燃气中H2 S、C02气体腐蚀反应的化学热力学计算

运用化学热力学理论与计算方法对燃气中H2 S、CO2 与金属腐蚀反应的标准吉布斯函数、反应平衡常数、平衡分压等进行计算 ,从而得出腐蚀反应ΔG0 T关系式。通过这些数据 ,从理论上解释H2 S、CO2 对金属发生腐蚀反应的可能性 ,并进而推断出燃气中H2 S、CO2 对设备腐蚀的可能性大小和条件     

金属管道在CO2/H2S环境中的腐蚀行为

金属管道因油气输送介质中含有CO2与H2S而遭受严重腐蚀,尤其是点蚀,导致其过早失效、油气水泄漏,增加了安全隐患与环境污染风险.对金属管道在含CO2、H2S环境中的腐蚀行为进行概述,论述了CO2与H2S共存体系中竞争协同效应与二者分压比的划分,探讨了CO2、H2S以及CO2/H2S腐蚀机理、腐蚀产物类型以及环境对管道腐...     

CO2分压对碳钢海底管道CO2/H2S腐蚀的影响

目的：研究 CO2分压对 CO2/H2S腐蚀的影响规律,为海底管道材料的选择提供参考依据。方法采用高温高压反应釜进行腐蚀模拟实验,对腐蚀前后的试样进行称量,计算腐蚀速率。通过SEM观察腐蚀产物膜形貌,通过 XRD 分析腐蚀产物膜成分。结果当 CO2/H2S 分压比较高（1200）时, CO2分压为0.3、0.5、1.0 MPa对应的腐蚀速率分别为1.87、3.22、5.35 mm/a,随着CO2分压升高,腐蚀速率几乎呈线性增大趋势。当CO2/H2S分压比较低（200）时,CO2分压为0.3、0.5、1.0 MPa对应的腐蚀速率分别为3.47、3.64、3.71 mm/a,CO2分压变化对腐蚀速率的影响并不显著。当CO2/H2S分压比较高（1200）时,腐蚀产物以FeCO3为主,腐蚀受CO2控制;此时低CO2分压下的腐蚀产物膜较完整致密,高CO2分压下的腐蚀产物膜局部容易破裂,对基体保护性下降,因此腐蚀速率随CO2分压升高而增大。当CO2/H2S分压比较低（200）时,腐蚀产物以FeS为主,腐蚀受H2S控制;此时在不同CO2分压条件下,腐蚀产物均较完整致密,因此腐蚀速率相对较低,并未随着CO2分压升高显著增大。结论 CO2分压对CO2/H2S腐蚀速率的影响与CO2/H2S分压比密切相关,海底管道材料选择不仅要考虑CO2分压的影响,还要考虑CO2/H2S分压比的影响。     

地面集输管道在CO2/H2S/O2体系下的腐蚀行为研究

目的 研究集输管道常用钢材在CO2/H2S/O2体系下的腐蚀行为,为新疆油田集输管道的腐蚀防控提供指导依据.方法 基于新疆油田重油热采现场工况,以L245NS钢为试材,316L钢为对照,采用高温高压釜试验,研究CO2/H2S/O2体系下温度和H2S含量对L245NS钢和316L不锈钢的腐蚀影响规律,并结合SEM/EDS+XPS+3D显微镜等手段对典型工况下的腐蚀产物进行测试分析.结果 在CO2/H2S/O2共存体系中,L245NS钢的腐蚀速率随温度的升高,呈先增大、后减小的趋势;而随H2S含量的升高,呈先减小、后增大的趋势.316L钢的腐蚀速率随温度的升高,呈先增大后减小的趋势;随H2S含量的升高,呈一直增大的趋势.L245NS钢腐蚀产物呈针状、菱状、颗粒状多种形态,而316L钢腐蚀产物较少.在CO2/H2S/O2共存体系中,L245NS钢的腐蚀产物主要包含FeS、FeS2、单质S、FeCO3、Fe(OH)3、FeOOH、Fe3O4、Fe2O3、Na2SO4等物质.结论 L245NS钢在CO2/H2S/O2体系(22PCO H S/P<200)下的腐蚀行为主要由H2S主导,生成的FeS分布在产物底层.O2具有促进腐蚀进程的三方面作用:与H2S发生交互作用生成了单质S;作为去极化剂参与阴极反应;作为强氧化剂氧化FeS、FeCO3,反应生成单质S、FeS2、Fe2O3、Fe3O4、FeO(OH)等物质.     

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.     

模拟CO2驱环境下产出水的平衡溶液性质研究

本文利用高压反应釜模拟CO2驱环境进行了腐蚀试验,通过CO2腐蚀反应的推导与计算,分析了其产出水中CO2平衡溶液化学性质及各阳极反应的腐蚀平衡电位。结果表明,CO2平衡溶液存在形式主要为水溶CO2、H2CO3、和HCO3-离子,水溶CO2浓度最高;基体Fe与溶液中H2CO3、HCO3-离子生成FeCO3反应为本试验CO2驱油环境下CO2腐蚀过程最主要阳极反应。     

温度和CO_2/H_2S分压比对BG90SS钢管腐蚀行为的影响

利用高温高压H2S/CO2腐蚀模拟实验及SEM,XRD等分析技术研究了H2S和CO2共存环境下温度和CO2/H2S分压比对BG90SS抗硫钢管腐蚀行为的影响。结果表明:在60~120℃的范围内,温度的变化对BG90SS油管钢的腐蚀速率的影响并不明显。在60℃和90℃条件下腐蚀由H2S控制,在120℃条件下腐蚀由H2S和CO2共同控制。CO2/H2S分压比低于14时,BG90SS的腐蚀速率变化不明显,分压比在14~28的范围内,腐蚀速率迅速升高,分压比高于28以后,腐蚀速率缓慢增加。随着CO2/H2S分压比的提高,腐蚀由H2S控制转变为H2S和CO2共同控制。     

经济型抗H2S＋CO2腐蚀油管BG110S-2Cr开发

根据Cr元素对低合金钢力学性能的影响规律,在3Cr系列经济型抗H2S和（或）CO2腐蚀钢种基础上,成功开发出110kpsi（758MPa）钢级经济型抗H2S＋CO2腐蚀油管BG110S-2Cr。试验表明,大生产BG110S-2Cr油管具有优良的抗H2S应力腐蚀开裂（SSC）性能。与常规P110油套管相比,在模拟油田典型腐蚀介质中其CO2腐蚀速率降低了一半以上。     

输油管道中的CO2腐蚀

输油管道有外腐蚀和内腐蚀。从设计开始就对外腐蚀采取周密的措施，而对内腐蚀只重视H2S的腐蚀，到目前为止还没有重视空气中的CO2腐蚀，其实CO2也是造成内壁腐蚀的一种主要原因。当气相CO2遇水时，一定量的CO2溶解于水中，形成具有一定CO2浓度的溶液，CO2在水中的溶解量取决于输送温度、CO2浓度和输送压力。溶解在水里的CO2和水反应生成碳酸，溶液中的H2CO3和铁反应促使铁腐蚀。     

P110SS钢在H2S和CO2环境中的腐蚀特征

利用高温高压哈氏合金反应釜对P110SS油套管钢在不同H2S和CO2环境下的腐蚀行为进行了实验。研究了H2S和CO2分压对P110SS油套管钢腐蚀规律的影响,利用SEM、EDS、XRD等方法分析了腐蚀试样的微观形貌与结构特征,发现P110SS在较低温度条件下,H2S浓度非常低时,腐蚀特征与单纯CO2腐蚀规律相似,腐蚀速率比较高。在相同的H2S分压条件下,随CO2浓度增加,腐蚀速率依次增加。通过应力腐蚀开裂试验表明,P110SS在高温205℃条件下应力腐蚀开裂敏感较小。     

Thermodynamics and phase diagrams in the binary systems Na2O-SiO2, Na2O-GeO2, Na2O-B2O3, Li2O-B2O3, CaO-B2O3, SrO-B2O3, and BaO-B2O3

We applied our model to the enthalpy of mixing data of the binary systems Na₂O-SiO₂, Na₂O-GeO₂, Na₂O-B₂O₃, Li₂O-B₂O₃, CaO-B₂O₃, SrO-B₂O₃, and BaO-B₂O₃. The most stable composition in the liquid, that is where the enthalpy of mixing is most negative, is with a metal-oxygen ratio of 4 to 3, for monovalent metals (Na and Li) and 3 to 4 for divalent metals (Ba and Ca) in liquid silicates or borates. The same applies to the CaO-SiO₂, CaO-Al₂O₃, PbO-B₂O₃, PbO-SiO₂, ZnO-B₂O₃, and ZnO-SiO₂ systems. The oxygen to metal ratio, its constant value in various types of systems, reflects and describes the structure of the liquid. Using the analyzed enthalpies of mixing data and the available phase diagrams, we calculated the enthalpies of formation of the various binary compounds. The results are in excellent agreement with data in the literature that were obtained from direct solid-solid calorimetry.     

Crystal structures and structural relationships of KFe2(SeO2OH)(SeO3)3 and SrCo2(SeO2OH)2(SeO3)2

The new phases KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ have been synthesized under low-hydrothermal conditions and their structures were determined by single-crystal X-ray methods. Both compounds are monoclinic; KFe₂(SeO₂OH)(SeO₃)₃: space group P2, A = 9.983(4), B = 5.270(1), C = 10.614(4) Å, β = 97.42(2)°, V = 553.7 ų, Z = 2; SrCo₂(SeO₂OH)₂(SeO₃)₂: space group P2ln, A = 14.984(2), B = 5.286(1), C = 13.790(2) Å, β = 94.72(1)°, V = 1088.5 ų , Z = 4. The refinements converged to R-values of 2.9 and 3.6% respectively.

The atomic arrangement in KFe₂(SeO₂OH)(SeO₃)₃ and SrCo₂(SeO₂OH)₂(SeO₃)₂ is based on isolated MO₆ octahedra (M = Fe³⁺, Co²⁺), which are corner-linked via trigonal pyramidal selenite groups to a framework structure. Interstitials are occupied by potassium or strontium atoms in ten- or eight-coordination respectively, and by the lone-pair electrons of the Se⁴⁺ atoms. Both compounds are not isotypic but are closely related and may be interpreted as different distortions of an idealized structure type in space group P2/m, which was modelled for a theoretical compound SrFe₂(SeO₃)₄ by distance least squares refinement (program ).     

MoS2 coated with Al2O3 for Ni-MoS2/Al2O3 composite coatings by pulse electrodeposition

The MoS₂ powders were coated with Al₂O₃ (5 wt.%) through controlling hydrolysis of Al (NO₃)₃·9H₂O. MoS₂ powder coated with Al₂O₃ was written as MoS₂/Al₂O₃ hereinafter. MoS₂/Al₂O₃ powders were put into Ni plating electrolyte bath. Cetyltrimethylammonium bromide (CTAB) — the surfactant was also put into the bath. The experiment proves that MoS₂/Al₂O₃ particles were absorbed onto the Ni plate. The amount of MoS₂/Al₂O₃ deposited on Ni plate rises with the increasing concentration of MoS₂/Al₂O₃ in the bath. The microhardness, micro-surface, phase and the tribological property of the MoS₂/Al₂O₃ multi-plating coating were measured and analyzed. The performances of microhardness and wear resistance of the Ni-MoS₂/Al₂O₃ composite are better than those of Ni-MoS₂ composite.     

Corrosion characteristics of LiBH4 film exposed to a CO2/H2O/O2/N2 mixture

LiBH₄ films were prepared by pulsed laser deposition using a LiB target in a background pressure of hydrogen. The corrosion characteristics of LiBH₄ films were measured by exposing them to a gas mixture of CO₂/H₂O/O₂/N₂ at ambient temperature for 1–24 h. Scanning electron microscopy images show some cracks on the surface of corrosion films, which could act as easy paths for H₂O and CO₂ to further react with Li⁺ and B³⁺. The X-ray photoelectron spectroscopy results and theoretical analysis show that LiBH₄ tends to react with H₂O and CO₂ to form Li₂B₄O₇, Li₂CO₃ and LiOH during the corrosion process.     

Synthesis and properties of CaCd2Sb2 and EuCd2Sb2

High density polycrystalline CaCd₂Sb₂ and EuCd₂Sb₂ intermetallics are synthesized by Spark Plasma Sintering and their thermoelectric properties are investigated. X-ray diffraction measurements reveal both materials have a structure in space group, containing a small amount of CdSb as a second phase. Thermoelectric measurements indicate both are p-type conductive materials. The figure of merit value of CaCd₂Sb₂ is 0.04 at 600 K and that of EuCd₂Sb₂ is 0.60 at 617 K. Theoretical calculations show that CaCd₂Sb₂ is a degenerate semiconductor with a band gap of 0.63 eV, while EuCd₂Sb₂ is metallic with DOS of 13.02 electrons/eV. For deeper understanding of the better thermoelectric properties of EuCd₂Sb₂, its low temperature magnetic, transport and heat capacity properties are investigated. Its Nèel temperature is 7.22 K, convinced by heat capacity anomaly at 7.13 K. Hall effect convinced that it is a p-type conductive material. It has high Hall coefficient, high carrier concentration and high carrier mobility of +1.426 cm³/C, 4.38 × 10¹⁸/cm³ and 182.40 cm²/Vs, respectively. They are all in the magnitude of good thermoelectric materials. The Eu 4f level around Fermi energy and antiferromagnetic order may count for the better thermoelectric properties of EuCd₂Sb₂ than that of CaCd₂Sb₂.     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Gd Mössbauer effect and magnetic properties of GdNi2Sb2, GdCu2Sb2 and GdAl2Ga2

We have investigated the magnetic properties and the ¹⁵⁵Gd Mössbauer spectra of the ThCr₂Si₂-type compounds GdNi₂Sb₂, GdCu₂Sb₂ and GdAl₂Ga₂. These three compounds were found to order antiferromagnetically, with T_N=6.5 K, 15.8 K, and 42.4 K respectively. The electric field gradient V₂₂ derived from the quadrupole splitting of the Mössbauer spectra gives rise to a sign change at the end of the T3d series in GdT₂Sb₂, as was observed previously also for the corresponding compounds with Si and Ge. This behaviour was explained in terms of decreasing hybridization between the Gd valence electron states and the d electron states of the T atoms.     

等离子球化制备球形CaF2/BaF2共晶粉末*

探究了使用大气等离子喷涂设备制备适合热喷涂使用的球形CaF2/BaF2共晶粉末的可能性。68%BaF2、32%CaF2粉末(质量分数)经过1 100℃真空烧结后,形成致密的块状氟化物共晶。机械破碎后的氟化物共晶经过等离子焰流重熔后得到了球形的氟化物共晶。使用F14-1流动性和松装密度测定仪测量球化前后粉末的流动性和松装密度。采用扫描电子显微镜,XRD表征球化前后粉末的形貌和物相组成。结果表明:球化后的粉末呈现较好的球形,球化后粉末的流动性和松装密度较球化前也有较大的改善:球化后共晶粉末的流动时间为55.20s/50g,松装密度为1.89g/cm3;另外,球化后共晶粉末还表现出良好的高温润滑性能:含有10%CaF2/BaF2共晶(质量分数)的镍基涂层在600℃和800℃的平均摩擦因数都小于0.3。     

Thermal cycle behavior of plasma sprayed La2O3, Y2O3 stabilized ZrO2 coatings

The effects of La₂O₃ addition on thermal conductivity, phase stability and thermal cycle life of Y₂O₃ stabilized ZrO₂ plasma sprayed coatings were investigated. Although low thermal conductivity as well as high resistance to sintering was achieved by La₂O₃ addition, it tended to also result in lower phase stability and thermal cycle life of the coatings. Optimization of the composition and structure of the coatings improved these properties, and the optimized coatings showed prolonged thermal cycle life.     

Crystal structures of VSn2, NbSn2 and CrSn2 with Mg2Cu-type structure and NbSnSb with CuAl2-type structure

Several binary stannides of the early transition metals T have been reported with the composition T₂Sn₃ previously. However, the present structure refinements from single-crystal X-ray data show that they have the compositions VSn₂, NbSn₂ and CrSn₂ (R = 0.028, R = 0.018 and R = 0.021 with 17 variable parameters and 828, 512 and 440 structure factors respectively). Their orthorhombic Mg₂Cu-type structure is closely related to the structures of MoSn₂ (Mg₂Ni type) and CuAl₂. The latter structure type was confirmed for NbSnSb by a structure refinement from single-crystal data (R = 0.010 for eight variables and 254 F values). Electrical conductivity measurements show CrSn₂ and MoSn₂ to be metallic conductors.