H_2S水溶液中的腐蚀与缓蚀作用机理的研究V.咪唑啉衍生物在H_2S溶液中的缓蚀作用特征

合成了１４种具有不同结构和官能团的咪唑啉衍生物,利用交流阻抗和动电位极化曲线,对其在Ｈ２Ｓ溶液中的缓蚀作用特征和性能,以及温度的变化对其缓蚀性能的影响进行了研究,结果表明咪唑啉化合物对Ｈ２Ｓ溶液中低碳钢的腐蚀具有良好的保护性能,这主要依赖于化合物分子与金属表面存在较强的化学作用;按其作用机制的不同,所研究的咪唑啉化合物大体可分为阳极型和阴极型缓蚀剂,且阳极型咪唑啉缓蚀性能优于阴极型;咪唑环上憎水或亲水支链的长短,或其它官能团的存在(如双键,羟基等),对化合物的缓蚀性能和作用机制有直接的影响．     

H2S水溶液中的腐蚀与缓蚀作用机理的研究——Ⅶ.H2S溶液中咪唑啉衍生物对碳钢腐蚀电极过程的影响

利用电化学测试技术，在H2S溶液中分别研究了14种咪唑啉衍生物浓度的变化对其缓蚀性能以及碳钢腐蚀电化学过程的影响，并对其缓蚀作用过程、缓蚀类型进行了分析探讨。结果表明，随药剂浓度升高，体系的自腐蚀电流和电极表面电容迅速减少，极化电阻增大，表明缓蚀剂分子在电极表面的吸附随药剂浓度的增加而增加，屏蔽效应增强；咪唑啉分子结构中憎水支链的长短对其缓蚀作用类型有重要影响，随支链中碳原子增加，化合物的缓蚀作用类型逐渐由阴极型向阳极型转变；按其对电极过程作用性质的不同，所研究的14种咪唑啉衍生物可分为阳极阴极缓蚀剂两组，其缓蚀作用主要是由于咪唑啉分子在电极表面的化学吸附所至。     

H2S水溶液中的腐蚀与缓蚀作用机理的研究——Ⅵ. H2S溶液中咪唑啉衍生物分子结构与其缓蚀性能的关系

利用交流阻抗、极化曲线和腐蚀失重法，在H2S溶液中研究了咪唑啉分子结构的变化与其缓蚀性能间关系。结果表明：位于中心咪唑环1，2位置上憎水和亲水支链长短结构的变化，极性官能团的存在对其缓蚀性能均具有较大的影响。当憎水支链碳原子为7和17时，化合物具有较好的缓蚀性能；憎水支链中双键的存在，可有效提高化合物的缓蚀性能，而羟基基团的引入，对其缓蚀性能却没有明显的改进。当亲水支链中含有两个氨基乙撑基团时，化合物缓蚀效果最好，硫脲基团的存在，也可有效提高咪唑啉化合物的缓蚀性能。唑咪环本身化学性质的改变，虽可改善其缓蚀性能，但因其水溶性较差不易用作缓蚀剂。     

双咪唑啉季铵盐的合成与缓蚀性能研究

利用两步法合成了双咪唑啉季铵盐化合物，通过失重法研究了该化合物在1g／L HCl 0．16g／L H2S 1g／L NaCl溶液和10％的盐酸溶液中对碳钢的缓蚀性能，讨论了用量、温度、时间对缓蚀性能的影响，并通过极化曲线和扫描电镜研究了该化合物的缓蚀机理。结果表明，该化合物在HCl-H2S-NaCl-H2O和10％的盐酸腐蚀环境中对碳钢具有良好的缓蚀作用，是一种以阳极控制为主的混合型缓蚀剂。     

H2S水溶液中的腐蚀与缓蚀作用机理的研究viii咪唑啉衍生物在H2S溶液中的吸附作用行为

依据咪唑啉衍生物在H2S溶液中的腐蚀电化学研究结果,分析探讨了系列咪唑啉化合物在碳钢电极表面的吸附作用规律及可能的吸附状态,并建立了该类化合物可能的吸附模型．结果表明,研究的13种咪唑啉衍生物的吸附均符合Langmuir单分子等温吸附规律,为具有较大表面吸附自由能的化学吸附;这种吸附主要来自分子中不饱和五元环与金属表面的强烈作用．其可能的吸附方式是分子中咪唑啉以近似平行金属表面的取向同金属表面发生相互作用,亲水支链骨架原子的奇偶性对分子的吸附作用方式具有重要影响,而憎水支链对分子的吸附过程贡献较小．     

含H2S/CO2环境中缓蚀剂对不同油管钢的缓蚀作用

选用一种自制缓蚀剂TG500(主要成分为咪唑啉含硫衍生物、有机硫代磷酸酯),对不同油管钢在含H2S/CO2腐蚀介质中进行试验。结果表明:TG500可明显降低溶液对N80、SM80SS、KO80SS油管钢的腐蚀速率,即使在较高的CO2/H2S分压下,缓蚀效率仍可达95%以上;油管钢中的合金元素Cr、Ni对于降低油管钢的腐蚀速率具有明显作用,但对于提高缓蚀剂的缓蚀效率无明显作用。     

H2S水溶液中的腐蚀与缓蚀作用机理的研究(Ⅷ)咪唑啉衍生物在H2S溶液中的吸附作用行为

依据咪唑啉衍生物在H2 S溶液中的腐蚀电化学研究结果 ,分析探讨了系列咪唑啉化合物在碳钢电极表面的吸附作用规律及可能的吸附状态 ,并建立了该类化合物可能的吸附模型 .结果表明 ,研究的 13种咪唑啉衍生物的吸附均符合Langmuir单分子等温吸附规律 ,为具有较大表面吸附自由能的化学吸附 ;这种吸附主要来自分子中不饱和五元环与金属表面的强烈作用 .其可能的吸附方式是分子中咪唑环以近似平行金属表面的取向同金属表面发生相互作用 ,亲水支链骨架原子的奇偶性对分子的吸附作用方式具有重要影响 ,而憎水支链对分子的吸附过程贡献较小     

X70钢在含H2S弱酸性溶液中的防腐研究

用静态失重法结合扫描电镜研究了以Zn为牺牲阳极的阴极保护法对X70钢在含H2S酸性溶液中的防腐作用,并采用交流阻抗法和动电位扫描法研究了6甲基-2巯基-4羟基嘧啶(HMMP)对X70钢在含H2S酸性溶液中的缓蚀作用。结果表明：以Zn作为牺牲阳极对含H2S酸性溶液中的X70钢具有较好的防腐效果;HMMP属于以抑制阳极过程为主的混合型缓蚀剂,在所研究的浓度范围内,随着其浓度的增大,缓蚀率逐渐增强。     

咪唑啉酰胺在HCl/NH_4Cl-H_2O和H_2S/NH_4HS-H_2O体系中对碳钢的缓蚀性能

采用失重法、电化学测试法,并结合扫描电镜和原子力显微镜观察,研究了在50℃条件下,N-(2-辛基-2咪唑啉)三亚乙基四酰胺(咪唑啉酰胺)分别在HCl/NH_4Cl-H_2O和H2S/NH_4HS-H_2O体系中对碳钢的缓蚀性能。结果表明:N-(2-辛基-2咪唑啉)三亚乙基四酰胺加量为15mg/L时,缓蚀率接近90%,缓蚀效果明显;该缓蚀剂为抑制阳极型缓蚀剂,溶液中加入缓蚀剂后,碳钢试样形成较长的钝化区间,交流阻抗半径大,腐蚀电流明显减小。形貌观察显示N-(2-辛基-2咪唑啉)三亚乙基四酰胺能够在碳钢表面形成致密的保护膜。     

咪唑啉和季铵盐类缓蚀剂对P110S钢的缓蚀作用和机理研究

采用失重法、极化曲线、电化学阻抗谱(EIS)和扫描电镜(SEM)研究了咪唑啉和季铵盐缓蚀剂在H_2S/CO_2环境中对P110S钢的缓蚀作用和缓蚀机理。结果表明,咪唑啉缓蚀剂和季铵盐缓蚀剂均为阳极型缓蚀剂;在120℃,H_2S分压为0.55 MPa、CO_2分压为0.80 MPa的环境中,两种缓蚀剂均有一定的缓蚀作用,能有效抑制P110S钢的腐蚀;添加浓度为200 mg·L~(-1)时,咪唑啉缓蚀剂的缓蚀效率可达87.23%。     

耐硫化氢腐蚀钢在硫化氢介质中的腐蚀行为

采用电化学方法、X射线光电子能谱仪和扫描电镜等方法对抗硫化氢腐蚀的套管钢BG110S在含饱和硫化氢的NACE溶液中的腐蚀行为进行了研究。结果表明:耐硫化氢腐蚀钢在25℃含饱和硫化氢的NACE溶液中与硫化氢发生了反应,形成双层结构的腐蚀产物膜,外层是以四方晶系FeS为主的腐蚀产物膜,内层为铬、铜等合金元素硫化物的腐蚀产物膜;腐蚀产物膜能够阻挡基体合金元素与硫化氢发生进一步的腐蚀反应,降低了氢原子渗透量,从而提高了耐硫化氢腐蚀钢的抗硫化氢腐蚀的性能。     

High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.     

H2S分压对油管钢CO2/H2S腐蚀的影响

1974-）,男,硕士研究生,研究方向为腐蚀与防护.〖ZK)〗 Tel：0379-4231846〓E-mail：FQ)〗〖HT〗〖HJ〗〖HT5”SS〗 〖JZ(〗〖HT2H〗〖STHZ〗〖WTHZ〗 采用高温高压釜,辅以失重法和扫描电镜,对不同H2S分压下(1.4 kPa,20 kPa,60 kPa,120 kPa)油管钢N80、P110的CO2/H2S腐蚀进行了研究.结果表明,在试验H2S分压范围内,随着H2S分压的升高,两种钢的腐蚀速率先增后降,且都在H2S分压为20 kPa时取得最大值.      

The corrosion of Fe-Mo alloys in H2/H2O/H2S atmospheres

The corrosion of Fe-Mo alloys containing up to 40 wt.% Mo was studied over the temperature range 600–980C in a H₂/H₂O/H₂S mixture having a sulfur pressure of 10^–5 atm. and an oxygen pressure of 10^–20 atm. at 850C. All alloys were two-phase, consisting of an Fe-rich solid solution and an intermetallic compound, Fe₃Mo₂. The scales formed on Fe-Mo alloys were bilayered, consisting of an outer layer of iron sulfide (FeS) and of a complex inner layer whose composition and microstructure were a function of the reaction temperature and of the Mo content of the alloys. No oxides formed under any conditions. The corrosion kinetics followed the parabolic rate law at all temperatures. The addition of Mo caused only a slight decrease of the corrosion rate. Platinum markers were always located at the interface between the inner and outer scales, indicating that outer scale growth was primarily due to outward diffusion of iron, while the inner scale growth had a contribution from inward diffusion of sulfur.     

不同H2S分压下N80油管钢的CO2/H2S腐蚀行为

采用高温高压釜试验,辅以失重法计算和扫描电镜分析,对不同H2S分压(O.0015 MPa,0.015 MPa,0.02MPa,0.06 MPa,0.12 MPa)下N80油管钢的CO2/H2S腐蚀行为进行了研究.结果表明,在试验H2S分压范围内,N80油管钢发生了极严重的CO2/H2S腐蚀;随着Hzs分压的升高,腐蚀速率先增加后降低,且在H2s分压为0.02 MPa时腐蚀速率取得最大值.     

H2S腐蚀的控制

本文总结了H2 S腐蚀控制的常用方法 (包括耐蚀材料的应用、腐蚀介质的处理、保护性覆盖层的使用等 ) ,对从事H2 S腐蚀控制的工作者有一定的参考作用     

The corrosion behavior of Fe-Nb-Al alloys in H2/H2O/H2S atmospheres

The corrosion behavior of eight Fe-Nb-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S atmospheres. The corrosion kinetics followed the parabolic rate law for all alloys at all temperatures. The corrosion rates were reduced with increasing Nb content for Fe-x Nb -3Al alloys, the most pronounced reduction occurred as the Nb content increased from 30 to 40 wt.%. The corrosion rate of Fe-30Nb decreased by six orders of magnitude at 700°C and by five orders of magnitude at 800°C or above by the addition of 10 wt.% aluminum. The scales formed on low-Al alloys (3 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with Al dissolved near the outer-/inner-layer interface) and an inner complex layer of Fe_xNb₂S₄(FeNb₂S₄ or FeNb₃S₆), FeS, Nb₃S₄ (only detected for Nb contents of 30 wt.% or higher) and uncorroded Fe₂Nb. No oxides were detected on the low-Al alloys after corrosion at any temperature. Platinum markers were found to be located at the interface between the inner and outer scales for the low-Al alloys, suggesting that the outer scale grew by the outward transport of cations (Fe and Al) and the inner scale grew by the inward transport of sulfur. The scales formed on high-Al alloys (5 wt.% Al) were complex, consisting primarily of Nb₃S₄, Al₂O₃ and (Fe, Al)_xNb₂S₄, and minor amounts of (Fe, Al)S and uncorroded intermetallics (FeAl and Fe₂Nb). The formation of Nb₃S₄ and Al₂O₃ blocked the transport of iron through the inner scale, resulting in the significant reduction of the corrosion rates.     

Untersuchungen der Hochtemperatursulfidierung von Stählen in H2/H2S- und H2/H2S/H2O-Gasgemischen

Investigations of high-temperature sulfidization of steels in H₂/H₂S- and H₂/H₂S/H₂O gas mixtures Various ferritic steels, one with aluminium as an alloying compound, and various austenitic steels were corroded in H₂S-H₂- and H₂S? H₂O? H₂-gas mixtures in the temperature range 300 to 700 °C. The overall pressure always was 1 bar and the H₂O partial pressure 0,1 mbar, whereas H₂S partial pressures were varied between 1 and 200 mbar. In thermogravimetric investigations the rate laws were found to be nearly linear for all ferritic steels and to a large extent parabolic for the austenitic steels. The sulfidization rate of all ferritic steels decreased with increasing chromium content, up to 18 wt% somewhat less significantly than for higher contents. The sulfidization rates of austenitic steels were decreased only moderately by increasing nickel content. The aluminium content of the steel X7 CrAl 15 5 reduced the constant of the linear rate law by more than one order of magnitude, as compared with aluminium-free steels. The improved corrosion resistance was caused by selective oxidation of aluminium, but the protection by Al₂O₃ was destroyed by creep deformation under mechanical stress. Cracks along grain boundaries were formed by stresses below 80 Mpa and for more than 80 Mpa transcrystalline cracks occurred. Metallographic examination revealed double layers on all steels. The outer layer of the ferritic steels predominantly consist of iron sulfide FeS, the inner layer, however, of a mixture of ironchromium sulfide. The outer sulfide layer of the austenitic steels contained apart from FeS chromium and nickel sulfides with low contents, too. In the inner sulfide layer a heterogeneous mixture of iron-chromium-spinells, iron-nickel-spinells and Ni₃S₂ was identified. Mechanisms for layer growth are proposed.     

The high-temperature corrosion behavior of Fe-Mo-Al alloys in H2/H2O/H2S mixed-gas environments

The corrosion behavior of 11 Fe-Mo-Al ternary alloys was studied over the temperature range 700–980°C in H₂/H₂O/H₂S mixed-gas environments. With the exception of Fe-10Mo-7Al, for which breakaway kinetics were observed at higher temperatures, all alloys followed the parabolic rate law, despite two-stage kinetics which were observed in some cases. A kinetics inversion was observed for alloys containing 7 wt.% Al between 700–800°C. The corrosion rates of Fe-20Mo and Fe-30Mo were found to be reduced by five orders of magnitude at all temperatures by the addition of 9.1 or higher wt.% aluminum. The scales formed on low-Al alloys (5 wt.% Al) were duplex, consisting of an outer layer of iron sulfide (with some dissolved Al) and a complex inner of Al_0.55Mo₂S₄, FeMo₂S₄, Fe_1.25Mo₆S_7.7, FeS, and uncorroded FeAl and Fe₃Mo₂. Platinum markers were always located at the interface between the inner and outer scales for the low-Al alloys, indicating that outer-scale growth was due mainly to outward diffusion of cations (Fe and Al), while the inner scale was formed primarily by the inward flux of sulfur anions. Alloys having intermediate Al contents (7 wt.%) formed scales that consisted of FeS and Al₂O₃. The amount of Al₂O₃ increased with increasing reaction temperature. The high-Al-content alloys (9.1 and 10 wt.%) formed only Al₂O₃ which was responsible for the reduction of the corrosion rates.     

The high-temperature corrosion of Fe-Nb alloys in a H2/H2O/H2S gas mixture

The corrosion of Fe-Nb alloys containing up to 40 wt.% Nb has been studied over the temperature range 600–980°C in a mixed gas of constant composition having sulfur and oxygen pressures ranging from 10^–8 to 10^–4 atm. and from 10^–27 to 10^–18 atm., respectively. All alloys were two-phase, consisting of an Fe-rich solid solution and an intermetallic compound, Fe₂Nb. The scales formed on the Fe-Nb alloys were duplex, consisting of an outer layer of iron sulfide (FeS) and an inner complex layer of Fe_xNbS₂(FeNb₂S₄ or FeNb₃S₆), FeS and unreacted Fe₂Nb. No oxides were detected at any temperature. The addition of Nb reduced the corrosion rate. The corrosion kinetics of Fe-Nb alloys followed the parabolic rate law, regardless of alloy composition and temperature. Platinum markers, attached to the original alloy surfaces, were always located at the interface between the inner and outer scales.