CN101874099A - 生物质快速热转化 - Google Patents

生物质快速热转化 Download PDF

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CN101874099A
CN101874099A CN200880117154A CN200880117154A CN101874099A CN 101874099 A CN101874099 A CN 101874099A CN 200880117154 A CN200880117154 A CN 200880117154A CN 200880117154 A CN200880117154 A CN 200880117154A CN 101874099 A CN101874099 A CN 101874099A
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巴里·A·弗里尔
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Abstract

本发明提供改进的快速热转化工艺，用于通过大规模生产将木材、其它生物质原料和其它碳质原料(包括烃)高效转化成高产率且有价值的液体产物如生物油。在一个实施方案中，生物质原料如木材进料至转化系统，在其中生物质原料与热的载热体如砂的上升流混合，将生物质热转化为热蒸气流。在一个或多个位于转化系统下游的冷凝室中用淬火介质使所述热蒸气流快速淬火。快速淬火使蒸气流冷凝成液体产物，从冷凝室中将其作为有价值的液体产物进行收集。在一个实施方案中，所述液体产物本身用作淬火介质。

Description

生物质快速热转化
技术领域
本发明涉及将木材和/或其它生物质快速热转化成高产率且有价值的液体产物，例如生物油。
背景技术
生物质在大部分人类历史上是能量的主要来源。在十九世纪和二十世纪，随着化石燃料经济发展的出现，世界能源中源自生物质的比例急剧下降，煤炭和石油产物占据了市场。尽管如此，世界能源的15％仍然源自生物质，并且在发展中世界，生物质对能源供应的贡献接近38％。
通常为木材或木材残余物的固体生物质通过施加热而转化成有用的产物如燃料或化学品。最常见的热转化实例是燃烧，其中加入空气并且使整个生物质原料燃烧以提供热燃烧气从而产生热和蒸汽。第二个实例是气化，其中一小部分生物质原料与空气一起燃烧，以将其余生物质转化为可燃性燃料气。称为发生炉煤气的可燃气表现出类似天然气的特性，但是其通常只有天然气能含量的10～30％。最后一个热转化实例是热解，其中固体生物质在基本无空气存在下转化成液体和炭以及气体副产物。
在一般意义上，热解是通过热作用将生物质转化为液体和/或炭，通常在转化单元中不使用直接燃烧。小量可燃气也是典型的副产物。历史上，热解是相对缓慢的过程，其中所得到的液体产物是粘性焦油和“木干馏”液体。常规慢热解通常发生在400℃以下并且处理时间从几秒钟到几分钟。用于木炭生产的一些慢热解过程所采用的处理时间可以为数小时。
在二十世纪70年代末发现了更现代的热解形式，称为快速热解，当时研究人员注意到产率非常高的轻质易流动液体可能来自生物质。事实上，如果热解温度适度提高并且使得转化在通常少于5秒的极短时间内发生，则液体产率有可能接近所输入的木材生物质原料重量的80％。
来自快速热解的均质液体产物具有蒸馏咖啡的外观并且已经公知为生物油。生物油作为燃料适用于锅炉中的清洁受控燃烧并且适用于柴油涡轮机和固定式涡轮机。这与以非常低的产率产生稠密且低质量的两相焦油-水混合物的慢热解形成鲜明对比。
在实践中，固体生物质的快速热解导致其固体有机物质的主要部分瞬间转化成气相。该气相既包括不可凝气体(包括甲烷、氢气、一氧化碳、二氧化碳和烯烃)，也包括可凝蒸气。正是可凝蒸气构成最终的液体生物油产物，这种生物油产物的产量和价值与下游的捕获和回收系统的方法和效率密切相关。快速热解过程中产生的可凝蒸气继续在气相中反应，因此必须在其可能劣化成为低价值的液体和气体产物之前使其在下游过程中迅速冷却或“淬火”。由于快速热解设备被扩大规模用以商业运行，因此必须特别注意液体生物油产物的迅速冷却、淬火和回收的策略和手段。
发明内容
本发明提供一种改进的生物质快速热转化方法，该方法通过大规模生产实现从气相高效回收高产率且有价值的液体产物(例如生物油)。
在一个实施方案中，将生物质原料例如木材进料至转化系统，在其中在基本无氧的环境和350～600℃的热转化温度范围下，使生物质原料与热的载热体如砂的上升流混合。热的载热体与生物质原料热接触，使得生物质转化成热蒸气流，所述热蒸气流被冷却、冷凝并且在下游回收为液体产物。在一个优选实施方案中，热转化的温度为约500℃，保留时间小于5秒，更优选小于2秒。
热蒸气流被引导至冷凝室或多个冷凝室，在其中热蒸气流从约350℃至600℃的转化温度在小于1秒的时间内快速冷却到低于100℃的温度，更优选在小于100毫秒的时间内冷却到低于50℃的温度，最优选在小于20毫秒的时间内冷却到低于50℃的温度。在一个优选实施方案中，向上流动的蒸气流通过利用向下流动的淬火介质快速淬火蒸气流而冷却。这种通过向下流动的淬火介质进行的快速直接的冷却或淬火使得蒸气流冷凝成液体产物。在一个优选实施方案中，将一部分冷凝的液体产物排出冷凝室或多个冷凝室，并将其冷却并循环回到冷凝室或多个冷凝室，以提供淬火介质。用作淬火介质的液体产物在循环回到冷凝室之前可以冷却到30℃～50℃的温度。优选地，淬火介质向下倾倒的速率为至少10gpm/ft2(加仑每分钟/平方英尺)冷凝室截面积，更优选的速率为至少50～100gpm/ft2。冷凝室内的液体产物作为有价值的液体产物如生物油进行收集，其可用作例如燃料和/或用于其它商业用途。本发明的方法能够生产高产率的有价值的液体产物，例如产率为约输入生物质原料的75％或以上。
在一个实施方案中，位于第一冷凝室下游的第二冷凝室用于冷凝在第一冷凝室中未冷凝的蒸气，以提高液体产物的产率。第二冷凝室可以使用与第一冷凝室相同或不同的淬火介质。
在一个实施方案中，除雾器和过滤器与第一和/或第二冷凝室相连，以清除离开冷凝室的气流中的微小颗粒，并从气流中收集附加的液体产物。
优选地，该转化和收集过程是在大气压或接近大气压下进行的，这使得生物质的进料、转化和液体产物的收集更容易也更安全。这也允许生物质以利于大规模工业生产液体产物的高速率连续进料到转化系统。
根据以下结合附图的详细说明，本发明各实施方案的上述及其它优点将显而易见。
附图说明
图1示出根据本发明的一个示例性实施方案的热转化和液体产物收集系统的图。
图2示出根据本发明的一个示例性实施方案的生物质原料进料到热转化系统的进料系统。
图3示出根据本发明的一个实施方案的用于再加热载热体的再加热器。
图4是示出根据本发明的实施方案的示例性热转化方法的结果的表。
具体实施方案
图1示出根据本发明的一个示例性实施方案的用于将生物质如木材转化成高产率液体产物的快速热转化系统10。
进料系统
进料系统15用于提供固体生物质原料到转化系统10的调节流量。优选地，生物质原料是干燥的木材原料，也可以是木屑的形式，但液相和蒸气相(气相)生物质原料可在快速热转化系统中使用可选的液相或气相进料系统进行有效处理。可用的生物质原材料包括但不限于：硬木、软木、树皮、农业和造林残留物和其它生物质碳质原料。本发明实施方案还可以应用于其它碳质原料的转化，所述碳质原料包括但不限于：塑料、聚合物、烃、石油、煤炭和精炼原料。由于转化系统在稍高于大气压力(即足够克服下游设备背压的压力)下运行，因此进料系统15应在稍高压力(1.2大气压)下向转化系统10提供原料，而同时在大气压力下从例如木材贮存仓接收原料物质。为了实现原料以这种方式持续供应，使用锁斗系统，其在图2中详细示出。
进料系统10包括原料缓冲仓17、料仓20和在原料缓冲仓17与料仓20之间的输送阀22，例如刀闸阀。阀22使缓冲仓17与料仓20隔开，并且优选包括弹性体座以确保气密密封。阀22允许在大气条件下将原料填充至缓冲仓17，同时保持料仓20密封，以使料仓20可以在高于大气压下运行。
原料缓冲仓17优选为碳素钢构建的圆筒形容器并且具有足以容纳足够原料的容积，例如在重新填充之前具有约30分钟的原料输送。缓冲仓17配备有底部出料系统和用于移出所容纳的生物质原料的内部桥断装置。桥断装置的例子包括具有或不具有指形突出物的扫臂、振动设备、回转链等。从缓冲仓17排放原料的速率可以是固定的并且是在约10分钟内完成的全输送周期。可以使用三个料位传感器(高料位开关高，低料位开关低，低-低料位开关)来激活原料输送。此外，可利用料位变送器实现连续监测缓冲仓17中的原料料位。当缓冲仓17中的料位下降到激活低料位开关时，原料将从原料存储系统(未显示)自动输送到缓冲仓17。高料位开关指示缓冲仓满并终止从原料储存系统输送原料。低-低开关是备份开关，用于在低料位开关未被触发时指示空仓。这可能在例如原料留在低料位开关上方导致给出误读的情况下发生。当缓冲仓进行填充时，阀22关闭。
当料仓20内的料位达到低料位开关时，原料自动从缓冲仓17输送到料仓20。在打开阀22之前，缓冲仓17的压力与料仓20的压力相等。当缓冲仓17位于料仓20的正上方而阀门22打开时，原料可以通过直接输送从缓冲仓17输送到料仓20。作为替代方案，如果箱仓偏置时，则可以使用螺钻或螺杆给料机系统(未显示)将原料从缓冲仓17输送到料仓20。螺钻或螺杆可根据两个仓的相对方位进行水平或倾斜设置。料仓20优选由碳钢构建并且装配有测定体积的底部出口给料器。测定体积的给料器提供计量原料流到恒速的转化进口螺杆输送机35，输送机35将原料输送到转化系统10。操作者可以通过调节螺杆输送机35的速度来调节所需的原料流。为了提供原料调节，引入内部桥断系统。
恒速螺杆输送机35由不锈钢构建并且配置有高温密封和轴承。输送机35可以恒定速度运行并且能够以高于测定体积给料器所提供的速率将原料排放至转化系统10。这确保了均匀、分散的原料流。为安全起见，螺杆35的出口装配有紧急隔离刀阀和水淬火系统。
热转化系统
热转化系统10包括反应器30，其在混合区域将原料与向上流动的热的载热体流例如砂混合。反应器是基本无氧的。原料在混合区正下方进入反应器30，并且与向上流动的热的载热体(砂)流及其输送流体(循环气体)接触。其结果是彻底和迅速的混合以及从载热体向原料进行导热传递(包括烧蚀(ablation))。热的载热体即刻将原料快速烧化成热蒸气，然后将热蒸气冷却、冷凝并且下游回收为液体产物。
原料的热转换在合适温度例如约500℃(约930°F)下在混合区中开始，并且继续通过位于反应器30下游的分离系统40。在反应器中的停留时间优选少于5秒，更优选小于2秒。在分离系统40中从产物蒸气流中移除固体载热体和副产物炭。优选地，分离系统装配有高耐磨内衬以尽量减少过早失效的可能性。通过分离系统40的产物蒸气流被引导至下游液体产物回收系统50。
在图1所示的实施方案中，分离系统40包括两个旋风分离器43和45。第一旋风分离器43将固体载热体和副产物炭与产物流分离。已在第一分离器43中移除的固体被引导至再加热器单元47。第二分离器45移除在第一分离器43中未被移除的炭。图3中更详细地示出再加热器单元47。
在再加热器单元47中，副产物炭通过加入空气而转化成热和燃气。通常，副产物炭和气体燃烧产生的热足以满足热转化过程的热需求(外部燃料如天然气很少使用，一般只用于系统启动)。来自再加热器的多余热量可以高效地用于其它用途，包括生物质干燥、产生蒸汽、空间加热、发电等。再加热器中产生的热量提升了固体载热体的温度，该固体载热体然后可被输送到反应器30中的原料，以达到所需的反应温度。
液体产物收集系统
来自固体分离系统40的热蒸气产物流经由绝热管引导到主收集柱或冷凝室50。优选地，热蒸气流从约350℃至600℃的转化温度在小于1秒内降到低于100℃。更优选地，热蒸气流在小于0.1秒(100毫秒)内降到低于50℃，最优选在小于20毫秒内降到低于50℃。主收集柱50配备有位于柱50上部的液体分配器53。冷却的液体产物或其它合适的淬火介质(如水、柴油、其它石油基液体、聚山梨醇酯等)通过分配器53循环，并且允许它们“落下”到进入的蒸气流上。可以采用各种类型的分配器系统。例子包括但不限于：叶片、管道、烟囱、指形分配器、喷头、喷嘴设计、托盘、填料等。优选地，至少10gpm/ft2(加仑每分钟/平方英尺)柱截面直径的淬火液体循环经过收集柱。更优选地，至少50～100gpm/ft2(加仑每分钟/平方英尺)柱截面直径的淬火液体循环经过收集柱。沿着柱流下的液体密集流不仅用来对进入的蒸气进行立刻冷却和淬火，而且为液体产物的收集提供成核位点。通常，热蒸气正好在柱50中收集的液体的正常操作液位上方进入收集柱50。未在主收集柱50中收集的蒸气与不可凝气体一起经过上出口端55离开柱50。这种运行模式是逆流的。在期望尽量减少热蒸气管道长度的另一运行模式中，热蒸气通过柱50的上部进入，并且在主收集柱50中未被收集的蒸气与不可凝气体一起经过位于柱下部(正好在正常液位上方)的端口离开。这种运行模式是并流的。柱50可在柱的气体出口段装配有除雾器以减少夹带进入第二收集柱60的液滴。
与向下流动的雾化淬火流合并的冷凝液聚集在柱50的下部。此外，重的冷凝液滴因重力沉降而下降到柱50的下部。柱50中的液位变送器用于监测和维持所需的液位。在一个实施方案中，一部分液体产物从柱50中抽出并且用冷凝泵57泵抽经过换热器58以冷却液体产物至例如30至50℃。换热器58的冷却介质可以是水。也可以使用其它冷却手段，包括乙二醇系统、空气冷却器等。冷却的液体产物循环回到柱分配系统53，用以为进入的蒸气流提供淬火介质。
将收集柱中的液体产物泵出到产物贮存罐(未显示)，以维持所需的液位。所收集的液体产物提供有价值的液体产物即生物油，它们可以用作例如燃料和/或用于其它商业用途。
蒸气迅速淬火是因为蒸气和液体产物是热不稳定的(在较高温度下发生化学反应)。通过使用高液体循环/淬火速率，进入的蒸气被迅速淬火，从而避免了在较高温度下发生不期望的化学反应如聚合反应。此外，用作淬火介质的液体产物的高循环速率防止淬火介质达到不期望的高温。
在主收集柱50或容器中未被收集的蒸气被引导至辅收集柱60(辅冷凝柱)。同样如主冷凝柱50中的情况一样，所收集的产物液体经由顶置分配系统63用作淬火介质。优选地，至少10gpm/ft2(加仑每分钟/平方英尺)柱截面直径的液体循环经过柱60。更优选地，至少50～100gpm/ft2(加仑每分钟/平方英尺)柱截面直径的液体循环经过柱60。柱60可在柱60的气体出口段装配有除雾器以减少夹带进入下游除雾器或过滤系统的液滴、雾或气溶胶。柱60的截面直径可以与主收集柱50的相同。但是，柱60的直径通常较小，因为更大的表观气体速度将有利于移除柱60的除雾器部分中的微细液滴或气溶胶。
离开辅收集柱60的雾、气溶胶和不可凝气体被引导至单独的除雾器系统70。如果辅收集柱60配备有内部除雾器单元，则可不需要下游单独的除雾器。除雾器系统70优选移除大于3微米的雾滴。倾向于在除雾器中通过惯性碰撞来捕获这些液滴。在气流中行进的这些颗粒在流经除雾系统70时由于其重量而不能突然改变随气体的流动方向。结果，它们撞击除雾器的纤维，然后被捕获。与除雾器纤维接触的雾粒通过弱范德华力粘合。累积的碰撞雾滴倾向于结合在一起形成较大的单个液滴，最后因重力沉降而落到除雾器容器的下部。
除雾器系统70可包括一系列除雾器单元。第一单元是叶片除雾器，其可消除约99％的低至10微米的雾。接着是具有约5lb/ft3的密度和0.011英寸线径的不锈钢丝网垫(表面积为45ft2/ft3并具有99.0％的空隙)。除钢外可使用的其它材料包括玻璃、合金20、聚四氟乙烯、聚丙烯等。然后是9lb/ft3的不锈钢丝网垫，线径同样为0.011英寸(表面积为85ft2/ft3并具有98.0％的空隙)。最后的除雾器单元是共编织类型，包括由纤维玻璃构造的金属丝。该垫的密度为9lb/ft3，线径为0.00036英寸(表面积为3725ft2/ft3并具有99.0％的空隙)。
微细气溶胶(即小于约3微米)、从除雾器系统70逸出的大于3微米的冷凝颗粒和来自辅冷凝柱60或除雾器系统70的不可凝气体来到最后的过滤系统80。过滤系统80可包括两个并联设置的纤维床80A和80B，如图1所示。同样地，如除雾器系统70的情况一样，大于约3微米的颗粒通过惯性碰撞被捕获。1至3微米的冷凝颗粒倾向于通过拦截而捕获，其中该颗粒遵循在纤维表面的约一个颗粒半径内的不可凝气体流线。而小于1微米的颗粒则通过扩散或布朗运动被捕获，其中颗粒由于其随机运动而倾向于自身附着到过滤器80的纤维上。同样，捕获的颗粒倾向于结合在一起形成较大的液滴。但是，在足够量的原料流到过滤容器的下部之前，跨越过滤器80的压力降可能超过预定限制。此外，由于液体局部负荷增加，过滤器的有效开口截面积降低，从而增大经过保留开口区域的气体流量，因此收集的原料可能会出现再夹带。该增大的气体流量导致速度增加，其可导致比预期更大的压力降，并可能出现再夹带和捕获液体的损失。因此，过滤系统80可以由多于一个的过滤单元组成，其可以根据需要并联或串联设置。通常采用2个并联的过滤单元80A和80B，其中一个过滤单元随时在线。过滤单元可保持在线约8～24小时(一般12小时)时间段。当过滤单元处于关闭离线状态时，其允许排空。过滤单元的压力降也可决定单元允许保持在线的时间段。超过预定限制的压力降(通常为100英寸水柱)可导致过滤单元的过滤元件失效(即在织物中可发展出撕裂孔)。
由于收集的雾和气溶胶液体在环境条件下倾向于是相对粘滞的，因此可在辅冷凝柱60和除雾器70和纤维床过滤器80A和80B之间使用再换热器90。作为替代方案，如果在辅冷凝柱60中并入除雾器，则再换热器将仅安装在纤维床过滤器80A和80B的上游。该再换热器90用于稍微提高蒸气流的温度(至约60～65℃)，并使得在下游系统70和80中捕获的液体的粘度能够充分降低，以允许充分排空。
经过滤系统80过滤的气体通过反应器风机95循环回到反应器30。循环的气体为反应器30的混合区中载热体的向上流动提供输送流体。
下面将讨论根据本发明实施方案的示例性热转化过程的结果。在这些实施例中，主收集柱和辅收集柱各自具有约4英尺的直径。生物质原料进入转化系统的进料速率在约2650至3400磅/小时之间不等。进入的蒸气的温度为约500℃，流量为约1100标准立方英尺每分钟(scfm)。在这些实施例中，各个收集柱的液体产物的一部分被冷却并循环回到收集柱以提供淬火介质。下表1示出了9个示例性过程参数的淬火温度和再循环速率。淬火温度是冷却的液体产物在注射回收集柱之前的温度，再循环速率是在收集柱顶部的液体产物的流量。
表1：淬火温度和再循环速率
  实施例   生物油淬火温度(℃)   生物油循环速率(GPM)
  1   36   750
  2   30   760
  3   41   715
  4   36   670
  5   30   675
  6   41   675
  7   36   625
  8   30   625
  9   41   625
这九个实施例的结果示出在图4的表2中。各个实施例过程在约12小时的时间段内进行。表2示出在主收集柱和辅收集柱或冷凝器中收集的生物油的百分比分布，其中辅收集柱中的收集包括来自除雾器和纤维床过滤器的生物油收集。表2还示出从主收集柱和辅收集柱中收集的生物油的特性。
虽然本发明在目前优选的实施方案方面进行了描述，但是应理解的是本公开内容不能理解为限制。在阅读本发明公开内容后，对本领域技术人员而言各种改动和修改无疑将变得显而易见。因此，旨在将所附权利要求解释为涵盖所有落入本发明的精神和范围内的改变和修改。

Claims (14)

1.一种将生物质或非生物质原料转化为液体产物的方法，包括：
在反应器中将原料与固体载热体混合，以在350～600℃的转化温度下将所述原料热转化为蒸气流；
将所述固体载热体与所述蒸气流分离；
在冷凝室中利用淬火介质将所述蒸气流在小于1秒内快速淬火至低于100℃的温度，以将所述蒸气流冷凝成液体产物；和
收集来自所述冷凝室的液体产物。
2.如权利要求1所述的方法，其中所述原料包括生物质原料。
3.如权利要求2所述的方法，其中所述生物质原料基本包括木材。
4.如权利要求1所述的方法，其中所述原料包括非生物质碳质原料。
5.如权利要求4所述的方法，其中所述非生物质碳质原料包括塑料、聚合物、烃、石油、煤炭或精炼原料。
6.如权利要求1所述的方法，还包括：
将液体产物泵抽出所述冷凝室；
将泵抽出的液体产物冷却到约30℃～50℃的温度；和
将冷却的液体产物循环回到所述冷凝室以提供所述淬火介质。
7.如权利要求6所述的方法，其中所述淬火介质以至少10加仑每分钟(gpm)每平方英尺所述冷凝室截面积的流量向下倾倒至所述蒸气流上。
8.如权利要求7所述的方法，其中所述淬火介质以至少50加仑每分钟(gpm)每平方英尺所述冷凝室截面积的流量向下倾倒至所述蒸气流上。
9.如权利要求1所述的方法，其中所述蒸气流在小于0.1秒内淬火至低于50℃的温度。
10.如权利要求9所述的方法，其中所述蒸气流在小于0.02秒内淬火至低于50℃的温度。
11.如权利要求1所述的方法，其中所述固体载热体基本包括砂。
12.如权利要求1所述的方法，其中所述热转化产生副产物炭，所述方法还包括：
将从所述蒸气流中分离出的所述副产物炭和所述载热体引入再加热器单元；
在所述再加热器单元中燃烧所述副产物炭以再加热所述载热体；和
将再加热的所述载热体引回到所述反应器以热转化进入的原料。
13.如权利要求1所述的方法，还包括：
将在所述冷凝室中未冷凝的所述蒸气流的一部分引导通过除雾器和过滤系统；
收集所述除雾器和过滤系统中的附加的液体产物；和
将从所述除雾器和过滤系统中输出的气体引导至所述反应器，以在所述反应器中提供载热体流。
14.如权利要求1所述的方法，还包括：
将在所述冷凝室中未冷凝的所述蒸气流的一部分引导至辅冷凝室；
在所述辅冷凝室中利用淬火介质将所引入的蒸气流快速淬火；和
收集来自所述辅冷凝室的附加的液体产物。
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