高效抗硫集输缓蚀剂研制及缓蚀机理研究
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摘要
本论文研究内容属于国家“十一五”规划重大科技专项课题。针对川东普光气田集输系统恶劣的腐蚀环境:P_(H2S)>1.5MPa、P_(CO2)>1.0MPa及平均矿化度159 000mg/l,合成了咪唑啉衍生物、曼尼希碱、吡啶季铵盐、喹啉季铵盐和新含氮稠杂环季铵盐五种缓蚀剂。通过设计正交试验,对各缓蚀剂的合成工艺进行了优化,并筛选了与之有较好缓蚀协同作用的增效剂,复配以各种表面活性剂和溶剂制成了成品缓蚀剂;用饱和H_2S/CO_2失重、高压H_2S/CO_2静态和动态失重、抗硫化氢应力腐蚀开裂、原子力显微镜(AFM)和环境扫描电镜(SEM)评价了各种缓蚀剂的抗硫性能;通过X能量衍射色散光谱(EDX)对试片表面产物膜的成分分析和量子化学密度泛函理论(DFT)探讨了缓蚀剂的作用机制及分子结构和抗硫性能的关系。
研究结果表明,正交试验优化后的工艺为各缓蚀剂的最佳合成工艺。咪唑啉衍生物、曼尼希碱和季铵盐缓蚀剂分别与苯基硫脲、丙炔醇和增效剂Y1(含S、N化合物)有着较好的协同抗硫效应;提高缓蚀剂的水溶性,抗硫性能变弱。
五类缓蚀剂在含硫环境中都有一定的缓蚀性能,其优劣顺序为:新含氮稠杂环季铵盐>喹啉季铵盐>吡啶季铵盐>咪唑啉衍生物>曼尼希碱。高效缓蚀剂在含硫环境中的作用机制主要是有效抑制CO_2/Cl~-腐蚀,并促使试片表面生成致密的碳化物和硫化物保护膜。
缓蚀剂的分子结构和抗硫性能关系密切。缓蚀剂分子的极性越高、E_(LUMO)越小、E_(HOMO)越大、最低非占轨道和最高占据轨的能隙即能量差ΔE(E_(LUMO)-E_(HOMO))越小,缓蚀性能越强。总的来说,缓蚀剂的静电吸附作用越强,空间位阻效应越小,中心吸附原子的电子云密度越大,缓蚀剂的抗硫效果越好。
The contents of this thesis belonged to the national "Eleventh Five-Year" plan major science and technology issues. Five kinds of corrosion inhibitors of imidazoline derivatives, Mannich bases, pyridine and quinoline and a new nitrogen-containing fused heterocyclic quaternary ammonium salts were synthetized for harsh corrosive environment of PuGuang gas gathering and transportation system, in which the partial pressure of hydrogen sulfide was more than 1.5 MPa, partial pressure of carbon dioxide was more than 1.0 MPa and the average salinity was 159 000mg/l. Synthesis conditions of various inhibitors were optimized by orthogonal experimental design and selected its’handsome synergist which had synergistic inhibition with it. After complexed with various surface active agents and solvents, the finished product inhibitors were gotten. Those inhibitors were evaluated through weight loss methods which saturated with H_2S/CO_2 and high pressure of H_2S/CO_2 at the static and dynamic conditions respectively. And the methods of Anti-hydrogen sulfide stress corrosion cracking, Atomic Force Microscope (AFM) and Environmental Scanning Electron Microscopy (SEM) were taken to evaluate the performance of corrosion resistance to sulfur. Inhibition mechanism and the relationship between molecular structure and anti-sulfur property were researched through composition analysis of the sample surface of product films obtained by X Energy Dispersive Diffraction Spectra (EDX) and quantum chemical paramaters obtained by Density Functional Theory (DFT).
The results showed that the optimized synthesis of orthogonal test were the best synthetic inhibitors. Imidazoline derivatives and Mannich bases, respectively, worked in coordination with phenyl thiourea, propargyl alcohol and quaternary ammonium salts had a good synergistic anti-sulfur effect with synergist Y1(a compound containing S and N elements). Corrosion inhibitive properties were weaker when improve water-soluble of all corrosion inhibitors. Five corrosion inhibitors all had some certain anti-sulfur properties in the corrosion environment containing H_2S/CO_2.The order of advantages and disadvantages was: New nitrogen-containing fused heterocyclic quaternary ammonium salt > quinoline quaternary ammonium salt > pyridine quaternary ammonium salt > imidazoline derivatives> Mannich base. The mechanism of corrosion inhibitor which have better inhibitive property of sulfur corrosion was mainly inhibit the corrosion of CO_2/Cl~-in the environment of H_2S/CO_2/Cl~-, and promoted dense carbide and sulfide protective film on the specimen surface.
The anti-sulfur performance was closely related to the molecular structure of corrosion inhibitors. Corrosion inhibitors were more efficient in the sulfur-containing environment that their molecules are higher polarity, smaller the E_(LUMO), greater the E_(HOMO) and smaller theΔE which stand for the energy gap of E_(LUMO) and E_(HOMO). In general, corrosion inhibitors, which have stronger electrostatic adsorption, smaller the steric effect, and larger the electron density of central adatom, would have better corrosion resistance to sulfur.
研究结果表明,正交试验优化后的工艺为各缓蚀剂的最佳合成工艺。咪唑啉衍生物、曼尼希碱和季铵盐缓蚀剂分别与苯基硫脲、丙炔醇和增效剂Y1(含S、N化合物)有着较好的协同抗硫效应;提高缓蚀剂的水溶性,抗硫性能变弱。
五类缓蚀剂在含硫环境中都有一定的缓蚀性能,其优劣顺序为:新含氮稠杂环季铵盐>喹啉季铵盐>吡啶季铵盐>咪唑啉衍生物>曼尼希碱。高效缓蚀剂在含硫环境中的作用机制主要是有效抑制CO_2/Cl~-腐蚀,并促使试片表面生成致密的碳化物和硫化物保护膜。
缓蚀剂的分子结构和抗硫性能关系密切。缓蚀剂分子的极性越高、E_(LUMO)越小、E_(HOMO)越大、最低非占轨道和最高占据轨的能隙即能量差ΔE(E_(LUMO)-E_(HOMO))越小,缓蚀性能越强。总的来说,缓蚀剂的静电吸附作用越强,空间位阻效应越小,中心吸附原子的电子云密度越大,缓蚀剂的抗硫效果越好。
The contents of this thesis belonged to the national "Eleventh Five-Year" plan major science and technology issues. Five kinds of corrosion inhibitors of imidazoline derivatives, Mannich bases, pyridine and quinoline and a new nitrogen-containing fused heterocyclic quaternary ammonium salts were synthetized for harsh corrosive environment of PuGuang gas gathering and transportation system, in which the partial pressure of hydrogen sulfide was more than 1.5 MPa, partial pressure of carbon dioxide was more than 1.0 MPa and the average salinity was 159 000mg/l. Synthesis conditions of various inhibitors were optimized by orthogonal experimental design and selected its’handsome synergist which had synergistic inhibition with it. After complexed with various surface active agents and solvents, the finished product inhibitors were gotten. Those inhibitors were evaluated through weight loss methods which saturated with H_2S/CO_2 and high pressure of H_2S/CO_2 at the static and dynamic conditions respectively. And the methods of Anti-hydrogen sulfide stress corrosion cracking, Atomic Force Microscope (AFM) and Environmental Scanning Electron Microscopy (SEM) were taken to evaluate the performance of corrosion resistance to sulfur. Inhibition mechanism and the relationship between molecular structure and anti-sulfur property were researched through composition analysis of the sample surface of product films obtained by X Energy Dispersive Diffraction Spectra (EDX) and quantum chemical paramaters obtained by Density Functional Theory (DFT).
The results showed that the optimized synthesis of orthogonal test were the best synthetic inhibitors. Imidazoline derivatives and Mannich bases, respectively, worked in coordination with phenyl thiourea, propargyl alcohol and quaternary ammonium salts had a good synergistic anti-sulfur effect with synergist Y1(a compound containing S and N elements). Corrosion inhibitive properties were weaker when improve water-soluble of all corrosion inhibitors. Five corrosion inhibitors all had some certain anti-sulfur properties in the corrosion environment containing H_2S/CO_2.The order of advantages and disadvantages was: New nitrogen-containing fused heterocyclic quaternary ammonium salt > quinoline quaternary ammonium salt > pyridine quaternary ammonium salt > imidazoline derivatives> Mannich base. The mechanism of corrosion inhibitor which have better inhibitive property of sulfur corrosion was mainly inhibit the corrosion of CO_2/Cl~-in the environment of H_2S/CO_2/Cl~-, and promoted dense carbide and sulfide protective film on the specimen surface.
The anti-sulfur performance was closely related to the molecular structure of corrosion inhibitors. Corrosion inhibitors were more efficient in the sulfur-containing environment that their molecules are higher polarity, smaller the E_(LUMO), greater the E_(HOMO) and smaller theΔE which stand for the energy gap of E_(LUMO) and E_(HOMO). In general, corrosion inhibitors, which have stronger electrostatic adsorption, smaller the steric effect, and larger the electron density of central adatom, would have better corrosion resistance to sulfur.
引文
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