【作者】 扈显琦；

【导师】 梁成浩；

【作者基本信息】 大连理工大学 ， 化学工程， 2006， 博士

【摘要】 溴化锂吸收式制冷机具有热效率高、热源广泛、能耗低以及零排放等优点，近年来得到广泛的应用。为了进一步提高溴化锂吸收式制冷机的热效率，制冷业研究发展三效式和多效式制冷循环。在优化设计的三效式制冷循环中，制冷机最高工作温度达到180℃，溴化锂溶液浓度也更高。而作为强腐蚀性介质，高浓度溴化锂溶液在三效式和多效式循环条件下会引起碳钢、铜以及铜合金等金属材料严重的腐蚀。这一问题制约了溴化锂吸收式制冷机技术的发展，已引起人们的重视。 采用化学浸泡实验、电化学测试技术和扫描电镜（SEM）、X射线衍射（XRD）、电子探针（EPMA）以及红外光谱（IR）等检测技术，对Li₃[PMo₁₂O₄₀]与SbBr₃复合缓蚀剂（PMA／SbBr₃）、强化溶解Li₂MoO₄缓蚀剂（E-Mo）、Na₃[PW₁₂O₄₀]（PWA）、H₄[PW₁₁VO₄₀]（PWVA）和PWVA／Sb₂O₃复合缓蚀剂在高温55％LiBr+0.07mol／L LiOH溶液中对SS41碳钢、磷脱氧铜和白铜的缓蚀行为进行研究，并探讨了缓蚀机理。结果表明，PMA／SbBr₃、PWA、PWVA和PWVA／Sb₂O₃缓蚀剂能够同时抑制碳钢、铜和白铜在55％LiBr+0.07mol／L LiOH溶液中的阴极和阳极反应过程，属于混合型缓蚀剂。E-Mo只能抑制阳极反应过程，而对阴极反应过程无影响，属于阳极型缓蚀剂。 PMA／SbBr₃缓蚀剂对碳钢在55％LiBr+0.07mol／L LiOH溶液中具有优异的高温缓蚀性能，对铜和白铜的腐蚀也具有较高的缓蚀效率。实验温度范围内，碳钢在含PMA／SbBr₃缓蚀剂的55％LiBr溶液中腐蚀反应的动力学方程式为lnk=11.447-3561.4／T，反应表观活化能E_a=29.61kJ／mol。PMA／SbBr₃缓蚀剂使碳钢在55％LiBr+0.07mol／L LiOH溶液中的反应表观活化能增大，腐蚀反应进行的难度增大。 55％LiBr溶液中添加20m／L 2-聚丙烯酸调聚物，Li₂MoO₄在55％LiBr溶液中的溶解度提高到850mg／L，得到E-Mo缓蚀剂。E-Mo缓蚀剂对碳钢在55％LiBr+0.07mol／LLiOH溶液中的腐蚀具有优异的缓蚀性能，尤其是溶液温度超过180℃时仍具有很高的缓蚀效率。溶液温度为240℃时，碳钢的腐蚀速度仅33.07μm／a，缓蚀效率仍高达91.5％。E-Mo对铜和白铜的腐蚀也具有一定程度的抑制作用。55％LiBr溶液中，碳钢的腐蚀电流密度i_corr与腐蚀电势E_corr之间的关系方程为lgi_corr=-2.66-3.54E_corr，阴极析氢反应塔菲尔常数β_c=282mV。 在55％LiBr+0.07mol／L LiOH溶液中，PWA缓蚀剂浓度为300mg／L时，对碳钢和白铜具有优异的缓蚀性能，对铜的腐蚀也具有一定程度的抑制作用。溶液温度为180℃时，碳钢腐蚀速度仅24.55μm／a，缓蚀效率为86.4％。PWA具有强氧化性，在55％LiBr+0.07mol／L LiOH溶液中使碳钢表面生成完整致密的Fe₂O₃钝化膜，铜表面沉积CuO和更多还原

【Abstract】 Lithium bromide absorption chiller has been applied widely in recent years, since it has many excellent characteristics, such as high thermal efficiency, wide heat sources, low energy consumption and zero release. To increase the thermal efficiency, triple-effect and multi-effect refrigeration cycles have been developed. In the triple-effect chiller, the maximum working temperature is 180℃ and the concentration of lithium bromide solution is concentrated. Lithium bromide solution is an aggressive medium, and may cause serious corrosion on carbon steel, copper and cupronickel under conditions of triple-effect and multi-effect cycles. This problem has limited the development of lithium bromide absorption chiller.The inhibition effects of PMA/SbBr₃, E-Mo, PWA, PWVA and PWVA/Sb₂O₃ on corrosion resistance of carbon steel, copper and cupronickel in 55%LiBr+0.07mol/L LiOH solution are studied by weight loss test, electrochemical measurements and physical detection technologies, such as SEM, XRD, EPMA and IR. The results indicate that PMA/SbBr₃, PWA, PWVA and PWVA/Sb₂O₃ can retard both anodic and cathodic reactions of carbon steel, copper and cupronikel in 55%LiBr+0.07mol/L LiOH solution, and behave as mixed inhibitors. E-Mo just inhibit anodic reactions, and can be classified as anodic inhibitor.PMA/SbBr₃ complex inhibitor shows excellent inhibition performance on carbon steel in 55%LiBr+0.07mol/L LiOH solution at high temperature. It can also inhibit the corrosion of copper and cupronickel effectively. At experimental temperatures, the thermodynamic equation of corrosion reaction of carbon steel in 55%LiBr+0.07mol/L LiOH solution with PMA/SbBr₃ inhibitor is lnk=11.447-3561.4/T and the apparent activation energy of the corrosion reaction is 29.61 kJ/mol. The apparent activation energy of the corrosion reaction is increased by the addition of PMA/SbBr₃ inhibitor, which means that the corrosion of carbon steel is retarded in the presence of PMA/SbBr₃ inhibitor.E-Mo inhibitor can be obtained by adding 20 mg/L 2-propenoic telomer into 55% LiBr solution, in which the solubility of Li₂MoO₄ can be increased to 850 mg/L. E-Mo inhibitor has excellent inhibition performance on carbon steel in 55%LiBr+0.07mol/L LiOH solution. Especially, when solution temperature is higher than 180 ℃, the inhibition efficiency is still very high. Even when the solution temperature is 240 ℃, the corrosion rates of carbon steel is only 33.07 μm/a, and inhibition efficiency is 91.5%. E-Mo can also inhibit the corrosion of copper and cupronickel. Under experimental condition, the relationship between corrosion更多还原