考虑盐浓度的天然气水合物三维相平衡曲面热力学预测模型

张更; 李文拓; 黄洪林; 罗鸣; 马传华; 吴艳辉; 李军

doi:10.12358/j.issn.1001-5620.2025.01.010

考虑盐浓度的天然气水合物三维相平衡曲面热力学预测模型

doi: 10.12358/j.issn.1001-5620.2025.01.010

张更^1,,
李文拓^{1, 2},
黄洪林^2, ,,
罗鸣²,
马传华²,
吴艳辉²,
李军^{1, 3}

1.
中国石油大学(北京)石油工程学院, 北京 102249
2.
中海石油(中国)有限公司海南分公司, 海口 570100
3.
中国石油大学(北京)克拉玛依校区, 新疆克拉玛依 834000

基金项目: 国家自然科学基金青年科学基金项目“超深水超浅层气钻井溢流井下智能识别与井筒压力控制方法”(52104012)；中国博士后科学基金资助项目“超深水超浅层气钻井地层-井筒耦合多相流动机理与溢流风险防控”(2024M753615)；国家资助博士后研究人员计划 “特超深井井筒多相流动机理与井下风险调控方法”(GZC20233105)；中国石油大学（北京）科研基金资助“超深油气井溢流早期智能监测与定量反演方法”(2462024XKBH006)。

详细信息

作者简介:
张更，博士后，1996年生，主要从事水合物防治、井筒多相流方面研究。E-mail：zhanggeng_96@163.com

通讯作者:
黄洪林，钻井工程师，1994年生，主要从事海洋复杂油气钻井方面研究。E-mail：huanghl_cup@163.com。

中图分类号: TE311
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出版历程
- 收稿日期: 2024-09-02
- 修回日期: 2024-10-30
- 刊出日期: 2025-02-01

A Thermodynamic Model for Predicting 3D Phase Equilibrium Surface of Natural Gas Hydrates Considering Salt Concentration

ZHANG Geng^1
,,
LI Wentuo^{1, 2},
HUANG Honglin^{2
, ,},
LUO Ming²,
MA Chuanhua²,
WU Yanhui²,
LI Jun^{1, 3}

1.
China University of Petroleum-Beijing, Beijng 102249
2.
Hainan Branch of CNOOC (China) Co., LTD., Haikou,Hainan 570100
3.
China University of Petroleum-Beijing at Karamay, Karamay,Xinjiang 834000

摘要

摘要: 准确预测含盐体系中天然气水合物的热力学稳定性，对预测水合物成藏范围、确定水合物分解域等具有重要意义。因此，综合考虑水合物晶穴非球形特征和含盐体系中电解质相互作用，建立考虑盐浓度的天然气水合物相平衡热力学模型，并与实验数据进行对比验证。研究结果表明，建立的三维相平衡曲面能有效预测天然气水合物热力学稳定性，纯水条件下的温度绝对平均相对偏差仅为0.08，且含盐条件下不超过0.15。在氯盐摩尔分数大于0.02、压力高于20 MPa时，化学因素导致p-T曲线发生平移。在压力较小时，平衡温度沿盐浓度方向的梯度剧烈变化，p-T曲线不再具有平移特性。同时，摩尔分数相同时，AlCl₃比其他氯盐对CH₄水合物的抑制作用更强。CH₄水合物的lnp-X-1/T三维曲面局部表现出较好的Clausius-Clapeyron线性行为，曲面整体具有非线性特征，且氯盐电解质对CH₄水合物的抑制效果越好，非线性特征越强。
- 天然气水合物 /
- 热力学模型 /
- 相平衡 /
- Clausius-Clapeyron线性特征
Abstract: Accurate prediction of the thermodynamic stability of gas hydrates in salt-bearing systems is of great significance for predicting the accumulation range and determining the decomposition domain of hydrate. Therefore, considering the non-spherical characteristics of hydrate crystal cavity and the electrolyte interaction in the salt-containing system, a thermodynamic model of gas hydrate phase equilibrium considering salt concentration was established, and compared with the experimental data. The results show that the established three-dimensional phase equilibrium surface can effectively predict the thermodynamic stability of NGH, and the absolute mean relative deviation of temperature is only 0.08 in pure water, and no more than 0.15 in salt. When the molar fraction of chloride is greater than 0.02 and the pressure is higher than 20 MPa, the chemical factors cause the p-T curve to shift. When the pressure is small, the equilibrium temperature changes dramatically along the gradient of salt concentration, and the p-T curve no longer has translation characteristics. At the same time, AlCl₃ has stronger inhibitory effect on CH₄ hydrate than other chlorine salts when the molar fraction is the same. The lnp-X-1/T three-dimensional surface of CH₄ hydrate exhibits better Clausius-Clapeyron linear behavior locally, and the surface as a whole has certain nonlinear characteristics. Moreover, the better the inhibition effect of chloride electrolyte on CH₄ hydrate, the stronger the nonlinear characteristics.
- Natural gas hydrate /
- Thermodynamic model /
- Phase equilibrium /
- Clausius-Clapeyron linear behavior

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图 1 模型求解流程图

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图 2 纯水条件下CH₄水合物相平衡预测结果对比

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图 3 在单一电解质溶液中CH₄水合物相平衡温度预测曲面

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图 4 混合溶液中CH₄水合物相平衡温度预测值

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图 5 不同盐浓度下CH₄水合物相平衡p-T曲线

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图 6 CH₄水合物相平衡温度梯度云图

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图 7 不同电解质下CH₄水合物相平衡p-T曲线

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图 8 不同电解质溶液下lnp-X-1/T曲面线性区域

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图 9 不同电解质下Clausius-Clapeyron线性特性

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表 1 气体的Kihara势能参数

气体类型	a /Å	$ \sigma $ /Å	$ \epsilon /k $ /Å
CH₄	0.3834	3.1650	154.54
C₂H₆	0.6760	3.1383	190.80
C₃H₈	0.8340	3.1440	194.55
N₂	0.5290	0.2569	150.03
H₂S	0.4920	3.1774	198.53
CO₂	0.1773	2.9605	170.97

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表 2 水合物分子几何参数^[22]

水合物结构	腔型	分子核间距/Å	腔体/ 单元壳	配位数	H₂O分子/ 单元壳
I	5¹²	3.95	2	20	46
I	5¹²6²	4.33	6	24	46
II	5¹²	3.91	16	20	136
II	5¹²6⁴	4.73	8	28	136

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表 3 三层球模型相关参数

结构及腔体类型		第一层		第二层		第三层		$ {n}_{0} $	$ {a}_{0} $
结构及腔体类型		$ {R}_{c} $/Å	z	$ {R}_{c} $/Å	z	$ {R}_{c} $/Å	z	$ {n}_{0} $	$ {a}_{0} $
I	小腔体	3.875	20	6.593	20	8.056	50	0.973	35.345
I	大腔体	4.152	21	7.078	24	8.255	50	0.828	14.116
II	小腔体	3.870	20	6.697	20	8.079	20	0.973	35.335
II	大腔体	4.703	26	7.464	28	8.782	50	2.313	782.847

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表 4 水合物热力学参数

参数	I型结构	II型结构
$ \mathrm{\Delta }{\mu }_{W}^{0} $ /(J/mol)	1120	931
$ \mathrm{\Delta }{h}_{W}^{0} $ /(J/mol)	1714 （T＜T₀）	1400（T＜T₀）
$ \mathrm{\Delta }{h}_{W}^{0} $ /(J/mol)	−4297（T＞T₀）	−4611（T＞T₀）
$ \mathrm{\Delta }{V}_{W} $ /(mL/mol)	2.9959 （T＜T₀）	3.396 44（T＜T₀）
$ \mathrm{\Delta }{V}_{W} $ /(mL/mol)	4.5959（T＞T₀）	4.996 44（T＞T₀）
$ \mathrm{\Delta }{C}_{pW} $ /(J/mol·K)	$ 3.315+0.012(T-{T}_{0}) $（T＜T₀）	$ 1.029+0.004(T-{T}_{0}) $（T＜T₀）
$ \mathrm{\Delta }{C}_{pW} $ /(J/mol·K)	$ -34.583+0.189(T-{T}_{0}) $ （T＞T₀）	$ -36.861+0.181(T-{T}_{0}) $ （T＞T₀）

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表 5 表征电解质之间相互作用的优化参数

溶液类型	n₁	n₂ /K⁻¹	n₃/(1/摩尔分数)
NaCl+LiCl	0.813	6.552e-4	8.725e-3
NaCl+KCl	0.676	2.263e-4	4.962e-3
NaCl+MgCl₂	0.729	7.607e-4	6.569e-3
NaCl+CaCl₂	0.557	2.673e-4	3.230e-3
NaCl+AlCl₃	0.842	5.362e-4	4.236e-3

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表 6 电解质二元优化参数

溶液类型	$ {\zeta }_{elw} $	$ {\zeta }_{wel} $
LiCl	11.509	6.375
NaCl	6.359	4.277
KCl	9.620	−10.496
MgCl₂	10.629	−3.264
CaCl₂	9.259	4.595
AlCl₃	18.397	−5.567

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表 7 BWRS状态方程相关参数

参数下标j	参数值
参数下标j	A_j	B_j
1	0.443 690	0.115 449
2	1.284 380	−0.920 731
3	0.356 306	1.708 710
4	0.544 979	−0.270 896
5	0.528 629	0.349 621
6	0.484 011	0.754 130
7	0.070 523	−0.044 448
8	0.504 087	1.322 450
9	0.030 745	0.179 433
10	0.073 283	0.463 492
11	0.006 450	−0.022 143

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表 8 气体的临界参数

气体类型	T_c/K	p_c/MPa	ρ_c/（kmol·m⁻³）	ω
N₂	126.15	3.394	11.0990	0.0350
CO₂	304.09	7.376	10.6380	0.2100
H₂O	647.30	22.048	17.8570	0.3440
CH₄	190.69	4.604	10.0500	0.0130
C₂H₆	305.38	4.880	6.7566	0.1018
C₃H₈	369.89	4.250	4.9994	0.1570

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表 9 电解质溶液中CH₄水合物相平衡预测结果

液体类型	浓度范围	T/K	P/MPa	AARD-T /%					N
液体类型	浓度范围	T/K	P/MPa	Haghighi	Hsieh	Li	Chin	本文	N
纯水		273.30～303.48	2.680～72.260	0.68	0.20	0.13	0.35	0.08	250
LiCl	0.050～0.200 (wt)	260.17～288.81	3.506～22.155	0.22	0.42	0.16	0.23	0.15	17
NaCl	0.040～0.090 (me)	261.85～278.05	2.390～11.000	0.26	0.36	0.15	0.30	0.13	23
KCl	0.050～0.100 (wt)	269.16～283.20	1.830～8.820	0.34	0.16	0.12	0.28	0.06	17
MgCl₂	0.030～0.150 (wt)	270.75～286.40	2.820～12.955	0.09	0.16	0.15	0.13	0.09	22
CaCl₂	0.008～0.053 (me)	260.00～284.40	4.920～10.290	0.25	0.17	0.20	0.62	0.10	26
AlCl₃	0.090～0.150 (wt)	272.15～278.15	4.040～8.380	0.21	0.26	0.24	0.34	0.03	8
NaCl+KCl	0.030～0.150 (wt)	263.58～281.46	2.569～9.379	0.11	0.09	0.26	0.52	0.04	37
NaCl+CaCl₂	0.030～0.100 (wt)	266.02～281.76	2.504～9.664	0.13	0.06	0.17	0.83	0.06	24
注：wt为质量分数，me为摩尔分数。

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