Coke formation during metal dusting of iron in CO‐H2‐H2O gas with high CO content

Iron carburisation and coke formation during metal dusting of iron have been investigated in the gas mixture of 75%CO‐24.8%H₂‐0.2%H₂O at 600°C and 700°C. In all cases, cementite is formed at the surface, together with a coke layer on the top. In the coke layer, two morphologies of graphite are identified: compact bulk graphite with a uniform thickness and a columnar structure, and filamentous carbon with iron‐containing phases at the tip or along its length. The examination of coke formation in different stages of reaction at 700°C reveals that the coke contains two layers. The inner layer is composed of filaments, while the outer layer consists of the compact columnar graphite. After 2 h reaction the top compact graphite layer has suffered a serious deformation and has formed fractures because of the growth of catalytic filamentous carbon underneath. These filaments grow outside from these fractures and finally cover the whole surface after 4 h reaction. At 600°C, however, the coke contains a thick bulk graphite layer and non‐uniformly distributed filaments on the top. The bulk graphite layer is composed of many graphite columns which are loosely piled and are vertical to the surface. Each graphite column consists of many fine graphite fibres in parallel with the columnar axis. Filaments grow outside preferably from the gaps among these graphite columns and along the grinding scratches. TEM analysis of the coke detects very convoluted filaments with iron‐containing particles at the tip or along their length. XRD and TEM analyses show that these particles are Fe₃C rather than metallic iron.     

Metal dusting of ferritic Fe‐Al‐M‐C (M = Ti,V, Nb,Ta) alloys in CO‐H2‐H2O gas mixtures at 650 °C

Iron aluminides are known for their resistance to high temperature oxidation and sulphidation. Only little information is available about carburisation and metal dusting of Fe‐Al alloys. Metal dusting experiments with Fe‐15Al and Fe‐15Al‐2M‐1C alloys (in at.%) with M = Ti, V, Nb, or Ta were conducted at 650°C in CO‐H₂‐H₂O gas mixtures with the carbon activity a_c = 28. The kinetics of the carbon transfer was measured using thermogravimetric analysis (TGA). It is shown that the mass gain kinetics decreases by adding the alloying elements Nb, Ta, V, or Ti with C. Alloying with titanium and carbon leads to the most significant decreasing effect. The metallographic cross section observation showed a general metal wastage for Fe‐15Al, but local pitting for the Fe‐15Al‐2Nb‐1C and Fe‐15Al‐2Ta‐1C alloys. For the Fe‐15Al‐2V‐1C and Fe‐15Al‐2Ti‐1C alloys no significant attack was observed. Needle‐ or plate‐like Fe₃AlC_x precipitates were detected in the carburised samples. The existence of this ternary carbide with perovskite structure was predicted by thermodynamic calculations using the software Thermo‐Calc. The morphology of graphite on the surface was analysed by scanning electron microscopy (SEM). Mainly fine filaments with iron containing particles were detected. Cementite was detected in the coke layer by X‐ray diffraction analysis (XRD).     

Occurrence of metal dusting – referring to failure cases

Twelve years of research on metal dusting at the Max‐Planck‐Institut for Iron Research have led to comprehensive knowledge on the mechanisms and kinetics of metal dusting and on ways and means for prevention of this corrosion phenomenon, – this knowledge is shortly summarized in this paper. Inspite of this state of understanding, the present opinion in industry is that metal dusting is mysterious and not predictable and cannot be controlled. This paper is intended to show that the occurrence of metal dusting and its reasons can be well understood, by describing and explaining five failure cases.     

Filamentous carbon formation caused by catalytic metal particles from iron oxide

The thermodynamic equilibrium between metallic iron, iron oxides, iron carbides and an hydrocarbon/hydrogen mixture was calculated at 600°C. On the basis of the metastable Fe‐C‐O phase diagram, both metallic iron and iron oxides can be directly converted into carbides in reducing and carburizing atmosphere. Thermogravimetric (ATG) measurements have been performed in iC₄H₁₀‐H₂‐Ar atmosphere at 600°C on reduced and pre‐oxidised iron samples. The kinetic of coke formation was studied on both surface states by sequential exposure experiments. The initial stages of the transformation were characterised by scanning electron microscopy (SEM) observations and X‐ray diffraction (XRD) analysis. On a reduced surface, the results are consistent with the mechanism currently proposed to explain catalytic coke formation. Cementite (Fe₃C) is formed on the iron surface after carbon supersaturation (a_c > 1). The graphite deposition on its surface (a_c = 1) induces its decomposition. Iron atoms from cementite diffuse through the graphite and agglomerate to small particles that act as catalysts for further carbon deposition. A new mechanism of catalytic particle formation is proposed when an oxide scale initially covers the iron surface. In the carburizing and reducing atmosphere, magnetite (Fe₃O₄) can be directly converted into cementite (Fe₃C). XPS analysis confirm that, in this process, metallic iron is not an intermediary specie of the oxide/carbide reaction. At the same time, graphite deposition occurs at the metal/oxide interface through the cracks present in the oxide scale. Iron carbide in contact with graphite is partially decomposed and acts as catalyst for graphitic filaments growth.     

Metal dusting behaviour of welded Ni‐base alloys with different surface finish

Welded Ni‐base alloys and Alloy 800 were exposed under metal dusting conditions at 600°C and 650°C for up to 6000 hours. Alloy 800 was attacked very strongly already in the first days and Alloy 600 also rather soon and widespread, on both materials attack started mainly in the heat affected zone. Several surface states of Alloy 600: brushed, ground, sand‐blasted and pickled were tried only grinding caused a modest delay and decrease of metal dusting attack. Generally the attack was less widespread but deeper at 650°C than at 600°C, also for Alloy 601 and 602. The latter alloys show minor, mainly local attack, but especially the welds are affected. TIG welding led to better resistance than hand‐welding.     

Characterisation of the coke formed during metal dusting of iron in CO-H2-H2O gas mixtures

Carbon deposits formed on the surface of iron samples during carburisation at 700 °C in a gas mixture of 75%CO-24.81%H₂-0.19%H₂O were characterised by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Mössbauer spectroscopy and transmission electron microscopy (TEM). Cross-section observation of the iron sample by light optical microscopy revealed the formation of cementite after only 10 min reaction, together with a thin layer of graphite. After 4 h reaction, a thick coke layer was formed on top of the cementite surface. SEM surface observation indicated the formation of filamentous carbon in the coke layer. Further analysis of the coke by XRD and Mössbauer showed the presence of mainly Fe₃C and small amount of Fe₂C but no metallic iron in the carbon deposit. TEM analysis of the coke detected very convoluted filaments with iron-containing particles at the tip or along their length. These particles were identified to be cementite by selected area diffraction. Carbon deposits produced at the same temperature but with other gas compositions were also analysed by using XRD. It was found that with a low content of CO, e.g. 5%, both α-Fe and Fe₃C were detected in the coke. Increasing CO content to more than 30%, iron carbide was the only iron-containing phase.     

Microprocesses of metal dusting on iron‐nickel alloys and their dependence on the alloy composition

Metal dusting of iron proceeds via the formation and disintegration of the metastable carbide Fe₃C, and the resulting fine Fe particles in the coke further catalyse carbon deposition. By contrast, nickel disintegrates directly, and larger grains are released. As revealed by TEM and AEM techniques, in both cases the disintegration proceeds by inward growth of thin graphite filaments, the atomic basal planes of which being oriented perpendicular to the surface thus effecting a high reactivity at the growth front. Consequently, successive alloying of iron with nickel should lead to a change over from one disintegration mechanism to the other, and, in fact, we could evidence that the carbide formation takes place only up to a nickel content of about 5 wt.%. Already at a Ni concentration of 10 wt.% a direct disintegration of the metal proceeds, as it is typical for pure nickel. Furthermore, in all investigated Ni‐Fe alloys a surface‐near enrichment of Ni was observed which indicates a selective corrosion of Fe, decreasing with increasing Ni content of the basic alloy.     

α‐Fe layer formation during metal dusting of iron in CO‐H2‐H2O gas mixtures

The formation of an α‐Fe layer between cementite and graphite was observed and investigated during metal dusting of iron in CO‐H₂‐H₂O gas mixtures at both 600°C and 700°C. The condition to form this phenomenon is determined by the gas composition which depends on temperature. The iron layer formation was observed for CO content less than 1 % at 600°C and less than 5 % at 700°C. With increasing CO contents, no α‐Fe layer was detected at the cementite/graphite interface by optical microscopy. In this case cementite directly contacts with the coke layer. The morphologies of the coke formed in the gas mixtures with low CO contents were also analysed. Three morphologies of graphite have been identified with 1 % CO at 600°C: filamentous carbon, bulk dense graphite with columnar structure, and graphite particle clusters with many fine iron containing particles embedded inside. At 700°C with 5 % CO the coke mainly consists of graphite particle clusters with some filamentous carbon at the early stage of reaction. Coke analysis by X‐ray diffraction shows that both α‐Fe and Fe₃C are present in the coke. The mechanism of α‐Fe accumulation between cementite and graphite is discussed in this paper.     

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     

Effect of gas composition on coking and metal dusting of 2.25Cr–1Mo steel compared with iron

The reaction of 2.25Cr–1Mo at 650 °C with CO–H₂–H₂O gas was investigated. Gas compositions were varied with respect to p_CO and nominal carbon activity which calculated assuming equilibrium of the synthesis gas reaction. After an induction period, the steel grew a cementite scale, covered by a graphite deposit containing cementite particles. Carbon uptake kinetics were roughly linear. The rates did not correlate with the carbon activity, but indicated the existence of three parallel reaction paths. Individual rate constants were greater than those for pure iron, an effect attributed to faster cementite scale disintegration caused by the presence of chromium-rich oxide particles.     

煤气中硫化氢含量对610L红色氧化铁皮的影响

针对汽车大梁钢表面存在的红色氧化铁皮缺陷,在生产汽车大梁钢610L时,根据在线表面检测仪采集的带钢表面红色氧化铁皮图像,按照红色氧化铁皮分布数量来量化其程度大小。结果表明,红色氧化铁皮的严重程度与加热时间直接相关,查询对应时间段的煤气中H2S含量达到300 mg/m3以上,可确认H2S是导致红色氧化铁皮的主要原因,为此减少了煤气中H2S含量,红色氧化铁皮得到有效遏制。     

Effect of pre‐oxidation on coke formation and metal dusting of electroplated Ni3Al–CeO2‐based coatings in CO–H2–H2O

Pre‐oxidation was introduced to improve the resistance of electroplated pure, 5 µm CeO₂‐dispersed, and 9–15 nm CeO₂‐dispersed Ni₃Al coatings to coke formation and metal dusting in 24.4%CO–73.3%H₂–2.3%H₂O at 650 °C. Coke formation and metal dusting of pre‐oxidized Ni₃Al‐based coatings were retarded up to 200 h owing to a thin Al₂O₃ scale induced during pre‐oxidation. The long‐term effectiveness of pre‐oxidation nonetheless depended on the integrity of Al₂O₃ scale. The pure Ni₃Al coating suffered severe spallation after pre‐oxidation and thereby showed the worst long‐term resistance. Two pre‐treated 9–15 nm CeO₂‐dispersed Ni₃Al coatings exhibited the best long‐term resistance to carbon attack because nano‐CeO₂ particles maintained a full coverage of Al₂O₃ scale on the coatings. Two 5 µm CeO₂‐dispersed Ni₃Al coatings showed significant spallation after pre‐oxidation because of an overdoping effect and experienced coke formation and metal dusting during long‐term exposure.     

H2S/CO2环境中Gemini表面活性剂对L360钢的缓蚀性能

采用静态失重法、动电位极化法和电化学阻抗法研究了三种Gemini表面活性剂12-2-12,16-2-16和18-2-18在H2S/CO2环境中对L360钢的缓蚀性能,并探讨了缓蚀机理.研究表明,在本试验条件下,三种表面活性剂均表现出一定的缓蚀性能,其中,12-2-12效果最优,16-2-16其次,18-2-18缓蚀效果...     

高温高压H2S/CO2腐蚀产物膜对低铬钢氢渗透行为的影响

目的探讨含Cr腐蚀产物膜对油管钢氢渗透行为的影响。方法对80SS、P110-3Cr和P110-7Cr油管钢试样进行高温高压H_2S/CO_2腐蚀模拟实验,并利用双电解池技术测量试样腐蚀前、后的氢渗透电流密度。通过扫描电子显微镜、能谱分析仪和X射线衍射仪对腐蚀产物膜的微观形貌、成分和物相组成进行分析。结果三种材料的腐蚀产物主要由亚稳态的马基诺矿型硫铁化合物构成,没有发现典型的CO_2腐蚀产物FeCO_3晶体,在P110-3Cr(7.4%Cr)和P110-7Cr(14.75%Cr)钢的腐蚀产物膜中有Cr元素富集。随着钢中Cr含量的提高,120℃腐蚀后,试样的表观扩散系数减小。80SS、P110-3Cr和P110-7Cr油管钢试样表面无腐蚀膜时,吸附氢浓度分别为0.98×10~(-5)、9.54×10~(-5)、9.3×10~(-5) mol/cm~3。120℃腐蚀后,带有腐蚀膜试样的膜层/基体界面钢基体侧的吸附氢浓度分别为0.93×10~(-5)、5.17×10~(-5)、8.52×10~(-5) mol/cm~3。结论三种油管钢的腐蚀过程均由H_2S控制。腐蚀产物膜中Cr元素富集有助于降低带有腐蚀膜试样的表观扩散系数。与不带腐蚀膜的试样相比,三种带腐蚀膜试样的膜层/基体界面钢基体侧的吸附氢浓度降低,腐蚀产物膜对氢渗透具有明显的阻碍作用。     

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。     

电网铜材在含H_2S大气中的腐蚀研究现状

铜材在H2S环境中引起的腐蚀及其所造成的损失已经受到广泛关注。论述了铜在含H2S大气环境中的腐蚀规律、腐蚀机理和腐蚀行为。分析了影响铜在含H2S大气中腐蚀的环境因素,介绍了大气环境腐蚀性的评估方法及腐蚀产物分析手段,并指出了相关的腐蚀防护措施。     

丙炔醇改性硫脲基咪唑啉在CO2/H2S共存体系中对X65钢的腐蚀抑制作用

目的 提高硫脲咪唑啉类缓蚀剂在CO2/H2S共存体系中的缓蚀效果,并揭示缓蚀机理.方法 利用丙炔醇对硫脲基咪唑啉(TAI)进行改性得到双炔丙基甲氧基硫脲基咪唑啉(DPFTAI),通过动态失重试验、极化曲线测试、交流阻抗测试分析其腐蚀性能.采用Material Studio 7.0软件模拟计算其分子轨道能量、Fukui指数、表面相互作用力和吸附状态、缓蚀剂分子与侵蚀性离子间的相互作用情况等,验证DPFTAI的缓蚀效果.结果 在不含H2S的条件下,TAI和DPFTAI的缓蚀效率均高于93％,当含有2000 mg/L H2S后,DPFTAI的缓蚀效率仍高达91.96％,且比TAI高出18.22％.模拟计算表明,DPFTAI有3个吸附中心,分别为其咪唑啉环上的2个N原子和DPFTAI分子侧链上的S原子,其与铁表面的相互作用能为29.66 kcal/mol,而TAI只有一个吸附中心,为其分子上的S原子,其与铁表面的相互作用能为22.46 kcal/mol;DPFTAI周围的HS–浓度明显大于TAI周围的HS–浓度.上述结果说明在CO2/H2S腐蚀体系中,DPFTAI在钢材表面的吸附效果明显优于TAI,因此缓蚀效果更好.结论 通过丙炔醇对TAI进行改性后,缓蚀剂DPFTAI抗CO2/H2S的腐蚀性能明显提高.吸附能力的提升是DPFTAI腐蚀抑制性能提高的主要原因.     

时效处理对针状铁素体管线钢力学性能和抗硫化氢行为的影响

在600℃左右进行时效处理,可使针状铁素体管线钢强度水平大幅度提高而基本不降低韧性和延性．在600℃保温10h,针状铁素体管线钢在保持塑、韧性的基础上,强度水平提升到接近X100级别要求,且明显改善了其抗H2S开裂性能．有利作用主要归因于时效处理促进了针状铁素体中微合金碳氮化物的进一步沉淀析出,马氏体／奥氏体(M／A)岛转变成回火马氏体,以及组织更加均匀化．时效处理为发展高强度级别针状铁素体管线钢提供了新的思路。     

腐蚀产物晶体结构及离子选择性对P110S低合金钢在H2S/CO2环境中腐蚀行为的影响

目的研究P110S低合金钢在H2S/CO2环境中的腐蚀行为及腐蚀产物对其影响机理。方法通过P110S低合金钢在不同温度下的腐蚀失重实验、微观SEM形貌观察、XRD分析和离子选择性实验,探究腐蚀产物的晶体结构以及离子选择性对腐蚀行为的影响。腐蚀实验环境为模拟我国西北某油田现场不同井深的腐蚀工况,其中CO2与H2S的分压比为2.5。结果温度低于100℃时,腐蚀产物主要为马基诺矿型FeS,其为阳离子选择性,能够阻碍阴离子与基体接触,起到抑制腐蚀的作用,因此腐蚀速率较低,约为0.15 mm/a,且随温度升高基本保持不变,试样表面的腐蚀产物膜平整未脱落;温度达到120℃后,腐蚀速率急剧增大,部分腐蚀产物由马基诺矿转变为磁黄铁矿,腐蚀产物膜因下层腐蚀产物挤压而发生破裂脱落,试样发生局部腐蚀;温度高于160℃时,腐蚀产物全部为磁黄铁矿型FeS,其为阴离子选择性,无法阻碍阴离子穿过腐蚀产物膜与基体接触,因此随着温度的升高,腐蚀速率逐渐增大并趋于平缓,达到3.6 mm/a。结论H2S/CO2环境中低合金钢腐蚀行为与腐蚀产物晶体构型及离子选择性密切相关,若腐蚀产物为马基诺矿型FeS时,其具有阳离子选择性,能够抑制金属基体腐蚀溶解;而若腐蚀产物为磁黄铁矿型FeS时,因其具有阴离子选择性,则不能抑制金属基体发生腐蚀溶解。     

Cl–对冷变形316L奥氏体不锈钢在H2S环境下应力腐蚀的影响

目的研究H2S环境下不同Cl^-浓度对冷变形316L奥氏体不锈钢应力腐蚀行为的影响,探究Cl^-造成影响的原因,为不锈钢安全服役提供理论数据。方法采用力学方法研究了冷变形316L奥氏体不锈钢的力学行为,通过计算延伸率损失表征材料的应力腐蚀敏感性,通过电化学手段表征了点蚀电位。最后为了研究点蚀与基体中氢含量的关系,进行了扩散氢含量的测试,通过测量试样的扩散氢含量,进一步理解应力腐蚀行为。结果随着Cl^-浓度的增加,316L奥氏体不锈钢的延伸率损失逐渐增大,应力腐蚀敏感性增强。断口形貌从杯状的等轴韧窝转变为解理型脆性断裂。动电位极化测试表明,Cl^-浓度的增加,点蚀电位逐渐降低,直至–0.0228V,试样更容易发生点蚀。扩散氢含量的测量进一步显示了点蚀坑的存在促进了氢进入到金属内部。结论 Cl^-对316L奥氏体不锈钢在H2S环境中的应力腐蚀行为有重要影响,随着Cl^-浓度的增加,应力腐蚀敏感性增强,结合点蚀电位的测量结果,可能是由于Cl^-破坏金属表面的钝化膜,产生点蚀坑,裂纹形核并扩展,同时点蚀坑还促进了氢进入金属内部,应力腐蚀敏感性增强。