CN1430699A - 处理含烃岩层的方法 - Google Patents

处理含烃岩层的方法 Download PDF

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CN1430699A
CN1430699A CN01810165A CN01810165A CN1430699A CN 1430699 A CN1430699 A CN 1430699A CN 01810165 A CN01810165 A CN 01810165A CN 01810165 A CN01810165 A CN 01810165A CN 1430699 A CN1430699 A CN 1430699A
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rock stratum
hydrocarbon
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CN1263939C (zh
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I·E·伯肯克
K·A·玛尔
E·德鲁菲格纳克
H·J·万嘉
S·L·威灵顿
E·张
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Shell Internationale Research Maatschappij BV
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    • EFIXED CONSTRUCTIONS
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    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
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    • C09K8/58Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/592Compositions used in combination with generated heat, e.g. by steam injection
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    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B36/00Heating, cooling, insulating arrangements for boreholes or wells, e.g. for use in permafrost zones
    • E21B36/001Cooling arrangements
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    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B36/00Heating, cooling, insulating arrangements for boreholes or wells, e.g. for use in permafrost zones
    • E21B36/04Heating, cooling, insulating arrangements for boreholes or wells, e.g. for use in permafrost zones using electrical heaters
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B41/00Equipment or details not covered by groups E21B15/00 - E21B40/00
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    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E21B43/2401Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection by means of electricity
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E21B43/243Combustion in situ
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    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/24Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
    • E21B43/243Combustion in situ
    • E21B43/247Combustion in situ in association with fracturing processes or crevice forming processes
    • EFIXED CONSTRUCTIONS
    • E21EARTH DRILLING; MINING
    • E21BEARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/30Specific pattern of wells, e.g. optimizing the spacing of wells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/582Recycling of unreacted starting or intermediate materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S48/00Gas: heating and illuminating
    • Y10S48/06Underground gasification of coal

Abstract

本发明提供一种从含烃地下岩层生产合成气的方法,所述的方法包括:给至少一部分地下岩层供热,以致至少一部分受热部分达到油母质的热解温度,生成热解产物;从地下岩层收集热解产物;将合成气生产用组分注入岩层的受热部分,通过合成气生产用组分与残留在岩层中的含碳质材料反应生产合成气;以及回收合成气。如此生产的合成气可用于费-托合成,用于氨、尿素、甲醇、甲烷和其他烃类的制备或用作能源,例如在燃料电池中。可将合成气应用中生成的二氧化碳隔绝在岩层中。

Description

处理含烃岩层的方法
本发明涉及一种从各种含烃岩层生产烃类和一氧化碳和/或氢的方法。
从地下岩层得到的含烃物质常常用作能源、原料和消费产品。对可获得的烃类资源枯竭的关注已导致开发各种更有效的开采、加工和利用可获得的烃类资源的方法。就地加工方法可用于从地下岩层中除去烃类物质。可能需要改变地下岩层中烃类物质的化学和/或物理性质,使烃类物质更容易从地下岩层中除去。化学和物理变化可包括产生可除去的流体的就地反应、岩层内烃类物质的溶解性变化、相变化和/或粘度变化。流体可为但不限于气体、液体、乳液、浆液和/或流动特性类似液体流的固体颗粒流。
例如,在US-A-2923535和US-A-4886118中公开了热用于油页岩岩层。对油页岩岩层加热,使油页岩岩层内的油母质热解。热也可使岩层断裂,以便提高岩层的渗透率。增加的渗透率可使烃类流体转移到从油页岩岩层除去流体的生产井。在US-A2923535的方法中,将含氧的气体介质送入可渗透的岩层,优选同时还引入由预热步骤产生的热,以便引发燃烧,生成更多的烃类蒸汽和液体产物。
可将含烃岩层中一部分初始的有机碳含量即其中进行热解的部分转变成烃类流体。显然,油母质热解以后,热的碳质材料仍留在岩层中。现已发现,受热的岩层可用来生产合成气。
因此,本发明提供一种从含烃地下岩层生产合成气的方法,所述的方法包括:
将热供给至少一部分地下岩层,以便使至少一部分受热的部分达到油母质的热解温度,生成热解产物;
收集地下岩层的热解产物;
将合成气生成用组分注入岩层的受热部分,通过合成气生成用组分与岩层中的碳质材料反应生成合成气;以及
回收合成气。
通常,合成气定义为氢和一氧化碳的混合物;但是,它也可含有另外的组分,例如水、二氧化碳、甲烷和其他气体。合成气由留在含烃岩层中的烃类生产。热裂常常使整个含烃岩层或其热裂的部分产生相对高的基本上均匀的渗透性。这样的相对高的基本上均匀的渗透性能以低的注入费用和岩层主要部分最小的分支和旁路来生产合成气。这一部分还有大的表面积和/或大的表面/体积比。在合成气生产过程中,大的表面积能合成气生产反应基本上处于平衡条件下。与未经热解的含烃岩层中的合成气生产相比,相对高的基本上均匀的渗透性可得到相对高的合成气回收率。在合成气生产用流体与岩层接触以前,可将岩层加热到400℃以上。合成气生产用流体例如水和/或二氧化碳与岩层中的碳和/或烃类物质接触生成合成气,如果含碳材料的温度足够高的话。合成气的生产通常为吸热过程。在合成气生产过程中,宜将外加的热加到岩层中,以便在岩层中维持高温。热量可从加热器井和/或从岩层中碳和/或烃类的氧化加入。生成的合成气可通过一个或多个生产井从岩层中除去。
合成气生产可在热裂产物生产降到不经济的水平以前和/或以后进行。用这种方法,提供给热解的热也可用于生产合成气。例如,如果在热解以后一部分岩层为270-375℃,那么为了将这一部分加热到足以支持合成气生产的温度,通常需要较少的外加热量。
在某些实施方案中,至少一些含烃材料的热解使约20%可利用的初始碳转化。合成气的生产可转化这部分中大约高达70%可利用的初始碳。用这一方法,从含烃岩层就地生产合成气可使这部分中更大数量的可利用初始碳转化。
一些实施方案包括从一个或多个热源供热,加热到足以能生产合成气的温度。至少一部分用于生产合成气的岩层的温度宜升至合成气生产用温度(例如400-1200℃)。生产的合成气的组成可能受岩层温度的影响,还受与合成气生产井相邻的岩层温度的影响。相对低的合成气生产温度得到高H2/CO比的合成气,但生成的合成气还可能含有大量的其他气体,例如水和CO2。相对高的岩层温度得到H2/CO比接近1的合成气,以致物流可主要含有(在一些情况下基本上只含有)H2和CO。在岩层温度为约620℃下,岩层可得到H2/CO比为2的合成气。
合成气生产用热源包括任何类型的热源,如下文所述。另一方面,加热包括热从传热流体例如水蒸汽或燃烧器得到的燃烧产物流到岩层中的许多井身。在合成气生产过程中,热源和/或岩层内用于热解和从岩层生产热解流体的生产井可用于不同的目的。用作热源的井或热解过程中的生产井可用作注入井,将合成气生产用流体注入岩层。用作热源的井或热解过程中的生产井可用于合成气生产过程中的生产井。用作热源的井或热解过程中的生产井可用作热源,在合成气生产过程中使岩层加热。由于相对高的基本上均匀的岩层渗透性,合成气生产井可远离热解生产井。宜将合成气生产井加热到相对高的温度,以致相邻生产的一部分岩层处于这样一温度,以便得到所需的合成气组成。相比较,热解流体生产井根本不加热,或仅可加热到这样一温度,以便防止热解流体在生产井中冷凝。热源之间的距离通常可为5-20米、优选8-15米。
合成气生产用流体例如液体水、水蒸汽、二氧化碳、空气、氧、烃类及其混合物可提供给岩层。例如,合成气生产用流体混合物可包含水蒸汽和氧。在一实施方案中,合成气生产用流体包含在岩层的一个或多个其他部分内的至少一些含烃物质热解生成的水。条件是合成气生产用流体可包含岩层的地下水面升高,使它流入岩层。合成气生产用流体也可通过注入井提供。合成气生产用流体通常与岩层中的碳反应生成H2、水、CO2和/或CO。一部分二氧化碳倾向于与岩层中的碳反应,生成一氧化碳。可将烃类例如C2-C6烷烃例如乙烷加到合成气生产用流体中。当加到岩层中时,烃类可裂化生成氢和/或甲烷。在生产的合成气中甲烷的存在使生成的合成气的热值增加。
合成气生成反应通常为吸热反应。在一实施方案中,将氧化剂加到合成气生产用流体中。氧化剂包括但不限于空气、富氧的空气、氧、过氧化氢、其他氧化用流体或其组合物。在一实施方案中,在连续生产中希望使用氧而不是空气作为氧化用流体。如果使用空气,一个缺点可能是,可能需要从合成气中分离氮气。由于制备基本上纯的氧的费用,使用氧作为氧化用流体可能增加生产费用。但是,从用于生产所需氧的空气分离装置得到的氮气副产物可用于换热器,以便从烃类热解过程中生产的热蒸汽物流中冷凝烃类。不过,氧化剂仍优选为空气。氧化剂可与岩层中的碳反应,放出热量。氧化剂与岩层中碳的反应可生产CO2和/或CO。氧化剂的送入并与岩层中的碳反应可经济地使岩层的温度升高到足以由岩层中的碳生成大量H2和CO。
合成气的生产可通过间歇法或连续法进行,正如在这里进一步描述的。合成气可由一个或多个有一个或多个热源的生产井生产。这样的热源可促进有所需组成的合成气的生产。
某些实施方案包括监测生产的合成气的组成,然后控制加热和控制合成气生产用流体的输入量,以便使生产的合成气的组成维持在所需的范围。例如,对于某些应用来说,生产的合成气的氢/一氧化碳比优选为约2∶1。
合成气可在宽的温度范围内生产,例如400-1200℃、更通常600-1000℃。在相对低的合成气生产温度下,可生产有高H2/CO比的合成气。相对高的岩层温度可生产H2/CO比接近1的合成气,而且物流主要为(在某些情况下基本上只为)H2和CO。在约700℃的岩层温度下,所述的岩层可生产H2/CO比为2的合成气。通常,可生产H2/CO摩尔比为1∶4至8∶1、更通常1∶2至4∶1,特别是1∶1至2.5∶1的合成气。某些实施方案可包括第一种合成气与第二种合成气混合,生产所需组成的合成气。第一种和第二种合成气可由不同部分的岩层生产。
这里所述的合成气可用于各种用途。例如可将合成气转化成较重的可凝烃类。例如,可用费-托烃类合成方法将合成气转化成分支的和未分支的C1-C30烷烃。由费-托合成法生产的烷烃可用于生产其他产品,例如柴油、喷气燃料和石脑油产品。生产的合成气也可用于催化甲烷化法生产甲烷。另一方面,生产的合成气可用于生产甲醇、汽油和柴油、氨和中间镏分油。合成气在费-托合成法中转化成烃类的方法的例子在U S-A-4096163、US-A-6085512、US-A-6172124和US-A-4594468中说明。催化甲烷化法的例子在US-A-3992148、US-A-4130575和US-A-4133825中说明。用于生产甲醇的方法的例子在US-A-4407973、US-A-4927857和US-A-4994093中说明。用于生产发动机燃料的方法的例子在US-A-4076761、US-A-4138442和US-A-4605680中说明。
生产的合成气也可作为燃烧燃料用于加热岩层。生产的合成气中的氢可用于油品改质。在另一些实施方案中,生产的合成气用作生产氨和尿素的进料气体。
合成气也可用于其他一些用途。它可作为燃料燃烧。合成气可通过在涡轮中降低其压力和/或利用合成气的温度来生产水蒸汽(然后驱动涡轮)来生产电力。合成气也可用于产能单元例如熔体碳酸盐燃料电池或其他类型燃料电池、涡轮、锅炉燃烧室或井下气体加热器。熔体碳酸盐燃料电池(“MCFC”)使用熔体碳酸盐混合物作为电解质。可改变电解质的组成。典型的电解质可含有碳酸锂和碳酸钾。在约600-650℃的操作温度下,电解质为液体和良好的离子导体。可将电解质悬浮在多孔的、绝缘的和化学惰性的陶瓷基质中。生成的电能可供给高压电力网。一部分生成的电力适合给电加热元件供能,以便使岩层加热。在一实施方案中,能量产生单元为锅炉燃烧室。燃烧室包括一完全或部分以窑壁建成的小型难熔衬里室,用于燃料燃烧。将空气或氧送入能量产生单元,以便使生成的合成气氧化。合成气氧化生成的水最好循环回岩层,以便生产更多的合成气。
生产的合成气也可在井下气体加热器中用作燃料。井下气体加热器例如这里所述的无焰燃烧器可用来加热含烃岩层。用这一方法,热传导过程基本上自行解决和/或大大减少或基本上不需要电力。因为无焰燃烧器的热效率接近90%,所以排放到环境中的二氧化碳量常常低于使用化石燃料生产的电力来加热含烃岩层的方法排放到环境中的二氧化碳量。
用于能量产生单元的合成气组成的H2/CO比可为约8∶1至12∶1(例如10∶1)。但是,低H2/CO比的合成气适用于能量生产。
某些实施方案包括从岩层内至少一些含烃材料的热解生产的流体中分离出燃料电池进料物流。燃料电池进料物流可含有H2和烃类。此外,某些实施方案可包括将燃料电池进料物流送入燃料电池,以便生产电力。在燃料电池中,由合成气或热解流体产生的电力最好用于电力加热器,后者用来加热至少一部分岩层。某些实施方案包括从燃料电池排出的流体中分离出二氧化碳。由燃料电池或岩层生产的二氧化碳可用于各种用途。
在一实施方案中,可将经过热解的和/或已生产合成气的一部分岩层冷却,在岩层内形成经冷却的废弃部分。例如,经加热的岩层部分可通过将热量传递给相邻的岩层部分而冷却。传热可自然地发生,也可通过送入传热流体,使它通过受热部分流入岩层较冷的部分来强制完成。另一方面,将水送入岩层的第一部分可使第一部分冷却。送入第一部分的水可作为水蒸汽从岩层中取出。可将取出的水蒸汽注入热的岩层部分用来生产合成气。使岩层冷却有某些好处,其中包括使岩层中岩石的强度提高,从而减缓岩层的下沉和提高岩层的吸收容量。
在生产热解流体和/或合成气以后,可将流体(例如二氧化碳)隔绝在岩层中。为了在岩层内贮存大量的流体,常常需要使岩层的温度小于约100℃。可将水送入至少一部分岩层,以便生产水蒸汽和降低岩层的温度。可将水蒸汽从岩层中取出。水蒸汽可用于各种用途,包括但不限于加热岩层的其他部分,在相邻的岩层部分生产合成气以及在贮油层中作为水蒸汽驱。在岩层冷却以后,可给流体(例如二氧化碳)加压,并隔绝在岩层内。将流体隔绝在岩层内可显著减少或消除由于就地转化过程排放到环境中的流体。
用于隔绝二氧化碳的方法的例子在US-A-5566756中说明。宜在压力下将二氧化碳注入经冷却的废弃的岩层部分。注入的二氧化碳可吸收到岩层的含烃材料中。二氧化碳可在热解、合成气生产和/或有用能量提取过程中产生。随后将水加到岩层中可抑制二氧化碳的解吸。在一实施方案中,生成的岩层流体被贮存在冷却的废弃的岩层部分中。在一些实施方案中,二氧化碳被贮存在相对深的煤层中,并用来脱附煤层的甲烷。
含烃岩层可从任何含烃类的地下资源中选择。这些岩层包括煤、油页岩、油砂、高粘度的重质烃类、含沥青岩层等。
优选的是,用于本发明的含烃岩层含有油母质。油母质为由于熟化过程转变成的有机物。含有油母质的含烃岩层例如为含煤岩层和含油母页岩岩层。另一方面,可处理不含油母质的含烃岩层,例如含重质烃类的岩层(例如油砂)。
可在至少一部分岩层的性质基础上选择用于就地处理的含烃岩层,以便从岩层生产高质量的流体。例如,可在油母质的镜质体反射的基础上评价或选择用于处理的含油母质的含烃岩层。镜质体反射常常与油母质的氢/碳元素比和氧/碳元素比有关。优选的是,镜质体反射为0.2-3.0%,更优选0.5-2.0%。这样的镜质体反射范围常常表明从岩层可生产相对高质量的烃类流体。
可在含烃岩层中烃类的元素氢含量的基础上来选择用于处理的含烃岩层。例如,一种处理含烃岩层的方法通常可包括选择含有元素氢含量大于2%、特别是大于3%、更特别是大于4%(重量)的烃类的处理用含烃岩层(按无法干基计)。优选的是,含烃岩层含有氢/碳元素比为0.5-2,特别是0.70-1.7的油母质。元素氢含量可显著影响生成的烃类流体的组成,例如可通过生成氢分子。
正如上述实施方案中任一个描述的,由于处理至少一部分含烃岩层,烃类的除去也可在微观规模出现。由于加热,烃类可从这部分内的含烃材料的微孔中除去。微孔通常规定为截面尺寸小于约1000埃的孔。用这种方法,烃类这样的除去可使至少所选的受热部分内的孔隙率基本上均匀地增加。正如上述实施方案中任何一个描述的,将这部分含烃岩层加热可使受热部分内所选部分的孔隙率基本上均匀地增加。在本发明中,“基本上均匀的孔隙率”指岩层内任何所选部分的评价的(例如计算的或估计的)孔隙率变化不超过这些所选部分的平均孔隙率的10倍。
可将含烃岩层加热到可发生热解的温度。热解温度范围可包括例如一直到900℃的温度。大部分烃类流体可在250-400℃,更优选260-375℃的热解温度范围内生产。足以使相对低渗透性的含烃岩层中的重质烃类热解的温度可为270-300℃。在其他一些实施方案中,足以使重质烃类热解的温度可为300-375℃。如果在整个热解温度范围内加热含烃岩层,那么岩层只能生产相对热解温度范围的上限的少量氢。可利用的氢耗尽以后,仅可从岩层生产很少的烃。
根据本发明,在热解和从岩层生产烃类流体的过程中控制压力。通常,使用至少1.0巴的压力、更通常至少1.5巴、特别是至少1.8巴。特别是,当热解温度为至少300℃时,可使用至少1.6巴的压力;压力的上限可由复盖层的结构和重量来确定。常常是,在实际条件下,压力小于70巴、更常常小于60巴或甚至小于50巴。可将压力很好地控制在2-18巴或2-20巴的范围内,或者另一方面控制在20-36巴范围内。
在一优选的实施方案中,正如上文所述,将维持一定的氢分压。通常,氢分压为至少0.5巴例如一直到20巴,更优选1-10巴、特别是5-7巴。在岩层内维持氢分压特别是使生产的烃类流体的API重度增加以及使长链烃类流体的产量减少。
热解以后,一部分含烃岩层的物理特性可类似于多孔床层的物理特性。例如,热解后的一部分含烃岩层可含有粒度为约几毫米的颗粒。这样的物理特性可能不同于注入气体使含烃岩层燃烧以便加热含烃材料的含烃岩层的物理特性。注入到未用过的或断裂的岩层的气体常常产生孔道并且不能均匀地在整个岩层分布。相反,注入到经热解的含烃岩层部分的气体可很容易和基本上均匀地接触残留在岩层中的含烃材料。此外,加热含烃材料产生的气体可在已加热的岩层部分转移很长的距离,有很小的压力损失。例如,在处理很深的含烃岩层中,这样的气体转移是特别有用的。
在一实施方案中,将其他组分与水蒸汽一起注入到岩层中可改变生成的合成气的组成。可将二氧化碳加在合成气生产用流体中,以便基本上抑制在合成气生产过程中从岩层生成的二氧化碳。二氧化碳可变更由岩层的碳生成二氧化碳的平衡,从而减少由岩层碳生成的二氧化碳数量。二氧化碳也可与岩层中的碳反应,生成一氧化碳。可将二氧化碳从合成气中分离出来,并与合成气生产用流体一起再次注入到岩层中。
在合成气生产过程中,可将含烃岩层的压力维持在相对高的压力。压力可为常压至岩层的静岩压力。因此,合成气可在宽的压力范围内生产,例如1-100巴、更通常2-80巴、特别是5-60巴。高的操作压力使H2的产量增加。高的操作压力可借助生成的合成气通过涡轮产生电力,并可用更小的收集导管来输送生产的合成气。
合成气可通过间歇注入或连续注入来生产。在间歇操作中,氧化用流体例如空气或氧可通过井口注入岩层。含烃材料的氧化可使一部分岩层加热。空气或氧的注入可持续到这部分岩层的平均温度达到所需的温度为止,例如约900至约1000℃。也可使用更高或更低的温度。在注入井和回收合成气的生产井之间的这部分岩层中可形成温度梯度。温度梯度中最高的温度可靠近注入井口。
当达到所需的温度时,或当氧化用流体已注入所需的时间时,可停止注入氧化用流体。然后可将合成气生产用流体例如水蒸汽或水注入不同的注入井,以便生产合成气。在注入井中,注入的水蒸汽或水的背压可强制生成的合成气和未反应的水蒸汽通过这一部分岩层。可通过注入氧化用流体的井眼生产产物流。如果产物的组成与所需的组成有很大差别,那么可停止注入水蒸汽,并再次注入空气或氧。
在连续操作中,可同时将氧化用流体和合成气生产用流体注入注入井,而在生产井生产合成气。例如,可按所需的比例(例如1∶2至1∶4)连续将氧和水蒸汽注入。
实施例1
通过在一部分含煤岩层中进行的就地实验,从一部分含煤岩层生产烃类流体。煤为高挥发性沥青C煤。它用电加热。现场实验体系至少包括在水泥壁内的含煤岩层。含煤岩层倾斜约36°角,截距厚约4.9米。三个热源,两个生产井和四个温度观测井用于现场实验体系。三个热源按三角形放置,每边间隔2米。一个中央生产井靠近热源图形的中心,与每一热源等距。第二个外生产井位于热源图形的外部,并与两个最近的热源等距。在热源图形和生产井周围形成水泥壁。水泥壁有柱状物,以便在就地实验过程中防止水流入该部分以及显著减少生成的烃类流体进入未加热的岩层部分造成的损失。
在实验过程中,在四个温度观测井中的每一个在不同的时间测量温度。将岩层在低于400℃的温度下加热3个月。通过中央生产井从岩层生产气体和液体。在热解阶段中,生成4桶油和282000标英尺3气体。在热解过程中,总的油当量桶为31.5 BOE。整个热解阶段持续134天。
随后,在一部分含煤岩层中生产合成气。在这一实验中,加热器井也用来注入和生产流体。在大约77000千瓦小时能量输入后开始合成气生产。在合成气生产过程中,在热解部分中煤的平均温度为约620℃。在合成气生产阶段生产约243000标英尺3气体。在合成气生产阶段生成的总油当量桶为6.9BOE。生产的合成气中所含的可利用能量小于热解流体中所含的可利用能量。由于以下两个原因,合成气生产的能效低于热解。首先,合成气反应产物的能量含量比热解中生产的低碳数烃类低。其次,吸热的合成气反应消耗一部分能量。
由于流入热的含煤岩层的天然水的存在,在水或水蒸汽注入以前,在合成气生产温度下,在岩层中可生成合成气。天然水可来自下面的岩层。在现场实验中,天然水的最大流入量为约5公斤/小时。将水分别以约2.7公斤/小时、5.4公斤/小时和11公斤/小时的速率注入中央生产井。在三个加热器井生产合成气。在水的总输入量超过7.7公斤/小时下每单位体积的注入水生成的合成气量不变,并在约2.7公斤/小时注入水量或7.7公斤/小时水的总输入量下开始下降。下降的原因是,水蒸汽通过含煤层流动太快,与岩层达到反应平衡,表明注入的水与约2.7公斤/小时注入水量或7.7公斤/小时水的总输入量的岩层处于反应平衡。
第二个实验对应于在一个加热器井注入水蒸汽和在中央生产井生产另外的气体。第二个实验得到基本上相同数量的另外的合成气。此外,在更高的注入速率下生产开始偏离平衡,因为停留时间不足以使另外的水与煤反应。随着温度升高,对于一定的注入水速率,可生成更大数量的另外合成气。原因在于,在较高的温度下,水生成合成气的反应速率和转化率都提高。
表I
    组分     %(摩尔)     %(重量)
甲烷     12.263     12.197
乙烷     0.281     0.525
乙烯     0.184     0.320
乙炔     0.000     0.000
丙烷     0.017     0.046
丙烯     0.026     0.067
丙二烯     0.001     0.004
丁烷     0.001     0.004
正丁烷     0.000     0.001
1-丁烯     0.001     0.003
异丁烯     0.000     0.000
顺-2-丁烯     0.005     0.018
反-2-丁烯     0.001     0.003
1,3-丁二烯     0.001     0.005
异戊烷     0.001     0.002
正戊烷     0.000     0.002
戊烯-1     0.000     0.000
反-2-戊烯     0.000     0.000
2-甲基-2-丁烯     0.000     0.000
顺-2-戊烯     0.000     0.000
己烷     0.081     0.433
H2     51.247     6.405
CO     11.556     20.067
CO2     17.520     47.799
    5.782     10.041
    0.955     1.895
硫化氢     0.077     0.163
合计     100.000     100.00
实验以间歇方式在约620℃下进行,由电加热器提供加热。氮和氧的存在是由于空气对样品的污染。H2、CO和CO2的摩尔百分数(不计所有其他物质的组成)可由上述数据来确定。例如,H2、CO和CO2的摩尔百分数可按比例增加,以致三个组分的摩尔百分数等于约100%。用这一方法,H2、CO和CO2的摩尔百分数(不计所有其他物种的组成)分别为63.8%、14.4%和21.8%。据认为甲烷主要来自加热器三角形外的热解部分。
将甲烷注入热煤中来进行实验。将甲烷注入中央生产井,从三个加热器井生产流体。在不同井中测量的平均温度如下:加热器井分别为746℃、746℃和767℃,而外生产井和中央生产井分别为606℃和769℃。当甲烷与岩层接触时,它可在岩层内裂化生成H2和焦炭。随着甲烷注入速率提高,H2的产量增加,表明甲烷裂化生成H2。甲烷的产量也增加,这表明不是所有注入的甲烷都裂化。测量的乙烷、丙烷和丁烷的组成可忽略不计。H2可用于燃料电池来生产电能。任何未裂化的甲烷可从H2中分离出来,并再次注入岩层。
在一分开的实验中,将乙烷注入中央生产井,并从三个加热器井生产流体。在不同井中测量的平均温度如下:加热器井分别为742℃、750℃和744℃,而外生产井和中央生产井分别为626℃和818℃。当乙烷与岩层接触时,它可在岩层中裂化,生成H2、甲烷、乙烷和焦炭。已发现,当乙烷的注入速率提高时,H2、甲烷、乙烷和乙烯的产量增加,表明乙烷裂化生成H2和低分子量组分。丙烷和丙烯的流速不受乙烷注入的影响。
在一分开的实验中,将丙烷注入中央生产井,而从加热器井生产流体。在不同的井中测量的平均温度如下:加热器井分别为737℃、753℃和726℃,而外生产井和中央生产井分别为606℃和759℃。当丙烷与岩层接触时,它可在岩层内裂化,生成H2、甲烷、乙烷、乙烯、丙烯和焦炭。当丙烷的注入速率提高时,H2、甲烷、乙烷、乙烯、丙烷和丙烯的产量增加,表明丙烷裂化生成H2和低分子量组分。
在一分开的实验中,将丁烷注入中央生产井,而从加热器井生产流体。在不同井中测量的平均温度如下:加热器井分别为772℃、764℃和753℃,而外生产井和中央生产井分别为624℃和830℃。当丁烷与岩层接触时,它可在岩层内裂化,生成H2、甲烷、乙烷、乙烯、丙烷、丙烯和焦炭。已发现,当丁烷的注入速率提高,H2、甲烷、乙烷、乙烯、丙烷和丙烯的产量增加,表明乙烷裂化生成H2和低分子量组分。
下表II说明在上述现场实验中,在处理以前和以后,即在热解和合成气生产以后由分析煤得到的结果。在离地表约36-37英尺中途进入煤层取煤芯,作为“处理前”和“处理后”两个例子。两个煤芯在大约相同的位置取出。在下表II中,“FA”指Fisher Assay,“as rec′d”指刚取得的未经任何进一步处理的样品,“Py-Water”指在热解过程中生成的水,“H/C Atomic Ratio”指氢/碳原子比,“daf”指“无灰干基”,“dmmf”指无矿物质干基,“mmf”指无矿物质。“处理后”煤芯样的密度为约0.85克/毫升,而“处理前”煤芯样的密度为约1.35克/毫升。
表II
分析结果     处理以前     处理以后
%镜质体反射PA(加仑/吨as-rec′d)FA(%(重量),as rec′d)FA Py-Water(加仑/吨,as-rec′d)H/C Atomic RatioH(%(重量),daf)O(%(重量),daf)N(%(重量),daf)灰分(%(重量),as rec′d)固定碳(%(重量),dmmf)挥发物(%(重量),dmmf)热值(英热单位/磅,湿基,mmf)     0.5411.816.1010.540.855.3117.081.4332.7254.4545.5512048     5.160.170.612.220.060.443.061.3556.5094.435.5714281
总之,上表II中所列的结果证明,在煤处理过程中,通过热解和合成气生产使大量的烃类和氢被除去。大量不希望的产物(灰分和氮)留在岩层中,而大量希望的产物(例如可凝烃类和气体)被除去。
实施例2
计算了煤与水反应的平衡气体干基摩尔分数。不包含甲烷反应和假设煤炭为碳。所述的分数代表由含烃岩层生成的通过冷凝器从中除去水的气体的特征。计算了H2、CO和CO2在2巴绝对压力下的平衡气体干基摩尔分数随温度的变化。在390℃下,液体的生产常常中断,气体的生产趋于开始。在这一温度下生成的气体含约67% H2和约33% CO2。在约410℃以下CO的数量可忽略不计。但是,在约500℃下,在生成的气中存在可测量数量的CO。例如,在500℃下,有约66.5% H2、约32% CO2和约2.5%CO。在700℃下,生成的气体含约57.5% H2、约15.5% CO2和约27%CO。
计算了煤与水反应的平衡温基摩尔分数。示出在2巴绝对压力下,水、H2、CO和CO2的平衡湿基摩尔分数随温度的变化。在390℃下,生成的气体含约89% H2O、约7% H2和约4%CO2。在500℃下,生成的气体含约66%H2O、约22%H2、约11%CO2和约1%CO。在700℃下,生成的气体含约18%H2O、约47.5%H2、约12%CO2和约22.5%CO。
这些计算结果说明,在可生成合成的温度范围的低端(即约400℃),平衡气相分数可能不利于从烃类和水蒸汽生产H2。随着温度升高,平衡气相分数不断有利于H2的生产。例如,H2的气相平衡湿基摩尔分数从400℃的约9%增加到610℃的约39%,而在约800℃下达到50%。计算结果进一步说明,在660℃以上,平衡气相分数比生成CO2更有利于生成CO。它们还说明,当温度从约400℃升高到约1000℃时,在这一范围内生成合成气的H2/CO比不降低。例如,在500℃、660℃和1000℃下,平衡气相H2/CO比分别为22∶1、约3∶1和约1∶1。在较低温度生成的合成气比在较高温度下生成的有更大数量的水和CO2。随着温度升高,合成气中CO和H2的总百分数可增加。
在现场实验中成功地证明了其他一些生产合成气的方法。这些方法包括连续注入水蒸汽和空气、水蒸汽和氧、水和空气、水和氧、水蒸汽、空气和二氧化碳。所有这些注入方法都在热的焦炭岩层中成功地生产合成气。

Claims (10)

1.一种从含烃地下岩层生产合成气的方法,所述的方法包括:
给至少一部分地下岩层供热,以致至少一部分受热的部分达到油母质的热解温度,生成热解产物;
从地下岩层收集热解产物;
将合成气生产用组分注入岩层的受热部分,通过合成气生产用组分与残留在岩层中的含碳质材料反应生产合成气;以及
回收合成气。
2.根据权利要求1的方法,其中合成气生产用流体为水和/或二氧化碳。
3.根据权利要求1或2的方法,其中在合成气生产以前或生产过程中,将另外的热加到岩层中。
4.根据权利要求1-3中任一项的方法,其中合成气生产用流体为水蒸汽和氧的混合物。
5.根据权利要求1-4中任一项的方法,其中合成气生产用组分与受热部分在400-1200℃反应。
6.根据权利要求1-5中任一项的方法,其中压力为常压至岩层的静岩压力。
7.根据权利要求1-6中任一项的方法,其中合成气生产用流体包含热解生成的水。
8.根据权利要求1-7中任一项的方法,其中回收的合成气用费-托烃类合成法转化成更重的可凝烃类。
9.根据权利要求1-8中任一项的方法,其中含烃岩层含有油母质。
10.根据权利要求9的方法,其中含烃岩层含有镜质体反射为0.2%至3.0%的油母质。
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