CN103930524B - 制备烃的方法 - Google Patents

制备烃的方法 Download PDF

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Publication number
CN103930524B
CN103930524B CN201280055636.5A CN201280055636A CN103930524B CN 103930524 B CN103930524 B CN 103930524B CN 201280055636 A CN201280055636 A CN 201280055636A CN 103930524 B CN103930524 B CN 103930524B
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bed
catalyst
speed
charcoal
product
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CN103930524A (zh
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A·A·德尔帕乔
M·J·罗伯茨
T·L·马克
L·G·费利克斯
M·B·林克
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
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Abstract

描述了一种将生物质转化为产物的方法。使生物质与氢气在加氢热解催化剂流化床的存在下、于加氢热解条件下的反应容器中接触；并将产物和炭从所述反应容器中移出。所述产物以离床速度离开所述流化床，所述炭具有小于所述离床速度的沉降速度，并且加氢热解催化剂具有大于所述离床速度的沉降速度。

Description

制备烃的方法
技术领域
本发明涉及一种由生物质制备烃的方法，其通过使所述生物质与加氢热解催化剂接触而实施。本发明还涉及所述催化剂与所述方法中所制备的固体之间的改进的分离方法。
背景技术
研发出将生物质转化为有价值的产物——尤其是可用作运输燃料或用于其它化学加工中的产物——的方法相当受人关注。
美国专利申请公布文本No.2010/0251600(将其内容通过援引加入的方式纳入本文)记载了一种由生物质制备液体产物的多级方法，其中将所述生物质在容纳分子氢和脱氧催化剂的反应容器中进行加氢热解，从而制得经部分脱氧的热解液体、炭和第一阶段过程热。将所述经部分脱氧的热解液体使用加氢转化催化剂进行氢化，从而制得基本上完全脱氧的热解液体、含一氧化碳和轻质烃气体(C1至C4)的气体混合物、和第二阶段过程热。然后将所述气体混合物在蒸汽重整装置中重整，从而制备经重整的分子氢。然后将所述经重整的分子氢引入所述反应容器中以对另外的生物质进行加氢热解。
需要对这种类型的方法继续改进以使得其在经济和技术方面是可行的并且能够以工业规模实施。
发明内容
本发明提供了一种将生物质转化为产物的方法，所述方法包括:
使所述生物质与氢气在加氢热解催化剂流化床的存在下、于加氢热解条件下的反应容器中接触；以及
将产物和炭从所述反应容器中移出，
其中所述产物以离床速度(exit bed velocity)离开所述流化床，所述炭具有小于所述离床速度的沉降速度，并且加氢热解催化剂具有大于所述离床速度的沉降速度。
本发明提供了一种将生物质转化为产物的方法，所述方法包括：
使所述生物质与氢气在新鲜的加氢热解催化剂流化床的存在下、于加氢热解条件下的反应容器中接触；
将产物和炭从所述反应容器中移出；
实施所述接触步骤和所述移出步骤一段时间使得所述新鲜的加氢热解催化剂在所述流化床中磨耗以形成小催化剂颗粒；以及
将所述小催化剂颗粒中的至少一部分与所述产物和炭一起移出；
其中所述产物以离床速度离开所述流化床，所述炭具有小于所述离床速度的沉降速度，所述新鲜的加氢热解催化剂具有大于所述离床速度的沉降速度，并且所述小催化剂颗粒具有小于所述离床速度的沉降速度。
附图说明
图1描绘了加氢热解方法的工艺流程。
图2描绘了操作期间反应容器的内部。
具体实施方式
本方法用以将生物质转化为可满足汽油、柴油机燃料、喷气发动机燃料和/或其它有价值的液体烃产物规格的液体产物。用于加氢热解反应器的生物质进料可包括各种各样通过生物学方法衍生的材料，包括从来自炼脂厂的脂肪到干鸡粪(dried chicken litter)的一切在内。可将来自城市固体废物堆的材料(例如塑料、纸张、卡纸板、庭园废物和食物残渣等)的混合物供入加氢热解反应器中。认为当加热时分解为沸点在汽油、柴油或煤油范围中的经氧化的烃和/或未氧化的烃的任何材料均可潜在地用作原料。优选的生物质原料包括木质素、木材和藻类。藻类可包括全藻(whole algae)和藻渣，例如在用以移除脂质、蛋白质和/或碳水化合物的任何提取方法后得到的残渣。通常通过筛分和干燥而制备生物质进料以用于所述反应中。对生物质以及进料处理方法的选择在所述反应中所形成的炭的特性中起到较大的作用。
所述方法的另一种进料为氢气。可引入氢气以用于该方法中，或可在蒸汽重整装置中制备氢气。可将所述加氢热解方法中所制得的轻质烃(C1至C4)和一氧化碳供入所述蒸汽重整装置中。
所述加氢热解反应在提供用于制备经部分脱氧的热解液体、炭、轻质烃(C1至C4)和一氧化碳的合适加氢热解条件下实施。所述反应的温度可在约300℃至约600℃的范围内，优选在约350℃至约540℃的范围内，更优选在约399℃至约450℃的范围内。所述反应的压力可在约1.38MPa至约6.00MPa的范围内，优选在约1.72MPa至约5.50MPa的范围内，更优选在约2.06MPa至约5.00MPa的范围内，最优选在约2.76MPa至约4.14MPa的范围内。
反应器中的加氢热解催化剂为流化床的形式。进料和产物向上通过床的速度足以使催化剂维持流化状态。产物中的大部分在加氢热解反应条件下处于气体形式，因此沿向上的方向通过所述床。它们通过床的上部分而离开催化剂床。气体产物离开所述催化剂床的速度在本文中称为离床速度。离床速度将是进料速率、反应速率、反应器压力和温度以及反应器尺寸的结果。
为了维持反应器中催化剂床的上部分，离床速度必须不能过高，以防止所述蒸汽夹带催化剂颗粒并携带它们与所述产物一起到塔顶。催化剂或在反应器中所形成的其它固体被蒸汽所夹带的趋势由各颗粒的沉降速度决定。
颗粒的沉降速度为颗粒在流体中移动时所达到的最终速度，并且当所述流体对所述颗粒的阻力与所述颗粒所受的重力相等且相反时达到。颗粒的沉降速度为颗粒的密度、颗粒的直径、流体(气体)密度和重力加速度的函数。参见Kunii,Daizo和Octave Levenspiel,FluidizationEngineering.第2版(Butterworth-Heinemann1991),第80页，将其内容通过援引加入的方式纳入本文。将形状和其它因素纳入通过实验确定的无量纲阻力系数中。
在流化床中，可将各颗粒的沉降速度和所述床中的气体速度结合以获得颗粒的净速度，即所述床中的气体速度减去所述颗粒的沉降速度将为所述颗粒的净速度。例如，具有向上的净速度的炭颗粒将被携带离开所述床并被气体产物所夹带，因为所述气体速度大于所述炭颗粒的沉降速度。另一方面，当催化剂颗粒的沉降速度大于所述床中的气体速度时，催化剂颗粒将具有负的(向下的)净速度，所述催化剂颗粒将倾向于保留在所述催化剂床中。
在该方法中，优选大部分催化剂保留在催化剂流化床中，并且优选大部分炭被气体产物夹带并携带离开所述反应。重要的是将尽可能多的催化剂保留在流化床中以维持反应活性并避免炭被催化剂上的金属所污染。
离床速度是方法条件和反应器结构的函数。具体而言，离床速度可如下计算:气体产物离开所述床的体积流速除以位于所述催化剂流化床的顶部的反应器的横截面积。优选所述催化剂的沉降速度为所述炭的沉降速度的至少1.5倍以实现炭与催化剂之间的有效分离，但实施该分离中的主要因素为离床速度。
加氢热解催化剂可为本领域普通技术人员已知可用于该反应中的任何催化剂。可用于本方法中的合适催化剂具有影响其在流化床加氢热解反应器中性能的某些物理特性。在本方法中，催化剂的沉降速度决定了所述催化剂是保留在流化床中还是从反应器中流出并被气体产物携带离开。如果催化剂的沉降速度大于离床速度，则所述催化剂将保留在流化床中，而不被所述气体产物所夹带。
所述催化剂的沉降速度可为大于所述离床速度的任何速度，优选大于所述离床速度的110％，更优选大于所述离床速度的125％，最优选大于所述离床速度的150％。
合适的加氢热解催化剂包括负载型和本体催化剂。对此而言合适的催化剂为在球形氧化铝载体上浸渍的硫化的CoMo或NiMo催化剂。将这些催化剂置于球形载体上以将在流化床反应器中使用时的磨耗减到最小。另一种合适的催化剂为在球形氧化铝载体上浸渍的镍铝尖晶石(nickel aluminate)或镍催化剂。在所有情况下，所述催化剂的活性均必须足以将氢加入到结构中并将焦化反应最小化。
除了这些催化剂之外，其它催化剂也可能奏效。玻璃-陶瓷催化剂可具有极其强的耐磨耗性，其可以热浸渍的或本体催化剂的形式制备。当以硫化的NiMo、Ni/NiO或Co基的玻璃-陶瓷催化剂形式使用时，所得催化剂为可易于获得的、但软的、常规NiMo、Ni/NiO或Co基催化剂的耐磨耗性形式。硫化的NiMo、Ni/NiO或Co基的玻璃-陶瓷催化剂特别适合用于热流化床中，因为这些材料可提供常规负载型催化剂的催化作用，但以坚硬得多的、具有耐磨耗性的形式提供。此外，由于所述催化剂具有耐磨耗性，当在加氢热解反应器中进行加氢热解反应时，生物质和炭同时被研磨成较小的颗粒。
所述方法期间生成炭。炭为所述加氢热解反应后仍然存在的固体生物质残余物。炭优选被气体产物所夹带并携带离开反应器。炭的物理特性决定了其是否会被气体产物所夹带。具体而言，如果炭的沉降速度小于离床速度，则所述炭将被气体产物所夹带并携带离开反应器。所述炭将不必然是均一的，因为其特性由生物质的类型、生物质预处理步骤和加氢热解反应条件决定。此外，所述炭的尺寸可通过在流化床中剧烈混合而减小。
所述炭的沉降速度可为小于所述离床速度的任何速度，优选小于所述离床速度的90％，更优选小于所述离床速度的75％，最优选小于所述离床速度的60％。应理解，在反应器中所形成的各炭颗粒可具有大于所述离床速度的初始沉降速度，但是随着时间的推移，所述炭颗粒的沉降速度可通过与催化剂和其它炭颗粒接触而减小直到所述炭颗粒的沉降速度小于所述离床速度。
所述催化剂在位于流化床反应器中之后的沉降速度将随着催化剂在流化床中的剧烈混合而产生的磨耗而随时间减小。随着催化剂颗粒的平均沉降速度减小，其将会达到这样一个点，在此点处经磨耗的催化剂或从所述催化剂中破裂出的小的催化剂颗粒的沉降速度将小于所述离床速度，并且所述经磨耗的催化剂或小催化剂颗粒将被气体产物所夹带并携带离开。合适的催化剂优选是耐磨耗的，从而使得催化剂磨耗的这个过程将十分慢地进行。
所述气体产物将包含固体颗粒，例如被所述气体产物所夹带的炭和催化剂颗粒。在对所述气体产物进行进一步加工之前，必须将这些固体颗粒从所述气体产物中移出，并且优选将所述炭从所述催化剂颗粒中分离出来。该分离可通过包括过滤器、旋风分离器、或者其他离心或向心分离器的任何合适的方法实施。
在一个实施方案中，将所述气体产物通过旋风分离器以移除炭，然后将其通过过滤器以移除催化剂细粉。可将炭通过旋风分离器从所述气体产物流中移除，或通过粗过滤移除。如果将所述炭通过热气体过滤(hotgas filtration)而分离，则将不得不周期性地移除过滤器上所捕获的尘饼(dust cake)。其将比较容易被移除，因为所述加氢热解反应中所产生的氢将会使自由基稳定并使所述反应中所产生的烯烃饱和。在常规的快速热解中，该尘饼的移除难得多，因为所述炭倾向于表面覆盖所述过滤器并且与经氧化的热解蒸汽反应以形成粘性涂层。
在一种实施方案中，首先使用旋风分离器以从离开所述流化床的工艺蒸汽中收集炭细粉，然后使用多孔过滤器以收集催化剂颗粒(与所述炭相比，其具有较大的颗粒密度，但具有小得多的直径)。此外，可并行使用两个多孔过滤器，以致于其中一个可通过反冲而清洁而另一个在运行。
在冷却和凝结所述热解液体之前，也可使用静电沉降或虚拟冲击器分离器从热气体产物流中移除炭和灰分颗粒。
在另一实施方案中，可将所述炭通过用循环液体对所述气体产物流鼓泡而从所述方法中移除，其中所述循环液体优选为成品油的高沸点部分。炭和催化剂细粉可被捕获在该液体中，然后可将其过滤以移除所述炭和催化剂颗粒并且/或者可将其循环至加氢热解反应器。
在另一实施方案中，将(布置在沸腾床中的)大尺寸的NiMo或CoMo催化剂用于炭移除，以提供在移除细粉微粒的同时进一步脱氧。这些催化剂颗粒的尺寸大，优选1/8至1/16英寸，所以其易于从所述加氢热解反应中携带离开的细粉炭中分离出来。
在移除所述炭之后，可将经部分脱氧的热解液体与来自所述加氢热解反应的氢气、一氧化碳、二氧化碳、水和轻质烃气体(C1-C4)一起进料至加氢转化反应器或可用于对所述热解液体进一步处理的另一种类型的反应区。
在一种优选实施方案中，所述加氢转化反应器在比所述加氢热解反应的温度低的温度(在约315℃至约425℃的范围内)下且在与所述加氢热解反应的压力大约相同的压力下运行。该步骤的液体时空速在约0.3至约2.0的范围内。应保护该反应器中所用的催化剂以免受催化剂毒物之害，所述催化剂毒物例如有钠、钾、钙、磷和可能存在于所述生物质中的其它金属。将通过在所述加氢热解反应器中所实施的催化精制而对所述催化剂进行保护以免受烯烃和自由基之害。为此步骤通常所选的催化剂为高活性加氢转化催化剂，例如硫化的NiMo和硫化的CoMo催化剂。在该反应阶段中，使用所述催化剂以催化水煤气变换反应(即CO+H2O发生反应以制备CO2+H2),从而使得能够在所述加氢转化反应器中原位制备氢气。
实施所述加氢转化步骤之后，液体产物几乎被完全脱氧。这些产物在通过高压分离器和低压分离器经由蒸馏而分离为汽油和柴油部分之后可用作运输燃料。离开所述加氢转化步骤的气体主要为一氧化碳、二氧化碳、甲烷、乙烷、丙烷和丁烷，它们可与水一起被送到任选的蒸汽重整器以形成待用于所述方法中的氢气。这些气体中的一部分也可燃烧以产生所述蒸汽重整步骤所需的热量。
所述加氢热解反应***100的一个实施方案将结合附图1进行描述。加氢热解反应***100包括含有催化剂流化床的加氢热解反应器110。将生物质通过生物质进料输送管线120进料到所述反应器中，并将氢气通过氢气进料输送管线122进料到所述反应器中。氢气和生物质在所述催化剂的存在下进行反应，所述产物——包括热解液体、轻质气体、一氧化碳和炭——被经由产物管线124携带离开所述反应器。使所述产物通过旋风分离器130，其中所述炭经由管线126分离出来并且产物经由管线128移出。其它实施方案包括使用过滤器和/或用于将固体从产物中分离出来的其它装置。小的催化剂颗粒也可经由管线124被携带离开所述反应器，这些催化剂颗粒会或与炭一起或单独地从所述产物中分离出来。
所述加氢热解反应的一个实施方案将结合附图2进行描述。加氢热解反应器210含有加氢热解催化剂流化床230。将所述生物质通过管线220进料并将所述氢气通过管线222进料。箭头240描述了所述气体离开所述催化剂床顶部的离床速度。颗粒232为经由管线224移出的气体产物流所夹带的固体炭颗粒或小的催化剂颗粒。
实施例
将加氢热解反应器在与上文所述条件一致的条件下运行，以示出生物质炭和经磨耗的催化剂颗粒通过夹带而从催化剂床中移除。所述加氢热解反应器由管状容器组成，其内直径为3.25cm。将催化剂床布置于所述反应器中。将处于约371℃的温度下的氢气进料入催化剂床的底部以使所述催化剂流化。在负载之前，筛分所述催化剂颗粒，从而使得各颗粒足够小以通过筛孔为500微米的筛网，但足够大以保留在筛孔为300微米的筛网上。将所述反应器在2.41MPa和布置在所述流化床中的热电偶(表示所述床的平均温度为约404℃)下运行。通过电加热器而维持并控制这个床层温度。氢气进入所述床的底部的流速使得蒸汽离开所述床的速度(离床速度)为0.13米/秒。将加热过滤器装置布置于所述流化床加氢热解反应器的下游，用以截留在实验期间离开所述流化床的任何颗粒(其由炭或经磨耗的催化剂组成)。维持所述过滤器的温度足够高以防止任何蒸汽在过滤器装置中冷凝以形成液体。
最初，将200克新鲜的、硫化的催化剂布置在所述加氢热解反应器中。经确认，0.13米/秒的离床速度太低以致于不能从所述床中移出任何可测量量的完整的催化剂颗粒。因此，发现所有完整的催化剂颗粒在所述床中的沉降速度比蒸汽从所述床中离开的速度大。应注意，所述催化剂颗粒在有负载时不是球形的，并且各颗粒的沉降速度不是直接测定的。已确认，所述颗粒足够小以被流化气体流剧烈流化和有效混合，但也足够大以被保留而不会被离开所述床的工艺蒸汽流携带离开。不对所述催化剂的空气动力学特性进行进一步表征。
然后向所述反应器中进料由粉末状硬木组成的原料。所述原料的最大粒径足够小以通过筛孔为250微米的筛网。所述原料以在输送期间各原料颗粒彼此不相互反应并且不显著升温的方式有效冷却并输送到所述流化床中。一旦所述原料颗粒到达床中，就通过与床中存在的热氢气、工艺蒸汽和催化剂颗粒相互作用从而被十分迅速地加热到床的温度。将各原料颗粒迅速脱去挥发组分，得到的蒸汽随后可以与反应器中存在的氢气发生反应。这些反应被存在的催化剂颗粒促进。一旦将所述原料颗粒脱去挥发组分，就仅留下主要由来自原始原料的碳组成的炭颗粒。这些炭颗粒的尺寸显著小于所述床中催化剂颗粒的尺寸，而且其颗粒密度也较低。结果，这些炭颗粒被迅速携带至流化床的顶部，然后输送离开所述加氢热解反应器并进入位于所述反应器的下游的被加热的过滤器组件中。
所述***运行三天。第一天将2100克原料加载于所述***中；第二天又将2100克原料加载于所述***中；第三天将1800克原料加载于所述***中。关闭所述***之后，回收了15克未被加工的原料。因此，在所述加氢热解反应中加工了5985克原料。
如上所述，最初将200克新鲜的催化剂加载于所述反应器中。在实验的第二天，将17克新鲜的催化剂输送到所述反应器中，以代替已在运行第一天之后经磨耗而移出的任何催化剂。第三天又将17克新鲜的催化剂加载于所述反应器中。关闭并卸载所述***时，床的重量为228克。所述床主要由催化剂组成，但还包含一些含碳的炭材料。
因为从所述反应器和过滤器组件中回收了固体，所以使用对固体的分析以确认大多数的催化剂被留在加氢热解反应器的流化床中，而未被带走而进入过滤器组件。此外，分析还确认大多数的生物质炭颗粒已从反应器的流化床中移出，且被带入过滤器组件中。当初始被加载至反应器时，催化剂不含有可检测量的碳。回收后，所述床含有22.5％的碳，这意味着床中剩余了51克碳。这些碳来源自所述原料中。
过滤器细粉重573克，其为78.7％的碳。这意味着从过滤器中的炭细粉回收了451克的碳。对在过滤器和床中的颗粒进行筛分，确认了来自过滤器组件的细粉颗粒比留在加氢热解反应器中的颗粒小得多。
有效地，90％的在反应器运行期间产生的炭被迅速携带离开流化床，并且在过滤器组件中累积。在反应器中留下的炭的比例与原料中所存在的最大的生物质颗粒有关。如果可以在停止向床中添加原料之后在所述床中维持更长时间的流化，那么这些颗粒最终将会被携带至过滤器组件。然而，所述实验在原料耗尽之后立即终止，不存在机会将残留的炭的尺寸减小到会被携带至所述过滤器组件的点。
来自所述加氢热解反应器的工艺蒸汽在通过所述过滤器组件之后被继续送往第二阶段反应器。在第二阶段反应器中，使所述工艺蒸汽与催化剂固定床接触，由此发生进一步的加氢处理。在实验结束后，对产物进行分析。基于不含水分和灰分的基准，占送入反应器中原料质量的26.7％的是汽油范围和柴油范围的烃。所述液态烃产物中的氧含量小于1质量％。
也对在过滤器组件中收集到的炭的堆积密度进行评估，确定其为0.3g/cc。测得流化床中催化剂的堆积密度为0.9g/cc。炭与催化剂颗粒的堆积密度之间的这个差异是所述炭与所述床有效分离的一部分原因，因为较低密度的炭颗粒可易于被携带离开所述床，而较高密度的催化剂的颗粒被保留。

Claims (10)

1.一种将生物质转化为产物的方法，包括：
a.使所述生物质与氢气在新鲜的加氢热解催化剂流化床的存在下、于加氢热解条件下的反应容器中接触；
b.将产物和炭从所述反应容器中移出；
c.实施接触步骤a和移出步骤b一段时间使得所述新鲜的加氢热解催化剂在所述流化床中磨耗以形成小催化剂颗粒；以及
d.将所述小催化剂颗粒中的至少一部分与所述产物和炭移出；
其中所述产物以离床速度离开所述流化床，所述炭具有小于所述离床速度的沉降速度，所述新鲜的加氢热解催化剂具有大于所述离床速度的沉降速度，并且所述小催化剂颗粒具有小于所述离床速度的沉降速度，其中所述炭的堆积密度在0.3至0.6g/cc的范围内，流化床中催化剂的堆积密度在0.8至1.5g/cc的范围内。
2.权利要求1所述的方法，其中所述炭的沉降速度小于所述离床速度的90％。
3.权利要求1所述的方法，其中所述炭的沉降速度小于所述离床速度的75％。
4.权利要求1所述的方法，其中所述新鲜的加氢热解催化剂的沉降速度大于所述离床速度的110％。
5.权利要求1所述的方法，其中所述新鲜的加氢热解催化剂的沉降速度大于所述离床速度的150％。
6.权利要求1所述的方法，其中所述小催化剂颗粒的沉降速度小于所述离床速度的90％。
7.权利要求1所述的方法，其中所述小催化剂颗粒的沉降速度小于所述离床速度的75％。
8.权利要求1所述的方法，还包括将所述产物分离出来以将一氧化碳和轻质烃从所述产物的剩余物中移出。
9.权利要求8所述的方法，还包括将所述产物的剩余物送至加氢转化反应器，其中使所述产物的剩余物与加氢转化催化剂于合适的加氢转化条件下接触以制备氧少于1％的可凝液体烃产物。
10.权利要求8所述的方法，其中所述小催化剂颗粒通过过滤器分离出来，而通过旋风分离器分离所述炭。
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