油气输送管道甜腐蚀传质规律

doi:10.16085/j.issn.1000-6613.2023-2056

摘要/Abstract

摘要：

含CO₂的“甜”腐蚀已成为油气输送管道面临的重要问题。为预测和防范腐蚀危害，很多一维腐蚀预测模型被提出。但这些模型对于管内复杂流动的考虑不足。为此本文构建了多场耦合有限元模型，讨论输送管道中的腐蚀传质规律。综合考虑CO₂水溶液中化学反应、腐蚀电化学反应及腐蚀产物形成的过程，电化学腐蚀的模型被耦合在流动计算中，从而模拟研究直管流动中CO₂腐蚀传质。结果显示管内流动腐蚀的传质边界层厚度小于流动边界层的1/10，流动增大了腐蚀传质速率，形成高流动腐蚀速率。流动腐蚀下，管道表面H⁺并未完全消耗。这使得腐蚀传质中H⁺舍伍德数（Sh）随雷诺数（Re）的变化在不同pH下规律不同。考虑管内的实际流动，研究得到预测油气管道流动腐蚀的传质经验关联式。

关键词: 流动腐蚀, 多场耦合, 电化学, 传质, 边界层, 湍流

Abstract:

The corrosion caused by CO₂, known as "sweet" corrosion, has become a significant challenge for oil and gas pipelines. Numerous one-dimensional corrosion prediction models have been proposed to forecast and prevent corrosion hazards. However, these models lack consideration of the complex flow within the pipeline. Therefore, a multi-field coupled finite element model was constructed to investigate the mass transfer law of corrosion in pipelines. The comprehensive consideration of chemical reaction, electrochemical corrosion reaction, and corrosion product formation in CO₂ aqueous solution was undertaken. The electrochemical corrosion model was integrated with flow calculations to simulate the mass transfer of CO₂ corrosion in straight pipe flow. The results indicated that the thickness of the mass transfer boundary layer was less than 1/10 of that of the flow boundary layer, and the presence of flow enhanced the rate of corrosion mass transfer, resulting in a higher flow corrosion rate. The consumption of H⁺ on the pipeline surface was not fully exhausted under flow corrosion, leading to distinct variations in the H⁺ Sherwood number (Sh) with Reynolds number (Re) in corrosion mass transfer at different pH. Considering the actual flow, the study derived an empirical correlation equation for mass transfer to predict flow corrosion in oil and gas pipelines.

Key words: flow corrosion, multi-field coupling, electrochemistry, mass transfer, boundary layer, turbulent flow

中图分类号:

TE988

房启超, 赵彦琳, 尉江涛, 姚军. 油气输送管道甜腐蚀传质规律[J]. 化工进展, 2024, 43(12): 6626-6633.

FANG Qichao, ZHAO Yanlin, WEI Jiangtao, YAO Jun. Law of corrosion mass transfer in oil and gas pipeline[J]. Chemical Industry and Engineering Progress, 2024, 43(12): 6626-6633.

图/表 8

表1 腐蚀体系化学平衡反应计算[16]

化学反应	平衡公式	平衡常数
$C O_{2} (g) \overset{}{⇌} C O_{2} (a q)$	$H_{C O_{2}} = \frac{p_{C O_{2} (g)} φ_{C O_{2} (g)}}{c_{C O_{2} (a q)}}$	$H_{C O_{2}} = e x p (13 - 0.01334 T - \frac{558.98}{T} - \frac{422580}{T^{2}})$
$H_{2} O \overset{}{⇌} H^{+} + O H^{-}$	$K_{w a} = \frac{k_{f, w}}{k_{b, w}} = c_{O H^{-}} c_{H^{+}}$	$K_{w a} = 10^{- (293868 - 0.0737549 T_{K} + 7.47881 \times 10^{- 5} T_{K}^{2})}$
$C O_{2} + H_{2} O \overset{}{⇌} H_{2} C O_{3}$	$K_{h y d} = \frac{k_{f, h y d}}{k_{b, h y d}} = \frac{c_{H_{2} C O_{3}}}{c_{C O_{2} (a q)}}$	$K_{h y d} = 0.06633 \times e x p (- \frac{9526}{R T})$ , $k_{f, h y d} = 3.22 \times 10^{11} \times e x p (- \frac{74011}{R T})$
$H_{2} C O_{3} \overset{}{⇌} H^{+} + H C O_{3}^{-}$	$K_{c a} = \frac{k_{f, c a}}{k_{b, c a}} = \frac{c_{H C O_{3}^{-}} c_{H^{+}}}{c_{H_{2} C O_{3}}}$	$K_{c a} = e x p [233.52 - \frac{11974.38}{T} - 36.51 l n T + (- \frac{450.8}{T} + \frac{21313.2}{T^{2}} + \frac{67.14}{T} l n T) p_{C O_{2}}]$
$H C O_{3}^{-} \overset{}{⇌} H^{+} + C O_{3}^{2 -}$	$K_{b i} = \frac{k_{f, b i}}{k_{b, b i}} = \frac{c_{C O_{3}^{2 -}} c_{H^{+}}}{c_{H C O_{3}^{-}}}$	$K_{b i} = e x p [- 151.18 - \frac{0.0887}{T} - \frac{1362.26}{T^{2}} + 27.8 l n T + (- \frac{295.15}{T} + \frac{13890.15}{T^{2}} + \frac{44.2}{T} l n T) p_{C O_{2}}]$

表1 腐蚀体系化学平衡反应计算[16]

化学反应	平衡公式	平衡常数
$C O_{2} (g) \overset{}{⇌} C O_{2} (a q)$	$H_{C O_{2}} = \frac{p_{C O_{2} (g)} φ_{C O_{2} (g)}}{c_{C O_{2} (a q)}}$	$H_{C O_{2}} = e x p (13 - 0.01334 T - \frac{558.98}{T} - \frac{422580}{T^{2}})$
$H_{2} O \overset{}{⇌} H^{+} + O H^{-}$	$K_{w a} = \frac{k_{f, w}}{k_{b, w}} = c_{O H^{-}} c_{H^{+}}$	$K_{w a} = 10^{- (293868 - 0.0737549 T_{K} + 7.47881 \times 10^{- 5} T_{K}^{2})}$
$C O_{2} + H_{2} O \overset{}{⇌} H_{2} C O_{3}$	$K_{h y d} = \frac{k_{f, h y d}}{k_{b, h y d}} = \frac{c_{H_{2} C O_{3}}}{c_{C O_{2} (a q)}}$	$K_{h y d} = 0.06633 \times e x p (- \frac{9526}{R T})$ , $k_{f, h y d} = 3.22 \times 10^{11} \times e x p (- \frac{74011}{R T})$
$H_{2} C O_{3} \overset{}{⇌} H^{+} + H C O_{3}^{-}$	$K_{c a} = \frac{k_{f, c a}}{k_{b, c a}} = \frac{c_{H C O_{3}^{-}} c_{H^{+}}}{c_{H_{2} C O_{3}}}$	$K_{c a} = e x p [233.52 - \frac{11974.38}{T} - 36.51 l n T + (- \frac{450.8}{T} + \frac{21313.2}{T^{2}} + \frac{67.14}{T} l n T) p_{C O_{2}}]$
$H C O_{3}^{-} \overset{}{⇌} H^{+} + C O_{3}^{2 -}$	$K_{b i} = \frac{k_{f, b i}}{k_{b, b i}} = \frac{c_{C O_{3}^{2 -}} c_{H^{+}}}{c_{H C O_{3}^{-}}}$	$K_{b i} = e x p [- 151.18 - \frac{0.0887}{T} - \frac{1362.26}{T^{2}} + 27.8 l n T + (- \frac{295.15}{T} + \frac{13890.15}{T^{2}} + \frac{44.2}{T} l n T) p_{C O_{2}}]$

表2 腐蚀阴阳极电流密度计算

电化学反应	腐蚀电流密度
Fe(s) $\overset{}{\to}$ Fe²⁺+2e^-	$i_{F e} = 2 F k_{F e} c_{H^{+}}^{s} e x p (\frac{1.4 F η}{R T})$
2H⁺+2e^- $\overset{}{\to}$ H₂	$i_{H^{+}} = - F k_{H^{+}} c_{H^{+}}^{s} e x p (\frac{0.5 F η}{R T})$

表2 腐蚀阴阳极电流密度计算

电化学反应	腐蚀电流密度
Fe(s) $\overset{}{\to}$ Fe²⁺+2e^-	$i_{F e} = 2 F k_{F e} c_{H^{+}}^{s} e x p (\frac{1.4 F η}{R T})$
2H⁺+2e^- $\overset{}{\to}$ H₂	$i_{H^{+}} = - F k_{H^{+}} c_{H^{+}}^{s} e x p (\frac{0.5 F η}{R T})$

图1 二维流动腐蚀计算域及近壁面网格

图2 流动腐蚀模拟方法验证

图3 不同速度下流动边界层变化规律

图4 20℃不同pH电极表面物质浓度变化

图5 20℃时不同流速流动腐蚀规律

图6 流动腐蚀传质随雷诺数变化规律

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