CN1430698A - 处理含烃岩层的方法 - Google Patents
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- Y10S48/06—Underground gasification of coal
Abstract
公开了一种就地处理含烃岩层和从所述岩层生产烃类流体的方法,其中岩层中存在的烃类在高压下热解,同时使用压力/温度控制,以致压力至少为可根据所选的温度由方程式(1)计算的压力或温度至多为可根据所选的压力由方程式(I)计算的温度,式中P为压力(巴,绝对),T为温度(℃),A和B为预定的参数,它们与生产的烃类流体的数量、组成或质量有关的性质有关。任选的是,所述的方法接着生产合成气的步骤,所述的步骤包括被本发明的方法部分消耗的含烃岩层与合成气生产用流体反应。任选的是,将如此生产的合成气转化成烃类和/或通过使如此生产的合成气膨胀和/或燃烧或将它用于燃料电池来产生能量。
Description
本发明涉及一种通过热解岩层中存在的烃类来就地处理含烃岩层以及从所述岩层生产烃类流体的方法。
从地下岩层得到的烃类常常用作能源、原料和消费产品。对可得烃类资源枯竭的关注已导致开发各种更有效的开采、加工和利用可得烃类资源的方法。就地处理方法可用于从地下岩层中移出烃类物质。可能需要改变地下岩层中烃类物质的化学和/或物理特性,使烃类物质更容易从地下岩层中移出。化学和物理变化可包括一些能生成可移出流体、岩层内烃类物质发生溶解性变化、相变化和/或粘度变化的就地反应。流体可以是但不限于是气体、液体、乳液、浆液和/或具有类似液流流动特性的固体颗粒流。
利用井下加热器的就地加工方法的例子在US-A-2634961、US-A-2732195、US-A-2780450、US-A-2789805、US-A-2923535和US-A-4886118中公开。
例如,在US-A-2923535和US-A-4886118中述及对油页岩岩层。在这里,对油页岩岩层加热。使油页岩岩层内的油母质热解。热也使岩层断裂,以便提高岩层的渗透率。增加的渗透率使烃类流体转移到从油页岩岩层除去流体的生产井。在US-A-2923535中,通过关闭所有的气体出口阀来施加压力,以便测试岩层对气体和蒸汽的孔隙率和渗透性。但是,US-A-2923535对在气体和蒸汽的生产过程中维持高压确未提及。
已作了大量努力来开发从含烃岩层经济地生产烃类、氢和/或其他产品的方法和体系。但是,目前仍然存在许多还不能从中经济地生产烃类、氢和/或其他产品的含烃岩层。因此,对从各种含烃岩层生产烃类、氢和/或其他产品的改进方法和体系仍有需求。
现已发现,热裂中生产的烃类流体的数量,组成和质量可通过控制与所用温度有关的压力(反之亦然)来控制。在这方面,烃类流体的数量、组成和质量可由一种或多种相关的性质来确定,例如API重度,烯烃/烷烃比、碳/氢元素比、生成的等价流体(气体和液体)、生成的液体、Fischer Assay百分数以及烃类流体内碳原子数大于25的烃类存在。可生产有相关性质的烃类流体的与所选温度有关的压力或与所述压力有关的温度可用一方程式,即下文中的“方程式1”来确定: 式中P为压力(巴,绝对),T为温度(℃),A和B为与相关性质有关的参数,可用经验来确定。因子0.07和参数A和B的量纲是这样的,以致与P有T的量纲符合。
在许多情况下,温度/压力控制的应用涉及到在热解过程中高压的应用。看来高压的应用有许多意想不到的优点。这些优点与本发明的温度/压力控制的应用无关。
在岩层中高压得到改进的烃类流体。随着岩层中压力升高,从岩层中生产的烃类流体包括更大量不可凝组分。用这一方法,在这样的压力下生产的大量(例如主要量)烃类流体比在相对低压力下生产的烃类流体有更轻和更高质量的可凝组分。
已发现在热岩层中维持高压能明显抑制碳数例如大于约25的烃类流体和/或多环烃类化合物的生产。在热岩层中维持高压还能使从岩层生产的烃类流体的API比重增加。因此,相对高的压力可提高具有更高API比重的相对短链烃类流体的产量。
此外,在岩层中维持高压还可抑制岩层下沉。在岩层中维持高压还倾向于用来输送可凝组分的收集导管的所需尺寸。在岩层中维持高压还可使由生产的不凝流体生产电力变得便容易。例如,生产的不凝流体可通过透平来生产电力。
因此,本发明提供一种就地处理含烃岩层以及从所述岩层生产烃类流体的方法,所述方法包含在从岩层生产烃类流的过程中,应用这样的压力/温度控制,在至少1.5巴的压力下热解岩层中存在的烃类,以致压力至少为可根据所选的温度由以下方程式计算出的压力,或温度至多为可根据所选的压力从以下方程式计算出的温度。 式中P为压力(巴,绝对),T为温度(℃),A和B为预定的参数,它们与生成的烃类流体的数量、组成或质量有关的性质有关。
本发明还提供一种生产合成气的方法,所述方法包括提供本发明处理的含烃岩层以及含烃岩层与合成气生产流体反应。
本发明还提供一种生产烃类的方法,所述方法包括提供根据本发明生产的合成气以及将该合成气转化成烃类。
本发明还提供一种生产能量的方法,所述方法包括提供根据本发明生产的合成气和将该合成气膨胀和/或燃烧。
US-A-5236039公开了一种使用射频加热源将岩层加热到热解温度来就地处理含烃岩层的方法。在这一专利中,并提到压力对这一方法或其结果的影响。但是,与所涉及的发明有关,提到50psi与高达575°F的热解温度相结合的附带公开内容(参见该专利表1)。在该专利的处理方法中,3.52巴(50psi)在高达301.7℃(575°F)下的应用与射频加热的应用相结合并未包括在该专利的保护权利中。
除非另加说明,术语“压力”在这里指绝对压力。在从岩层生产烃类流体或在合成气生产过程中,采用的温度和压力在生产井中紧靠发生热解或生产合成气的岩层相关部分测量。
优选的是,用于本发明的含烃岩层含有油母质。油母质由熟化过程已转变的有机物质组成。含油母质的含烃岩层例如为含煤岩层和含油页岩岩层。另一方面,不含油母质的含烃岩层也可处理,例如含重质烃类的岩层(例如油砂)。
可在至少一部分岩层性质的基础上这样选择就地处理的含烃岩层,以致可从岩层生产高质量的流体。例如,用于处理含有油母质的含烃岩石层可在油母质的镜质体反射的基础上评价或选择。镜质体反射常与镜质体的氢/碳元素比和氧/碳元素有关。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可从岩层中生产相对更高质量的烃糊涂充体。
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(按无灰干计算)。优选的是,含烃岩层中的烃类的氢/碳元素比为0.5-2、特别是0.70-1.7的烃类。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。例如,如果岩层中存在的氢太少,那么对生成流体的数量和质量会有负面影响。维持氢分压是有利的,如果天然存在的氢太少,那么可将氢或其他还原流体加到岩层中。
岩层中烃类的元素氧重量百分数通常小于20%、特别是小于15%、更特别是小于10%(按无灰干计算)。通常,氧/碳元素比小于0.15。用这一方法,可减少从含烃材料的就地转化过程中生成的二氧化碳和其他氧化物。常常氧/碳元素比为0.03-0.12。
加热含烃岩层的过程包括将大量能量提供给岩层内的热源。含烃岩层可含有水。含烃岩层中存在的水倾向于进一步提高加热含烃岩层所需的能量,因为可能需要大量的能量来从岩层中汽化水。所以,为了加热含相对高水含量的岩层,可能需要过量的热和/或过长的时间。所以,为了加热含相对高水含量的岩层,可能需要过量的热和/或过长的时间。优选的是,含烃岩层的水含量小于15%、更优选小于10%(重量)。
进行热解的含烃岩层或其部分的宽度例如可为至少0.5米、或至少1.5米、或至少2.4米、或甚至少3.0米。所述的宽度可高达100米、或高达1000米、或甚至高达2000米或更宽。进行热解的含烃岩层或其部分的层厚例如可为至少2米、更通常4-100米、更通常6-60米。含烃岩层的覆盖层的厚度例如可至少10米、更特别是20-800米,或20-1000米或更厚。
含烃岩层可按本专业已知的方法用加热井中一个或多个热源加热到足以使岩层中存在的烃类热解的温度。
加热井可紧靠含烃岩层或优选在含烃岩层内。优选的是,使用多个热源,以使大部分含烃岩层可被加热,优选热源产生的热重叠。热的重叠可缩短达到热解温度所需的时间。热的重叠可允许在相邻热源之间有相对大的间隔,反过来它可提供含烃害层的相对缓慢的加热速度。热的重叠还提供均匀的加热,以致可控制温度,在便在整个(大部分)含烃岩层中均匀地生产希望性质的流体。
热源之间的间隔通常为5-20米、优选8-12米。基本上等距的热源以三角形放置是优选的,因为与其他形式例如六角形相比,它提供对岩层更加均匀的加热。此外,与其他形式例如六角形相比,为达到预定的温度,三角形常常提供更快的加热。
可使用任何传统的热源。优选使用适合于传导加热的热源,例如任何类型的电加热器或任何类型的燃烧加热器。采用射频加热的热源不太优选。
因为在加热岩层中渗透率和/或孔隙率相对迅速地增加,生南的蒸汽可通过岩层流动相对长的距离。并有相对很小的压差。由于水的汽化、烃类和除去和/或断裂的产生,受热部分质量的减少使渗透透增加。为了烃类流体的开采,可建生产井,优选在岩层的上表面附近。在含烃岩层内产生的流体可随蒸汽通过含烃岩层移动相当长的距离。这样的相当长的距离例如可为50-1000米。由于岩层受热部分的渗透性,蒸汽穿过相当长的距离可能有相对小的压降。由于这样的可渗透性,可能每两个热源单元或每三个、四个、五个、六个热源单元只需提供一个生产井,所述的热源单元都可为多个加热井,例如两个、三个或六个。生产井可为有生产滤网或多孔套管的套管井。此外,生产井可用砂子或砾石围绕,使流体进入套管的压降减到最小,使孔的堵塞减到最小。
此外,可设置抽水井或真空井,以便从含烃岩层中除去液体水。例如,许多个水井可围绕要加热的整个岩层或其一部分。
生产的烃类流体其他子结构中含有碳和氢的物质。它也可含有其他元素,例如卤素、金属元素、氮、氧和硫。
将含烃岩层加热到可发生热解的温度。热解温度的范围例如可包括一直到900℃。主要的烃类流体可在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270-375℃。在另外一些实施方案中,足以使重质烃类热裂的温度为300-375℃。如果将含烃岩层加热到整个热解温度范围,岩层只能生产相对热解温度范围的上限的少量氢,可利用的氢耗尽后,仅可从岩层生产很少的烃。
优选的是,将用于热解的含烃岩层或其一部分以低加热速率加热。通常,加热速率至多50℃/天。通常,加热速率小于10℃/天、更通常小于3℃/天、特别是小于0.7℃/天。加热速率常常大于0.01℃/天、特别是大于0.1℃/天。特别是,这样的低加热速率用于所述热解温度范围。更特别的是,含烃岩层的受热部分可能这样的速率加热,其用时跨越热解温度范围所需时间的50%以上优选75%以上、或更优选90%以上的时间。
加热含烃岩层的速率可能影响从含烃岩层生产的烃类流体的数量和质量。例如,以高加热速率下加热可从含烃岩层中生产更大数量的流体。但是,这样一过程的产品可能比用相对低加热速率得到的产品有低得多的质量。此外,控制加热速率在小于3℃/天通常在含烃岩层内得到更好的温度控制。
本发明有关加热速率的内容是适用的,与本发明的温度/压力控制的应用无关。
含烃岩层加热到热解温度可能在含烃岩层内产生相当大的渗透性以前出现。最初渗透性的缺乏可能阻止从热解段产生的流体在岩层内输送。用一这方法,随着热开始从热源传递到含烃岩层,靠近热源的含烃岩层内的流体压力可升高。
由岩层中产生的烃类流体或其他流体膨胀产生的压力初期可升高,当通向生产井的通路或任何其他压力变换在岩层中尚未存在时。此外,流体的压力可能超过岩石静压,以致可从热源到生产井形成含烃岩层的裂缝。由于通过生产井生产烃类流体,在受热部分内裂缝的产生使压力下降。
为了在烃类流体的生产过程中,维持含烃岩层内的压力,可在生产井处维持一个背压。所述的压力可通过阀门和/或将气体注入含烃岩层来控制,例如注入氢、二氧化碳、一氧化碳、氮或甲烷、或水或水蒸汽。注入氢是特别优选的。
可用阀门来维持、改变和/或控制含烃岩层内的压力。例如,放置在含烃岩层内的热源可连接到一个阀上。可用阀门通过热源从岩层释放出流体以及用于将气体注入含烃岩层。另一方面,可将压力阀与生产井连接。可将通过阀门释放的流体收集并输送到用于进一步加工和/或处理的地表单元。
根据本发明,在热解过程中和在从岩层生产烃类流体的过程中,控制压力和温度,以便控制与烃类流体的数量、组成和质量有关的某些性质。参数A和B的数值可由实验来确定。通常,参数A的数值可为5000-60000,而参数B的数值可为10-90。下文给出一些例子。
为了生产低含量的碳数为25或更多的烃类的烃类流体,例如小于25%(重量),优选使用压力至少是可根据所选的温度由方程式1计算的压力或温度至多是可根据所选的压力由方程式1计算的温度,其中A等于约14000和B等于约25,优选A等于14206和B等于25.123更优选A等于15972和B等于28.442,特别是A等于17912和B等于31.804,更特别是A等于19929和B等于35.349,最特别是A等于21956和B等于38.849。在实践中,这样的压力和温度常常对操作是足够的,所述的压力至多为可根据所选的温度由方程式1计算的压力而所述的温度至少为可根据所选的压力由方程式1计算的温度,其中A等于24146和B等于43.349。
为了生产高API重度例如至少30°的可凝烃类的烃类流体,优选压力至少为可根据所选的温度由方程式1计算的压力或温度至多为可根据所选的压力由方程式1计算的温度,其中A等于30864和B等于50.676,更优选A等于21719和B等于37.821,特别是A等于16895和B等于31.170。在实践中,这样的压力和温度常常可足以操作,以致所述的压力至多为可根据所选的温度由方程式1计算的压力,或温度至少为可根据所选的压力由方程式1计算的温度,其中A等于16947和B等于33.603。正如这里使用的,“可凝的烃类”为在1巴下沸点至少为25℃的烃类。
为了生产低乙烯/乙烷比例如至多0.1的烃类流体,优选使用至少为可根据所选的温度由方程式1计算的压力或至多为可根据所选的压力由方程式1计算的温度,其中A等于57379和B等于83.145,更优选A等于16056和B等于27.652,特别是A等于11736和B等于21.986。在实践中,这样的压力和温度常常足以操作,以致所述的压力至多为可根据所选的温度由方程式1计算的压力或温度至少为可根据所选的压力由方程式1计算的温度,其中A等于5492.8和B等于14.234。
为了生产高氢/碳元素比例如至少1.7的可凝烃类的烃类流体,优选压力至少为可根据所选的温度由方程式1计算的压力或温度至多为可根据所选的压力由方程式1计算的温度,其中A等于38360和B等于60.531,更优选A等于12635和B等于23.989、特别优选A等于7953.1和B等于17.889。在实践中,这样的压力和温度是足够的,以致压力至多为可根据所选的温度由方程式1计算的压力,或温度至少为可根据所选的压力由方程式1计算的温度,其中A等于6613.1和B等于16.364。
可从含烃岩层生产的烃类流体潜在总量可由Fischer Assay确定。Fischer Assay是一种标准方法,它包括将含烃物质的样品加热到约500℃,收集由受热样品生产的产品以及定量分极该产品。为了从含烃岩层生产大量的烃类流体,例如用Fischer Assay表示的至少60%的数值,优选压力至多为可根据所选的温度由方程式1计算的压力或温度至少为可根据所选的压力由方程式1计算的温度,其中A等于11118和B等于23.156,更优选A等于13726和B等于26.635,特别优选A等于20543和B等于36.191在实践中,这样的压力和温度是足够的,以致压力至少为可根据所选的温度由方程式1计算的压力或温度至多为可根据所选的压力由方程式1计算的温度,其中A等于28554和B等于47.084。
在一些情况下,这样控制压力和温度是最有利的,以致它们属于这样的A和B数值,这些数值表示如上文所述的相对低的优选范围的条件。例如,当希望产品的数量、组成和质量的某种组合时,情况就这样。因此,上面的公开内容还包括所有可由A和B的组合确定的子范围。特别是,在烃类流体的生产过程中,保持相关性质基本上不变可能是有利的,它可能通过在参数A和B的恒定的数值下操作来达到。
在热解过程中和在从岩层生产烃类流体的过程中,压力可在宽范围内选择。通常,使用至少1.5巴的压力,更通常至少1.6巴、特别是至少1.8巴。常常,当热解温度为至少300℃时,可使用至少1.6巴的压力,而当温度低于300℃时,可使用至少1.8巴的压力。压力的上限可由覆盖层的结构和重量来确定。常常在实践条件下,压力小于70巴,更常常小于60巴,或甚至小于50巴。最好将压力控制在2-18巴或2-20巴或另一方面控制在20-36巴。
在一优选的实施方案中,正如上述,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,更通常1-10巴,特别是5-7巴。在岩层中维持一定的氢分压特别使生产的烃类流体的API重度增加和长链烃类流体的产量减少。
有关氢分压的公开内容是适用的,与本发明的温度/压力控制无关。
含烃岩层或其一部分进行热解时,有机碳初始总含量中至少20%、通常至少25%、优选至少35%可转变成烃类流体。在实践中,含烃岩层或其一部分进行热解时,有机碳总含量中常常至多90%可转变成烃类流体,更常常为至多80%或至多70%或至多60%。
在一些实施方案中,在热解之后,可由残留在含烃岩层内的烃类生产合成气。热解可在整个含烃岩层或已热解部分中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在合成气中不生成大量烃类流体的情况下生产合成气。所述部分还有大的表面积和/或大的表面积/体积。大的表面积可在合成气生产过程中使合成气生产反应基本上处在平衡条件下。与未经热解的含烃岩层中生产合成气相比,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。这一公开内容是适用的,与本发明的温度/压力控制无关。
在这一些实施方案中,至少一些含烃岩层的热解可转化20%可利用的初始碳。合成气生产可转化至少另外10%和通常一直到另外70%的可利用的初始碳。用这一方法,从含烃岩层就地生产合成气可使其中更大数量的可利用的初始碳转化。
可在从岩层生产烃流体以前或以后从岩层中生产合成气。合成气虽然通常规定为氢(H2)和一氧化碳(CO)的混合物,但它还可含有另外的组分,例如水、二氧化碳(CO2)、甲烷和其他气体。
合成气产生过程可在烃类流体产量下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来生产合成气。例如,如果热解以后一部分岩层为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,通常需要相对少的外加热量。在某些情况下,可从一个或多个热源提供热量。将岩层加热到足以进行合成气生产的温度(例如从400-1200℃或更高)。在所述温度范围的上限,生产的合成气可主要含有H2和CO,例如摩尔比为1∶1。在这一温度范围的下限,生产的合成气可能有相对高的H2/CO比。在合成气生产过程中,可利用在岩层中用于热解和从岩层生产烃类流体的加热井、热源和生产井作为送入合成气生产用流体的注入井、作为生产井或作为加热岩层的热源。用于合成气生产的热源可包括任何一种热源。另一方面,加热可包括传递传热流体例如水蒸汽或燃烧器的燃烧产物的热量,在岩层中的多个井身内流动。
合成气生产用流体例如液体水、水蒸汽、二氧化碳、空气、氧、烃类及其混合物提供给岩层。例如,合成气生产用用流体混合物可包含水蒸汽和氧。合成气生产用流体可包含在另一部分岩层内含烃物质热解生成的含水流体。条件是合成气生产用流体可包含将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将与岩层中的碳反应形成H2、水(液体水或水蒸汽)、CO2和/或CO。
可将CO2从合成气中分离出来,并可与合成气生产用流体一起再注入岩层。通过变更点优势的化学平衡反应,加入到合成气生产用流体中的二氧化碳可基本上抑制在合成气生产过程中进一步生成二氧化碳。二氧化碳也可与岩层中碳反应生成一氧化碳。
可将烃类例如乙烷加到合成气生产用流体中。当烃类加到岩层中时,它们可裂化生成氢和/或甲烷。在生成的合成气中甲烷的存在可提高它的热值。生产合成气的反应通常为吸热反应。在合成气生产过程中可将热加到岩层中,以便使岩层的温度保持在所需的水平。热可从热源和/或从送入的温度高于岩层的合成气生产用流体加入。作为另一供选择的方案,可将氧化剂加到合成气生产用流体中,例如空气、富氧的空气、氧气、过氧化氢、其他氧化性流体或它们的组合形式。氧化剂可与岩层中的碳反应产生热量,并生成CO2和/或CO。在一优选实施方案中,将氧和水(或水蒸汽)送入岩层,例如摩尔比为1∶2至1∶10、优选1∶3至1∶7、例如1∶4。
在合成气生产过程中,可将含烃岩层维持在相对高的压力下。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。高的操作压力可得到高的H2产量。高的操作压力能借助将所生产的合成气通过透平来生产电力,以及能用相对小的收集导管来输送生成的合成气。
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,且料流主要包括(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范围、更典型是从1∶2至4∶1范围,特别是1∶1至2.5∶1的合成气。某些实施方案可包括将第一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。
可将经过热解和任选经合成气生产的含烃岩层或其部分冷却形式冷却的废岩层。生产烃类流体和/或合成气以后,可将流体(例如二氧化碳)隔绝在岩层内。为了将大量流体贮存在岩层内,岩层的温度常常需要低于100℃,例如降到20℃。将水送入岩层以产生水蒸汽并降低岩层的温度。可从岩层中除去水蒸汽。水蒸汽可用于各种应用目的,例如用于加热岩层的另一部分、用于在岩层相邻部分中生产合成气或在油层中用作蒸汽驱。在岩层冷却以后,可将流体加压并隔绝在岩层中。将流体隔绝在岩层中可减少或消除由于在就地加工中的操作释放到环境中的流体。废岩层特别适用于这一目的,因为对流体特别是气休具有大的孔隙性和渗透性的结构。
可将要隔绝的流体在例如5-50巴下注入冷却的废岩层并吸收在岩层的含烃物质上。水随后加入岩层的水可阻止二氧化碳的脱附。US-A-5566756中说明了隔绝二氧化碳的方法的一个例子。
这里描述的合成气可转化成烃类(包括甲烷)或其他产物(例如氨)。例如,可用费托烃类合成过程配套将合成气转化成烷烃。合成气也可用于催化甲烷来生产甲烷。另一方面,合成气可用来生产甲醇、汽油和柴油、氨和中间馏分油。
合成气也可用作能源。例如,它可用作燃烧燃料,用来加热含烃岩层或用来生产水蒸汽,然后推动涡轮生产电力。合成气可通过合成气在涡轮中减压或利用合成气的温度来生产水蒸汽然后推动涡轮来产生电力。也可将合成气用于这样一种能量生产单元,例如熔融碳酸盐燃料电池、固体氧化物燃料电池或其他类型燃料电池。
用作费-托合成反应进料气体的合成气其H2/CO摩尔比通常为约2∶1费-托合成法通常是生产分支和未分支的烷烃,它们可通过加氢裂化转化成例如包括柴油、喷气燃料和石脑油在内的烃类产品。合成气在费一托合成法中转化成烃类的方法的例子在US-A-4096163、US-A-4594468、US-A-6085512和US-A-6172124说明。
生成的可用作催化甲烷化法进料气体合成气的组成的H2/CO摩尔比为3∶1至4∶1可能是希望的。催化甲烷化法的例子在US-A-3992148、US-A-4130575和US-A-4133825中说明。
由合成气生产甲醇的方法的例子在US-A-4407973、US-A-4927857和US-A-4994093中说明。
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。
以下的实施例例示说明本发明。
实施例1
将美国科罗拉多州的格林河油页岩沉积物的各种样品在不同的温度和压力下热解,以确定热解温度和压力对所生成烃流体的质量和数量的影响。
不锈钢压力容器用来装油页岩样品。容器和与所述容器相连的流动管线绕有电热带,以便给整个容器和出油管提供基本均匀的加热。流动管线有用于在升压下试验的背压阀。通过阀门以后,产物在常压下在常用的实验室玻璃冷凝器中冷却分析。试验结果用于通过方程式1和参数A和B确定产品的特定质量和产率的压力/温度关系,以上所述。结果表明,通过提高压力,碳数为25或更大的烃类的含量减少,API重度增加、乙烯/乙烷比下降H/C比增加以及相对于Fischer Assay的烃类产率降低。
Claims (20)
1.一种就地处理含烃岩层以及从所述岩层生产烃类流体的方法,所述的方法包括在从岩层生产烃类流体的过程中热解岩层中存在的烃类,同时使用压力/温度控制,以致压力至少为可根据所选的温度由以下方程式计算的压力或温度至多为可根据所选的压力由以下方程式计算的温度:
式中P为压力(巴,绝对),T为温度(℃),A和B为预定的参数,它们与生产的烃类流体的数量、组成或质量有关的性质有关。
2.根据权利要求1的方法,其中含烃岩层含有油母质,例如煤或油页岩或重质烃类例如油砂。
3.根据权利要求1或2的方法,其中使用适用于通过传导加热岩层的热源。
4.根据权利要求1-3中任一项的方法,其中通过在250-400℃、特别是260-375℃的温度下加热使岩层中存在的烃类热解。
5.根据权利要求1-4中任一项的方法,其中压力为至少1.4巴和其中如果压力为3.52巴和热解在高达301.7℃的温度下进行,那么使用一种不是仅提供射频加热的热源。
6.一种就地处理含烃岩层以及从所述岩层生产烃类流体的方法,所述的方法包括在从岩层生产烃类流体的过程中热解岩层中存在的烃类,同时使用压力/温度控制,以致压力至少为可根据所选的温度由以下方程式计算的压力或温度至多为可根据所选的压力由以下方程式计算的温度:
式中P为压力(巴,绝对),T为温度(℃),A和B为预定的参数,它们与生产的烃类流体的数量、组成或质量有关的性质有关以及在氢分压为至少0.5巴,例如1-10巴、特别是5-7巴的氢存在下。
7.根据权利要求1-6中任一项的方法,其中A等于14000和B等于25。
8.根据权利要求1-6中任一项的方法,其中A等于24146和B等于43.349。
9.根据权利要求1-6中任一项的方法,其中A等于30864和B等于50.676。
10.根据权利要求1-6中任一项的方法,其中A等于16947和B等于33.603。
11.根据权利要求1-6中任一项的方法,其中A等于57379和B等于83.145。
12.根据权利要求1-6中任一项的方法,其中A等于5492.8和B等于14.234。
13.根据权利要求1-6中任一项的方法,其中A等于38360和B等于60.531。
14.根据权利要求1-6中任一项的方法,其中A等于6613.1和B等于16.364。
15.根据权利要求1-6中任一项的方法,其中A等于28554和B等于47.084。
16.根据权利要求1-6中任一项的方法,其中A等于11118和B等于23.156。
17.一种生产合成气的方法,所述的方法包括—提供含烃岩层,它按照就地处理含烃岩层和所述的岩层生产烃类流体的方法处理,所述的方法包括在从岩层生产烃类流体的过程中热解岩层中存在的烃类,同时使用压力/温度控制,以致压力至少为可根据所选的温度由以下方程式计算的压力或温度至多为可根据所选的压力由以下方程式计算的温度: 式中P为压力(巴,绝对),T为温度(℃),A和B为预定的参数,它们与生产的烃类流体的数量、组成或质量有关的性质有关,以及——随后至少一部分经处理的含烃岩与合成气生产用流体反应。
18.一种生产烃类的方法,所述的方法包括提供按权利要求17生产的合成气以及将合成气转化成烃类。
19.根据权利要求18的方法,其中用费-托烃类合成法将合成气转化成烷烃,然后将烷烃在加氢裂化反应器中进行转化。
20.一种生产能源的方法,所述的方法包括提供按权利要求17生产的合成气并将合成气膨胀和/或燃烧或将合成气用于燃料电池。
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- 2001-04-24 CN CNB018104533A patent/CN1270051C/zh not_active Expired - Fee Related
- 2001-04-24 US US09/841,636 patent/US20020049360A1/en not_active Abandoned
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- 2001-04-24 AT AT01943286T patent/ATE276425T1/de not_active IP Right Cessation
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- 2001-04-24 WO PCT/US2001/013452 patent/WO2001081239A2/en active Application Filing
- 2001-04-24 WO PCT/EP2001/004644 patent/WO2001086115A2/en active IP Right Grant
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- 2001-04-24 EP EP01927922A patent/EP1276959B1/en not_active Expired - Lifetime
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- 2001-04-24 AU AU6590301A patent/AU6590301A/xx active Pending
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- 2001-04-24 AU AU7237901A patent/AU7237901A/xx active Pending
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2002
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2003
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2007
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2010
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2012
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2013
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103114831A (zh) * | 2013-02-25 | 2013-05-22 | 太原理工大学 | 一种油页岩油气资源原位开采方法 |
CN103114831B (zh) * | 2013-02-25 | 2015-06-24 | 太原理工大学 | 一种油页岩油气资源原位开采方法 |
CN108590614A (zh) * | 2018-03-23 | 2018-09-28 | 中国石油天然气股份有限公司 | 油藏不同温度二次启动驱替压力的表征方法及装置 |
CN108590614B (zh) * | 2018-03-23 | 2020-02-14 | 中国石油天然气股份有限公司 | 油藏不同温度二次启动驱替压力的表征方法及装置 |
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