3Cr抗CO2和H2S腐蚀系列油套管开发

CO2、H2S腐蚀是石油天然气开采过程中的主要腐蚀问题。文章在分析油井管CO2腐蚀行为和腐蚀特点的基础上，介绍了抗CO2、H2S腐蚀油套管的研制过程并开发出腐蚀性能良好的3Cr系列经济型油套管。文章重点介绍了80、95、110等不同钢级成品管的力学性能，抗CO2、H2S应力腐蚀开裂性能。运用SEM扫描电境、X光电子能谱仪、X射线衍射、体视显微镜等分析了钢经腐蚀后的表面腐蚀产物的组成、结构，并对Cr元素改善钢的抗CO2腐蚀行为及机理进行了分析。     

高含H2S和CO2环境中L80钢的腐蚀规律

 采用失重腐蚀方法研究了在模拟气田井下腐蚀环境中腐蚀影响因素(总压力、温度、腐蚀时间、H2S、Cl-、溶液流速),对套管钢(L80)腐蚀的影响规律,并用扫描电镜分析了腐蚀产物膜形貌。结果表明：60 ℃为L80钢在H2S+CO2腐蚀环境中的腐蚀临界温度,此时,L80钢的腐蚀速率最小;当总压力大于等于9 MPa,温度为120 ℃,H2S、CO2达到各自的超临界点,L80钢的腐蚀速率比温度为90 ℃时小;随腐蚀时间延长,腐蚀速率明显下降;相对在单一的CO2环境下,引入H2S可降低腐蚀速率;Cl-可促进L80钢的腐蚀;溶液流速加快,腐蚀速率提高。     

Corrosion Behavior of 110S Tube Steel in Environments of High H2S and CO2 Content

 The corrosion behavior of the 110S tube steel in the environments of high H2S and CO2 content was investigated by using a high-temperature and high-pressure autoclave, and the corrosion products were characterized by scanning electron microscopy and X-ray diffraction technique. The results showed that all of the corrosion products under the test conditions mainly consisted of different types of iron sulfides such as pyrrhotite of Fe0. 95S, mackinawite of FeS0. 9, Fe0. 985S and FeS, and the absence of iron carbonate in the corrosion scales indicated that the corrosion process was controlled by H2S corrosion. The corrosion rate of the 110S steel decreased firstly and then increased with the rising of temperature. The minimum corrosion rate occurred at 110 ℃. When the H2S partial pressure PH2S below 9 MPa, the corrosion rate declined with the increase of PH2S. While over 9 MPa, a higher PH2S resulted in a faster corrosion process. With the increasing of the CO2 partial pressure, the corrosion rate had an increasing trend. The morphologies of the corrosion scales had a good accordance with the corrosion rates.     

低铬抗硫套管的H_2S/CO_2腐蚀行为研究

通过高温高压及H2S应力腐蚀开裂(SSC)实验,采用SEM、EDS、XRD和TEM技术,研究3Cr110S在模拟环境中的H2S/CO2腐蚀行为。结果表明:在模拟H2S/CO2高温高压腐蚀环境中,H2S腐蚀占主导作用,3Cr110S的均匀腐蚀速率为0.1272 mm/a,局部腐蚀轻微,试样表面腐蚀产物为FeS;在施加应力为72%、80%的最低屈服强度时,3Cr110S试样均未发生应力腐蚀开裂,具有良好的抗SSC性能;3Cr110S回火索氏体组织的条束之间位相差大,铬元素在晶界及晶内以粒状碳化物析出、位错纠结、弥散分布碳化物的位错定扎对SSC裂纹扩展起着良好的阻碍作用。     

CO2分压对油管钢CO2/H2S腐蚀的影响

采用高温高压釜、失重法和扫描电镜，对不同CO2分压(310．2642、930．7926、1551．3210、2171．8494kPa)条件下油管钢N80和P110的CO2／H2S腐蚀进行了研究。结果表明，随着CO2分压的升高，两种钢的CO2／H2S腐蚀速率均单调增加；除了CO2分压极低的情况以外，P110钢的腐蚀速率总是大于N80钢。     

Influence of Chromium on Mechanical Properties and CO2/H2S Corrosion Behavior of P110 Grade Tube Steel

Four kinds of P110 grade tube steels containing different chromium contents were designed to probe the in- fluence of Cr on the properties of tube steel. The microstrueture, mechanical properties and corrosion behavior of the four kinds of P110 grade tube steels were studied deeply and thoroughly. The analysis of the mechanical properties indicated that tensile strength and yield strength of the steel plates were improved, while transverse and longitudinal impact energy and elongation first increased and then decreased when Cr content rose. The impact energy and elonga tion reached the peak when Cr content was 1 ~. Cr precipitates were found only in 3 ~ Cr steel, with （Nb, Ti）（C, N） or Nb（C,N） as the core of precipitation and then grew up. The corrosion experiments demonstrated that the scales on the four steels had a two layer structure under the corrosion of CO2 and H2 S. The outer layer was mainly com- posed of FeS or FeS1 x and the inner layer consisted of FeCOa and Cr compounds. Cr was rich in the inner layer and the Cr content of the inner layer increased with the Cr content in matrix. The enriched Cr enhanced the compactness of the scales, further hindering the diffusion of ions from liquid to the surface of steel, thus reducing corrosion rate.     

抗硫化氢腐蚀压力容器钢板的开发及生产实践

介绍湿硫化氢腐蚀开裂的原因和影响因素.通过降低钢中含硫磷量、控制钙硫比、提高钢水纯净度等措施,并结合控制轧制、钢板正火或正火加回火等热处理工艺,生产出力学性能优良、组织均匀、抗H2S腐蚀性能好的钢板.     

Fe-30Ce合金在H_2/H_2S混合气体中的腐蚀

研究了含３０ｗｔ．％Ｃｅ的Ｆｅ－Ｃｅ合金在６００～８００℃、Ｈ２／Ｈ２Ｓ混合气中的腐蚀行为，其硫的分压为１．０１×１０－３Ｐａ。结果表明，Ｆｅ－３０Ｃｅ合金的腐蚀速度比纯Ｆｅ慢得多，但比纯Ｃｅ快得多，随温度升高其腐蚀速度加快。该合金硫化后形成复杂的腐蚀产物膜，最外层为纯Ｆｅ的硫化物层，其下为Ｃｅ的硫化物与Ｆｅ的硫化物的混合物层，内层为Ｃｅ的内硫化区，与之相邻的基体金属层中没有贫Ｃｅ现象发生，Ｃｅ不能从合金的腐蚀区中扩散出去，而是在腐蚀区中形成Ｃｅ的硫化物与Ｆｅ的硫化物的混合物。尽管与纯Ｆｅ相比，Ｆｅ－Ｃｅ合金的腐蚀速度下降了，但在合金的表面上仍形成了连续的ＦｅＳ层，可见，３０ｗｔ．％的Ｃｅ亦不足以阻止基体金属的腐蚀，以及复杂氧化膜结构的形成，可能与Ｃｅ在基体金属中有限的溶解度及合金中金属间化合物相的出现有关。     

超级13Cr在H2S和CO2共存环境下的腐蚀行为影响研究

对CO2和H2S共存环境中95 ksi钢级超级13Cr钢的腐蚀行为进行了研究,发现常温条件下H2S和CO2共存环境中,无论是采用恒载荷的方法还是四点弯曲的方法,都在试样的表面出现了局部腐蚀,而在高温条件下未发生点蚀和应力腐蚀现象。分析结果表明,95 ksi钢级的超级马氏体不锈钢在常温H2S和CO2共存环境中出现的局部腐蚀主要是因为夹杂物在应力集中和酸性溶液的作用下形成点蚀,并沿着相同应力水平的区域扩展,局部腐蚀增加了应力腐蚀开裂的敏感性。     

抗挤抗硫套管用CrMo钢在硫化氢介质中的电化学行为

测定了宝钢φ177.8×9.19 mm规格B110TS抗挤抗硫套管的抗挤抗硫性能,采用电化学测试技术研究了抗挤抗硫套管用CrMo钢在饱和硫化氢盐溶液的极化和析氢行为.通过TEM、XPS和SEM观察了微观组织及析出相,发现铜的添加能够改变钢的电化学行为,钢基体以及碳化物在硫化氢介质中的溶解行为是影响抗硫化氢腐蚀性能的重要因素,提出了这种材料在硫化氢介质中的腐蚀机制.     

Preferential Oxidation of CO in H2 over CuO／CeO2 Catalysts

Over the past few years, the design and researchon fuel cells have been made a great development. Avariety of fuel cells for different applications has beenunder development[1,2]: solid polymer fuel cells(SPFC), also know as proton exchange …     

Catalytic effect of iron on decomposition of carbon monoxide: II. Effect of additions of H2, H2O,CO2, SO2 and H2S

In this work the effect of additions of H₂, H₂O, CO₂, SO₂, and H₂S on the catalytic decomposition of CO by iron has been investigated at 400, 600, and 800°C and atmospheric pressure. The catalyst was porous iron formed by the reduction of hematite ore granules with hydrogen. The relative importance of carbon deposition by the reactions 2CO → C + CO₂ and H₂ + CO → C + H₂O was determined as a function of hydrogen concentration. It was found that even low concentrations of hydrogen greatly enhanced the rate of decomposition of CO, presumably by a catalytic action of adsorbed hydrogen on iron. The presence of water vapor had a dual effect. At low concentrations of hydrogen the rate of decomposition of CO increased with the addition of H₂O, apparently by a catalytic effect. At high concentrations of hydrogen, however, carbon deposition was retarded because of the effect of the reverse reaction H₂O + C → H₂ + CO. In CO-CO₂ mixtures the rate of carbon deposition decreased with increasing CO₂ content, because of the effect of the reverse reaction CO₂ + C → 2CO. The presence of traces of sulfur-bearing gaseous species, such as SO₂ and H₂S, retarded the decomposition of CO on iron and brought about the early cessation of carbon deposition. This strong effect may be due to the retardation of the decomposition of the intermediate product, cementite, and the formation of pyrrhotite on the surface of the iron catalyst.     

PMTA对镀银层抗H2S腐蚀性能的研究

论述了1-苯基-5巯基四氮唑(PMTA)所具有的独特性质在防银变色方面的应用.考察了温度、浓度、溶剂等因素对其防银变色效果的影响,通过测定PMTA钝化膜的抗H2S腐蚀能力及其接触电阻,得出了较好的防银变色缓蚀剂配方及操作工艺.     

Resistance of Trip 800 Steels in a Sour Environment Containing H2S

We have evaluated the resistance of two samples of TRIP 800 steel prepared under laboratory conditions at the Faculty of Metallurgy and Materials Engineering (FMME) V?B (Technical University of Ostrava, Czech Republic) in a sour environment containing H₂S. The first steel investigated had a C–Mn–Si composition, and the second steel had a C–Mn–Si–Al composition. Both TRIP steels were characterized using the yield strength in the range 420 to 450 MPa and tensile strength in the range 880 to 900 MPa. The TRIP steel samples were in the form of sheets with a thickness of 1.5 mm. The residual austenite content was 11% and 13%, respectively, in the two steels studied. The resistance to hydrogen embrittlement was evaluated in a sour environment that contained hydrogen sulphide using hydrogen‐induced cracking (HIC) and sulphide stress cracking (SSC) tests performed in accordance with NACE standards. Both TRIP 800 steels showed a high resistance to hydrogen embrittlement, and no SSC cracks were observed. Some cracking arising from HIC was observed in both steels. The measured parameters showed some variation; in some cases they were lower than recommended limits, but in other cases the measured parameters were higher (e.g., the crack length ratio was up to 70%). The cracks initiated preferentially at non‐metallic inclusions, either at elongated manganese sulphide particles, or at oxide stringers that were rich in Al.     

Reduction of solid wustite in H2/H2O/CO/CO2 gas mixtures

The reduction of dense wustite in H₂/H₂O/CO/CO₂ gas mixtures has been carried out at temperatures between 1073 and 1373 K. The critical conditions for the formation of porous iron product morphologies have been identified and the results discussed in relation to the breakdown of dense iron layers on wustite surfaces. Formerly with the University of Queensland.     

钯与氢(H2,D2)反应的热力学性质研究

采用PVT方法精确测定了 40～ 60目的海绵钯 (Pd)粉末在 5～ 5 0℃范围内吸放H2 ,D2 的P C T曲线。结果表明 :2 5℃ ,0 .1MPa时H2 ,D2 在Pd中的溶解度分别为 75 .8和 70 .4ml(STP)·g- 1 Pd;Pd与H2 ,D2 反应的坪台热力学函数分别为 :ΔHa=-18.7kJ·mol- 1 H ,-17.6kJ·mol- 1 D ,ΔSa=-4 6.4J·K- 1 ·mol- 1 H ,-4 9.6J·K- 1 ·mol- 1 D ;ΔHd=2 1.3kJ·mol- 1 H ,18.7kJ·mol- 1 D ,ΔSd=5 0 .8J·K- 1 ·mol- 1 H ,49.1J·K- 1 ·mol- 1 D。H ,D在α相的溶解热力学函数为 :ΔHr→ 0 =-6.5kJ·mol- 1 H ,-5 .6kJ·mol- 1 D ;ΔSr→ 0 =-5 3 .5J·K- 1 ·mol- 1 H ,-5 3 .7J·K- 1 ·mol- 1 D。Pd Q(Q =H ,D)体系存在明显的迟滞效应 ,升高温度可改善吸放氢循环的压力迟滞效应 ,但不能消除。伴随迟滞效应的吉布斯自由能损失 (ΔGloss)在低于 5 0℃时保持不变 ,对Pd H和Pd D体系分别为 1.2 8和 1.2 5kJ·mol- 1 H(D) ;当高于 5 0℃时ΔGloss分别减小约 4%和 11%。     

温度对3Cr钢在CO2-O2环境中腐蚀的影响

摘要：为了研究注多元热流体吞吐热力采油过程中温度对油套管钢的影响,利用高温高压电化学釜模拟注多元热流体采油工况,分别在60、100和100～60℃循环的温度条件下,对3Cr钢进行失重腐蚀挂片试验和电化学腐蚀试验,利用高温高压电化学釜得到了3Cr钢在模拟工况下的腐蚀速率和极化曲线,并利用SEM、XRD、EDS分析了腐蚀产物膜形貌和成分。结果表明,温度由60升高至100℃时,腐蚀速率由0.552增长至1.920mm/a,在100-60℃高-低温循环时,腐蚀速率进一步升高至4.292mm/a;60和100℃时,腐蚀产物均为单层膜结构,且存在点蚀坑;在100-60℃高 低温循环时,腐蚀产物为双层膜结构,且存在直径约为4μm的腐蚀坑。温度主要影响3Cr钢腐蚀产物膜的结构和点蚀的形态,60和100℃时,点蚀坑内的聚集的Cl-离子使点蚀向纵深处发展,在100.60℃高 低温循环时,溶液中的O2促进了点蚀的横向发展,而腐蚀坑底部富集的Cr将阻碍点蚀的纵向发展。注多元热流体热力采油过程应充分考虑温度变化对3Cr钢腐蚀的影响,同时也要考虑温度变化引起3Cr钢点蚀的敏感性。