CN104593024A - 由生物质制备甲烷的方法 - Google Patents

由生物质制备甲烷的方法 Download PDF

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Publication number
CN104593024A
CN104593024A CN201410721548.5A CN201410721548A CN104593024A CN 104593024 A CN104593024 A CN 104593024A CN 201410721548 A CN201410721548 A CN 201410721548A CN 104593024 A CN104593024 A CN 104593024A
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Prior art keywords
hydropyrolysis
reformer
methane
steam
biomass
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Inventor
T.L.马克
L.G.菲利克斯
M.B.林克
H.S.迈尔
D.勒平
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GTI Energy
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Institute of Gas Technology
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Abstract

由生物质制备甲烷的方法，其中该生物质在含有分子氢和脱氧催化剂的反应器容器中加氢热解，其输出物流使用加氢转化催化剂加氢。将加氢转化步骤的输出物流供给到水煤气变换工艺，以提供H2O与包含CO2、H2和甲烷的产物气体的混合物。将该混合物的各组分分离，得到基本上仅包括甲烷的产物流。

Description

由生物质制备甲烷的方法
本申请是一项发明专利申请的分案申请，其母案的申请日为2011年6月9日、申请号为201180038507.0 (PCT/US2011/001048)、发明名称为“由生物质制备甲烷的方法”。
技术领域
本发明涉及用于通过热化学转化将生物质直接转化成甲烷的集成的方法。当用于本文时，术语“生物质”是指来自活的或死的有机体的生物材料，并包括木质纤维素如木材、水生材料如藻类、水生植物、海草，和动物副产品和废料，例如肉屑、脂肪、和污泥。在一个方面，本发明涉及用于由生物质制备甲烷的多段加氢热解工艺。
背景技术
常规的生物质的热解，通常是快速热解，并不使用或需要H2或催化剂并且产生浓稠的、酸性的、反应性液体产物，其中含有水、油和工艺中形成的焦。通过常规的快速热解可以得到高的甲烷收率；但是，在无氢存在的快速热解中通常会得到较高的焦收率，其与本发明的方法相比降低了甲烷的收率。还可以通过常规的热解和厌氧消化工艺来由生物质制备甲烷。此外，可以采用在气化之后甲烷化来由生物质制备甲烷。
发明内容
本发明的一个目的是提供用于制备甲烷的方法和装置，与常规的厌氧消化、气化或快速热解相比，其提供了更高的甲烷收率。
本发明的一个目的是提供用于制备甲烷的方法和装置，与可比较的厌氧消化或快速热解相比，其占用更少的物理占地面积。生物质在厌氧消化器中的转化需要较长的时间（在消化器中20-30天的停留时间），需要非常大的厌氧消化器。
本发明的另一个目的是提供用于制备甲烷的方法和装置，其与常规的蒸汽和氧加压气化之后甲烷化相比成本更低。气化是资金密集型的，因为它在高温下运行，需要空气分离设备来制备所需的氧气，其中空气分离设备是资金密集型的。
本发明的另一个目的是提供用于由生物质制备甲烷的方法和装置。
本发明的这些和其它目的是通过用于由生物质制备甲烷的多段方法和装置来实现的，其包括如下步骤：在含有氢分子和脱氧催化剂的加氢热解反应容器中，在高于约1000℉的加氢热解温度和在从约100psig到约600psig范围内的加氢热解压力下使生物质加氢热解，来产生包含焦和气体的加氢热解产物，其中该气体中除H2、CO、CO2和H2O（蒸汽）外，还含有较大比例的甲烷、极少量的包括不饱和烃在内的高级烃，当进料中有硫时还含有H2S，但是不含焦油状的材料，从加氢热解产物中分离出焦，得到脱焦后的加氢热解产物，以及在加氢转化反应器容器中使用加氢转化催化剂，在高于约850℉的加氢转化温度和在从约100psig到约600psig范围内的加氢转化压力下使脱焦后的加氢热解产物加氢转化。从而产生含有大量甲烷的加氢热解产物流。将加氢转化产物冷却并引入水煤气变换反应器以通过与蒸汽的反应使大部分的CO转化，来制备含有水和气态混合物的水煤气变换产物，所述气态混合物除了降低水平的CO之外，包括CO2、H2和甲烷。然后分离CO2、H2和甲烷，制备CO2流、H2流和甲烷产物流。H2可以例如通过PSA单元回收并再循环回到加氢热解单元。然后甲烷流可以压缩并分割为产物气，其必要时经甲烷化以通过转化为甲烷来去除任何残余的CO或H2或者这两者，从而制备对于最终气体购买用户的管道输送天然气而言可以接受的甲烷产物，并且其余部分的甲烷送至蒸汽重整器，在其中在添加适当水平的蒸汽以防止在重整器的炉室内悬浮的催化剂管中形成碳之后，一部分（通常10-15%）用作供至重整器炉室的燃料，而其余部分经蒸汽重整以制备用于加氢热解单元的氢气。来自重整器的氢气流的一部分与进入所述甲烷化单元的CO、CO2和H2的水平相称，它们在这种氢气添加被引入到前述甲烷化容器之前进入甲烷化单元。在那里，氢气与甲烷产物流中的任何残余量的碳氧化物（CO2和CO）反应，生成额外的甲烷并由此使甲烷产物流中的碳氧化物最小化。正如本领域的技术人员所了解的那样，当需要时，可以提供多个反应器和最终段反应器来获得所期望的转化程度以及容纳由甲烷化反应释放的热量。
附图说明
由以下结合附图的详细说明可以更好地理解本发明的这些和其它目的和特征。
图1是本发明的一种实施方式的用于由生物质制备甲烷的工艺的流程示意图；和
图2是本发明的另一实施方式的用于制备甲烷的工艺的流程示意图。
具体实施方式
如图1所示，本发明工艺是用于将生物质热化学地转化为甲烷的紧凑、集成的多段工艺。该工艺的第一反应阶段或步骤采用了加压的、催化剂增强的、加氢热解反应器容器10来制备自其中除去焦的部分脱氧的低焦加氢热解产物。尽管可以采用任何适用于加氢热解的反应器容器，但是优选的反应器容器是流化床反应器。加氢热解步骤采用快速升温，其中颗粒内部的平均温度以约10,000℃/秒的速率升高。热解蒸气在反应器容器内的停留时间少于约1分钟。形成对照的是，焦的停留时间相对较长，因为它并不通过反应器容器底部去除并因此必须使颗粒尺寸减小直至这些颗粒的空气动力学直径充分减小至使得它们能够被临近反应器容器顶部排出的蒸气洗脱并携带走。必要时，第二反应阶段（在除焦之后）采用加氢转化反应器容器11，在其中在与第一反应阶段基本相同的压力下实施加氢转化步骤以将任何烯烃转化为甲烷。第二反应阶段的产物然后被送至水煤气变换反应器12，在其中产物被转化成包含CO2、H2O、H2和甲烷的混合物的变换产物，并且CO的浓度得到降低。变换产物经冷却并采用高压分离器13分离成水和气态组分，其中水在经过水处理后用于在蒸汽重整器14中使部分甲烷产物蒸汽重整，重整器自身也是集成的重整器-PSA单元15的组件。CO2、H2和甲烷的混合物提供到H2回收单元16，在其中H2从混合物中分离出来并与来自集成的重整器-PSA单元的H2结合。然后在蒸汽驱动的压缩机17中将H2压缩并且再循环回到加氢热解反应器容器10用于其中的加氢热解过程。带有少量CO和CO2的剩余混合物被压缩。离开H2分离单元16的富甲烷流中可能仍含有少量的CO作为超出了天然气管道系统可接受的甲烷所允许的程度的杂质。一部分的剩余甲烷被送至甲烷化器19，在其中任何残存的CO都与来自集成的重整器-PSA单元的H2的一部分反应生成额外的甲烷。取决于H2S的水平，可能需要痕量硫去除系统或保护床来自保护会硫中毒的甲烷化催化剂。从甲烷化器19中排出的物流是高纯度的甲烷流，仅含有痕量的CO、CO2、H2和水蒸气。该物流经脱水并且压缩到适于进入天然气传输或其它排放管路的压力。来自H2回收分离单元16的其余部分的甲烷与蒸汽形式的水一起送至蒸汽重整器14，用于将甲烷转化成H2和CO2。一部分的甲烷气在炉子或其它燃烧器20中燃烧以将其余部分的甲烷气加热至蒸汽重整器的操作温度，其约为1700℉。可选择地，该炉子可以使用自加氢热解反应器10下游的加氢热解产物流中脱除的焦作为燃料。蒸汽重整器在其进料中要求3/1的蒸汽-烃比率以避免生成碳并将反应平衡向CO变换为H2推移，但是这远多于重整反应所需的量。过量的水经回收，必要时经处理用于锅炉进水并再循环至蒸汽重整器。CO2通过变压吸附（PSA）从工艺中去除而没有送到甲烷化器19的任何H2再循环回到工艺的第一反应阶段（加氢热解，发生于加氢热解反应器10中）。
本发明的关键方面在于工艺中所需的热能是由脱氧反应的反应热提供的，该反应为放热反应，在第一和第二阶段中均有发生。本发明的另一关键方面在于生物质进料无需严格干燥并且事实上，在进料中添加水或将其作为单独的进料对于该工艺来说是有利的，因为它通过水煤气变换反应提高了原位的H2生成。
本发明工艺中采用的生物质进料可以是松散的生物质颗粒的形式，其中大部分的颗粒具有优选小于约3mm的尺寸，或者是生物质/液体浆料的形式。但是，本领域的技术人员能够理解生物质进料可以经过一定方式的预处理或者其它加工使得可以适用较大的颗粒尺寸。适用于将生物质进料引入加氢热解反应器容器的手段包括，但不限于，绞龙、快速移动的载气流（大于约5m/秒）例如惰性气体或CO2气体和H2、和定量送料泵、叶轮或涡轮泵。
在反应器容器中在高于约1000℉的温度下，优选在从约1000℉到约1200℉范围的温度下，和在约100psig到约600psig范围的压力下进行加氢热解。生物质的加热速率优选高于约10,000/秒。该步骤的重时空速（WHSV）以克生物质/克催化剂/小时计在约0.2到约10的范围内。
如前所述，在本发明的加氢热解步骤中，固体生物质进料被快速加热，优选在热流化床中，从而将生物质转化为无焦产物，与常规的快速热解得到的收率相当并且还可能更好。但是，在加氢热解过程中，加氢热解的蒸气处于流化床内的催化剂和较高的H2分压存在下，这提供了氢化活性及一些的脱氧活性。氢化活性对于防止反应性烯烃的聚合来说是非常期望的，由此降低了不稳定的自由基的生成。类似地，脱氧活性是重要的，使得由放热性的脱氧反应提供加氢热解的反应热，由此消除了对于加氢热解反应器外部加热的需求。加氢热解超出现有的热解工艺的优点在于加氢热解避免了热解的逆向反应，后者通常在惰性气氛下发生，在无H2存在时和通常在无催化剂存在时几乎必然发生，并由此促进了不希望的多环芳族化合物、自由基和原始生物质中不存在的烯烃化合物的形成。若加氢热解在较低的温度下进行，会趋向于产生较长链的分子。若加氢热解在较高的温度下进行，这些分子会趋向于断裂，产生具有更短的碳链的分子并增加该步骤期间产生的甲烷的比例。
本发明的第一阶段的加氢热解步骤是在比常规的加氢转化工艺的典型温度更高的温度下操作，由此所述生物质迅速脱除挥发成分。因此，该步骤需要活性催化剂来稳定加氢热解的蒸气，但不能活性过高使得催化剂迅速结焦。催化剂颗粒尺寸优选大于约100微米。尽管在加氢热解步骤中可以采用任何尺寸的适用于该工艺的温度范围的脱氧催化剂，但是按照本发明的优选实施方式的催化剂为如下：
玻璃-陶瓷催化剂 — 玻璃-陶瓷催化剂是极为结实和耐磨的并且可以制备为热浸渍的（即负载型的）或本体催化剂。当用作硫化的NiMo、Ni/NiO、CoMo、或Co基玻璃-陶瓷催化剂、硫活化的催化剂时，得到的催化剂是易得的但是更软的常规NiMo、Ni/NiO、或Co基催化剂的耐磨型式。玻璃陶瓷的硫化的NiMo、Ni/NiO、或Co基催化剂尤其适用于热的流化床，因为这些材料可以更结实、更耐磨得多的形式，提供常规负载型催化剂的催化作用。此外，由于催化剂的耐磨性，当加氢热解反应在反应容器中进行时，生物质和焦同时被磨成较小的颗粒。由此，由于催化剂的极高的强度和耐磨性，最终回收的焦基本上不含来自催化剂的催化剂污染。按照标准的、高速喷射杯磨损指数测试测定，催化剂的磨损率通常小于约2重量%/小时，优选小于1重量%/小时。定期添加催化剂以补充催化剂的损耗。
磷化镍催化剂 — 磷化镍催化剂工作时不需要硫，也不会硫中毒，因此在无硫环境中与在含H2S、COS和其它含硫化合物的环境中具有同样的活性。因此，该催化剂对于基本不含或不含硫的生物质与对于含硫的生物质（如，玉米秸）具有同样的活性。该催化剂可以浸渍到炭上作为单独的催化剂或是直接浸渍到生物质进料本身内。
铝土矿 — 铝土矿是极为价廉的材料，因此可以用作一次性催化剂。铝土矿上也可以浸渍其它材料例如Ni、Mo、或者硫化。
浸渍有NiMo或CoMo并硫化形成的加氢转化催化剂的小尺寸的喷雾干燥的二氧化硅-氧化铝催化剂 — 市售的NiMo或CoMo催化剂通常以1/8到1/6英寸的较大尺寸的片提供以用于固定床中。在当前情况下，NiMo浸渍在喷雾干燥的二氧化硅氧化铝催化剂上并用于流化床。该催化剂与常规的NiMo或CoMo催化剂相比表现出更高的强度而且具有流化床中适用的尺寸。
氧化铝载体也可以用作加氢热解催化剂。该氧化铝载体可以是具有适当表面积和尺寸的γ氧化铝，或者如通常用作加氢处理催化剂载体时那样在其上配置有磷。
在加氢热解和加氢转化步骤之间，从加氢热解产物中去除焦，通常通过惯性分离，例如旋风分离器、或屏障过滤如卡口式过滤器。在常规的快速热解中，难以达到有效地去除焦，因为当焦捕获在过滤器表面上时，它会与源自热解的高度氧化的烃蒸气反应生成焦油状的烃，其覆盖并将捕获的焦结合形成密实的尘饼并持久地堵塞热的工艺过滤器。与在惰性气氛中进行的快速热解相比，在加氢热解中，所产生的氢化蒸气是非反应性的、低分子量的烃，其在整个过程中保持气体状态并通过屏障过滤器而不会发生反应或沉积。因此，在集成的加氢热解和加氢转化中，可以按照本发明工艺通过过滤从蒸气流中去除焦。可以采用脉冲反洗来从过滤器上去除焦，只要在本发明工艺中使用的氢充分氢化并由此降低离开加氢热解反应器的加氢热解蒸气的反应性。静电集尘、惯性分离、磁性分离、或这些技术的结合也可以用于从热的蒸气流中去除焦和灰分颗粒。
基于其耐磨性，玻璃-陶瓷催化剂更易于通过能量惯性分离技术与焦分离，该技术通常采用能量冲击、拦截、和/或扩散工艺，有时与静电除尘结合来将焦分离、浓缩和收集到第二物流用于回收。这些材料的额外优点在于它们易于通过磁性分离（在还原状态下，会被永久磁场或电感应磁场吸引），也可以采用磁性技术以及磁性、惯性和静电手段的结合来从这些不可能具有更软材料的催化剂中分离焦。
按照本发明的一种实施方式，热气体过滤可以用于去除焦。在加氢热解的情况下，由于氢已经稳定了自由基并使烯烃饱和，因此过滤器上捕获的尘饼比在常规快速热解中产生的气溶胶的热过滤中去除的焦更加易于清洁。
按照本发明的另一种实施方式，热气体过滤可以结合注入适合的吸附剂或吸附剂混合物来去除某些杂质。在该实施方式中，吸附剂在过滤器元件上在载有颗粒的气体进入之前形成滤饼，或者在第二个、后续的热气体过滤器中形成滤饼，在该后续过滤器处来自加氢热解或加氢气化的细粉/粉尘颗粒已经被去除了。可以提供冷却从而使过滤器在最佳条件下操作，其通过所选的吸附剂或吸附剂组合来去除特定的污染物或污染物组合。可以提供装置来脉冲反洗累积的吸附剂和/或积聚在过滤器上的吸附剂/细粉饼，由此去除在选定的操作条件下与所用的吸附剂反应的杂质。
在去除焦之后，将来自第一反应阶段加氢水解步骤的输出引入第二阶段的加氢转化反应器容器11，在其中使它经受第二反应阶段的加氢转化步骤以将任何烯烃转化为甲烷。该步骤优选在比第一反应阶段加氢热解步骤更低的温度（850-950℉）下和与第一反应阶段加氢热解步骤基本相同的压力下（100-600psig）进行。该步骤的重时空速（WHSV）在从约0.2到约3的范围内。若加氢转化催化剂能够被保护免于中毒，则催化剂的寿命有望增加。因此，应当保护该步骤中使用的催化剂免受Na、K、Ca、P和生物质中存在的其它会毒害该催化剂的金属的作用。该催化剂还应当通过在加氢热解反应器中进行的催化剂升级来保护它免受烯烃和自由基的作用。通常选择用于该步骤的催化剂是高活性加氢转化催化剂，例如硫化的NiMo和硫化的CoMo催化剂。在该第二反应阶段中，催化剂可以用于催化CO+H2O的水煤气变换反应来制备CO2+H2，由此能够原位制备氢气，继而减少了加氢转化对于氢气的需求。
按照本发明的一种实施方式，生物质进料是水生生物质，可能含有较高比例的脂质，例如藻类，或是含较低脂质的水生植物，例如浮萍。本发明的集成的工艺对于水生生物质的转化是十分理想的，因为它可以用于通常仅部分脱水的水生生物质并且仍然能够产生较高品质的产品气体收率。
图2显示了本发明方法的另一实施方式，其中将来自CO2分离单元18的输出供应到甲烷水合物回收工艺25，其产生纯净的甲烷流和H2流，其中H2流可以再循环回到第一阶段的加氢热解反应器容器10。甲烷水合物回收工艺的采用消除了对于甲烷化器的需求并且制备出纯净得多的甲烷产物。
尽管在前述的说明中已经结合某些优选的实施方式对本发明进行了描述，而且更多的细节也已经阐述作为说明之用，但是本领域的技术人员容易理解本发明易于做出其它的实施方式并且本文所述的某些具体细节可以合理地变化而不会背离本发明的基本原理。

Claims (26)

1.用于由生物质制备甲烷的方法，其包括以下步骤：
a) 在含有分子氢和脱氧催化剂的加氢热解反应器容器中使生物质加氢热解，产生包含焦和蒸气的加氢热解产物；
b) 从所述加氢热解产物中分离出所述焦，产生脱焦后的加氢热解产物；
c) 在加氢转化反应器容器中使用加氢转化催化剂使所述脱焦后的加氢热解产物加氢转化，产生加氢转化产物；
d) 从所述加氢转化产物分离冷凝的液态水和气态混合物，所述气态混合物包含CO2、H2和甲烷，其中所述气态混合物不含焦；和
e) 将所述气态混合物的至少第一部分作为进料引入蒸汽重整器，产生重整器CO2和重整器H2；以及
f) 将所述气态混合物的至少第二部分引入甲烷化反应器，形成额外的甲烷，
其中加氢热解步骤a)和加氢转化步骤c)均为放热的。
2.权利要求1的方法，其中将所述冷凝的液态水引入所述蒸汽重整器中用于重整所述甲烷。
3.权利要求2的方法，其中将来自外部来源的水引入所述蒸汽重整器中用于重整所述甲烷。
4.权利要求1的方法，其中将进料给蒸汽重整器的所述进料的第一部分引入燃烧器并燃烧，由此加热进料给蒸汽重整器的所述进料的第二部分，其与蒸汽一起引入到所述蒸汽重整器中，形成所述重整器CO2和所述重整器H2。
5.权利要求1的方法，其中在炉子中燃烧从加氢热解产物中分离出的焦的一部分，从而加热进料给所述蒸汽重整器的所述进料，其与水一起引入所述料流重整器，形成所述重整器CO2和所述重整器H2。
6.权利要求1的方法，其中在蒸汽锅炉的燃烧室中燃烧所述焦的一部分以产生蒸汽，该蒸汽与进料给所述蒸汽重整器的所述进料一起引入所述蒸汽重整器中。
7.权利要求1的方法，其中将所述重整器H2的至少一部分引入所述甲烷化反应器中，以形成额外的甲烷。
8.权利要求1的方法，其中将所述重整器H2的至少一部分再循环回到所述加氢热解反应器容器用于所述生物质的所述加氢热解。
9.权利要求1的方法，其中所述脱氧催化剂和所述加氢转化催化剂中的至少一者是玻璃-陶瓷材料。
10.权利要求1的方法，其中所述加氢热解在约0.2到约10克生物质/克催化剂/小时的重时空速下进行。
11.权利要求1的方法，其中所述加氢转化在约0.2到约3克生物质/克催化剂/小时的重时空速下进行。
12.权利要求1的方法，其中所述加氢热解反应器容器是包含流化床的流化床反应器。
13.权利要求12的方法，其中在所述加氢热解反应器容器中的气体停留时间小于约1分钟。
14.权利要求12的方法，其中基本上仅自所述流化床上方从所述流化床反应器中去除所述焦。
15.权利要求1的方法，其中所述加氢热解反应器容器是包含流化床的流化床反应器，并且通过采用惯性、静电、和磁性工艺中的至少一者的能量型焦分离来从所述流化床反应器中去除所述焦。
16.权利要求1的方法，其中所述脱氧催化剂选自硫化的CoMo、硫化的NiMo、催化活性的玻璃-陶瓷、铝土矿、焦、和它们的混合物及组合。
17.权利要求1的方法，其中使用通过注入混合物或者单一的所选吸附剂预热的热气体过滤器来从自加氢热解反应器容器和加氢转化反应器容器中一者排出的气体中去除所选的杂质。
18.权利要求7的方法，其中引入所述甲烷化反应器的重整器H2的所述部分是使用变压吸附(PSA)与所述重整器CO2分离的H2。
19.权利要求1的方法，其中在步骤(d)中分离的包含CO2、H2和甲烷的所述气态混合物是对所述加氢转化产物的气体进行的水煤气变换反应的产物。
20.加氢热解方法，包括：
a) 在流化床加氢热解反应器中在脱氧催化剂存在下使用用于流化的含氢气体使生物质加氢热解，以产生加氢热解产物；
b) 在加氢转化反应器中在加氢转化催化剂和氢气存在下使所述加氢热解产物加氢转化，以产生加氢转化产物；
c) 从所述加氢转化产物分离冷凝的液态水和气态混合物，所述气态混合物包含CO2、H2和甲烷；以及
d) 将所述气态混合物的至少第一部分引入甲烷水合物回收工艺，以产生纯净的甲烷流和氢气，该氢气被再循环到加氢热解反应器，
其中加氢热解步骤a)和加氢转化步骤b)均为放热的。
21.权利要求20的方法，还包括将所述气态混合物的至少第二部分作为进料引入蒸汽重整器，产生重整器CO2和重整器H2。
22.权利要求21的方法，其中将所述冷凝的液态水引入所述蒸汽重整器中用于重整所述甲烷。
23.权利要求21的方法，其中将进料给蒸汽重整器的所述进料的第一部分引入燃烧器并燃烧，由此加热进料给蒸汽重整器的所述进料的第二部分，其与蒸汽一起引入到所述蒸汽重整器中，形成所述重整器CO2和所述重整器H2。
24.权利要求21的方法，其中将所述重整器H2的至少一部分再循环回到所述加氢热解反应器容器用于所述生物质的所述加氢热解。
25.权利要求20的方法，其中使用通过注入混合物或者单一的所选吸附剂预热的热气体过滤器来从自加氢热解反应器和加氢转化反应器中一者排出的气体中去除所选的杂质。
26.权利要求1的方法，其中在步骤(c)中分离的包含CO2、H2和甲烷的所述气态混合物是对所述加氢转化产物的气体进行的水煤气变换反应的产物。
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