化工学报 ›› 2024, Vol. 75 ›› Issue (3): 789-800.DOI: 10.11949/0438-1157.20231235
陈好奇1(), 史博会1,2(), 彭琪1, 康琦3, 宋尚飞1, 姚海元4, 陈海宏4, 吴海浩1, 宫敬1
收稿日期:
2023-11-28
修回日期:
2024-02-07
出版日期:
2024-03-25
发布日期:
2024-05-11
通讯作者:
史博会
作者简介:
陈好奇(1997—),男,博士研究生,1649618546@qq.com
基金资助:
Haoqi CHEN1(), Bohui SHI1,2(), Qi PENG1, Qi KANG3, Shangfei SONG1, Haiyuan YAO4, Haihong CHEN4, Haihao WU1, Jing GONG1
Received:
2023-11-28
Revised:
2024-02-07
Online:
2024-03-25
Published:
2024-05-11
Contact:
Bohui SHI
摘要:
油气开发的井流物多以油气水混相形式存在。对于酸性油气田,还常伴有硫化氢或二氧化碳等酸性气体。为了避免水合物生成堵塞管道,加注醇类防冻剂是常用的方法。因而油气田井流物易于呈现含酸、含醇的多相烃水混输状态。含酸/醇烃水体系相平衡的准确计算,是预测其物性特征的基础,也是支持该复杂体系多相混输流动仿真的关键。但目前被广泛应用的基于经典立方型状态方程计算油气水体系相平衡的方法,存在对液烃及水相分布预测准确性不高的问题。为此,引入稳定性分析的方法,构建适用于含酸/醇烃水体系的稳定性检验方式,结合SRK-HV状态方程,建立了耦合稳定性分析的含酸/醇烃水多相多组分相平衡计算模型及算法。经多角度验证,本研究所提模型具有较高的准确性与稳定性。
中图分类号:
陈好奇, 史博会, 彭琪, 康琦, 宋尚飞, 姚海元, 陈海宏, 吴海浩, 宫敬. 基于稳定性分析的含酸/醇烃水体系相平衡计算[J]. 化工学报, 2024, 75(3): 789-800.
Haoqi CHEN, Bohui SHI, Qi PENG, Qi KANG, Shangfei SONG, Haiyuan YAO, Haihong CHEN, Haihao WU, Jing GONG. Phase equilibrium calculation of acid/alcohol hydrocarbon and water system based on stability analysis[J]. CIESC Journal, 2024, 75(3): 789-800.
第二组分 | 甲醇 | 水 | ||||
---|---|---|---|---|---|---|
[(g12-g22)/R]/K | [(g21-g11)/R]/K | α12 | [(g12-g22)/R]/K | [(g21-g11)/R]/K | α12 | |
H2O | 288 | 276 | 1.20 | — | — | — |
N2 | 357 | 1130 | 0.40 | 689 | 3921 | 0.15 |
CO2 | 247 | 2970 | 0.40 | 16 | 1652 | 0.15 |
H2S | 58 | 886 | 0.40 | 118 | 1294 | 0.15 |
C1 | 77 | 2094 | 0.40 | 410 | 2291 | 0.15 |
C2 | 255 | 1610 | 0.40 | 492 | 2281 | 0.15 |
C3 | 465 | 1418 | 0.40 | 847 | 2650 | 0.15 |
iC4/nC4 | 516 | 1049 | 0.40 | 793 | 2501 | 0.15 |
iC5 | 675 | 1056 | 0.40 | 1120 | 2900 | 0.15 |
nC5 | 774 | 1195 | 0.40 | 1109 | 2901 | 0.15 |
nC6 | 829 | 1164 | 0.40 | 1187 | 2878 | 0.15 |
表1 甲醇/水与第二组分所构成二元体系的SRK-HV方程交互作用参数[4]
Table 1 Interaction parameters for binary mixtures of methanol/water and the indicated second component [4]
第二组分 | 甲醇 | 水 | ||||
---|---|---|---|---|---|---|
[(g12-g22)/R]/K | [(g21-g11)/R]/K | α12 | [(g12-g22)/R]/K | [(g21-g11)/R]/K | α12 | |
H2O | 288 | 276 | 1.20 | — | — | — |
N2 | 357 | 1130 | 0.40 | 689 | 3921 | 0.15 |
CO2 | 247 | 2970 | 0.40 | 16 | 1652 | 0.15 |
H2S | 58 | 886 | 0.40 | 118 | 1294 | 0.15 |
C1 | 77 | 2094 | 0.40 | 410 | 2291 | 0.15 |
C2 | 255 | 1610 | 0.40 | 492 | 2281 | 0.15 |
C3 | 465 | 1418 | 0.40 | 847 | 2650 | 0.15 |
iC4/nC4 | 516 | 1049 | 0.40 | 793 | 2501 | 0.15 |
iC5 | 675 | 1056 | 0.40 | 1120 | 2900 | 0.15 |
nC5 | 774 | 1195 | 0.40 | 1109 | 2901 | 0.15 |
nC6 | 829 | 1164 | 0.40 | 1187 | 2878 | 0.15 |
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | ||||
---|---|---|---|---|---|---|---|---|
N2 | 0.64 | 3.394 | 126.194 | 0.040 | ||||
CO2 | 3.10 | 7.370 | 304.100 | 0.239 | -0.0315 | |||
C1 | 72.74 | 4.641 | 190.699 | 0.011 | 0.0278 | 0.0960 | ||
C2 | 8.01 | 4.884 | 305.428 | 0.099 | 0.0407 | 0.1400 | -0.0089 | |
C3 | 4.26 | 4.257 | 369.898 | 0.152 | 0.0763 | 0.1370 | 0.0180 | -0.0020 |
iC4 | 0.73 | 3.648 | 408.096 | 0.185 | 0.0944 | 0.1370 | 0.0000 | -0.0100 |
nC4 | 1.49 | 3.797 | 425.199 | 0.201 | 0.0700 | 0.1410 | 0.0000 | 0.0000 |
iC5 | 0.53 | 3.334 | 460.398 | 0.222 | 0.0867 | 0.1300 | 0.0215 | 0.0000 |
nC5 | 0.64 | 3.375 | 469.600 | 0.254 | 0.0878 | 0.1350 | 0.0000 | 0.0000 |
C6 | 0.81 | 3.124 | 509.108 | 0.291 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C7 | 1.08 | 2.875 | 535.314 | 0.332 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C8 | 1.20 | 2.669 | 556.575 | 0.368 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C9 | 1.08 | 2.446 | 580.830 | 0.414 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C10 | 3.70 | 2.278 | 601.487 | 0.456 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
表2 Mixture 2的组分数据[4, 12, 31]
Table 2 Component data of Mixture 2[4, 12, 31]
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | ||||
---|---|---|---|---|---|---|---|---|
N2 | 0.64 | 3.394 | 126.194 | 0.040 | ||||
CO2 | 3.10 | 7.370 | 304.100 | 0.239 | -0.0315 | |||
C1 | 72.74 | 4.641 | 190.699 | 0.011 | 0.0278 | 0.0960 | ||
C2 | 8.01 | 4.884 | 305.428 | 0.099 | 0.0407 | 0.1400 | -0.0089 | |
C3 | 4.26 | 4.257 | 369.898 | 0.152 | 0.0763 | 0.1370 | 0.0180 | -0.0020 |
iC4 | 0.73 | 3.648 | 408.096 | 0.185 | 0.0944 | 0.1370 | 0.0000 | -0.0100 |
nC4 | 1.49 | 3.797 | 425.199 | 0.201 | 0.0700 | 0.1410 | 0.0000 | 0.0000 |
iC5 | 0.53 | 3.334 | 460.398 | 0.222 | 0.0867 | 0.1300 | 0.0215 | 0.0000 |
nC5 | 0.64 | 3.375 | 469.600 | 0.254 | 0.0878 | 0.1350 | 0.0000 | 0.0000 |
C6 | 0.81 | 3.124 | 509.108 | 0.291 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C7 | 1.08 | 2.875 | 535.314 | 0.332 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C8 | 1.20 | 2.669 | 556.575 | 0.368 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C9 | 1.08 | 2.446 | 580.830 | 0.414 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
C10 | 3.70 | 2.278 | 601.487 | 0.456 | 0.0800 | 0.1500 | 0.0000 | 0.0000 |
组分 | ni /%(mol) | 气相 | 油相 | 水相 | ||||||
---|---|---|---|---|---|---|---|---|---|---|
xi,cal/%(mol) | xi,exp/%(mol) | Δx①/% | xi,cal/%(mol) | xi,exp/%(mol) | Δx/% | xi,cal/%(mol) | xi,exp/%(mol) | Δx/% | ||
Mixture 2 | 84.76 | 99.946 | 99.957 | -0.01 | 99.460 | 99.799 | -0.34 | — | — | — |
甲醇 | 2.99 | 0.0426 | 0.0429 | -0.70 | 0.221 | 0.201 | 9.95 | 18.240 | 18.680 | -2.36 |
水 | 7.32 | — | — | — | — | — | — | 81.410 | 81.320 | 0.11 |
表3 6.03 MPa、276.75 K下气-油-水相平衡结果对比
Table 3 Comparison of gas-oil-water equilibrium results at 6.03 MPa and 276.75 K
组分 | ni /%(mol) | 气相 | 油相 | 水相 | ||||||
---|---|---|---|---|---|---|---|---|---|---|
xi,cal/%(mol) | xi,exp/%(mol) | Δx①/% | xi,cal/%(mol) | xi,exp/%(mol) | Δx/% | xi,cal/%(mol) | xi,exp/%(mol) | Δx/% | ||
Mixture 2 | 84.76 | 99.946 | 99.957 | -0.01 | 99.460 | 99.799 | -0.34 | — | — | — |
甲醇 | 2.99 | 0.0426 | 0.0429 | -0.70 | 0.221 | 0.201 | 9.95 | 18.240 | 18.680 | -2.36 |
水 | 7.32 | — | — | — | — | — | — | 81.410 | 81.320 | 0.11 |
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | |||
---|---|---|---|---|---|---|---|
CO2 | 42.0 | 7.370 | 304.100 | 0.239 | |||
nC5 | 3.0 | 3.375 | 469.600 | 0.254 | 0.1350 | ||
nC10 | 9.0 | 2.108 | 617.598 | 0.488 | 0.1340 | 0.0000 | |
H2S | 15.0 | 9.008 | 373.600 | 0.081 | 0.1150 | 0.0709 | 0.0000 |
H2O | 31.0 | 22.120 | 647.299 | 0.344 | 0.0000 | 0.0000 | 0.5000 |
表4 含酸气烃水混合物[17, 31]
Table 4 A mixture of acidic gas, hydrocarbon and water[17, 31]
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | |||
---|---|---|---|---|---|---|---|
CO2 | 42.0 | 7.370 | 304.100 | 0.239 | |||
nC5 | 3.0 | 3.375 | 469.600 | 0.254 | 0.1350 | ||
nC10 | 9.0 | 2.108 | 617.598 | 0.488 | 0.1340 | 0.0000 | |
H2S | 15.0 | 9.008 | 373.600 | 0.081 | 0.1150 | 0.0709 | 0.0000 |
H2O | 31.0 | 22.120 | 647.299 | 0.344 | 0.0000 | 0.0000 | 0.5000 |
组分 | pci /MPa | Tci /K | ωi | ||
---|---|---|---|---|---|
C1 | 4.641 | 190.699 | 0.011 | ||
CO2 | 7.370 | 304.100 | 0.239 | 0.0960 | |
H2S | 9.008 | 373.600 | 0.081 | 0.0755 | 0.1150 |
H2O | 22.120 | 647.299 | 0.344 | 0.0000 | 0.0000 |
表5 含CO2的烃水混合物物性参数[18, 31]
Table 5 Component data for hydrocarbon and water mixtures containing CO2 [18, 31]
组分 | pci /MPa | Tci /K | ωi | ||
---|---|---|---|---|---|
C1 | 4.641 | 190.699 | 0.011 | ||
CO2 | 7.370 | 304.100 | 0.239 | 0.0960 | |
H2S | 9.008 | 373.600 | 0.081 | 0.0755 | 0.1150 |
H2O | 22.120 | 647.299 | 0.344 | 0.0000 | 0.0000 |
组分 | T/K | p/MPa | ni①/%(mol) | 计算耗时/ms | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
单相检验 | 两相闪蒸 | 两相检验 | 三相闪蒸 | 闪蒸过程② | |||||||||
文献数据 | 本文模型 | 文献数据 | 本文模型 | 文献数据 | 本文模型 | 文献数据 | 本文模型 | 文献数据 | 本文模型 | ||||
C1/ CO2/ H2S/ H2O | 37.8 | 7.60 | (14.88, 29.91, 4.94, 50.27) | 0.211 | 0.104 | 0.117 | 0.208 | 0.223 | 0.119 | 0.551 | 0.431 | ||
107.2 | 12.93 | (14.96, 30.09, 4.98, 49.97) | 0.213 | 0.119 | 0.123 | 0.518 | 0.197 | 0.130 | 0.533 | 0.767 | |||
176.7 | 18.17 | (4.96, 4.94, 40.00, 50.00) | 0.228 | 0.108 | 0.192 | 0.321 | 0.230 | 0.178 | 0.650 | 0.607 | |||
37.8 | 6.26 | (5.04, 5.03, 39.86, 50.08) | 0.272 | 0.151 | 0.139 | 0.400 | 0.234 | 0.254 | 1.980 | 0.511 | 2.625 | 1.316 |
表6 不同工况下稳定性分析与闪蒸计算耗时对比
Table 6 Comparison of stability analysis and flash calculation time under different conditions
组分 | T/K | p/MPa | ni①/%(mol) | 计算耗时/ms | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
单相检验 | 两相闪蒸 | 两相检验 | 三相闪蒸 | 闪蒸过程② | |||||||||
文献数据 | 本文模型 | 文献数据 | 本文模型 | 文献数据 | 本文模型 | 文献数据 | 本文模型 | 文献数据 | 本文模型 | ||||
C1/ CO2/ H2S/ H2O | 37.8 | 7.60 | (14.88, 29.91, 4.94, 50.27) | 0.211 | 0.104 | 0.117 | 0.208 | 0.223 | 0.119 | 0.551 | 0.431 | ||
107.2 | 12.93 | (14.96, 30.09, 4.98, 49.97) | 0.213 | 0.119 | 0.123 | 0.518 | 0.197 | 0.130 | 0.533 | 0.767 | |||
176.7 | 18.17 | (4.96, 4.94, 40.00, 50.00) | 0.228 | 0.108 | 0.192 | 0.321 | 0.230 | 0.178 | 0.650 | 0.607 | |||
37.8 | 6.26 | (5.04, 5.03, 39.86, 50.08) | 0.272 | 0.151 | 0.139 | 0.400 | 0.234 | 0.254 | 1.980 | 0.511 | 2.625 | 1.316 |
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | |
---|---|---|---|---|---|
H2O | 75.0 | 22.120 | 647.299 | 0.344 | |
C3 | 15.0 | 4.257 | 369.898 | 0.152 | 0.0 |
nC16 | 10.0 | 1.419 | 717.000 | 0.742 | 0.5 |
表7 H2O/ C3/ nC16混合物组成及参数[4, 19]
Table 7 Component data for H2O/ C3/ nC16 mixture [4, 19]
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | |
---|---|---|---|---|---|
H2O | 75.0 | 22.120 | 647.299 | 0.344 | |
C3 | 15.0 | 4.257 | 369.898 | 0.152 | 0.0 |
nC16 | 10.0 | 1.419 | 717.000 | 0.742 | 0.5 |
试验相假设条件 | yi /%(mol) {H2O, C3, nC16} | TPD函数极小值 | 体系是否稳定 |
---|---|---|---|
类油相 | {7.46, 3.82, 88.72} | -1.04 | 否,作为闪蒸计算初值 |
类气相 | {82.94, 14.84, 2.22} | -0.02 | 否 |
类水相 | {99.99, 4.29×10-3, 3.80×10-22} | -0.92 | 否 |
表8 6 MPa、473 K下H2O/C3/nC16混合物单相检验结果
Table 8 Single phase stability analysis results of H2O/C3/nC16 mixture at 6 MPa and 473 K
试验相假设条件 | yi /%(mol) {H2O, C3, nC16} | TPD函数极小值 | 体系是否稳定 |
---|---|---|---|
类油相 | {7.46, 3.82, 88.72} | -1.04 | 否,作为闪蒸计算初值 |
类气相 | {82.94, 14.84, 2.22} | -0.02 | 否 |
类水相 | {99.99, 4.29×10-3, 3.80×10-22} | -0.92 | 否 |
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | |||||
---|---|---|---|---|---|---|---|---|---|
H2O | 0.302 | 22.120 | 647.299 | 0.344 | |||||
MeOH | 0.042 | 8.097 | 512.640 | 0.565 | 0.0000 | ||||
N2 | 0.385 | 3.394 | 126.194 | 0.040 | 0.0000 | ||||
CO2 | 3.268 | 7.370 | 304.100 | 0.239 | 0.0000 | -0.0315 | |||
C1 | 86.249 | 4.641 | 190.699 | 0.011 | 0.0000 | 0.0278 | 0.0960 | ||
C2 | 5.486 | 4.884 | 305.428 | 0.099 | 0.0000 | 0.0407 | 0.1400 | -0.0089 | |
C3 | 2.061 | 4.257 | 369.898 | 0.152 | 0.0000 | 0.0763 | 0.1370 | 0.0180 | -0.0020 |
iC4 | 0.396 | 3.648 | 408.096 | 0.185 | 0.0000 | 0.0944 | 0.1370 | 0.0000 | -0.0100 |
nC4 | 0.520 | 3.797 | 425.199 | 0.201 | 0.0000 | 0.0700 | 0.1410 | 0.0215 | 0.0000 |
iC5 | 0.239 | 3.334 | 460.398 | 0.222 | 0.0000 | 0.0867 | 0.1300 | 0.0000 | 0.0000 |
nC5 | 0.177 | 3.375 | 469.600 | 0.254 | 0.0000 | 0.0878 | 0.1350 | 0.0000 | 0.0000 |
nC6 | 0.208 | 3.025 | 507.600 | 0.300 | 0.0000 | 0.1650 | 0.1420 | 0.0000 | 0.0000 |
nC7 | 0.291 | 2.740 | 540.200 | 0.350 | 0.5000 | 0.0800 | 0.1090 | 0.0000 | 0.0000 |
nC8 | 0.208 | 2.490 | 568.700 | 0.399 | 0.5000 | 0.0800 | 0.1350 | 0.0000 | 0.0000 |
nC9 | 0.104 | 2.290 | 594.600 | 0.445 | 0.5000 | 0.0800 | 0.1350 | 0.0000 | 0.0000 |
nC10 | 0.062 | 2.108 | 617.598 | 0.488 | 0.5000 | 0.1280 | 0.1340 | 0.0000 | 0.0000 |
表9 含酸/醇烃水组分及参数[4, 27, 31]
Table 9 Component data for acid/alcohol hydrocarbon and water mixtures [4, 27, 31]
组分 | ni /%(mol) | pci /MPa | Tci /K | ωi | |||||
---|---|---|---|---|---|---|---|---|---|
H2O | 0.302 | 22.120 | 647.299 | 0.344 | |||||
MeOH | 0.042 | 8.097 | 512.640 | 0.565 | 0.0000 | ||||
N2 | 0.385 | 3.394 | 126.194 | 0.040 | 0.0000 | ||||
CO2 | 3.268 | 7.370 | 304.100 | 0.239 | 0.0000 | -0.0315 | |||
C1 | 86.249 | 4.641 | 190.699 | 0.011 | 0.0000 | 0.0278 | 0.0960 | ||
C2 | 5.486 | 4.884 | 305.428 | 0.099 | 0.0000 | 0.0407 | 0.1400 | -0.0089 | |
C3 | 2.061 | 4.257 | 369.898 | 0.152 | 0.0000 | 0.0763 | 0.1370 | 0.0180 | -0.0020 |
iC4 | 0.396 | 3.648 | 408.096 | 0.185 | 0.0000 | 0.0944 | 0.1370 | 0.0000 | -0.0100 |
nC4 | 0.520 | 3.797 | 425.199 | 0.201 | 0.0000 | 0.0700 | 0.1410 | 0.0215 | 0.0000 |
iC5 | 0.239 | 3.334 | 460.398 | 0.222 | 0.0000 | 0.0867 | 0.1300 | 0.0000 | 0.0000 |
nC5 | 0.177 | 3.375 | 469.600 | 0.254 | 0.0000 | 0.0878 | 0.1350 | 0.0000 | 0.0000 |
nC6 | 0.208 | 3.025 | 507.600 | 0.300 | 0.0000 | 0.1650 | 0.1420 | 0.0000 | 0.0000 |
nC7 | 0.291 | 2.740 | 540.200 | 0.350 | 0.5000 | 0.0800 | 0.1090 | 0.0000 | 0.0000 |
nC8 | 0.208 | 2.490 | 568.700 | 0.399 | 0.5000 | 0.0800 | 0.1350 | 0.0000 | 0.0000 |
nC9 | 0.104 | 2.290 | 594.600 | 0.445 | 0.5000 | 0.0800 | 0.1350 | 0.0000 | 0.0000 |
nC10 | 0.062 | 2.108 | 617.598 | 0.488 | 0.5000 | 0.1280 | 0.1340 | 0.0000 | 0.0000 |
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