CO<sub>2</sub>-CH<sub>4</sub>置换水合物开采方法及其强化技术研究进展

王佳贤; 刘昌岭; 宁伏龙; 纪云开

doi:10.16562/j.cnki.0256-1492.2022032101

CO₂-CH₄置换水合物开采方法及其强化技术研究进展

1.
中国地质科学院，北京 100037

2.
中国地质大学（武汉）工程学院，武汉 430074

3.
自然资源部天然气水合物重点实验室，青岛海洋地质研究所，青岛 266237

4.
青岛海洋科学与技术试点国家实验室海洋矿产资源评价与探测技术功能实验室，青岛 266237

基金项目: 国家自然科学基金“南海沉积物中水合物降压分解动力学行为及控制机理研究”（41876051）；山东省泰山学者特聘专家计划（ts201712079）；国家重点研发计划政府间国际科技创新合作重点专项“天然气水合物开采过程中井周储层动态响应行为与控制”（2018YFE0126400）

详细信息

作者简介: 王佳贤(1995—)，男，博士研究生，从事水合物生成微观机理研究，E-mail：wjxcz@cug.edu.cn

通讯作者: 刘昌岭(1966—)，男，博士，研究员，从事天然气水合物模拟实验研究，E-mail：qdliuchangling@163.com

中图分类号: P744.4

收稿日期: 2022-03-21

修回日期: 2022-05-17

刊出日期: 2023-02-28

Technological research progress on CO₂-CH₄replacement for hydrate exploitation and enhancement

1.
Chinese Academy of Geological Sciences, Beijing 100037, China

2.
Faculty of Engineering, China University of Geosciences, Wuhan 430074, China

3.
Key Laboratory of Gas Hydrate of Ministry of Natural Resources, Qingdao Institute of Marine Geology, Qingdao 266237, China

4.
Laboratory for Marine Mineral Resources, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266237, China

More Information

Corresponding author: LIU Changling, qdliuchangling@163.com

Received Date: 21 March 2022

Revised Date: 17 May 2022

Publish Date: 28 February 2023

摘要

摘要:
天然气水合物具有资源储量大、分布范围广等特点，是一种潜力巨大的替代能源，经济、高效、安全地开发天然气水合物是目前研究的热点。CO₂-CH₄置换水合物开采法既可以置换出水合物储层中的甲烷，同时还将CO₂封存其中以保持地层稳定，受到了广泛的关注。本文从CO₂-CH₄置换的可行性、实验模拟与数值模拟的角度综述了近些年CO₂-CH₄置换水合物开采法的最新研究进展，并针对置换过程效率低、速度慢等缺点，探讨了改变CO₂注入相态、CO₂协同小分子气体以及CO₂置换联合开采法等强化置换技术，指出了不同强化方法的技术壁垒及应用局限，展望了CO₂-CH₄置换水合物开采技术的研究方向和发展前景。
- 水合物 /
- CO₂-CH₄置换 /
- 实验研究 /
- 数值模拟 /
- 强化技术
Abstract:
Considering the huge reserve and wide distribution in nature, natural gas hydrates have a great potential to become an alternative energy resource in future. How to economically and safely recovery natural gas from hydrate reservoirs is the focus of current researches. The method by using carbon dioxide (CO₂) to replace methane (CH₄) within natural gas hydrates has drawn enormous interests due to its two-fold bonus: CH₄ recovery for energy and CO₂ sequestration for safety. The latest experimental and numerical research in technology on CO₂-CH₄ replacement for hydrate exploitation, and the feasibility as well as its challenges were summarized. For the challenges to the low efficiency and slow rate in the replacement process, various methods and technologies to enhance the replacement processes were analyzed on examples of the usage of different phase CO₂, cooperation with small-molecule gas, and combination with other exploitation methods. Finally, technical barriers and application limitations of different enhancement technologies were pointed out, and the research direction and development prospect of CO₂-CH₄ replacement for hydrate exploitation were prospected.
- hydrate /
- CO₂-CH₄ replacement /
- experimental research /
- numerical simulation /
- enhancement technology

HTML全文

图 1 不同水合物开采方法原理^[9]

Figure 1.

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图 2 CO₂-CH₄水合物四相平衡图^[72]

Figure 2.

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表 1 不同相态CO₂的强化置换效果

Table 1. Enhanced displacement effect with CO₂ in different states

CO₂相态	检测手段	介质体系	温度/K	压力/MPa	甲烷回收效率	文献来源
液	GC	冰粒/纯水	263/275	9	14%/40.3%	Lee等^[56]
液	Raman	纯水	273.2	3.6/5.4/6	37.6%/27%/29%	Ota等^[62-63]
液	GC	纯水	283.5	4.5/5.0	20.60%/18.11%	张凤琦等^[64]
液	GC	石英砂+水	282.15	6～8	13%～45.4%	Zhang等^[42]
液	GC	石英砂+盐水	275.2	4.19～4.21	26%～33%	Yuan等^[33]
液	GC	石英砂+盐水	280.2	4.2	35%	Yuan等^[33]
液	GC	石英砂+ SDS溶液	281.2	5	18.6%	Zhou等^[65]
液	GC	石英砂+盐水	273.2	4	26.4%	Wang等^[66]
液	Raman+SEM	纯水	277	6	11.4%	Falenty等^[67]
液	MRI	砂岩+盐水	273.2	8.3	59%	Kvamme等^[68]
乳液	GC	石英砂+ SDS溶液	281.2	5	17%/27.1%	Zhou等^[65,69]
乳液	GC	石英砂+水	281	5	27.1%	周锡堂等^[70]
超临界	GC	石英砂+冰颗粒/盐水	275.2	7.5	37.5%	Deusner等^[71]
超临界	GC	石英砂+冰颗粒/盐水	275.2/281.2/283.2	13	3.4%/40.7%/10.7%	Deusner等^[71]
注：GC：气相色谱技术，Raman：拉曼光谱技术，SEM：扫描电子显微镜技术，MRI：核磁共振成像技术。

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表 2 不同CO₂/N₂注气比的强化置换效果

Table 2. Enhanced displacement effect at different CO₂/N₂ injection ratios

气体成分(CO₂/N₂)	检测手段	介质体系	温度/K	压力/MPa	甲烷回收效率	文献来源
10%CO₂+90%N₂	NMR+DSC	多孔硅胶+水	274	11.54/14.59/18.59	77%/80%/79%	Lee等^[74]
10%CO₂+90%N₂	GC	纯水+SDS溶液	298.15	9.05	41%	Pandey等^[88]
14.6%CO₂+85.4%N₂	GC	硅砂+水	273.3	4.2	53.3%	Yang等^[89]
19%CO₂+81%N₂	GC	石英砂+冰粒	274.15	15.8	6.1%	王曦等^[90]
20%CO₂+80%N₂	Raman+NMR	粉末冰颗粒	274.15	12	85%	Park等^[91]
20%CO₂+80%N₂	SEM	黏土+水	273.15	15	85%	Koh等^[92]
20%CO₂+80%N₂	NMR+GC	多孔硅胶+水	273	10	42%	Cha等^[93]
20%CO₂+80%N₂	GC	玻璃珠+水	275.15	9.8	49.2%	Koh等^[94]
20%CO₂+80%N₂	GC	玻璃珠+水	274	9.5	39.3%	Youn等^[95]
22%CO₂+78%N₂	GC	石英砂+盐水	273.2	5.0	36.9	Liu等^[87]
23%CO₂+77%N₂	Raman+GC	石英砂+水	281	10	90%	Schicks等^[35]
25%CO₂+75%N₂	GC	砂土+水	274.2	10	25%	Pan等^[96]
25%CO₂+75%N₂	GC	高岭石+水	274.2	10	24.5%	潘栋彬等^[97]
25%CO₂+75%N₂	GC	伊利石+水	274.2	10	25%	潘栋彬等^[97]
25%CO₂+75%N₂	GC	蒙脱石+水	274.2	10	18.2%	潘栋彬等^[97]
28%CO₂+72%N₂	GC+CCD	纯水+ SDS溶液	284.2	9.02	13.2%	Niu等^[98]
40%CO₂+60%N₂	NMR+GC	多孔硅胶+水	274	10	51%	Seo等^[99]
50%CO₂+50%N₂	Raman+CCD+GC	纯水	273.9	5/6.67	8.3%/17.7%	Zhou等^[100]
53%CO₂+47%N₂	GC	石英砂+冰粒	274.15	2.1/3.4	12.6%/19%	王曦等^[90]
53%CO₂+47%N₂	GC	纯水	279.15	8.01	52.42%	Ouyang等^[101]
53%CO₂+47%N₂	GC	石英砂+热水	274.15	14	91.6%	操原^[102]
59%CO₂+41%N₂	GC	石英砂+水	277.15	7	40.8%	Yasue等^[86]
60%CO₂+40%N₂	GC	石英砂+水	277.15/280.15	7	30%	Masuda等^[103]
60%CO₂+40%N₂	Raman+FTIR+GC	纯水	274	4.5	73.42%	Xu等^[41]
75%CO₂+25%N₂	GC	石英砂+冰粒	275.15	3	41.4%	Li等^[82]
75%CO₂+25%N₂	GC	石英砂+水	275.65	4.8	68.8%	Tupsakhare等^[104]
75%CO₂+25%N₂	Raman+CCD+GC	纯水	274	2.6/3.11/3.5	9.5%/12.6%/17.9%	Zhou等^[100]
87.6%CO₂+12.4%N₂	GC	石英砂+水	277.15	8.9	46.32%	Mu等^[75]
注：DSC：差式扫描量热技术，NMR：核磁共振技术，CCD：影像检测技术，FTIR：红外光谱技术。

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表 3 不同热激发方式的强化置换效果

Table 3. Enhanced replacement effects in different thermal excitation methods

热激发方式	介质体系	温度/K	压力/MPa	甲烷回收效率（无热激发）	甲烷回收效率（有热激发）	文献来源
热烟气(CO₂/N₂)	硅砂+水	273.3	4.2	15.9%	53.3%	Yang等^[89]
短暂升高温度	玻璃珠+水	273.7	3.69	11.55%	59.16%	Zhang等^[108]
重复注热+分阶段注热	石英砂+冰粒	271.15	3	28%	82%	Stanwix等^[109]
间歇式原位加热	纯水	280.15	8	35.64%	64.80%	欧阳潜^[110]
间歇式原位加热+脉冲注热	纯水	275.15	4	19.83%	35.50%	Ouyang等^[101]
脉冲注热	纯水	279.15	8	40%	55%	张育诚^[111]
热电偶原位加热	石英砂+水	275.65	3.3	24%	99%	Tupsakhare等^[112]
热电偶原位加热+注入CO₂/N₂	石英砂+水	275.65	4.8	50%	68.8%	Tupsakhare等^[104]

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表 4 不同强化方法对置换效率的影响对比

Table 4. Comparison of the effects in different strengthening methods on the replacement efficiency

强化方法类型	突出优势	主要影响因素
注液态CO₂	特定成核位置的CO₂浓度更高，有利于快速成核	水合物储层粒径
注CO₂乳化液	具有更高的反应温度以及更好的传导性和扩散能力	乳化液的含量和种类
注CO₂/N₂混合气	降低CH₄分压，置换出5¹²小笼子中的CH₄分子	不同气体比
与热激发法联合	缓解CH₄水合物分解引起的局部热损	水合物储层饱和度
与降压法联合	CH₄水合物的局部分解为CO₂的渗透作用提供了更加丰富的孔隙通道	压降梯度
与注化学剂法联合	使相平衡条件向有利于CH₄水合物分解和CO₂水合物合成的方向移动	化学剂浓度

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CO2-CH4置换水合物开采方法及其强化技术研究进展

作者简介: 王佳贤(1995—)，男，博士研究生，从事水合物生成微观机理研究，E-mail：wjxcz@cug.edu.cn

通讯作者: 刘昌岭(1966—)，男，博士，研究员，从事天然气水合物模拟实验研究，E-mail：qdliuchangling@163.com

Technological research progress on CO2-CH4 replacement for hydrate exploitation and enhancement

Corresponding author: LIU Changling, qdliuchangling@163.com

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CO₂-CH₄置换水合物开采方法及其强化技术研究进展

Technological research progress on CO₂-CH₄replacement for hydrate exploitation and enhancement