CN102639435A - 整合的强化采油方法 - Google Patents
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Abstract
本发明涉及一种与诸如气化或转化的合成气生产方法整合的强化采油方法,其包括对供EOR使用的酸性二氧化碳流进行捕集和回收。
Description
发明领域
本发明涉及一种与诸如气化或转化的合成气生产方法整合的强化采油方法,其包括对供EOR使用的酸性二氧化碳流进行捕集和回收。
发明背景
鉴于原油供应日益减少,强化采油(EOR)技术开始重新受到人们的关注。
通常,利用油藏的自然压力将原油驱入井眼中,原油通过井眼由普通泵带到地表,以此生产油料。生产一段时间后,油藏的自然压力降低,产量也逐渐减小。在20世纪40年代,生产者利用注入水、蒸汽和/或天然气将原油驱入井眼中,然后将原油泵送到地表,以此来结合二次开采。
一旦易于提取的油已被采出,生产者就可能转向三次开采或强化采油(EOR)技术。一种已知的此类EOR技术是注入高压CO2,这有助于使油藏再增压。高压CO2还充当溶剂,溶解残油,从而降低残油粘度并且提高其流动特性,以将残油从老化油藏中泵出。
利用CO2提高产油量的困难之一在于其需要大量的CO2,如此大量CO2的可获得性受到限制。
可利用天然源的CO2 ,但通常需要天然源靠近油藏以避免使这种利用不经济的管道的建造和使用。
还考虑利用来自燃烧源(例如发电厂)的CO2(参见例如US7299868和其中引用的出版物),但CO2与燃烧气体的分离困难并且通常被认为不经济。
近来,考虑将来自合成气生产操作的CO2用于EOR中。参见例如US7481275。合成气生产操作包括例如催化气化和加氢甲烷化方法、非催化气化方法和甲烷转化方法。这些方法通常产生甲烷、氢气和/或合成气(氢气和一氧化碳的混合物)中的一种或多种作为粗气态产物,这些粗气态产物可经处理并最终用于发电和/或其他工业应用。这些方法还产生CO2,其经由酸气去除方法而去除,正如相关领域的普通技术人员通常所知。以前,一直简单地将这种CO2排放到大气中,但鉴于对环境的关注,对这种CO2的捕集和封存/应用变得日益必要。因此,EOR对于来自合成气生产操作的CO2流而言是一种合理的出路(outlet)。
至少一种此类将CO2副产物流用于EOR的合成气生产操作目前位于大平原合成燃料厂(Great
Plains Synfuels Plant)(靠近Beulah, North
Dakota USA)。在此设备中,煤/褐煤气化成含二氧化碳的合成气流,该合成气流经由溶剂型酸气去除技术分离。所得CO2流(其大于95%纯)被压缩并经由205英里超临界CO2管道输送至加拿大的油田以供EOR操作。此操作在Perry和Eliason的“CO2 Recovery and Sequestration at Dakota
Gasification Company” (October 2004)(可获自www.gasification.org)和达科他气化公司(Dakota
Gasification Company)网站(www.dakotagas.com)中有更加详细地描述。
此操作的缺点在于管道,这是因为认为超临界CO2是有害物质。超临界CO2管道(尤其是长达205英里的管道)的建造、准入、操作和维护成本昂贵。因此非常需要从合成气操作中获取CO2以用于EOR现场的更有利的方式。
一种注入CO2的变型是使用含有硫化氢的酸性CO2流。已证实CO2流中H2S的存在会潜在地降低特定油料的最低互溶压力,并从而潜在地改善基于CO2的EOR的效率。
含有硫化氢的酸性CO2流,特别是超临界CO2流被认为是有害的,因此不可在标准管道中输送。
因此,非常希望将合成气生产方法与EOR方法以一定的方式整合,使得将CO2向大气中的释放降至最低(使CO2的捕集和封存最大化),减少对长CO2输送管道的需求,提供用于EOR的酸性CO2流并改善两种方法的总体整合性、效率和经济性。本发明提供这种整合。
发明内容
在第一方面,本发明提供一种整合方法,以(i)产生贫酸气的烃产物气流,(ii)经由烃生产井从地下油气藏产生含烃流体以及(iii)提高得自所述地下油气藏的所述含烃流体的产量,所述方法包括以下步骤:
(1)将加压的酸性二氧化碳流注入所述地下油气藏中以提高经由所述烃生产井得自所述地下油气藏的所述含烃流体的产量;
(2)回收产自所述烃生产井的所述含烃流体;
(3)将所述含烃流体分离成(a)液态烃产物流和(b)任选包含硫化氢的气态烃产物流;
(4)由含碳原料生产合成气流,所述合成气流包含(a)一氧化碳和二氧化碳中的至少一种、(b)氢气和甲烷中的至少一种,和(c)任选硫化氢;
(5)在酸气去除单元中对所述合成气流和任选所述气态烃产物流进行处理,以产生所述贫酸气的烃产物气流和酸性二氧化碳流;
(6)对所述酸性二氧化碳流进行加压以产生所述加压的酸性二氧化碳流,
其中(i)所述合成气流和所述气态烃产物流中的至少一种包含超过痕量的硫化氢,和(ii)如果所述气态烃产物流包含超过痕量的硫化氢,则在酸气去除单元中对所述合成气流和所述气态烃产物流进行处理以产生所述贫酸气的烃产物气流和所述酸性二氧化碳流。
在第二方面,本发明提供一种通过将加压的酸性二氧化碳流注入地下油气藏中来提高经由烃生产井得自地下油气藏的含烃流体的产量的方法,其中所述加压的酸性二氧化碳流通过包括以下步骤的方法产生:
(I)回收产自所述烃生产井的所述含烃流体;
(II)将所述含烃流体分离成(a)液态烃产物流和(b)任选包含硫化氢的气态烃产物流;
(III)由含碳原料生产合成气流,所述合成气流包含(a)一氧化碳和二氧化碳中的至少一种、(b)氢气和甲烷中的至少一种,和(c)任选硫化氢;
(IV)在酸气去除单元中对所述合成气流和任选所述气态烃产物流进行处理以产生贫酸气的烃产物气流和酸性二氧化碳流;和
(V)对所述酸性二氧化碳流进行加压以产生所述加压的酸性二氧化碳流,
其中(i)所述合成气流和所述气态烃产物流中的至少一种包含超过痕量的硫化氢,和(ii)如果所述气态烃产物流包含超过痕量的硫化氢,则在酸气去除单元中对所述合成气流和所述气态烃产物流进行处理以产生所述贫酸气的烃产物气流和所述酸性二氧化碳流。
在第三方面,本发明提供一种用于产生含烃流体和贫酸气的烃产物气流的设备,所述设备包括:
(A)适于由含碳原料生产合成气的合成气生产系统,所述合成气包含(i)一氧化碳和二氧化碳中的至少一种、(ii)氢气和甲烷中的至少一种以及(iii)任选超过痕量的硫化氢;
(B)与包含含烃流体的地下油气藏流体连通的注入井,所述注入井适于将加压的酸性二氧化碳流注入地下油气藏中以进行强化采油;
(C)与所述地下油气藏流体连通的烃生产井,所述烃生产井适于去除地下油气藏中的含烃流体;
(D)与所述烃生产井流体连通的分离装置,所述分离装置适于(i)接收来自所述烃生产井的烃类流体,和(ii)将所述烃类流体分离成液态烃产物流和任选包含硫化氢的气态烃产物流;
(E)与所述合成气生产系统和任选所述分离装置流体连通的酸气去除单元,所述酸气去除单元适于(i)接收来自所述合成气生产系统的合成气和任选来自所述分离装置的气态烃产物流,和(ii)对所述合成气和任选所述气态烃产物流进行处理以去除酸气并产生所述贫酸气的烃产物气流和酸性二氧化碳流;和
(F)与所述酸气去除单元和所述注入井流体连通的压缩机单元,所述压缩机单元适于(i)接收所述酸性二氧化碳流,和(ii)压缩所述酸性二氧化碳流以产生所述加压的酸性二氧化碳流,以及(iii)向所述注入井提供所述加压的酸性二氧化碳流。
在第三方面的具体实施方案中,所述酸气去除单元适于接收所述合成气和所述气态烃产物流的合并流,并对所述合并流进行处理以去除酸气并产生贫酸气的烃产物气流和酸性二氧化碳流。
在第三方面的另一个具体实施方案中,所述酸气去除单元适于接收来自所述分离装置的气态烃产物流,并对所述气态烃产物流进行处理以去除酸气并产生贫酸气的气态烃产物流。在这种情况下,所述贫酸气的烃产物气流将包含所述贫酸气的气态烃产物流和贫酸气的合成气流(单独的或合并的)。
通过阅读以下详细描述,本领域的普通技术人员将更容易地理解本发明的这些和其它实施方案、特征和优点。
附图简述
图 1是本发明的整合方法的实施方案的示意图。
图 2是本发明的整合方法的第一具体实施方案的示意图。
图 3是图2的整合方法的气体处理部分的实施方案的示意图。
图 4是本发明的整合方法的第二具体实施方案的示意图。
图 5是图4的整合方法的气体处理部分的实施方案的示意图。
详描
本发明涉及将合成气生产方法与强化采油方法整合。其它详细内容在下文提供。
在本说明书的上下文中,如果未另外指明,本文提及的所有出版物、专利申请、专利和其它参考文献均以引用的方式全文并入本文以用于所有目的,如同完全阐述一般。
除非另有规定,本文所用的所有技术和科学术语的含义与本公开所属领域中的普通技术人员通常所理解的含义相同。如有冲突,以本说明书(包括定义)为准。
除了明确注明的地方,商标均以大写字母示出。
本文描述了合适的方法和材料,尽管与本文所述相似或等同的方法和材料可用于实施或测试本发明。
除非另有说明,所有百分比、份数、比率等均以重量计。
除非另有说明,以psi单位表示的压力为表压力,而以kPa单位表示的压力为绝对压力。
当量、浓度或其它值或参数以范围或一系列上限值和下限值给定时,这应被理解为是具体公开由任何一对任何上限值和下限值所形成的所有范围,无论是否分别公开各范围。当本文中提及一个数值范围时,除非另有说明,该范围旨在包括其端点,以及该范围内的所有整数和分数。当限定一个范围时,并不旨在将本发明的范围限制在所述特定值。
当在描述值或范围端点中使用术语“约”时,本发明应当理解为包括所涉及的特定值或端点。
如本文所用,术语“包含”、“包括”、“具有”或它们的任何其它变型都旨在涵盖非排他性的包括。例如,包括一系列要素的工艺、方法、制品或装置不必限定于仅这些要素,而是能够包括未明确列出的或此类方法、方法、制品或设备固有的其它要素。此外,除非明确相反地说明,“或”表示包含性的“或”而非排他性的“或”。例如,条件A或B是由以下中的任一种满足:A为真(或存在)而B为假(或不存在);A为假(或不存在)而B为真(或存在);以及A和B都为真(或存在)。
本文用于描述多个要素或组分的“一(种)”的使用仅出于方便考虑且给出所公开的一般含义。除非明显有相反含义,该说明书应当理解为包括一个(种)或至少一个(种),并且单数形式还包括复数形式。
如本文所用,术语“大部分”,除非本文中另外定义,是指大于约90%的提及物质,优选大于约95%的提及物质,并且更优选大于约97%的提及物质。当提及分子(例如甲烷、二氧化碳、一氧化碳和硫化氢)时百分比以摩尔计,否则以重量计(例如含烃流体的液态组分)。
如本文所用,术语“主要部分”,除非另有定义,是指大于约50%的提及物质。当引用分子(例如氢气、甲烷、二氧化碳、一氧化碳和硫化氢)时百分比以摩尔计,否则以重量计(例如含烃流体的液态组分)。
如本文所用,术语“含烃流体”是指包含任何烃液和/或烃气的流体。含烃流体还可包含固体颗粒。油料、凝析油等及其与其它液体例如水的混合物可为含烃流体中所含液体的实例。任何气态烃(例如甲烷、乙烷、丙烷、丙烯、丁烷等)以及气态烃的混合物可包含在含烃流体中。在本发明的上下文中,含烃流体回收自地下油气藏,例如含油地层、凝析气藏、天然气藏等。
如本文所用,术语“含碳”与烃同义。
如本文所用,术语“含碳物质”为包含有机烃内容物的物质。含碳物质可分为本文所定义的生物质或非生物质物质。
如本文所用,术语“生物质”是指来源于最近(例如在过去的100年内)活生物体的含碳物质,包括植物基生物质和动物基生物质。为清楚起见,生物质不包括化石基含碳物质,例如煤。例如参见US2009/0217575A1和US2009/0217587A1。
如本文所用,术语“植物基生物质”是指来源于绿色植物、农作物、藻类和树木的物质,例如但不限于甜高粱、甘蔗渣、甘蔗、竹、杂交杨、杂交柳、合欢树、桉树、苜蓿、三叶草、油棕、柳枝稷、苏丹草、稷黍、麻风树和芒属植物(例如芒草奇岗(Miscanthus x giganteus))。生物质还包括来自农业耕种、处理和/或降解的废物,如玉米芯和玉米壳、玉米秸秆、稻草、坚果壳、植物油、芥花籽油、菜籽油、生物柴油、树皮、木片、锯末和庭院垃圾。
如本文所用,术语“动物基生物质”是指从动物养殖和/或利用产生的废物。例如,生物质包括但不限于来自禽畜养殖和处理的废物,如动物粪便、海鸟粪、家禽粪、动物脂肪和城市固体垃圾(例如,污物)。
如本文所用,术语“非生物质”是指本文所定义的术语“生物质”不包括的那些含碳物质。例如,非生物质包括但不限于无烟煤、烟煤、次烟煤、褐煤、石油焦、沥青质、液体油料残渣或其混合物。例如参见US2009/0166588A1、US2009/0165379A1、US2009/0165380A1、US2009/0165361A1、US2009/0217590A1和US2009/0217586A1。
如本文所用,术语“石油焦(petroleum coke/petcoke)”包括(i)在油料处理中得到的高沸点烃馏分的固体热分解产物(重质残渣-“残石油焦”);和(ii)处理焦油砂的固体热分解产物(沥青砂或油料砂-“焦油砂石油焦”)两者。此类碳化产物包括例如生石油焦、煅烧石油焦、针石油焦和流化床石油焦。
残石油焦也可来源于原油,例如通过用于提高重质残余原油质量的焦化方法,这种石油焦包含灰分作为微量组分,其基于焦的重量计通常为约1.0重量%或更少,并且更通常为约0.5重量%或更少。通常,这种较低灰分焦中的灰分包含金属,如镍和钒。
焦油砂石油焦可从油料砂得到,例如,通过用于提高油料砂质量的焦化方法。焦油砂石油焦包含灰分作为微量组分,其基于焦油砂石油焦的总重量计通常在约2重量%至约12重量%的范围内,并且更通常在约4重量%至约12重量%的范围内。通常,这种较高灰分焦中的灰分包含诸如二氧化硅和/或氧化铝的物质。
石油焦具有通常在约0.2至约2重量%范围内(基于石油焦总重量计)的固有低水分含量;其通常还具有很低的水浸湿能力,以允许常规催化剂浸渍方法。所得颗粒组合物包含例如较低平均水分含量,这相对于常规干燥操作提高了下游干燥操作的效率。
基于石油焦总重量计,石油焦可包含至少约70重量%碳,至少约80重量%碳或至少约90重量%碳。通常,基于石油焦重量计,石油焦包含小于约20重量%无机化合物。
如本文所用,术语“沥青质”在室温下为芳族含碳固体,并且可来源于例如原油和原油焦油砂处理。
如本文所用,术语“煤”指泥炭、褐煤、次烟煤、烟煤、无烟煤或其混合物。在某些实施方案中,煤具有基于煤总重量计小于约85重量%,或小于约80重量%,或小于约75重量%,或小于约70重量%,或小于约65重量%,或小于约60重量%,或小于约55重量%,或小于约50重量%的碳含量。在其它实施方案中,煤具有基于煤总重量高达约85重量%或高达约80重量%或高达约75重量%的碳含量。可用煤的实例包括但不限于Illinois #6、Pittsburgh #8、Beulah
(ND)、Utah Blind Canyon和粉河盆地(PRB)煤。无烟煤、烟煤、次烟煤和褐煤可分别包含基于煤总干重量计约10重量%、约5至约7重量%、约4至约8重量%和约9至约11重量%的灰分。然而,任何具体煤源的灰分含量取决于煤的等级和来源,这为本领域的技术人员所熟悉。参见例如“Coal
Data: A Reference”,美国能源部,煤、核、电和替代燃料能源情报部门(Energy
Information Administration,Office of Coal,Nuclear,Electric and
Alternate Fuels,U.S. Department
of Energy),DOE/EIA-0064(93),1995年2月。
由煤燃烧产生的灰分通常包括飞灰和底灰两者,这为本领域的技术人员所熟悉。来自烟煤的飞灰可包含基于飞灰总重量计约20至约60重量%的二氧化硅和约5至约35重量%的氧化铝。来自次烟煤的飞灰可包含基于飞灰总重量计约40至约60重量%的二氧化硅和约20至约30重量%的氧化铝。来自褐煤的飞灰可包含基于飞灰总重量计约15至约45重量%的二氧化硅和约20至约25重量%的氧化铝。参见例如Meyers等人“Fly Ash. A Highway Construction Material”,联邦公路管理局,报告编号FHWA-IP-76-16,哥伦比亚特区华盛顿市,1976。
来自烟煤的底灰可包含基于底灰总重量计约40至约60重量%的二氧化硅和约20至约30重量%的氧化铝。来自次烟煤的底灰可包含基于底灰总重量计约40至约50重量%的二氧化硅和约15至约25重量%的氧化铝。来自褐煤的底灰可包含基于底灰总重量计约30至约80重量%的二氧化硅和约10至约20重量%的氧化铝。参见例如Moulton, Lyle K,“Bottom
Ash and Boiler Slag”,Proceedings of
the Third International Ash Utilization Symposium,美国矿务局,信息通报编号8640,哥伦比亚特区华盛顿市,1973。
诸如甲烷的含碳物质可能为以上定义下的生物质或非生物质,这取决于其来源。
术语“单元”指单元操作。在描述存在多于一个“单元”时,那些单元以平行方式操作。然而,单一“单元”可包括多于一个的串联或平行单元,这取决于上下文。例如,酸气去除单元可包括脱硫化氢单元与后面串联的脱二氧化碳单元。作为另一个实例,污染物去除单元可包括用于第一污染物的第一去除单元与后面串联的用于第二污染物的第二去除单元。作为另一个实例,压缩机可包括将料流压缩至第一压力的第一压缩机与后面串联的进一步将料流压缩至第二(较高)压力的第二压缩机。
术语“酸性二氧化碳”是指二氧化碳加上超过痕量的硫化氢。
物质中的“超过痕量的硫化氢”是指硫化氢的含量大于针对所述物质的常规管道(其为相关领域的普通技术人员通常所知)可输送的量,因此必须在输送之前对所述物质进行处理以减少/去除硫化氢。例如,如下文所述,“管道质量天然气”必须基本上不含腐蚀性污染物。在一个实施方案中,超过痕量的硫化氢是指大于约4ppm,或大于约2ppm,或大于约1ppm(以体积计)。
本文中的物质、方法和实施例仅为说明性,除非明确说明,并不旨在进行限制。
通用工艺信息
在本发明的一个实施方案中,贫酸气的产物气流(38)和含烃流体(82)在整合的EOR和合成气生产方法中产生,如图1-5所示。
为了有利于整合,在一个实施方案中,酸气去除操作邻近EOR位置(油田),例如位于同一地块或邻接地块。在另一个实施方案中,所述酸气去除操作和合成气生产系统(设备)两者均邻近EOR位置(油田),例如位于同一地块或邻接地块,特别是当合成气流(50)包含超过痕量的硫化氢时。
强化采油
参照图1,所述方法的EOR部分包括利用相关领域的普通技术人员所熟知的技术将加压的酸性二氧化碳流(89)经由注入井(500)(一个或多个)注入地下油气藏(20)。
如上所述,通常呈超临界流体状态的加压的酸性二氧化碳流(89)用于通过通常包括地下油气藏的再加压和截留烃的粘度降低(改善流动性)的机制的组合来提高得自生产井(600)的烃类流体(82)的产量。通常,将在至少约1200psig(约8375kPa)或至少约1500psig(约10444kPa)或至少约2000psig(约13891kPa)的压力下将加压的酸性二氧化碳流(89)注入地下油气藏中。
正如本领域的普通技术人员所熟知,基于二氧化碳的EOR还可包括共同注入(在相同时间,相同位置)、同时注入(在相同时间,不同位置)、连续或交替注入(一个接一个,在相同或不同的位置)或通过这些技术的某种组合注入加压水、蒸汽、氮气和其它流体,以及加压的富二氧化碳流(例如加压的酸性二氧化碳流(89))、水/蒸汽流和/或氮气流,例如前面并入的美国专利申请序列号__/___,___(代理人档案号FN-0057
US NP1,名称为Integrated Enhanced Oil Recovery Process),其与本文同时提交。
实际使用的基于二氧化碳的EOR方法对于本发明最广泛的意义而言并不关键。
所得含烃流体(82)通过烃生产井(600)(一个或多个)生产和回收。产生的含烃流体(82)通常包含液态和气态烃组分以及其它液态和气态组分,这取决于油气藏和EOR条件。液态烃组分可通常被认为是原油,而气态烃组分将通常包括在环境条件下为气体的烃,例如甲烷、乙烷、丙烷、丙烯和丁烷(典型的天然气组分)。其它典型的液体组分包括水或盐水。含烃流体(82)还可包含二氧化碳,并且可包含其它气态组分,例如硫化氢和氮气。含烃流体(82)还可包含固体碳和矿物质。
使产生的含烃流体(82)通过分离装置(300)以将气态组分与液态/固态组分分离,产生气态烃产物流(84)、液态烃产物流(85)和任选包含来自含烃流体(82)的固态组分的料流(86)。固体还可任选地由液态烃产物流(85)携带以便随后分离,或通过诸如沉降、离心和/或过滤的熟知技术在进入分离装置(300)之前分离出。在一个实施方案中,较大/较致密固体通过分离装置(300)进行联合分离,而液态烃产物流(85)中可能夹带的较细固体随后通过诸如过滤的熟知技术分离。
用作分离装置(300)的合适的分离装置为本领域的普通技术人员所熟知,并且包括例如单级和多级卧式分离器和旋风分离器。实际使用的分离装置对于本发明最广泛的意义而言并不关键。
液态烃产物流(85)因此将通常包含来自含烃流体(82)的液态组分(包括例如原油和水/盐水)的至少主要部分(或大部分或基本上全部)。随后可对液态烃产物流(85)进行处理以分离出水和其它污染物,然后进一步处理(如炼制)成各种最终产物或用于各种最终用途,如相关领域的普通技术人员所熟知。
如果存在包含固态组分的料流(86),则其通常将作为浓缩浆料或与含烃流体(82)的一部分液体内容物一起从分离装置(300)中去除。可能随料流(86)中的固体排出的油料可经由洗涤或相关领域的普通技术人员熟知的其它技术从固体中回收。
离开分离装置(300)的所得气态烃产物流(84)通常包含来自含烃流体(82)的气态组分的至少大部分(或基本上全部),包括来自含烃流体(82)的气态烃(和在一定程度上存在的二氧化碳)的至少大部分(或基本上全部)。气态烃产物流(84)还可包含微量的水蒸汽(其应在进入例如如下所述的酸气去除单元(200)中进一步处理之前基本上被去除)以及其它其它污染物(如果存在的话),例如硫化氢。
如果含烃流体(82)包含例如超过痕量的酸气(如二氧化碳和/或硫化氢),则所得气态烃流(84)将包含所述酸气的大部分(或基本上全部),并且在一个实施方案中进行酸气去除以对所述酸气进行去除和回收。
离开分离装置(300)的气态烃产物流(84)的全部或部分可与合成气流(50)合并,或以其它方式与合成气流(50)在酸气去除单元(200)中进行共同处理,如下文所述。在一个实施方案中,如果气态烃产物流(84)包含超过痕量的硫化氢,则气态烃产物流(84)将与合成气流(50)合并或以其它方式与合成气流(50)在酸气去除单元(200)中进行共同处理,如下文所述。
在与合成气流(50)合并或在酸气去除单元(200)中进行共同处理之前,气态烃产物流(84)可任选地被压缩或加热(未示出)至适于合并或其它如下进一步描述的下游处理的温度和压力条件。
作为补充或替代,气态烃产物流(84)(或贫酸气的气态烃产物流(31))的全部或部分可在发电模块(760a)中燃烧,例如以产生电能(79a)和/或蒸汽。
合成气产生
(100)
合成气流(50)包含(a)一氧化碳和二氧化碳中的至少一种、(b)氢气和甲烷中的至少一种,和(c)任选硫化氢。合成气流(50)的实际组成将取决于合成气方法和用于产生料流的含碳原料,包括进入酸气去除单元(200)或任选地与气态烃产物流(84)合并之前可能发生的任何气体处理。
在一个实施方案中,合成气流(50)包含二氧化碳和氢气。在另一个实施方案中,合成气流(50)包含二氧化碳和甲烷。在另一个实施方案中,合成气流(50)包含二氧化碳、甲烷和氢气。在另一个实施方案中,合成气流(50)包含一氧化碳和氢气。在另一个实施方案中,合成气流(50)包含一氧化碳、甲烷和氢气。在另一个实施方案中,合成气流(50)包含二氧化碳、一氧化碳、甲烷和氢气。
合成气流(50)还可包含其它气态组分,例如硫化氢、蒸汽和其它气态烃,这同样取决于合成气生产方法和含碳原料。在一个实施方案中,合成气流(50)包含硫化氢或超过痕量的硫化氢。
合成气流(50)在合成气生产系统(100)中产生。本发明的上下文中可利用任何合成气生产方法,只要该合成气生产方法(包括任选地与气态烃流(84)合并之前或进入酸气去除单元(200)之前的气体处理)产生本发明的上下文中所需要的合成气流。合适的合成气方法通常为相关领域的普通技术人员所知,并且许多适用技术可商购获得。
在下文对不同类型的合适合成气生产方法的非限制性实例进行论述。这些方法可单独使用或组合使用。所有合成气生产方法均包括反应器,反应器在图3和5中一般示为(110),在此将对含碳原料(10)进行处理以产生合成气,可将所述合成气在任选地与气态烃流(84)合并之前和/或在进入酸气去除单元(200)之前进行进一步处理。可在下述各种合成气生产方法的上下文中对图3和5进行总体参照。
基于气体的甲烷转化
/
部分氧化
在一个实施方案中,合成气生产方法基于气送甲烷的部分氧化/转化方法,例如非催化气体部分氧化、催化自热转化或催化料流-甲烷转化方法。这些方法是相关领域中通常所熟知的。参见例如Rice和Mann,“Autothermal Reforming of Natural Gas to Synthesis Gas,
Reference: KBR Paper #2031,” Sandia National
Laboratory Publication No. SAND2007-2331 (2007);和Bogdan
Albrecht,“Reactor Modeling and Process Analysis
for Partial Oxidation of Natural Gas”,Febodruk,
B.V., ISBN: 90-365-2100-9 (2004)印刷。
潜在地适合与本发明结合使用的技术和反应器可商购自Royal Dutch Shell plc、Siemens AG、General
Electric Company、Lurgi AG、Haldor Topsoe A/S、Uhde
AG、KBR Inc.以及其它公司。
参照图3和5,这些基于气体的方法将作为含碳原料(10)的气态含甲烷流在反应器(110)中转化成作为合成气流(50)的合成气(氢气和一氧化碳),其根据具体方法将具有不同的氢气:一氧化碳比率,其通常将包含微量二氧化碳,并且可包含微量的其它气态组分例如蒸汽。
可用于这些方法的含甲烷流包含主要量的甲烷,并且可包含其它气态烃和组分。常用的含甲烷流的实例包括天然气和合成天然气。
在非催化气体部分氧化和自热转化中,将富氧气流(14)连同含碳原料(10)供给到反应器(110)中。任选地,还可将蒸汽(16)供给到反应器(110)中。在蒸汽-甲烷转化中,将蒸汽(16)连同含碳原料(10)供给到反应器中。在一些情况下,还可将微量的其它气体,例如二氧化碳、氢气和/或氮气供给到反应器(110)中。
反应和其它操作条件以及各种反应器和技术的设备和构造在广义上为相关领域的普通技术人员所知,并且对于本发明最广泛的意义而言并不关键。
基于固体
/
液体的气化制备合成气
在另一个实施方案中,合成气生产方法基于非催化热气化方法,例如部分氧化气化方法(如吹氧气化器),其中将非气态(液态、半固态和/或固态)烃用作含碳原料(10)。多种生物质和非生物质物质(如上述所)可用作这些方法中的含碳原料(10)。
潜在地适合与本发明结合使用的吹氧固体/液体气化器在广义上为相关领域的普通技术人员所知,并且包括例如那些基于可得自Royal
Dutch Shell plc、ConocoPhillips
Company、Siemens AG、Lurgi
AG (Sasol)、General Electric Company以及其它公司的技术的气化器。其它潜在合适的合成气发生器描述于例如US2009/0018222A1、US2007/0205092A1和US6863878中。
这些方法将固态、半固态和/或液态含碳原料(10)在反应器(110)例如吹氧气化器中转化成作为合成气流(50)的合成气(氢气和一氧化碳),其根据具体方法和含碳原料将具有不同的氢气:一氧化碳比率,其通常将包含微量二氧化碳,并且可包含微量的其它气态组分,例如甲烷、蒸汽、硫氧化物和氮氧化物。
在这些方法的某些中,将富氧气流(14)连同含碳原料(10)供给到反应器(110)中。任选地,还可将蒸汽(16)以及其它气体例如二氧化碳、氢气、甲烷和/或氮气供给到反应器(110)中。
在这些方法的某些中,蒸汽(16)在高温下还可用作氧化剂以取代全部或部分富氧气流(14)。
反应器(110)中的气化通常发生在含碳原料(10)的流化床中,含碳原料(10)通过富氧气流(14)、蒸汽(16)和/或其它可供给到反应器(110)的流化气体(如二氧化碳和/或氮气)的流动而流化。
通常,热气化为非催化方法,因此无需将气化催化剂添加到含碳原料(10)或反应器(110)中;然而,可使用促进合成气形成的催化剂。
这些热气化方法通常在高的温度和压力条件下操作,并且可根据方法和含碳原料在渣化或非渣化操作条件下进行。
反应和其它操作条件以及各种反应器和技术的设备和构造在广义上为相关领域的普通技术人员所知,并且对于本发明最广泛的意义而言并不关键。
催化气化
/
加氢甲烷化制备富甲烷气体
在另一个替代实施方案中,合成气生产方法为催化气化/加氢甲烷化方法,其中在反应器(110)中在蒸汽和催化剂存在下发生非气态含碳原料(10)的气化,产生作为合成气流(50)的富甲烷气流,其通常包含甲烷、氢气、一氧化碳、二氧化碳和蒸汽。
碳源至甲烷的加氢甲烷化通常包括四个并发反应:
蒸汽碳:C + H2O → CO + H2
(I)
水-气转化:CO +
H2O → H2 +
CO2 (II)
CO甲烷化:CO+3H2 → CH4 + H2O
(III)
氢-气化: 2H2
+ C → CH4
(IV)
在加氢甲烷化反应中,前三个反应(I-III)占优势从而产生以下总反应:
2C + 2H2O → CH4
+ CO2
(V)。
该总反应基本上是热平衡的;然而,由于过程热量损失和其它能量要求(例如随原料进入反应器的水分蒸发所需的能量),必须添加热量以保持热平衡。
这些反应也在合成气(氢气和一氧化碳)方面是基本上平衡的(合成气产生并消耗);因此,当一氧化碳和氢气与产物气体一起回收时,需按需要向反应中添加一氧化碳和氢气以避免不足。
为了将反应的净热保持至尽可能接近中间状态(仅略微放热或吸热)并保持合成气平衡,通常将蒸汽(16)和合成气(12)(一氧化碳和氢气)的过热气流供给到反应器(110)(单独地或组合地)。通常,一氧化碳和氢气流为从产物气体分离的循环流和/或通过转化产物甲烷的一部分来提供。任选地,可通过将富氧流(14)直接供给到反应器(110)来就地产生合成气的全部或部分。
可用于这些方法中的含碳原料包括例如多种生物质和非生物质物质。
用于这些方法中的催化剂包括例如碱金属、碱土金属和过渡金属及其化合物、混合物和复合物。
催化气化/加氢甲烷化方法中的温度和压力操作条件通常比非催化气化方法温和(较低的温度和压力),这有时可具有成本和效率方面的优点。
催化气化/加氢甲烷化方法和条件在例如以下专利申文献中公开:US3828474、US3998607、US4057512、US4092125、US4094650、US4204843、US4468231、US4500323、US4541841、US4551155、US4558027、US4606105、US4617027、US4609456、US5017282、US5055181、US6187465、US6790430、US6894183、US6955695、US2003/0167961A1和US2006/0265953A1以及共同拥有的US2007/0000177A1、US2007/0083072A1、US2007/0277437A1、US2009/0048476A1, US2009/0090056A1、US2009/0090055A1, US2009/0165383A1、US2009/0166588A1、US2009/0165379A1、US2009/0170968A1、US2009/0165380A1、US2009/0165381A1、US2009/0165361A1、US2009/0165382A1、US2009/0169449A1、US2009/0169448A1、US2009/0165376A1、US2009/0165384A1, US2009/0217582A1、US2009/0220406A1、US2009/0217590A1、US2009/0217586A1、US2009/0217588A1、US2009/0218424A1、US2009/0217589A1、US2009/0217575A1、US2009/0229182A1、US2009/0217587A1、US2009/0246120A1、US2009/0259080A1、US2009/0260287A1、US2009/0324458A1、US2009/0324459A1、US2009/0324460A1、US2009/0324461A1、US2009/0324462A1、US2010/0121125A1、US2010/0120926A1、US2010/0071262A1、US2010/0076235a1、US2010/0179232A1、US2010/0168495A1和US2010/0168494A1;美国专利申请序列号12/778,538(代理人档案号FN-0047
US NP1,名称为Process for Hydromethanation of a
Carbonaceous Feedstock)、12/778,548(代理人档案号FN-0048 US NP1,名称为Processes
for Hydromethanation of a Carbonaceous Feedstock)和12/778,552(代理人档案号FN-0049 US NP1,名称为Processes
for Hydromethanation of a Carbonaceous Feedstock),各提交于2010年5月12日;美国专利申请序列号12/851,864(代理人档案号FN-0050
US NP1,名称为Process for Hydromethanation of a
Carbonaceous Feedstock),其提交于2010年8月6日;和美国专利申请序列号12/882,415(代理人档案号FN-0051
US NP1,名称为Process for Hydromethanation of a
Carbonaceous Feedstock)、12/882,412(代理人档案号FN-0052 US NP1,名称为Integrated
Hydromethanation Combined Cycle Process)、12/882,408(代理人档案号FN-0053 US NP1,名称为Integrated
Hydromethanation Combined Cycle Process)和12/882,417(代理人档案号FN-0054 US NP1,名称为Process
for Hydromethanation of a Carbonaceous Feedstock),各提交于2010年9月15日。
各种催化气化/加氢甲烷化反应器和技术的总反应和其它操作条件可在以上参考文献中找到,并且对于本发明最广泛的意义而言并不关键。
合成气流(50)中的硫化氢
如上所述,在一个实施方案中,合成气流(50)包含超过痕量的硫化氢。这在含碳原料包含硫分并且合成气生产方法在以还原为主的环境中操作时发生。这通常在除了含碳原料之外蒸汽为主要反应物且不存在大量氧气的合成气生产方法中(例如在蒸汽气化方法中)发生。
在一个实施方案中,合成气生产方法为以上总体上描述的催化气化/加氢甲烷化方法。
热交换
(140)
所有上述合成气生产方法通常会产生合成气流(50),其温度高于适于供给下游气体方法(包括酸气去除单元(200))和/或与气态烃流(84)合并的温度,因此从反应器(110)离开时,通常使合成气流(50)通过热交换单元(140)以去除热能并产生冷却的合成气流(52)。
例如,可使用热交换单元(140)中回收的热能来产生蒸汽和/或使各种工艺流过热,如本领域的普通技术人员会认识到的。所产生的任何蒸汽均可用于例如满足内部工艺要求和/或用于产生电能。
在一个实施方案中,所得冷却的合成气流(52)将通常以约450℉(约232℃)至约1100℉(约593℃),更通常约550℉(约288℃)至约950℉(约510℃)范围内的温度和适于随后进行酸气去除处理(考虑任何中间处理)的压力离开热交换单元(140)。通常,此压力为约50psig(约446kPa)至约800psig(约5617kPa),更通常为约400psig(约2860kPa)至约600psig(约4238kPa)。
酸气去除之前的气体处理
合成气流(50)和气态烃产物流(84)可经单独处理,或可任选地在各时刻合并并且在各处理方法中经单独处理或共同处理,或在酸气去除单元(200)处或在其中任选地合并且经共同处理。其中合成气流(50) 和气态烃流(84)经合并和/或共同处理的具体实施方案在图2-5中示出。合并时刻和处理变化将主要取决于两料流的组成、温度和压力以及任何所需的最终产物。
酸气去除之前的处理选择通常包括例如酸气转化(sour shift)(700)(水-气转化)、污染物去除(710)和脱水(720)中的一种或多种。虽然这些中间处理步骤可以任何顺序进行,但脱水(720)将通常就在酸气去除(工序中最后一步)之前进行,因为合成气流(50)和气态烃流(84)中任何水的大部分有利地应在进入酸气去除单元(200)中处理之前去除。
在图2和3示出的一个实施方案中,将合成气流(50)和气态烃流(84)在进入酸气去除单元(200)之前进行合并以产生合并气流(60)。在一个具体实施方案中,合成气流(50)和气态烃流(84)在脱水(720)之前合并。在另一个具体实施方案中,合成气流(50)和气态烃流(84)分别脱水(720和720a),并且在酸气去除之前或期间合并。
两料流的合并可能还需要对料流之一或两者进行压缩或膨胀。通常,气态烃流(84)在与合成气流(50)合并之前会需要至少某种程度的压缩。
在图4和5示出的另一个实施方案中,将合成气流(50)和气态烃流(84)在酸气去除单元(200)内进行共同处理,如下文更详细地论述的。
酸气转化
(700)
在某些实施方案中,特别是在其中料流包含可感知量的一氧化碳并且希望使氢气和/或二氧化碳产量最大化的实施方案中,此类料流(例如合成气流(50))的全部或部分可被供应至酸气转化反应器(700)。
在酸气转化反应器(700)中,气体在含水介质(例如蒸汽)存在下发生酸气转化反应(也称为水-气转化反应,参见上式(II)),以将CO的至少主要部分(或大部分或基本上全部)转化成CO2,这还提高了H2的比率,从而产生富氢气流(54)。
酸气转化过程详细描述在例如US7074373中。该过程包括添加水,或使用气体中所含的水,并且使所得水-气体混合物在蒸汽转化催化剂上进行绝热反应。典型的蒸汽转化催化剂包括在耐热载体上的一种或多种VIII族金属。
用于针对含CO的气流进行酸气转化反应的方法和反应器是本领域中的技术人员所熟知的。合适的反应条件和合适的反应器可根据必须从气流中清除的CO的量而改变。在一些实施方案中,酸气转化可在单个阶段中在从约100℃,或从约150℃,或从约200℃到约250℃,或到约300℃,或到约350℃的温度范围内进行。在这些实施方案中,转化反应可由本领域中的技术人员已知的任何合适催化剂来催化。此类催化剂包括但不限于Fe2O3基催化剂,例如Fe2O3-Cr2O3催化剂以及其它过渡金属基和过渡金属氧化物基催化剂。在其它实施方案中,酸气转化可分多个阶段进行。在一个特定实施方案中,酸气转化分两个阶段进行。此两阶段转化方法使用高温工序,随后使用低温工序。高温转化反应的气体温度的范围为约350℃至约1050℃。典型的高温催化剂包括但不限于任选地与少量的氧化铬结合的氧化铁。低温转化的气体温度的范围为约150℃至约300℃,或约200℃至约250℃。低温转化催化剂包括但不限于承载于氧化锌或氧化铝上的氧化铜。酸气转化过程的合适方法描述于前述并入的US2009/0246120A1中。
酸气转化反应是放热的,因此通常采用换热器(未示出)进行以允许有效使用热能。采用这些特征的转化反应器为本领域的技术人员所熟知。回收的热能来可用于,例如产生蒸汽、使各种工艺料流过热和/或预热锅炉给水以用于其它蒸汽生产操作。合适的转化反应器的例子在前面并入的US7074373中进行描述,但本领域中的技术人员已知的其它设计也是有效的。
如果存在酸气转化并且希望保持一定的一氧化碳含量,可将料流的一部分分离以绕过酸气转化反应器(700)并在进入酸气去除单元(200)之前的某个时刻与富氢气流(54)合并。这在希望回收单独的甲烷副产物时特别有用,因为保留的一氧化碳可随后被甲烷化,如下所述。
污染物去除
(710)
正如本领域的技术人员所熟悉的,合成气流(50)的污染程度将取决于含碳原料的性质和合成气生产条件。例如,石油焦和某些煤可具有高含硫量,从而导致较高的硫氧化物(SOx)、H2S和/或COS污染。某些煤可包含显著量的汞,这些汞可在合成气生产期间挥发。其它原料可能具有高氮含量,从而导致形成氨气、氮氧化物(NOx)和/或氰化物。
通常在酸气去除单元(200)中去除这些污染物中的一些,例如H2S和COS。其它污染物,例如氨气和汞,通常需要在进入酸气去除单元(200)之前移除。
当存在时,特定污染物的污染物去除应从经此处理的清洁气流(56)中去除该污染物的至少大部分(或基本上全部),通常达到或低于所需酸气去除单元(200)或所需最终产物的规格限值。
尽管在图3中,示出气态烃流(84)和冷却合成气流(54)可在进入污染物去除单元(700)之后合并,这仅示出用于举例说明,因为两料流可在进入污染物去除单元(710)之前合并,或分别进行处理以按需进行污染物去除,并随后合并。
污染物去除过程在广义上为相关领域的普通技术人员所熟知,如许多前面并入的参考文献所示。
脱水
(720)
此外,在进入酸气去除单元(200)之前,应对单独或合并的合成气流(50)和气态烃流(84)进行处理以经由脱水单元(720)(和(720a),如果存在)减少残余水分,从而产生脱水料流(58)(和(58a),如果脱水单元(720a)存在)。
合适脱水单元的实例包括分离罐或类似的水分离装置和/或吸水过程,例如二醇处理。
此类脱水单元和过程在广义上同样为相关领域的普通技术人员所熟知。
酸气去除
(200)
根据本发明,至少将合成气流(50)(或中间处理产生的衍生物流)在酸气去除单元(200)进行处理,以去除二氧化碳和其它酸气(例如硫化氢,如果存在),以及产生富酸性二氧化碳流(87)和贫酸气的合成气流,作为贫酸气的产物气流(38)。
任选地,将合成气流(50)和气态烃产物流(84)(或中间处理产生的衍生物流)在酸气去除单元(200)进行共同处理,以去除二氧化碳和其它酸气(例如硫化氢,如果存在),以及产生富酸性二氧化碳流(87)和贫酸气的产物气流(38),其可为由合成气流(50)和气态烃产物流(84)(或中间处理产生的衍生物流)的组合产生的单一料流或由所述两种流衍生的单独料流。参见例如,共同拥有的美国专利申请序列号12/906,552(代理人档案号FN-0055 US NP1,名称为Integrated
Enhanced Oil Recovery Process)和12/906,547(代理人档案号FN-0056 US NP1,名称为Integrated
Enhanced Oil Recovery Process),均提交于2010年10月18日.
如图2和3中所示且在下文进一步所论述的,将合成气流(50)和气态烃产物流(84)进行共同处理以产生富酸性二氧化碳流(87)和合并的贫酸气的气态烃产物流(80)(作为贫酸气的产物气流(38))。
如图4和5中所示且在下文进一步所论述的,将合成气流(50)和气态烃产物流(84)进行共同处理以产生富酸性二氧化碳流(87)和单独的贫酸气的气态烃产物流(31)以及单独的贫酸气的合成气流(30)(贫酸气的产物气流(38))。
酸气去除方法通常包括使气流与溶剂(例如单乙醇胺、二乙醇胺、甲基二乙醇胺、二异丙胺、二甘醇胺、氨基酸的钠盐溶液、甲醇、热碳酸钾等)接触,以产生负载CO2和/或H2S的吸收剂。一种方法可能包括使用具有两个系列的Selexol® (UOP LLC, Des
Plaines, IL USA)或Rectisol®
(Lurgi AG, Frankfurt am Main, Germany)溶剂;每个系列包含H2S吸收剂和CO2吸收剂。
一种去除酸气的方法描述于前面并入的US2009/0220406A1中。
CO2和/或H2S(和其它留下的痕量污染物)的至少大部分(例如基本上全部)应经由酸气去除方法而去除。酸气去除上下文中的“基本上”是指去除足够高百分率的组分使得可产生所需最终产物。因此实际去除量可能因组分各异。有利地,尽管根据所需最终产物可允许较高量的CO2,但应当仅痕量(至多)的H2S存在于贫酸气的产物流中。
通常,基于供给到酸气去除单元(200)的料流中所含的那些组分的量计,应去除至少约85%,或至少约90%,或至少约92%的CO2,以及至少约95%,或至少约98%,或至少约99.5%的H2S。
除富酸性二氧化碳流(87)之外,还可任选地产生产物富酸性二氧化碳流(90),其可经进一步处理以分离CO2和H2S。任何由酸气去除回收的H2S可通过本领域中的技术人员所知的任何方法(包括克劳斯法(Claus
process))转化成元素硫。可将硫作为熔融液体回收。
图
2
和
3
的实施方案
如此前文所示的本实施方案中,合成气流(50)和气态烃流(84)可在进入酸气去除单元(200)之前在各个阶段进行合并,以形成供给到酸气去除单元(200)的合并气流(60),或两料流可在某个时刻在酸气去除单元(200)中进行合并且经共同处理。
所得贫酸气的气态烃产物流(80)将通常包含CH4和H2中的一种或两种、来自气态烃流(84)的其它气态烃以及任选CO(用于下游甲烷化),以及通常不超过污染量的CO2、H2O、H2S及其它污染物。
还产生富酸性二氧化碳流(87),其包含来自合成气流(50)和气态烃流(84)两者的二氧化碳和硫化氢的大部分。还可任选地产生产物富酸性二氧化碳流(90),如上所示。
图
4
和
5
的实施方案
在此实施方案中,将合成气流(50)和气态烃流(84)(或中间处理产生的衍生物流)在酸气去除单元中进行共同处理以去除二氧化碳和其它酸气(例如硫化氢,如果存在),以及产生富酸性二氧化碳流(87)、贫酸气的气态烃产物流(31)和贫酸气的合成气流(30)。
在酸气去除单元中,首先将合成气流(50)和气态烃流(84)分别在第二酸气吸收剂单元(210)和第一酸气吸收剂单元(230)进行单独处理,以产生单独的贫酸气的合成气流(30)和第二富酸气吸收剂流(35),和单独的贫酸气的气态烃产物流(31)和第一富酸气吸收剂流(36)。
所得贫酸气的气态烃产物流(31)将通常包含CH4和来自气态烃流(84)的其它气态烃,以及通常不超过污染量的CO2、H2O、H2S及其它污染物。所得贫酸气的合成气流(30)将通常包含CH4和H2中的一种或两种、任选地CO(用于下游甲烷化),以及通常不超过污染量的CO2、H2O、H2S及其它污染物。
可对所得贫酸气的气态烃产物流(31)和贫酸气的合成气流(30)进行共同处理或单独处理,如下文进一步所述。
将所得第一富酸气吸收剂流(36)和第二富酸气吸收剂流(35)在吸收剂再生单元(250)中进行共同处理,以最终产生酸气流,其包含从合成气流(50)和气态烃流(84)两者去除的合并酸气(和其它污染物)。可将第一富酸气吸收剂流(36)和第二富酸气吸收剂流(35)在进入吸收剂再生单元(250)之前或在其内部进行合并以用于共同处理。产生贫酸气吸收剂流(70),其可根据需要连同补充吸收剂一起循环回到第一酸气吸收剂单元(230)和第二酸气吸收剂单元(210)之一或两者。
还产生富酸性二氧化碳流(87),其包含来自合成气流(50)和气态烃流(84)两者的二氧化碳和硫化氢的大部分。
将富酸性
二氧化碳流
(87)
用于
EOR
在一个实施方案中,将富酸性二氧化碳流(87)用于EOR。
在此实施方案中,回收的富酸性二氧化碳的流(87)全部或部分经由压缩机(400)压缩,以产生用于本发明方法的EOR部分的加压的二氧化碳流(89)。
用于将富酸性二氧化碳流(87)压缩至EOR的适宜的压力和条件的合适压缩机在广义上为相关领域的普通技术人员所熟知。
对贫酸气
产物流的任选的进一步处理
可将贫酸气的产物气流(38)(图1)、贫酸气的气态烃产物流(80)(图2和3),或贫酸气的合成气流(30)和贫酸气的气态烃产物流(31)(图4和5)(单独地,或全部或部分合并)的全部或一部分处理成各种最终产物或用于各种最终用途,如相关领域的普通技术人员所熟知。
下文参照图3和5对非限制性选择进行论述。尽管图3和5仅示出用于贫酸气的气态烃产物流(80)和贫酸气的合成气流(30)的选择中的某些,但这些选择(及其它选择)在适当的情况下可用于贫酸气的气态烃产物流(31)(或合并流)。
氢气分离
(730)
可根据本领域的技术人员已知的方法(例如低温蒸馏、使用分子筛、气体分离(例如陶瓷或聚合物)膜和/或变压吸附(PSA)技术)从贫酸气的气态烃产物流(80)或贫酸气的合成气流(30)的全部或部分分离出氢气。
在一个实施方案中,利用PSA装置进行氢气分离。用于将氢气与包含甲烷(和任选的一氧化碳)的气体混合物分离的PSA技术通常为相关领域的普通技术人员所熟知,如例如US6379645(及其中参考的其它引文)中所公开。PSA装置通常是市售的,例如基于得自Air
Products and Chemicals Inc. (Allentown, PA), UOP LLC (Des Plaines, IL)和其它公司的技术。
在另一个实施方案中,可使用氢气膜分离器,然后使用PSA装置。
此类分离提供高纯度氢气产物流(72)和贫氢气流(74)。
回收的氢气产物流(72)的纯度优选为至少约99摩尔%,或至少99.5摩尔%,或至少约99.9摩尔%。
回收的氢气可例如用作能源和/或用作反应物。例如,氢气可用作氢燃料电池,或例如发电模块(760)中发电和/或蒸汽生产的能源。氢气还可用作各种氢化过程(例如存在于化学和石油炼制工业中的氢化过程)中的反应物。
贫氢气流(74)将基本上包含轻质烃(例如甲烷)以及任选的微量一氧化碳(主要取决于酸气转化反应和分流的程度)、二氧化碳(主要取决于酸气去除方法的效率)和氢气(主要取决于氢气分离技术的程度和效率),并且可按如下所述进行进一步处理/利用。
甲烷化
(740)
如果贫酸气的气态烃产物流(80)或贫酸气的合成气流(30)(或贫氢气的脱硫气流(74))包含一氧化碳和氢气,可将该料流的全部或部分供给到(修整)甲烷化单元(740),以由一氧化碳和氢气(见上式(III))产生额外的甲烷,从而得到富甲烷气流(75)。
甲烷化反应可在任何合适的反应器(例如单级甲烷化反应器、一系列单级甲烷化反应器或多级反应器)中进行。甲烷化反应器包括但不限于固定床、移动床或流化床反应器。参见例如US3958957、US4252771、US3996014和US4235044。甲烷化反应器和催化剂通常可商购获得。用于甲烷化的催化剂和甲烷化条件通常为相关领域的普通技术人员所知,并且将取决于例如进气流的温度、压力、流速和组成。
由于甲烷化反应是放热的,富甲烷气流(75)可例如进一步提供至热交换单元(750)。虽然热交换单元(750)被示为独立单元,但其可以此形式存在和/或结合到甲烷化单元(740)中,因此能够冷却甲烷化单元(740)并除去富甲烷流(75)中热能的至少一部分,以降低温度并产生冷却的富甲烷流(76)。例如,可利用回收的热能由水和/或蒸汽源产生工艺蒸汽流。
富甲烷流(75)的全部或部分可作为甲烷产物流(77)回收,或可在需要时通过本领域的技术人员已知的任何合适的气体分离方法包括但不限于低温蒸馏、使用分子筛或气体分离(如陶瓷)膜对其进行进一步处理,以分离和回收CH4。
管道质量天然气
(Pipeline-Quality Natural Gas)
在某些实施方案中,贫酸气的烃流(80),或贫酸气的合成气流(30),或贫酸气的气态烃产物流(31),或贫酸气的合成气流(30)与贫酸气的气态烃产物流(31)的组合,或贫氢气流(74)和/或富甲烷气流(75)为“管道质量天然气”。“管道质量天然气”通常指天然气,其(1)热值在纯甲烷(其在标准大气条件下的热值为1010btu/ft3)热值的±5%范围内;(2)基本上不含水(通常具有约-40℃或更低的露点);和(3)基本上不含毒性或腐蚀性污染物。
气态烃产物流的用途
上述料流的全部或部分可例如用于在发电模块(760,
760a)中燃烧和/或产生蒸汽,以产生可在工厂中利用或可在电网上出售的电能(79,
79a)。
这些料流的全部或部分还可用作循环烃流(78),例如用作气体部分氧化/甲烷转化方法中的含碳原料(10),或用于产生加氢甲烷化方法(例如,气体部分氧化/甲烷转化方法)中使用的合成气进料流(12)。这些用途均可(例如)最终使氢气产物流(72)和富酸性二氧化碳流(87)的产量得以优化。
发电模块
(760, 760a)
如上文所详述,本方法可与发电模块(760, 760a)整合以产生作为整合方法产物的电能(79, 79a)。发电模块(760, 760a)的构造与整体煤气化联合循环(IGCC)应用中通常所用的构造类似。
其它具体实施方案的实施例
在一个实施方案中,将含甲烷流用作含碳原料,通过催化蒸汽甲烷转化方法来生产合成气流。
在另一个实施方案中,将含甲烷流用作含碳原料,通过非催化(热)气体部分氧化过程来生产合成气流。
在另一个实施方案中,将含甲烷流用作含碳原料,通过催化自热转化方法来生产合成气流。
用于这些方法中的含甲烷流可为天然气流、合成天然气流或其组合。在一个实施方案中,含甲烷流包含贫酸气的气态烃产物流(或这些料流经下游处理后的衍生物)的全部或部分。
从这些方法得到的合成气流将包含至少氢气以及一氧化碳和二氧化碳中的一种或两种(取决于酸气去除之前的气体处理)。
在另一个实施方案中,将非气态含碳物质用作含碳原料(例如煤、石油焦、生物质及其混合物),通过非催化热气化方法来生产合成气流。
从此方法得到的合成气流将包含至少氢气以及一氧化碳和二氧化碳中的一种或两种(取决于酸气去除之前的气体处理)。
在另一个实施方案中,将非气态含碳物质用作含碳原料(例如煤、石油焦、生物质及其混合物),通过催化加氢甲烷化方法来生产合成气流。
从此方法所得的合成气流将包含至少甲烷、氢气和二氧化碳以及任选一氧化碳(这取决于酸气去除之前的气体处理)。
Claims (10)
1.一种用于(i)产生贫酸气的烃产物气流,(ii)经由烃生产井从地下油气藏产生含烃流体以及(iii)提高得自所述地下油气藏的所述含烃流体的产量的整合方法,所述方法包括以下步骤:
(1)将加压的酸性二氧化碳流注入所述地下油气藏中以提高经由所述烃生产井得自所述地下油气藏的所述含烃流体的产量;
(2) 回收产自所述烃生产井的所述含烃流体;
(3)将所述含烃流体分离成(a)液体烃产物流和(b)任选包含硫化氢的气态烃产物流;
(4)由含碳原料生产合成气流,所述合成气流包含(a)一氧化碳和二氧化碳中的至少一种、(b)氢气和甲烷中的至少一种,和(c)任选硫化氢;
(5)在酸气去除单元中对所述合成气流和任选所述气态烃产物流进行处理,以产生所述贫酸气的烃产物气流和酸性二氧化碳流;
(6)对所述酸性二氧化碳流进行加压以产生所述加压的酸性二氧化碳流,
其中(i)所述合成气流和所述气态烃产物流中的至少一种包含超过痕量的硫化氢,和(ii)如果所述气态烃产物流包含超过痕量的硫化氢,则在所述酸气去除单元中对所述合成气流和所述气态烃产物流进行处理以产生所述贫酸气的烃产物气流和所述酸性二氧化碳流。
2.根据权利要求1所述的方法,其特征在于,所述合成气流是将含甲烷流用作所述含碳原料通过催化蒸汽甲烷转化方法来生产,或所述合成气流是将含甲烷流用作所述含碳原料通过非催化气体部分氧化方法来生产或所述合成气流是将含甲烷流用作所述含碳原料通过催化自热转化方法来生产。
3.根据权利要求1或权利要求2所述的方法,其特征在于,所述合成气流是将非气态含碳物质用作所述含碳原料通过非催化热气化方法来生产。
4.根据权利要求1-3中任一项所述的方法,其特征在于,所述合成气流包含氢气以及一氧化碳和二氧化碳中的一种或两种。
5.根据权利要求1所述的方法,其特征在于,所述合成气流是将非气态含碳物质用作所述含碳原料通过催化加氢甲烷化方法来生产。
6.根据权利要求1或权利要求5所述的方法,其特征在于,所述合成气流包含甲烷、氢气和二氧化碳以及任选一氧化碳。
7.根据权利要求1-6中任一项所述的方法,其特征在于,在所述酸气去除单元中对所述气态烃产物流进行处理。
8.根据权利要求7所述的方法,其特征在于,所述贫酸气的产物气流包含贫酸气的气态烃产物流和贫酸气的合成气流。
9.一种用于产生含烃流体和贫酸气的烃产物气流的设备,所述设备包括:
(A)适于由含碳原料生产合成气的合成气生产系统,所述合成气包含(i)一氧化碳和二氧化碳中的至少一种、(ii)氢气和甲烷中的至少一种以及(iii)任选硫化氢;
(B)与包含含烃流体的地下油气藏流体连通的注入井,所述注入井适于将加压的酸性二氧化碳流注入所述地下油气藏中以进行强化采油;
(C)与所述地下油气藏流体连通的烃生产井,所述烃生产井适于去除所述地下油气藏中的含烃流体;
(D)与所述烃生产井流体连通的分离装置,所述分离装置适于(i)接收来自所述烃生产井的所述烃类流体,和(ii)将所述烃类流体分离成液体烃产物流和任选包含硫化氢的气态烃产物流;
(E)与所述合成气生产系统和任选所述分离装置流体连通的酸气去除单元,所述酸气去除单元适于(i)接收来自所述合成气生产系统的所述合成气和任选来自所述分离装置的所述气态烃产物流,和(ii)对所述合成气和任选所述气态烃产物流进行处理以去除酸气并产生所述贫酸气的烃产物气流和酸性二氧化碳流;和
(F)与所述酸气去除单元和所述注入井流体连通的压缩机单元,所述压缩机单元适于(i)接收所述酸性二氧化碳流,和(ii)压缩所述酸性二氧化碳流以产生所述加压的酸性二氧化碳流,以及(iii)向所述注入井提供所述加压的酸性二氧化碳流。
10.根据权利要求9所述的设备,其特征在于,所述酸气去除单元适于接收所述合成气和所述气态烃产物流的合并流,并对所述合并流进行处理以去除酸气并产生贫酸气的烃产物气流和酸性二氧化碳流。
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CN111536504A (zh) * | 2020-05-09 | 2020-08-14 | 江苏亦通石油科技有限公司 | 一种以石油焦为燃料的石油热采多元热流体发生系统 |
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AU2010339952A1 (en) | 2012-07-12 |
AU2010339952B2 (en) | 2013-11-14 |
WO2011084580A2 (en) | 2011-07-14 |
AU2010339952B8 (en) | 2013-12-19 |
US8733459B2 (en) | 2014-05-27 |
WO2011084580A3 (en) | 2012-01-12 |
CA2780375A1 (en) | 2011-07-14 |
US20110146979A1 (en) | 2011-06-23 |
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