,微观结构为花瓣状,主要成分为Fe(OH)_2、Fe(OH)_3、Fe_2O_3·H_2O,腐蚀类型以全面腐蚀为主;随着腐蚀时间延长,腐蚀产物发生变化,腐蚀受到抑制;在腐蚀35 d后,腐蚀转而以点蚀为主,红褐色的腐蚀产物为团簇状且致密排布,主要成分为Fe_2O_3·H_2O、Fe3O_4、FeSO_4·4H_2O。基于试验结果,推导出Q235B钢在脱硫液中的腐蚀机理:腐蚀初期主要以吸氧腐蚀为主;随着时间延长腐蚀受到抑制,腐蚀以FeSO_4的氧化水解形成酸、酸的循环再生机制进行。
Removing sulfur dioxide from exhausted gas by treating with aqueous alkali hydroxide has been a hot research focus,and desulfurizing liquid is a new corrosive system. In order to study the influence of desulfurizing liquid from exhausted gas of marine on Q235B steel,the corrosion behavior of Q235B steel in desulfurizing liquid from exhausted gas of marine was investigated by means of immersion test and mass loss measurement. Moreover,the structure,composition,element distribution and morphology of the samples before and after immersion treatment were characterized by SEM,EDS,EPMA and XRD techniques. Results indicated that at the primal immersion stage,Q235B steel suffered from corrosion and the surface was covered by scale of jasper flocculent corrosion sediment. The corrosion product possessed nano-flower appearance in microscale,and the main compositions were Fe( OH)_2,Fe( OH)_3 and Fe_2O_3·H_2O. Furthermore,the dominant corrosion type was general corrosion. As the corrosion process went on,the layer of corrosion sediment gradually changed and the corrosion became restrained. When immersion time was up to 35 days,the dominant corrosion type was pitting corrosion. The outer corrosion products became compact stack of cluster and appeared rufous,and the components were Fe_2O_3·H_2O,Fe3 O4 and FeSO_4·4 H_2O. Finally,based on the above results,the corrosion mechanism of Q235B in desulfurizing liquid was discussed in detail. In the initial stage,the oxygen absorption played a prominent role. As the process went on,the corrosion was inhibited,and it was carried out with oxidation hydrolysis of FeSO_4 and the cycle regeneration of acid.
Removing sulfur dioxide from exhausted gas by treating with aqueous alkali hydroxide has been a hot research focus,and desulfurizing liquid is a new corrosive system. In order to study the influence of desulfurizing liquid from exhausted gas of marine on Q235B steel,the corrosion behavior of Q235B steel in desulfurizing liquid from exhausted gas of marine was investigated by means of immersion test and mass loss measurement. Moreover,the structure,composition,element distribution and morphology of the samples before and after immersion treatment were characterized by SEM,EDS,EPMA and XRD techniques. Results indicated that at the primal immersion stage,Q235B steel suffered from corrosion and the surface was covered by scale of jasper flocculent corrosion sediment. The corrosion product possessed nano-flower appearance in microscale,and the main compositions were Fe( OH)_2,Fe( OH)_3 and Fe_2O_3·H_2O. Furthermore,the dominant corrosion type was general corrosion. As the corrosion process went on,the layer of corrosion sediment gradually changed and the corrosion became restrained. When immersion time was up to 35 days,the dominant corrosion type was pitting corrosion. The outer corrosion products became compact stack of cluster and appeared rufous,and the components were Fe_2O_3·H_2O,Fe3 O4 and FeSO_4·4 H_2O. Finally,based on the above results,the corrosion mechanism of Q235B in desulfurizing liquid was discussed in detail. In the initial stage,the oxygen absorption played a prominent role. As the process went on,the corrosion was inhibited,and it was carried out with oxidation hydrolysis of FeSO_4 and the cycle regeneration of acid.
引文
[1] Martínez A H. Study of exhaust gas cleaning systems for vessels to fulfill IMO III in 2016[J]. Universitat Politcnica De Catalunya,2011(5):37-41.
[2] MARK M N. Urea-Based NO Reduction System for Engine75 to 2 250 k W[J]. Diesel and Gas Turbine Worldwide,2000(2):45-48.
[3]杨国华,胡文佳,周江华,等.船舶尾气臭氧氧化——海水吸收的脱硫脱硝新工艺研究[J].内燃机学报,2008,26(3):278-282.
[4] ANTTILA M,Hamalainen R,TUOMINIEMI S. Method and an equipment for reducing the sulphur dioxide emissions of a marine engine:20070798720[P]. 2007-05-16.
[5] REGISTER L. Understanding exhaust gas treatment systems.Guidance for ship owners and operators[R]. London:[s.n.],2012.
[6] MENDOZA A R,CORVO F. Outdoor and indoor atmospheric corrosion of carbon steel[J]. Corros Sci,1999,41(1):75-86.
[7] MUNIER G B,PSOTA L A,REAGOR B T,et al. Contamination on Zinc and Aluminum Surfaces After Extended Urban Exposures[J]. Surface Contamination,1979(1):183-193.
[8] CHIDIEBERE M A,OGUZIE E E,LIU L,et al. Adsorption and corrosion inhibiting effect of riboflavin on Q235 mild steel corrosion in acidic environments[J]. Materials Chemistry&Physics,2015,156:95-104.
[9] LEYGRAF C,GRAEDEL T E. Atmospheric corrosion[J].Materials and Corrosion,2000,52:946-947.
[10] SINGH D D N,YADAV S,SAHA J K. Role of climatic conditions on corrosion characteristics of structural steels[J]. Corros Sci,2008,50(1):93-110.
[11]程庆利,陶彬,刘栓,等.原油沉积水对Q235B碳钢的腐蚀影响[J].中国腐蚀与防护学报,2017,37(2):126-134.
[12]曹淑云,赵阳,梁平,等. Q235B低碳钢在不同含水量的布朗斯特酸离子液体中的腐蚀行为[J].材料保护,2014,47(6):35-37.
[13]李东亮,付贵勤,朱苗勇,等.湿热海洋大气中SO2污染对Q235B钢腐蚀行为的影响[J].钢铁,2017,52(1):64-70.
[14]刘斌,金凯峰,谢建丽,等.低浓度亚硝酸盐对A106B碳钢材料腐蚀的影响[J].腐蚀与防护,2013,34(3):228-231.
[15] WEISSENRIEDER J,KLEBER C,SCHREINER M,et al.In Situ Studies of Sulfate Nest Formation on Iron[J]. J Electrochem Soc,2004,151(9):B497-B504.
[16]黄涛,陈小平,王向东,等. p H值对Q235钢在模拟土壤中腐蚀行为的影响[J].中国腐蚀与防护学报,2016,36(1):31-38.
[17] MISAWA T,KYUNO T,Su3taka W,et al. The mechanism of atmospheric rusting and the effect of Cu and P on the rust formation of low alloy steels[J]. Corros Sci,1971,11(1):35-48.
[18]张慧,杜艳霞,李伟,等.不同环境介质中X70钢的交流腐蚀行为及腐蚀产物膜层分析[J].金属学报,2017,53(8):975-982.
[19]陈文娟,郝龙,董俊华,等.模拟工业-海岸大气中SO2对Q235B钢腐蚀行为的影响[J].金属学报,2015,51(2):802-810.
[20]聂向晖,李云龙,李记科,等. Q235碳钢在滨海盐土中的腐蚀形貌、产物及机理分析[J].材料工程,2010(8):24-28.
[21]董杰,董俊华,韩恩厚,等.低碳钢在模拟酸雨大气条件下的锈蚀演化[J].腐蚀科学与防护技术,2009,21(1):1-4.
[22]王凤平,康万利,敬和民,等.腐蚀电化学原理、方法及应用[M].北京:化学工业出版社,2008.
[23] YAN M,SUN C,XU J,et al. Role of Fe oxides in corrosion of pipeline steel in a red clay soil[J]. Corros Sci,2014,80(3):309-317.
[24] REFFASS M,SABOT R,JEANNIN M,et al. Effects of NO-2ions on localised corrosion of steel in Na HCO3+Na Cl electrolytes[J]. Electrochimica Acta,2007,52(27):7 599-7 066.
[25] OKADA T. A two-step initiation hypothesis of pitting corrosion in passive metals[J]. Corros Sci,1990,31:453-458.
[26] LIN C,ZHAO Q,LIU Y E,et al. Evolution of Corrosion Products of 20 Carbon Steel in Atmosphere Containing SO2[J]. Acta Metall Sin,2010,46(3):358-365.
[27] WU Y H,LIU T M,SUN C,et al. Effects of simulated acid rain on corrosion behaviour of Q235 steel in acidic soil[J].British Corrosion Journal,2010,45(2):136-141.
[28] CHENG Q,TAO B,SONG L,et al. Corrosion behaviour of Q235B carbon steel in sediment water from crude oil[J].Corrosion Science,2016,111:61-71.
[29] SUN M,XIAO K,DONG C. Electrochemical Behaviors of Ultra High Strength Steels With Corrosion Products[J].Acta Metallurgica Sinica,2011,47(4):442-448.
[30] SINGH A K,ERICSSON T,HAEGGSTROEM L,et al.Chem Inform Abstract:M9ssbauer and X-Ray Diffraction Phase Analysis of Rusts from Atmospheric Test Sites with Different Environments in Sweden[J]. Corros Sci,1985,25(10):931-945.
[31] HAN D,JIANG R J,CHENG Y F. Mechanism of electrochemical corrosion of carbon steel under deoxygenated water drop and sand deposit[J]. Electrochimica Acta,2013,114:403-408.
[32] GEORGE R P,MURALEEDHARAN P,SREEKUMARI K R,et al. Influence of surface characteristics and microstructure on adhesion of bacterial cells onto a type 304 stainless steel[J]. Biofouling,2003,19(1):1-8.
[2] MARK M N. Urea-Based NO Reduction System for Engine75 to 2 250 k W[J]. Diesel and Gas Turbine Worldwide,2000(2):45-48.
[3]杨国华,胡文佳,周江华,等.船舶尾气臭氧氧化——海水吸收的脱硫脱硝新工艺研究[J].内燃机学报,2008,26(3):278-282.
[4] ANTTILA M,Hamalainen R,TUOMINIEMI S. Method and an equipment for reducing the sulphur dioxide emissions of a marine engine:20070798720[P]. 2007-05-16.
[5] REGISTER L. Understanding exhaust gas treatment systems.Guidance for ship owners and operators[R]. London:[s.n.],2012.
[6] MENDOZA A R,CORVO F. Outdoor and indoor atmospheric corrosion of carbon steel[J]. Corros Sci,1999,41(1):75-86.
[7] MUNIER G B,PSOTA L A,REAGOR B T,et al. Contamination on Zinc and Aluminum Surfaces After Extended Urban Exposures[J]. Surface Contamination,1979(1):183-193.
[8] CHIDIEBERE M A,OGUZIE E E,LIU L,et al. Adsorption and corrosion inhibiting effect of riboflavin on Q235 mild steel corrosion in acidic environments[J]. Materials Chemistry&Physics,2015,156:95-104.
[9] LEYGRAF C,GRAEDEL T E. Atmospheric corrosion[J].Materials and Corrosion,2000,52:946-947.
[10] SINGH D D N,YADAV S,SAHA J K. Role of climatic conditions on corrosion characteristics of structural steels[J]. Corros Sci,2008,50(1):93-110.
[11]程庆利,陶彬,刘栓,等.原油沉积水对Q235B碳钢的腐蚀影响[J].中国腐蚀与防护学报,2017,37(2):126-134.
[12]曹淑云,赵阳,梁平,等. Q235B低碳钢在不同含水量的布朗斯特酸离子液体中的腐蚀行为[J].材料保护,2014,47(6):35-37.
[13]李东亮,付贵勤,朱苗勇,等.湿热海洋大气中SO2污染对Q235B钢腐蚀行为的影响[J].钢铁,2017,52(1):64-70.
[14]刘斌,金凯峰,谢建丽,等.低浓度亚硝酸盐对A106B碳钢材料腐蚀的影响[J].腐蚀与防护,2013,34(3):228-231.
[15] WEISSENRIEDER J,KLEBER C,SCHREINER M,et al.In Situ Studies of Sulfate Nest Formation on Iron[J]. J Electrochem Soc,2004,151(9):B497-B504.
[16]黄涛,陈小平,王向东,等. p H值对Q235钢在模拟土壤中腐蚀行为的影响[J].中国腐蚀与防护学报,2016,36(1):31-38.
[17] MISAWA T,KYUNO T,Su3taka W,et al. The mechanism of atmospheric rusting and the effect of Cu and P on the rust formation of low alloy steels[J]. Corros Sci,1971,11(1):35-48.
[18]张慧,杜艳霞,李伟,等.不同环境介质中X70钢的交流腐蚀行为及腐蚀产物膜层分析[J].金属学报,2017,53(8):975-982.
[19]陈文娟,郝龙,董俊华,等.模拟工业-海岸大气中SO2对Q235B钢腐蚀行为的影响[J].金属学报,2015,51(2):802-810.
[20]聂向晖,李云龙,李记科,等. Q235碳钢在滨海盐土中的腐蚀形貌、产物及机理分析[J].材料工程,2010(8):24-28.
[21]董杰,董俊华,韩恩厚,等.低碳钢在模拟酸雨大气条件下的锈蚀演化[J].腐蚀科学与防护技术,2009,21(1):1-4.
[22]王凤平,康万利,敬和民,等.腐蚀电化学原理、方法及应用[M].北京:化学工业出版社,2008.
[23] YAN M,SUN C,XU J,et al. Role of Fe oxides in corrosion of pipeline steel in a red clay soil[J]. Corros Sci,2014,80(3):309-317.
[24] REFFASS M,SABOT R,JEANNIN M,et al. Effects of NO-2ions on localised corrosion of steel in Na HCO3+Na Cl electrolytes[J]. Electrochimica Acta,2007,52(27):7 599-7 066.
[25] OKADA T. A two-step initiation hypothesis of pitting corrosion in passive metals[J]. Corros Sci,1990,31:453-458.
[26] LIN C,ZHAO Q,LIU Y E,et al. Evolution of Corrosion Products of 20 Carbon Steel in Atmosphere Containing SO2[J]. Acta Metall Sin,2010,46(3):358-365.
[27] WU Y H,LIU T M,SUN C,et al. Effects of simulated acid rain on corrosion behaviour of Q235 steel in acidic soil[J].British Corrosion Journal,2010,45(2):136-141.
[28] CHENG Q,TAO B,SONG L,et al. Corrosion behaviour of Q235B carbon steel in sediment water from crude oil[J].Corrosion Science,2016,111:61-71.
[29] SUN M,XIAO K,DONG C. Electrochemical Behaviors of Ultra High Strength Steels With Corrosion Products[J].Acta Metallurgica Sinica,2011,47(4):442-448.
[30] SINGH A K,ERICSSON T,HAEGGSTROEM L,et al.Chem Inform Abstract:M9ssbauer and X-Ray Diffraction Phase Analysis of Rusts from Atmospheric Test Sites with Different Environments in Sweden[J]. Corros Sci,1985,25(10):931-945.
[31] HAN D,JIANG R J,CHENG Y F. Mechanism of electrochemical corrosion of carbon steel under deoxygenated water drop and sand deposit[J]. Electrochimica Acta,2013,114:403-408.
[32] GEORGE R P,MURALEEDHARAN P,SREEKUMARI K R,et al. Influence of surface characteristics and microstructure on adhesion of bacterial cells onto a type 304 stainless steel[J]. Biofouling,2003,19(1):1-8.