CN102264997B - 从烃水合物中生产天然气同时将二氧化碳存储在地层中的方法 - Google Patents
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Abstract
本发明涉及一种从甲烷水合物中提取甲烷的方法，其包括以下步骤：将二氧化碳加入甲烷水合物沉积物；使得所述二氧化碳作用于甲烷水合物以释放甲烷并将二氧化碳储存为二氧化碳水合物；和移出释放的甲烷，其特征在于加入的二氧化碳是超临界二氧化碳。
Description
本发明涉及一种生产存储在气体水合物中的甲烷同时在地质底土(geological subsoil)中存储二氧化碳(CO2)的方法。
大量天然气存储在海床中，为土、冰状甲烷水合物。这些天然沉积物与我们这颗行星上所有常规的煤、油和气体沉积物相比可能含有更多的能量和碳(约3000Gt C)。因此，气体水合物作为未来的天然气源扮有重要角色。已证实甲烷水合物存在于几乎所有的水下约400米深度的大陆架上。它们仅在高压和低温下是稳定的。在充足的有机碳嵌入沉积物且压力和稳定条件允许甲烷固定在甲烷水合物中时发生。很多沿海国家有大量天然沉积物(例如，中国、印度、日本、韩国、巴西、智利、美国、加拿大、挪威和俄罗斯)。在陆地上在厚永冻层沉积物下检测到甲烷水合物。这些水合物沉积物已知都来自西伯利亚、加拿大和阿拉斯加。
图1示出甲烷在海水中的相图。甲烷水合物仅在高压和低温下稳定。水合物和气体之间的相界表示晶格类型I的纯甲烷水合物和盐含量为35重量％的海水。
相界表示纯的具有晶格类型I的甲烷水合物。甲烷水合物以不同的晶格类型存在。类型I是最普遍和最广泛存在的变型。
图2示出晶格类型I的甲烷水合物簇；这种类型中，平均一个甲烷分子对应5.7个水分子。甲烷分子用大球表示，而由黑线连接的小球表示水分子组成的水合物晶格。
目前全世界都在开发甲烷水合物沉积物来生产天然气。为了提取天然气，首先必须分解地质底土中的水合物。这种方法中，固定于水合物水笼(watercage)中的甲烷被释放为气体，可以使用常规技术通过一个或多个钻孔来提取该气体。目前，必须通过以下不同的方法进行：
-降低沉积物的压力；
-升高沉积物的温度；
-添加化学物质来分解水合物。
US 7,222,673公开了用二氧化碳(CO2)代替气体水合物中的甲烷而不破坏水合物结构。该方法中，将水合物与液态CO2接触。不需要外部供应能量反应即发生，这是因为形成的CO2水合物比天然甲烷水合物更稳定。这种方法提取天然气具有额外的优点：使地球温度升高的气候相关的温室气体CO2同时可被安全地存储在地下并从而从大气中去除。这种方法的缺点是同时维持水合物结构的取代反应速度低，这仅能得到极低的生产速率。
WO2005/076904描述了一种通过引入气态CO2至甲烷水合物田将CO2存储在海床下的方法。一旦形成CO2水合物，释放的热量导致甲烷水合物离解并释放甲烷。计划收集并使用释放的甲烷气体。使用释放的甲烷气体经过燃烧产生能量时，高浓度的气态CO2是一个缺点。由于甲烷仅在借助于CO2水合物形成时释放的热量时才有可能从甲烷水合物中释放，因此其生产速率可能也很低。
因此本发明的目的是提供一种以生产速率高于先前可能的生产速率从水合物中提取碳水合物(carbon hydrate)(特别是甲烷)、同时将CO2存储在地层(geological formations)中的方法。
具有权利要求1特征的方法能实现所述目的。从属权利要求表明本发明的设计优点。
要提取天然气并将CO2存储在底土中，建议将超临界CO2注入水合物沉积物。本方法中，甲烷水合物在注入孔周围的大范围内高速热学和化学性地分解，从而实现高的天然气生产速率。
图3示出海水中CO2作为压力和温度的函数的相图。水合物和液态CO2之间的相限表示晶格类型I的CO2水合物和盐含量为35重量％的海水。CO2临界点为7.4Mpa和31.48℃。较高的温度和压力下，CO2转化为所谓的超临界相。该相的特点是没有气态和液态之间的急变和能量势垒；不再有气相和液相的区别。超临界CO2与液态或气态CO2不同。它由仅松散互连的CO2簇组成。表现出特别适合于生产来自水合物的天然气的特殊属性。
超临界CO2自动快速地与甲烷水合物反应，这是由于甲烷水合物同时被热学地和化学性地分解。温度高于31.48℃时，甲烷水合物不稳定，从而被超临界CO2熔融。甲烷水合物的热分解以比缓慢的气体分子交换高得多的速度发生，同时保持水合物结构。同时，水笼受到与CO2簇发生的化学反应的攻击并分解。由于热能和化学能同时作用，使用超临界CO2将天然气从甲烷水合物中释放比使用液态或气态CO2或使用同样温度的温水能更快地进行。
注入的超临界CO2流具有低粘度和高流动性。因此热量通过孔空间中低粘度超临界CO2的快速对流在底土中快速传播，这样甲烷水合物在注入钻孔周围的较大面积中熔融。由于超临界CO2的流动性质，本发明来自甲烷水合物的天然气释放比使用同样温度的温水能相当有效地进行，这是由于在同样的温度下，超临界CO2具有比温水明显更低的粘度和更高的传播速度。
本方法的另一个优点是，由于局部温度增加，注入钻孔周围没有CO2水合物或仅有很少的CO2水合物产生，从而避免堵塞进料管道和孔空间。
在本发明提出的方法中，更进一步地，孔空间和剩余的形成水经CO2饱和，从而避免逆反应，即由释放的天然气形成甲烷水合物。
使用本发明所述的方法，能实现非常经济的天然气生产速率。这样，可以免除使用分解甲烷水合物的其他方法，例如注入温水、降低压力或添加化学物质。
超临界CO2保留在底土中。它将随时间缓慢地冷却并最终转化为CO2水合物。
根据本发明，甲烷水合物最初熔融并分解，在天然气的产生部分或全部结束且热量经传导离开贮藏处之后，CO2水合物在较晚的时间点适时形成。
所述方法可以以不同的变化形式实现。例如，可以使用单独的注入钻孔来向沉积物引入超临界CO2。出于这一目的，钻孔必须是绝热的，从而将钻井平台和沉积物之间的热量损失降至最低。可以通过单独的钻孔来提取释放的甲烷气体。也可以通过同一个钻孔来进行CO2的注入和天然气的提取。此外，也可以进行水平钻孔或使用水力破碎(hydro fracturing)方法来增加含水合物沉积层的渗透性。
Claims (6)
1.一种从甲烷水合物中提取甲烷的方法，其包括以下步骤：
-将二氧化碳加入甲烷水合物沉积物；
-使所述二氧化碳作用于甲烷水合物，同时释放甲烷并将二氧化碳储存为二氧化碳水合物；
-移出释放的甲烷，
其特征在于，加入的二氧化碳是超临界二氧化碳。
2.如权利要求1所述的方法，其特征在于，所述加入的二氧化碳处于大于7.4Mpa的压力，且温度保持在超过31.48℃。
3.如上述权利要求中任一项所述的方法，其特征在于，将所述超临界二氧化碳加入天然甲烷水合物沉积物。
4.如权利要求3所述的方法，其特征在于，所述天然甲烷水合物沉积物是浸没于水中的。
5.如上述权利要求1或2所述的方法，其特征在于，将所述超临界二氧化碳从热绝缘的管道加入所述甲烷水合物沉积物。
6.如上述权利要求1或2所述的方法，其特征在于，将所述超临界二氧化碳注入所述甲烷水合物沉积物。
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| DE102009007453A DE102009007453B4 (de) | 2009-02-04 | 2009-02-04 | Verfahren zur Erdgasförderung aus Kohlenwasserstoff-Hydraten bei gleichzeitiger Speicherung von Kohlendioxid in geologischen Formationen |
| DE102009007453.8 | 2009-02-04 | ||
| PCT/DE2010/000059 WO2010088874A2 (de) | 2009-02-04 | 2010-01-22 | Verfahren zur erdgasförderung aus kohlenwasserstoff-hydraten bei gleichzeitiger speicherung von kohlendioxid in geologischen formationen |
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| US9291051B2 (en) * | 2010-10-28 | 2016-03-22 | Conocophillips Company | Reservoir pressure testing to determine hydrate composition |
| DE102010043720A1 (de) | 2010-11-10 | 2012-05-10 | Siemens Aktiengesellschaft | System und Verfahren zum Extrahieren eines Gases aus einem Gas-Hydrat-Vorkommen |
| WO2013056732A1 (en) | 2011-10-19 | 2013-04-25 | Statoil Petroleum As | Improved process for the conversion of natural gas to hydrocarbons |
| EP2666958A1 (en) | 2012-05-23 | 2013-11-27 | Linde Aktiengesellschaft | Method of fraccing a well |
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| CN103343678B (zh) * | 2013-07-23 | 2015-06-17 | 中国石油大学(华东) | 一种注二氧化碳开采水溶气的系统和方法 |
| CN104563974B (zh) * | 2015-01-29 | 2017-09-29 | 中国石油大学(华东) | 一种超临界二氧化碳射流喷射钻井开采水合物装置 |
| DE102015107252A1 (de) * | 2015-05-08 | 2016-11-10 | Geomar Helmholtz-Zentrum Für Ozeanforschung Kiel - Stiftung Des Öffentlichen Rechts | Mechanisches Tiefseesedimente-, marine Rohstofflagerstätten- und/oder Unterseehang- Stabilisierungsverfahren und/oder Regulierungs-/Konditionierungsverfahren der hydraulischen Eigenschaften von Tiefseesedimenten |
| CN105464634A (zh) * | 2015-12-15 | 2016-04-06 | 中国科学院力学研究所 | 一种利用埋存二氧化碳开采甲烷水合物的方法 |
| CN105422056A (zh) * | 2016-01-26 | 2016-03-23 | 辽宁石油化工大学 | 一种二氧化碳法开采深层海底天然气水合物的方法 |
| CN106437653B (zh) * | 2016-09-27 | 2018-07-20 | 大连理工大学 | 一种注生石灰和二氧化碳法的水合物开采及二氧化碳封存联合方法 |
| CN107620590B (zh) * | 2017-08-08 | 2018-06-22 | 广州海洋地质调查局 | 一种海底水合物开采过程相平衡动态的可视化方法及装置 |
| CN110159232A (zh) * | 2019-06-05 | 2019-08-23 | 重庆大学 | 一种开采海底天然气水合物装置和方法 |
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| US20050121200A1 (en) * | 2003-12-04 | 2005-06-09 | Alwarappa Sivaraman | Process to sequester CO2 in natural gas hydrate fields and simultaneously recover methane |
| FR2870752B1 (fr) * | 2004-05-27 | 2006-09-01 | Inst Francais Du Petrole | Methodes pour injecter des composes acides dans un reservoir souterrain |
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| EP2058471A1 (en) * | 2007-11-06 | 2009-05-13 | Bp Exploration Operating Company Limited | Method of injecting carbon dioxide |
| US7726404B2 (en) * | 2008-04-16 | 2010-06-01 | Schlumberger Technology Corporation | Use of carbon-dioxide-based fracturing fluids |
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| JP2004003326A (ja) * | 2002-04-26 | 2004-01-08 | Hitoshi Koide | 非燃焼方式原位置炭層ガス化回収方法及び非燃焼方式地下有機物・化石有機物原位置ガス化回収方法 |
| GB2445120A (en) * | 2005-08-26 | 2008-06-25 | Central Res Inst Elect | Method for production, substitution or digging of gas hydrate |
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|---|---|
| NZ593290A (en) | 2013-09-27 |
| CY1115612T1 (el) | 2017-01-04 |
| DK2394021T3 (da) | 2014-07-21 |
| US8590619B2 (en) | 2013-11-26 |
| PT2394021E (pt) | 2014-07-29 |
| EP2394021A2 (de) | 2011-12-14 |
| CN102264997A (zh) | 2011-11-30 |
| RU2011126008A (ru) | 2012-12-27 |
| UA98432C2 (ru) | 2012-05-10 |
| KR101370147B1 (ko) | 2014-03-04 |
| JP2012516954A (ja) | 2012-07-26 |
| KR20110125630A (ko) | 2011-11-21 |
| DE102009007453B4 (de) | 2011-02-17 |
| WO2010088874A2 (de) | 2010-08-12 |
| JP5468622B2 (ja) | 2014-04-09 |
| GEP20156249B (en) | 2015-02-25 |
| CA2754356A1 (en) | 2010-08-12 |
| WO2010088874A3 (de) | 2010-10-28 |
| CA2754356C (en) | 2016-08-16 |
| RU2498057C2 (ru) | 2013-11-10 |
| BRPI1007791A2 (pt) | 2016-02-23 |
| DE102009007453A1 (de) | 2010-08-12 |
| EP2394021B1 (de) | 2014-05-28 |
| US20120012321A1 (en) | 2012-01-19 |
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