CN1342256A - 天然气的深冷分离精制 - Google Patents
天然气的深冷分离精制 Download PDFInfo
- Publication number
- CN1342256A CN1342256A CN00804607A CN00804607A CN1342256A CN 1342256 A CN1342256 A CN 1342256A CN 00804607 A CN00804607 A CN 00804607A CN 00804607 A CN00804607 A CN 00804607A CN 1342256 A CN1342256 A CN 1342256A
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- CN
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- Prior art keywords
- refrigerant
- heat exchanger
- gas
- heat exchange
- regenerator
- Prior art date
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- Pending
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Images
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- Y10S62/909—Regeneration
Abstract
分离包括CO2及第二气体的气体混合物中CO2的一种设备(2、20、200),该设备(2、20、200)包括一活性换热器(216)及一再生换热器(221)。该活性换热器(216)包括与该气体混合物接触的换热表面。该气体混合物以预定压力存在于该活性换热器(216)中,选择预定压力,要做到在用温度低于预定压力下CO2凝固温度的致冷剂冷却其表面时能使CO2凝固在换热表面上。再生换热器(221)包括与该致冷剂接触并也与凝固CO2层接触的换热表面。该致冷剂进入再生换热器,其温度在CO2凝固层中CO2的升华温度以上。固体CO2的升华使通过膨胀阀(215)进行膨胀之前的致冷剂冷却,使致冷剂温度降低到预定压力下CO2的冰点以下的温度。该致冷剂在离开活性换热器(216)之后,受到压缩机(60、160、218)的再压缩。在本发明优选实施方案中,由再生换热器(221)释放的气态CO2用于预冷却进入的气体混合物。第二预冷却换热器(167)通过构成与离开活性换热器(216)的致冷剂的热接触,预冷却此压缩后的致冷剂。
Description
发明领域
本发明涉及对甲烷气源精制的方法,更具体地说,涉及对含高浓度二氧化碳的甲烷气源的深冷精制。
发明背景
低品位的甲烷气源,诸如由于有机物料腐烂的甲烷气源,已被公认为可用至少50年的潜在能源。这种气源包括由拉圾填埋场及厌氧煮解池产生的主要包括甲烷及二氧化碳的“沼气”的气体。沼气中也存在数量不同的许多其它痕量杂质、氧气及氮气。从拉圾填埋场逸散出来的沼气既危害环境也影响安全。而且,沼气中甲烷及二氧化碳这两种组分,只要适当地加以精制,都是具有潜在价值的产物。因此,摄取沼气的能量,又消除对环境及安全的危害,应是有益的。尽管客观需要利用来自填埋场及煮解器的沼气,但这种甲烷气源仍然利用不足,因为还存在涉及对这种气体进行有效精制,即脱除痕量的有毒物质,及接着有效分离甲烷与二氧化碳组分的一些问题。采用厌氧腐烂有机物料方法产生的沼气流约三分之一至一半都是二氧化碳。因此,未精制的沼气流的容积能量含量实质上比管道天然气的更低。因此,对于未精制的沼气,不加处理,脱出这种气体混合物中的二氧化碳及其他杂质,是不能输入气体管线或用于常规设备中的。
已经提出有许多精制沼气源的体系。基于薄膜、变压吸附、变温吸附、化学吸收及深冷处理的分离体系均有报导。对于有大量沼气可供处理或其最终纯度在95%以下就合格的场合,这些体系都有可能在现场对沼气进行成功的精制。但是,它们之中没有哪个体系能经济有效地处理一至二百万标准立方英尺/日以下的沼气源。对于每日生产低于此容积量的沼气源或需要高纯度的场合,资本投资、生产费用及/或体系的复杂性都限制了现有体系的实际或经济运用。
拉圾填埋场的恶劣、腐蚀性及连续操作的环境限制了体系要求维护、管理或化学添加剂的有效性。复杂体系一般投资及保养费用都较高。
原则上,对沼气都可利用蒸馏技术使之深冷分离为其组分。但不幸的是,蒸馏技术对于二氧化碳及甲烷沼气混合物的分离更为困难,因为平衡混合物相中有若干独特的特点。深冷分离可大致分为连续法及间断(间歇)法。连续深冷体系利用了通过组分间相的差异使二氧化碳及甲烷彼此连续分离的区或区域。例如,在低于700磅/平方英寸绝压(psia)的恒压下,要获得纯度>98%的甲烷,必须从这种混合物进料流中分离出易形成固体的CO2。为保持清晰的相和允许相分离,要求在该混合物的临界点以下进行操作。对于这种常规低温蒸馏可提供的温度及压力范围是十分有限的。
在已有技术中,对二氧化碳及甲烷的分离提出有许多深冷方法。例如,霍姆斯(A.S.Holmes)等人(US 4,462,814)提出了避免蒸馏中二氧化碳固相的一种方法及设备。通常被称为瑞安-霍尔姆斯法(Ryan-Holmesprocess),将链烷添加剂,诸如丙烷或丁烷,用于基于液体蒸馏的分离过程中,避免固体CO2的形成。在与CH4蒸馏后,分离出CO2中的丁烷或丙烷,并再循环至蒸馏塔中。将重质烃类(C3+)加入进料流中,使操作压力降低和温度升高,不致形成固体CO2。在进料流中添加正丁烷,可使混合物的蒸馏在液-汽相内充分进行,避免了在蒸馏塔内形成固体CO2。另外,提高混合物的临界压力,以产生更大范围的容许操作压力。
但是,瑞安-霍尔姆斯法用于沼气精制有二个明显限制。首先,该体系复杂,以致投资费用高,不能适应较小的进料流。如上所指,对于填埋场回收体系,这样的投资也是有问题的。第二,这种方法需要供给一般在拉圾填埋场所不具备的丙烷或更重的烷烃。
近年来,珀特兹(Potts,Jr.)等人(US 5,120,338)提出利用蒸馏及控制凝固区来分离多组分进料流的方法。这种方法不同于瑞安-霍尔姆斯法,因为它可按所控制的方式形成固体二氧化碳。将这种固体融化并掺混至液相的液体部分中。使第三气相富集最易挥发的组分,甲烷,使其分离。通过小心控制固体形成的条件以及气-液蒸馏的条件,可使这些组分分离成三股物流。实质上,这种体系可使产品达到要求的纯度,而勿须去避免形成固体二氧化碳或使用添加剂。这种方法的主要限制与其可缩放性有关。这种体系的复杂性及投资费用也要求沼气源大于二百万立英尺/日,才能成为经济可行的。这种方法也太复杂,投资费用过高,对较小气源仍不可行。
还提出过几种采用部分冷却与第二类型分离机理相结合的方法。例如,斯威尼(Sweeney)等人(US 5,570,582),索飞尔(Soffer)等人(US5,649,996)及欧桕(Ojo)等人(US 5,531,808)提出了通过在低温或深冷温度下操作强化吸附体系操作的一些方法。洛克汉德瓦拉(Lokhandwala)(US 5,647,227)指出了分离甲烷、氮气及至少一种其它组分(二氧化碳)的混合物的一种方法及设备。这种方法采用通过薄膜强化的深冷分离。这些体系并不依赖固相形成或蒸馏来实现分离。这些混杂体系的成本及复杂性也限制其用于流量大于约二百万立方英尺/日的沼气流。
在US 5,642,630中,阿卜杜玛勒克(Abdelmalek)等人公开了对固体废物填埋场气体的一种处理及分离方法,其申请专利保护的是其对高品质液化天然气流、液化二氧化碳流及压缩天然气流的生产方法。该专利提出,采用能产生高达1800psia压力的四级压缩机和三个闪蒸罐,采用化学添加剂及多再循环回路,来获得目的产品。这种体系的复杂性及相关投资费用限定在小规模拉圾填埋场上实用。
在US 4,681,612中,欧’布赖恩(O’Brien)等人公开一种深冷分离体系,这种体系产生一种燃料级的甲烷产品流和构成对二氧化碳产品流的选择。这种方法依赖于低温蒸馏塔,其中甲烷更易挥发,因此塔顶产物富集甲烷。此外,使用选择性薄膜,可进一步分离塔顶产物中的甲烷。塔底产物主要含二氧化碳及杂质,可进一步在单独的提纯蒸馏塔中加以精制,如果需要,塔底产物也可作为一种产品流。这种方法有二个问题。首先,因为该体系是一种混杂体系,既采用了蒸馏塔,又用了薄膜,增大了其复杂性及投资费用。第二,不采用后续加工步骤及追加投资费,不易生产出高纯度的二氧化碳及甲烷。不能生产高纯度的产品,这种方法的实用性有限。
对采用化学添加剂分离填埋场气体及其他气物流中的二氧化碳及甲烷的几种方法,也有报导。甲醇通常被用作为一种化学添加剂(见阿普菲尔(Apffel)(US 4,675,035))。在蒸馏过程中往气体混合物中添加甲醇,会降低形成固体二氧化碳的温度和压力范围。这样就可使甲烷蒸馏进行得更完全,从而获得更高纯度的产品。只要蒸馏完成,就可分离甲醇与二氧化碳,并循环甲醇。通常被称为“冷甲醇”的分离,提供了迄今为止分离沼气的最好方法。但是,由于体系复杂、投资费用及与组合吸收及蒸馏操作装置相关联的生产费用,这些体系不适应较小的沼气源。
采用化学添加剂的第二种体系,由阿卜杜玛勒克(Abdelmalek)(US5,642,630)提出。这种方法是一种采用化学吸收促进分离的方法。正如前面提到的那样,需要化学添加剂及吸收的体系,由于添加剂费用、投资费用以及添加剂分离和再循环的复杂性,增加了生产费用。对于二百万标准立方英尺/日以下的沼气生产源,这些体系不经济可行。
概括地说,本发明目的在于提供一种改良分离体系的方法及设备,用于分离含至少二氧化碳及甲烷两种的气流,使之成为高纯度甲烷及高纯度二氧化碳的产品流。
本发明还有进一步的目的在于,提供利用形成固体二氧化碳实现高效分离的一种分离体系。
本发明进一步目的在于,提供比已有技术体系投资费用更低的一种分离体系。
本发明还有另一目的在于,提供比已有技术体系复杂程度更低的一种分离体系。本发明还有更进一步目的在于,提供比已有技术体系生产费用更低的一种分离体系。
对本领域技术人员,阅读以下本发明的详细说明及附图,本发明的这些及其它目的都是会显得很清楚的。
发明综述
本发明涉及从包括CO2与第二气体的气体混合物中分离CO2的一种设备,该设备包括活性换热器及再生换热器。该活性换热器包括与该气体混合物接触的换热表面。该气体混合物以预定压力存在于活性换热器中,该预定压力要选择在用其温度低于在此预定压力下CO2凝固温度的致冷剂冷却换热表面时CO2能凝固在此换热表面上的压力。再生换热器包括与该致冷剂接触并也与凝固的CO2层接触的换热表面。该致冷剂是在其温度高于CO2凝固层中CO2升华温度下进入该再生换热器的。在致冷剂通过膨胀阀膨胀之前,固体CO2的升华冷却了该致冷剂,使致冷剂的温度降低至预定压力下CO2的冰点以下。该致冷剂在离开活性换热器之后受到压缩机的再压缩。在本发明优选实施方案中,由再生换热器释放出来的气态CO2用于预冷却进入的气体混合物。第二预冷却换热器通过提供与离开活性换热器的致冷剂的热接触,预冷却该压缩后的致冷剂。在本发明优选实施方案中,是用第一和第二换热器来构成该活性和再生换热器的。任何时候对换热器是活性换热器的选择,都通过一个活门体系控制气体混合物及致冷剂流往返于活性换热器与再生换热器之间来完成。
附图简述
图1是按照本发明沼气精制体系部分的简图。
图2是按照本发明生产LNG的沼气精制体系优选实施方案的简图。
图3是本发明在略低温下生产高纯度增压甲烷气的简图。
发明详述
本发明提供对利用单段方法分离CO2及CH4为高纯度产品流而无须进一步精制提高产品纯度的技术改进。此外,在分离二氧化碳与甲烷的同一阶段中,可液化甲烷产品流,形成高价值的产品。将这种处理结合至一步深冷中,会使体系投资费用较低、生产费用较低及复杂性降低。这种新而便宜的方法可开发利用许多用已有技术已不经济的较小填埋场,并可使那些能够或目前正在用现行技术进行开发的较大填埋场达到更高的气体处理能力。
图1是按照本发明的CO2精制体系200的简化方案简图,用于分离沼气进料流中CO2与甲烷,参看图1会更易理解本发明获得效益的方法。为简化以下的讨论,只示出了其半个周期的体系结构。
按照本发明的沼气精制体系利用了二个换热器,以216及221表示,和一台压缩机,压缩用于冷却沼气至固体CO2析出程度的致冷剂。在以下讨论中,分离CO2与甲烷的换热器被称为“活性换热器”。另一换热器称为“再生换热器”,其理由通过以下讨论会更为清楚。在图1所示结构中,换热器221是再生换热器,换热器216是活性换热器。
在图1所示体系的简化方案中,沼气在换热器216中被通过膨胀阀215膨胀的致冷剂冷却。CO2从沼气中沉淀析出,在换热表面上构成一层覆盖层,如214所示。
离开换热器216的致冷剂,经压缩机218压缩,在通过阀门215膨胀之前在换热器221中被预冷却。换热器221以前是活性换热器,现在却成为了再生换热器。换热器221的换热表面上有一层CO2固体覆盖层,如222所示。此覆盖层的升华对穿过换热器221的致冷剂提供冷却源。因此,在换热器221为活性换热器期间固化CO2使之从沼气中沉析时所做的功,在换热器221进行再生期间作为有用功而被再吸收。
如果沼气含有明显量的水、非甲烷及CO2的气体、或其它在最终甲烷流中不允许的有机化合物,则可使进料沼气通过一种碳及/或沸石的分离器或其它装置加以处理,以脱除这些组分。这种分离体系在本领域是已知的,因此,此处不再对其详加论述。
如上所述,图1所示体系只说明半个分离循环。在后半个循环中,换热器216和221的作用是相反的。这就是说,换热器221成为再生换热器,换热器216成为活性换热器。一旦再生换热器中的固体CO2耗尽,就必须使这种作用反向。然而,只要再生换热器回收了其传热量,即可切换换热器。
现在参考图2,图2是按照本发明的CO2精制体系实施方案的简图,用于分离混合进料流为纯CO2和CH4产品流。含至少CO2和CH4的进料流5进入分离体系冷箱7,冷箱7中包括一个预冷却/回热(recuperative)换热器10。该进料流被看成为无任何明显有机或无机痕量杂质。该进料流在压力约200磅/平方英寸表压(psig)下进入。脱除通常填埋场气中存在的杂质的预处理体系,对本领域技术人员都是已知的,在此不予详述。对于更完全的讨论,读者可参阅 “填埋场气体:资源评估与进展”(Landfill Gas:Resource Evaluation andDevelopment),(天然气研究所报告(GRI Report 85/0259)85/0259,芝加哥,IL,1985,8月)。本发明所用进料流一般含约45-60%甲烷,35-50%二氧化碳,和1-5%氮及氧。冷箱7用于使分离设备与环境隔热。预冷却回热式换热器10起冷却入口物流5的作用,以便按以下论述通过升华CO2回收最大量的热能。保持换热器10的温度使换热器10中不形成固体CO2。
冷却后的进料流出换热器10后,流入转换阀15,转换阀15引导进料流至当前活性换热器表面。在当前的实施例中,转换阀15引导预冷后的进料流进入左换热表面组件20,左换热表面组件中包含外冷换热表面25,当前它正起着固化析出工艺流中CO2的作用。
由输送流过的冷致冷液建立组件20中的温度梯度,此组件的进料流入口端比出口端更热。例如,此组件冷端可接近150K°,热端接近195K°。随着固体CO2沉积在换热表面25上,进料流不断冷却,变为富CH4的。在图2所示实施方案中,组件20出口端的温度是冷的,足以在约200磅/平方英寸表压下液化进料流中的纯甲烷组分。液化天然气(LNG)产品流30流出组件20,并流向阀门35,阀门35引导LGN经导管40离开冷箱。
如果最终产品是压缩天然气(CNG),则LGN在深冷泵中可受到压缩,并通过进入的工艺流的回热进行汽化,形成高纯度的压缩天然气(CNG)。LGN的汽化可用于预冷却进入的进料流或致冷剂,从而基本回收用于液化天然气的能量。在换热器10中,进料流5被高纯度是CO2气流12预冷却,CO2气流压力处于或接近15磅/平方英寸表压。此物流在第二换热组件45中产生,也就是说与组件20相同的,也另外用其循环。如图2所示,组件45以前已用作活性换热器,CO2层51已聚集在其换热表面50上。组件45上CO2固体侧的压力被降低至近似于大气压。在这样的压力下CO2在约195K°温度下升华。因此,组件45可用于冷却致冷剂流至近似这个温度。在此致冷器回路中致冷液提供热源加温再生组件的换热表面,促成升华迅速进行。组件45换热器表面的温度梯度从在冷端195K°至在热端近220K°之间变化。升华能是通过将能量传递给在进入膨胀阀75前流过组件45的致冷液的方式加以回收的。关闭在组件45下端的阀35,迫使升华产生的CO2气体离开组件45,并流动穿过转换阀15。纯CO2的冷气体在换热器10中起预冷却入口进料流的作用,回收CO2气体中的显热。这种附加回收体系大大提高了该体系的效率。精制后的CO2流在略低温度及大气压下流出换热器10及冷箱7。
该深冷分离单元中的冷却是由一种制冷剂回路提供的。在此实施方案中,致冷剂55进入压缩机60,其入口压力为约50磅/平方英寸表压,并在出口压力300磅/平方英寸表压下流出。该致冷剂流出压缩机60,其温度高于环境温度,并通过后冷却器65被冷却至近似同于环境的温度。然后,该致冷剂进入冷箱7和回热式换热器67。换热器67使该致冷剂在进入转换阀70之前冷却。在该优选实施方案中,换热器67是一种焊接板翅式换热器或一种盘管式换热器。转换阀70将致冷剂引导至适宜组件中,以进行通过阀门75膨胀之前的预冷却,使致冷剂冷却至活性换热表面的操作温度。在图2所示结构中,将高压致冷剂引导至组件45,使之在流经传热面50的无沼气侧时进一步受到固体CO2升华热的预冷却。因为在给定压力下CO2平衡升华温度是已知及恒定的,不论再生每个阶段的固体CO2存在量多少,只要有一些固体残留,进行准确而又一致预测的预冷却是有可能的。在再生组件中预冷后,该致冷剂通过膨胀阀75进行等焓膨胀,从约300磅/平方英寸表压膨胀至约50磅/平方英寸表压,使该致冷剂进一步冷却至略低于有效凝固组件20冷端所需的低温。然后,此近150K°的冷致冷剂进入组件20内换热表面25的无沼气侧,在它对表面25冷却及对CO2进行凝固时受到加热。然后,较热致冷剂进入换热器67,在它对高压致冷剂流预冷却时,进一步受到加热。此致冷剂在流出冷箱7并进入压缩机60以完成致冷剂循环之前,被加热至略低温的温度。
尽管此优选实施方案利用一种膨胀阀来冷却进入CO2固化换热器之前的致冷剂,但也可采用其它气体膨胀机装置或其它制冷方法而不会偏离本发明内容。例如,可采用一种透平膨胀机代替阀门,膨胀及冷却该致冷剂。
应该承认,控制机构、补充气体组成、相分离器、致冷剂过滤器、驱动马达、及气体-循环致冷器的其他常见部件都已从图2中删除,以简化描绘。致冷器的这些部件及元件都属于本领域常规的。
也应注意,本发明所用的具体冷却体系对于分离体系的有效运行并非关键性的。尽管在该优选实施方案中采用了一种低压混合致冷剂体系,但其它回热式致冷器也可运行。例如,该回热式制冷体系可基于等熵透平膨胀机循环,诸如克劳德(Claude)或布瑞顿(Brayton)循环,采用氮气、氩气、或纯甲烷气作为其致冷剂。其它膨胀循环,比如林德(Linde)、高气压混合致冷剂,或串级循环也都可采用。优选制冷体系可利用产生高约300磅/平方英寸表压压力的一种压缩机和使致冷剂由此压力膨胀至约50磅/平方英寸表压压力的一种膨胀阀布局。这些压缩机均可由Carrier or Copeland公司提供。这种致冷器是优选的,因为它合理有效、制造便宜和使用非常可靠。如上所述,在所有商业体系运作领域中,其资本投资和可靠性两方面都属重要的方面。在本发明优选实施方案中,所用的致冷剂是按其摩尔百分率计分别为23、8、23、34、和12的丁烷、丙烷、乙烷、甲烷和氩气的一种混合物。但是,其它那些避免使用丁烷和丙烷的致冷剂混合物也可使用。
在换热表面25上积累足量CO2固体,造成传热不足或者因CO2固体堵塞换热表面20导管,导致压力降增大,而受到限制时,另一组件45则应是无固体CO2的。此刻转换阀15就起到切换物流的作用,阀35则起到令物流40从组件45流出的作用。同样,转换阀60改变制冷剂回路,使组件20起预冷致冷剂流的作用。应当注意,为简化描绘,膨胀阀75表示为一种可逆阀。实际上,这种阀门是由使通过单膨胀阀的物流重新定向的阀门体系构成的。这些阀门的调节变化可直接使组件20从有效凝固设备切换为CO2升华的再生设备。这种转换对组件45也是如此。致冷剂流反向使预膨胀冷却单元变为组件20,CO2凝固单元变为组件45。
在本发明优选实施方案中,阀门顺序允许短期不使进料流进入活性换热器组件,直至由流动的致冷剂流在组件20和45中重新建立起所要求的温度梯度。物流短暂中断大致为一个操作循环总时间的5%,可能持续时间几分钟。在这个时候,入口阀98关闭,以防止进料流进入该体系。
本发明可做到在略低温下生产纯甲烷气流,而非液体甲烷。参考图3,可更易理解本发明的这种变异,图3为按照本发明的气体处理体系的简化方案示意图,用于分离沼气进料流为纯CO2和CH4产品流。进料流105基本上为如上参照图2所述。
冷箱107是用于使分离设备与环境隔热。预冷却回热式换热器110是利用回收由CO2流112升华的能量和精制后甲烷物流195来冷却入口流105的,如以下论述。在该优选实施方案中,换热器110为一有三路物流通过的换热器。保持换热器110中的温度,以使换热器110中没有固体CO2形成。
冷却后的进料流在流出换热器110后,进入转换阀115,阀115起引导进料流至用于精制的活性换热器的作用并选择当前再生换热器作为一种冷却源产出。转换阀115引导预冷却后物流105进入换热表面组件120,换热表面组件120包含从其上脱出进料流中CO2的换热表面125。换热器120和145基本按对图2所示换热器20和45所述的操作。
在当前的实施方案中,物流中的甲烷组分以液态离开活性换热器,其压力约200磅/平方英寸表压(psig)。甲烷产品流130流出组件120和流向阀门135,阀门135引导甲烷流至换热器137。在换热器137中LGN通过由高压致冷剂传递的热能进行汽化。物流140离开换热器137,进入回热/预冷换热器110,在110它用于预冷却进入的沼气进料流,随着在流出冷箱作为物流195之前它升温到接近环境的温度。必须小心操作,保证物流140在换热器137中升温到足以使换热器110中没有固粒形成。
在换热器110中,沼气进料液流105被物流112预冷却,物流112是一种高纯度的CO2气流,其压力接近15磅/平方英寸表压。此物流在第二换热表面组件145中形成,在某种意义上类似于参考上述图2所示的本发明实施方案。
采用类似于上述参照图2的一种气体-循环致冷剂回路构成深冷分离单元进行的冷却。在此实施方案中,致冷剂155进入压缩机160,其入口压力约50磅/平方时表压,出口压力为300磅/平方时表压。该致冷剂流出压缩机160在环境温度以上,并通过后冷却器165被冷却至近似等于环境的温度。然后,该致冷剂进入冷箱107和回热式换热器167。在该致冷剂进入转换阀170之前受换热器167冷却。转换阀170引导该致冷剂至再生组件进行预冷却。致冷剂在再生组件中经预冷却后,通过转换阀180被引导至预冷却换热器137,在137通过冷甲烷流130使之进一步冷却。随后在换热器137中进行第三预冷却阶段,该致冷剂通过膨胀阀175进行等焓膨胀,从约300磅/平方英寸表压膨胀到约50磅/平方英寸表压。这种膨胀使致冷剂冷却至略低于有效凝固组件120冷端所需的低温。然后,该致冷剂被送往活性换热器转换阀180。然后此约150K°的冷致冷剂进入组件120中换热表面125的无沼气侧,并在它通过使CO2凝固来冷却表面125时受到加热。然后,该温热的致冷剂,进入换热器167,在它预冷却高压致冷剂流时进一步受到加热。该致冷剂在流出冷箱107并进入压缩机160至完成致冷剂循环之前,被加热至略低温度。换热器137对气体分离体系的操作是重要的,因为它降低了跨越膨胀阀的温度,并能使甲烷流140升温至不致引起换热器110中形成固体的温度。
在本发明该实施方案中,所用致冷体系基本上与上述参照图2所示的实施方案相同。因此,在此不再对其论述。
在本发明的此实施方案中,对活性与再生换热器的转换基本如上所述参照图2所示的实施方案相同。当活性换热器积累足够固体CO2至明显降低其性能时,就用再生后的换热器切换它。
重要的是要注意,通过CO2升华提供的冷却是在低于开始高压液化及凝固沼气流中CO2所要求的压力下进行的。这样可使致冷剂膨胀所跨越的温度大大降低,又使组件20/120及45/145中循环蓄热物质的温度大大降低。因此,升华组件的操作压力对有效设计至关重要。这个温度可随升华组件中所保持的压力多少降低或升高一些。LGN的出口压力应接近于LNG储罐的压力。较冷的LGN被认为更有价值。此外,LGN中残留的CO2是压力和温度的函数。必须小心操作,保证CO2不在换热组件下游能固化。应该保持换热器10/110及67/167中一致的温度梯度、入口端温度及出口端温度。此外,应该小心操作,保证在循环过程中通过换热器的流动不反向。同样,在循环过程中通过膨胀阀75/175的流动不应明显变向或波动。对离开再生换热表面组件的致冷剂出口气温,只要有CO2固体存在,就应该保持其恒定。因此,这个温度的升高是再生完成和循环应反向的标志。因此,在本发明优选实施方案中这个温度受到监控,并用于起始对活性及再生换热器的互换。
为了达到对CO2的适宜分离,图2及3中的换热器20/120必须运行在压力接近200磅/平方英寸表压及最冷温度低于约150K°之下。这些条件可保证流出换热器20/120的气体含有不超过约0.02%的CO2。另外,也可希望生产一种较高CO2含量的甲烷气产品。如果活性换热器中的最冷温度提高到约150K°以上,精制产出的甲烷流会保持为气体,且会使之在离开活性换热器后的CO2浓度相应较高。调节活性换热器中的最冷温度,CO2的浓度是可直接控制的。调节这个温度可成为一种控制产出气体品质的手段,也可使本发明能够由沼气来生产管输品级的天然气,使CO2的容许浓度通常在2体积%以下。
虽然此优选实施方案预定使用沼气,但对于含二氧化碳及甲烷的其它气流也同样可用本发明来精制。例如,本发明可用于精炼含大量二氧化碳的井口气。
根据上述说明及附图对本发明的各种改进,对于本领域技术人员都会是明显的。因此,本发明完全受以下申请专利的范围限制的。
Claims (5)
1、一种用于从包括CO2及第二气体的气体混合物中分离CO2的设备[2、20、200],所述设备[2、20、200]包括:
用于凝固所述混合物中CO2的一种活性换热器[216],所述活性换热器[216]包括与该气体混合物接触的换热表面,该气体混合物以预定压力存在,该换热表面通过一种致冷剂进行冷却,所述致冷剂温度低于所述预定压力下的CO2凝固温度;
用于预冷却该致冷剂的一种再生换热器[221],所述再生换热器[221]包括与该致冷剂接触也与所述CO2凝固层接触的换热表面,该致冷剂进入再生换热器,其温度高于所述CO2凝固层中CO2升华的温度;
用于使在再生换热器[221]中预冷后进入活性换热器[216]之前的致冷剂进行膨胀的膨胀阀[215];及
用于压缩已离开活性换热器[216]的致冷剂的压缩机[60、160、218],所述压缩机[60、160、218]设有接受已离开活性换热器[216]的致冷剂的入口,和排放压缩后致冷剂的出口。
2、按照权利要求1的设备[2、20、200],其中所述设备[2、20、200]包括第一和第二换热器[2、25、120、145],在任何给定时间下,所述换热器[2、25、120、145]中之一就是所述活性换热器[216],另一个换热器就是所述再生换热器[221],所述设备[2、20、200]还包括用于选择第一和第二换热器为活性换热器[216]的一个阀门体系[15、75、115、170、180]。
3、按照权利要求2的设备[2、20、200],其中各所述换热器包括:
具有接受致冷剂的入口端和排放致冷剂的出口端的换热盘管[50],所述换热盘管[50]具有与流过该换热盘管的致冷剂进行热接触的外表面;及
用于使气体与该换热盘管外表面接触的舱室,该舱室具有接受与排放经与换热盘管[50]外表面接触而被冷却的气体的入口和出口,
其中所述阀门体系[15、75、115、170、180]包括第一阀门体系[70、170],此阀门体系用于连接压缩机[60、160、218]出口与再生换热器[221]中的换热盘管的入口端和用于连接在活性换热器[216]中换热盘管的出口端与压缩机[60、160、218]的入口端;和
用于输送所述气体混合物至活性换热器[216]的入口的第二阀门体系[15、115]。
4、按照权利要求1的设备[2、20、200],还包括一种进入气体的预冷却换热器[110],用于通过使该气体混合物与离开再生换热器[221]的CO2进行热接触,来预冷却所述气体混合物。
5、按照权利要求1的设备[2、20、200],还包括致冷剂预冷却换热器[167],用于在压缩后的致冷剂进入再生换热器[221]之前,通过使该压缩后的致冷剂与离开活性换热器[216]的致冷剂进行热接触,来冷却该压缩后的致冷剂。
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- 2000-01-26 WO PCT/US2000/001857 patent/WO2000046559A1/en not_active Application Discontinuation
- 2000-01-26 AU AU26299/00A patent/AU2629900A/en not_active Abandoned
- 2000-01-26 MX MXPA01007954A patent/MXPA01007954A/es not_active Application Discontinuation
- 2000-01-26 CN CN00804607A patent/CN1342256A/zh active Pending
- 2000-01-26 KR KR1020017009836A patent/KR20010101983A/ko not_active Application Discontinuation
- 2000-01-26 EP EP00904562A patent/EP1153252A4/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102326044B (zh) * | 2008-12-19 | 2015-08-19 | 乔治洛德方法研究和开发液化空气有限公司 | 使用低温冷凝的co2回收方法 |
CN102648385A (zh) * | 2009-12-05 | 2012-08-22 | 伊诺维尔2000股份有限公司 | 用于净化第一液体内容物且同时加热第二液体内容物的系统和方法 |
CN102636002A (zh) * | 2012-03-31 | 2012-08-15 | 贾林祥 | 天然气中co2低温脱除方法及应用该方法的天然气液化装置 |
CN109178286A (zh) * | 2018-08-24 | 2019-01-11 | 广东珠海金湾液化天然气有限公司 | 液化天然气运输船船舱的预冷工艺 |
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EP1153252A1 (en) | 2001-11-14 |
MXPA01007954A (es) | 2003-07-14 |
AU2629900A (en) | 2000-08-25 |
CA2361809A1 (en) | 2000-08-10 |
WO2000046559A1 (en) | 2000-08-10 |
KR20010101983A (ko) | 2001-11-15 |
EP1153252A4 (en) | 2003-05-21 |
US6082133A (en) | 2000-07-04 |
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