CN102405379A - 用于太阳热气化生物质的系统和方法 - Google Patents

用于太阳热气化生物质的系统和方法 Download PDF

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CN102405379A
CN102405379A CN2010800174291A CN201080017429A CN102405379A CN 102405379 A CN102405379 A CN 102405379A CN 2010800174291 A CN2010800174291 A CN 2010800174291A CN 201080017429 A CN201080017429 A CN 201080017429A CN 102405379 A CN102405379 A CN 102405379A
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steam
gas
methane
reactor
solar energy
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W·西蒙斯
C·普尔金斯
Z·约凡诺维克
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Sundrop Fuels Inc
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Sundrop Fuels Inc
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Abstract

用于太阳能驱动化学设备的方法、装置和系统,其可包括太阳热接收器,其具有带有内壁的腔体,其中对准所述太阳热接收器,以便从以下的一种或多种吸收会聚太阳能:1)定日镜阵列,2)聚太阳能盘,以及3)两者的任意组合。一些实施方式可以包括太阳能驱动化学反应器,其具有位于所述太阳热接收器的腔体内的多个反应器管,其中由辐射热驱动的化学反应发生在所述多个反应器管中,并且其中生物质的颗粒在同时发生的蒸汽重整和蒸汽生物质气化反应中、在蒸汽(H2O)载气和甲烷(CH4)的存在下被气化,以便利用来自所述多个反应器管中所吸收的会聚太阳能的太阳热能,产生包括氢和一氧化碳气体的反应产物。

Description

用于太阳热气化生物质的系统和方法
相关申请
本申请要求于2009年10月2日提交的题目为“Various Methods andApparatuses for Sun Driven Processes(用于太阳驱动过程的各种方法和装置)”的美国临时专利申请系列号61/248,282,和于2009年6月9日提交的题目为“VARIOUS METHODS AND APPARATUSES FORSOLAR-THERMAL GASIFICATION OF BIOMASS TO PRODUCESYNTHESIS GAS(用于太阳热气化生物质以产生合成气的各种方法和装置)”的美国临时专利申请系列号61/185,492的权益,两者在此通过引用的方式全文并入本文。
版权通告
本专利文献公开的一部分包含受到版权保护的材料。版权所有者不反对当其出现在专利和商标局专利文件或记录中时通过软件引擎及其模块的任何一种进行复制,但在其它方面无论什么都保留全部版权。
技术领域
本发明的实施方式一般地涉及用于炼制生物质和其它材料的系统、方法和装置。更具体地,本发明实施方式的一个方面涉及用于炼制生物质和其它材料的太阳能驱动系统、方法和装置。
背景技术
生物质气化是一个吸热过程;必须在该过程中投入能量,以驱动其气化。通常,这通过部分氧化(燃烧)生物质本身来完成。必须消耗生物质的30%至40%来驱动该过程,在该过程通常限制(因为效率原因)的温度下,转化通常是有限的,造成更低的产量。相比之下,所提出的太阳能驱动生物炼制设备利用外部能源(太阳能)来提供反应所需的能量,因此不需要消耗生物质来实现转化。与之前的技术相比,这可产生显著更高的每吨生物质汽油加仑产量,因为用于驱动转化的能源是可再生并且无碳的。另外,化学反应器通常设计成在不变的条件下昼夜不停地运行。
发明内容
一些实施方式涉及太阳能驱动化学设备,其包括具有带有内壁的腔体的太阳热接收器,其中可对准该太阳热接收器,以便从以下的一种或多种吸收会聚太阳能:1)定日镜阵列,2)聚太阳能盘,以及3)两者的任意组合。
在一些实施方式中,具有多个反应器管的太阳能驱动化学反应器位于太阳热接收器的腔体内。由辐射热驱动的化学反应发生在多个反应器管中。生物质的颗粒可以在同时发生的蒸汽重整和蒸汽生物质气化反应中,在蒸汽(H2O)载气和甲烷(CH4)的存在下被气化,以便利用来自多个反应器管中所吸收的会聚太阳能的太阳热能,产生包括氢和一氧化碳气体的反应产物。
在一些实施方式中,太阳能驱动反应器可位于接收器内,该接受器是将太阳辐射能转变为热能的腔体。该接收器可包括多个反应器管,所述多个反应器管允许甲烷或天然气以及蒸汽通过惰性颗粒的流化床,以引起蒸汽甲烷反应。当天然气通过流时发生甲烷反应,其中CO2和甲烷发生干重整。另外,多个反应器可并入接收器中。
附图说明
附图涉及本发明的实施方式,其中:
图1说明了根据本文描述的系统和方法的实例工艺流程的实施方式的框图;
图2说明了根据本文描述的系统和方法的实例多个管式反应器的实施方式的图;
图3说明了根据本文描述的系统和方法的具有接收器和定日镜区域的实例太阳能塔的实施方式的图;
图4说明了生物质与甲烷太阳热气化的模拟结果;
图5说明了根据本文描述的系统和方法的具有气化器管的太阳热接收器的实施方式的图;
图6说明了根据本文描述的系统和方法的进料系统的实施方式的框图;
图7说明了根据本文描述的系统和方法的太阳能驱动生物炼制设备的实施方式的图;以及
图8说明了本文描述的系统和方法的实施方式的流程图。
尽管本发明可具有各种修改和可选形式,但其具体实施方式已通过实例在图中示出并将在此进行详细描述。本发明应该被理解为不限于所公开的特定形式,而相反地,本发明覆盖了落入本发明精神和范围的所有修改、等同物和可选方案。
详细讨论
在以下的描述中,列举了很多具体细节,例如具体数据信号、命名的组件、连接、反应器管数等的实例,以提供本发明的透彻理解。然而,对本领域技术人员来说,没有这些具体细节,本发明也可实施,这将是显而易见的。在其它情况,没有详细描述熟知的组件或方法,而只是在框图中对其进行描述,以避免不必要地混淆本发明。此外,可做出具体的数字提及,例如第一反应器管。然而,具体的数字提及不应被解释为字面上的连续顺序,而应被解释为第一反应器管是不同于第二反应器管的。因此,列举的具体细节仅仅是示例性的。该具体细节可变化自本发明精神和范围,并且仍被认为在本发明精神和范围内。术语“连接的”(coupled)被定义为直接连接至该组件或通过另一组件间接与该组件相连接的意思。
在一些实施方式中,太阳能驱动化学反应器可具有位于太阳热接收器腔体内的多个反应器管。在腔体内,化学反应可由辐射热驱动。该反应可发生在多个反应器管中。另外,生物质的颗粒可在同时发生的蒸汽重整和蒸汽生物质气化反应中,在蒸汽(H2O)载气和甲烷(CH4)的存在下被气化。可利用来自多个反应器管中所吸收的会聚太阳能的太阳热能,产生包括氢和一氧化碳气体的反应产物。
在一些实施方式中,太阳能驱动反应器位于接收器内,该接受器是将太阳辐射能转变为热能的腔体。该接收器可包括多个反应器管,所述多个反应器管允许甲烷或天然气以及蒸汽通过惰性颗粒的流化床,以引起蒸汽甲烷反应。当天然气通过流时发生甲烷反应,其中CO2和甲烷发生干重整。
图1说明了根据本文描述的系统和方法的实例工艺流程的框图。一些实施方式包括了太阳能驱动生物质气化为液体燃料/电的过程。该过程也可包括用于太阳能产生的合成气衍生产物或其它相似技术过程的生产、化学加工或生物焦炭。在具体实例实施中,所描述过程为太阳能驱动生物质气化为“绿色”液体燃料的过程。在一个实施方式中,该过程包括以下过程步骤的一个或多个。
生物质研磨或致密化、运输和卸载100可为全部过程的一部分。可通过压实机使生物质捆包压缩和致密化,以便于通过由双压缩实现的致密化原位运输。将捆包的大小形成为可例如符合标准箱车尺寸或符合标准压实机尺寸。夹带流生物质进料系统前面可为装备有机械切割设备和颗粒分选器的研磨系统,例如多孔筛或旋风器,以控制颗粒的大小。研磨系统具有机械切割设备例如螺杆,和具有微米大小的孔/筛直径大小的孔的过滤器组,以控制颗粒大小。机械螺杆和过滤器组协作以研磨和粉碎原料生物质成为颗粒,到达过滤器的微米大小的孔,随后将生物质的颗粒送入太阳能驱动化学反应器并在太阳能驱动化学反应器中气化。在一个实施方式中,生物质可为非食品原料生物质。在其它情况下,也可加工食品原料生物质或两者的结合。
在102,生物质可被储存。根据需要,生物质可被送入104本申请的实例系统或装置。例如,在研磨和粉碎生物质成为颗粒后,可将生物质的颗粒送入太阳能驱动化学反应器并在太阳能驱动化学反应器中气化。两条或多条进料线供应具有平均最小尺寸大小在50微米(μm)和2000μm之间的生物质颗粒至化学反应器。夹带气体生物质进料系统用夹带载气将以颗粒进料的各种生物质源移动进入太阳能驱动化学反应器。
太阳接收器和气化器106可用于粉碎生物质。生物质气化器设计和运行的例子可包括太阳能化学反应器和太阳能接收器,以生成合成气组分。
可以从生物质气化器106提供淬火、气体清除和灰分去除108。一些非试验性(non-pilot)合成气可离开系统112。一些气体可为废产物,而其它气体可被压缩114然后进行储存118或例如进行甲醇合成116。随后甲醇可被储存120,用于以后甲醇到汽油的转化122。
在一些实施方式中,可以使用原位燃料合成反应器,其与化学反应器在地理上位于相同的位置,并且将其一体化以接收来自气化反应的氢和一氧化碳产物。另外,原位燃料合成反应器具有入口以接收氢和一氧化碳产物并在烃燃料合成过程中使用它们,以产生液体烃燃料。将原位燃料合成反应器通过距离通常小于15英里的管线与设备设施的剩余部分相连接。原位燃料合成反应器可向控制系统供应不同的反馈参数和其它要求。例如,原位燃料合成反应器可要求控制系统改变淬火产生的合成气的H2与CO的比率,并且设备的气体清除部件和控制系统也将这样工作。
在不同的实施方式中,合成气体可被供应至另一技术应用。实例包括至其它化学转化过程的合成气。产生的其它化学品或多种化学品可包括液化燃料例如运输液化燃料。在基于烃的燃料的实例中,甲醇116可由合成气形成。甲醇可被进一步转化为汽油或其它燃料122,并且可将不同的产物从汽油124或合成气中分离出来。然后这些产物,例如汽油,可作为能源储存以备后用。
如所述,这些生物质原料资源可包括能源作物例如芒属(miscanthus)和柳枝稷草(switchgrass),其为高效果和高收率的能源作物。具有低木质素含量的生物质将使太阳能气化器中的气化和加工更容易。
可将原料生物质例如稻米杆、稻米壳、玉米秸秆、高生物质高粱、柳枝稷、芒属的捆包双倍压缩,以便于通过双倍压缩实现的致密化进行运输,允许在火车车厢中的很高装载量。
一些实施方式利用了天然气的蒸汽重整,有时指的是蒸汽甲烷重整(SMR)。SMR是一种生产用于合成气的氢和一氧化碳的方法。在高温(700~1500℃)并且在例如金属基催化剂(镍)的存在下,蒸汽与甲烷反应产生一氧化碳和氢。在一些实例中,天然气可为地层下的沉积物中发现的甲烷和其它气体的混合物,并且可包含少量的CO2
能量+CH4+H2O→CO+3H2
可通过与产生的一氧化碳进行较低温度的气体变换反应重新获得额外的氢。将该反应概括为:CO+H2O→CO2+H2。然而,有时消除该水煤气变换反应是有益的,以便降低存在于生成的合成气体中的CO2的量。水煤气变换反应的消除可通过在10秒之内将反应器生成的产物在大于900摄氏度的出口温度快速淬火至400度或更低来完成。
在一些实施方式中,二氧化碳重整(也已知为甲烷与CO2的干重整)是一种从二氧化碳与烃例如甲烷的反应生产合成气体(氢和一氧化碳的混合物)的方法。
甲烷二氧化碳重整反应可由下式表示:CO2+CH4→2H2+2CO
在一些利用生物质气化的实施方式中,从夹带流生物质进料系统供应含碳生物质材料颗粒。该颗粒在离开包括以下方面的反应器管前可经历气化反应几个不同的化学过程。例如,最初,含碳生物质颗粒的热解可产生含碳焦炭和蒸发为气体产物的易挥发组分。
在一些实施方式中,包括木质素部分的含碳焦炭的完全气化产生了包括一氧化碳、氢和焦油、以及大于99%的纯含碳灰分的气态产物。另外,统称为焦油的包括较大烃和芳香族化合物的焦油的裂解,可在大于1000℃下发生,以使大量的焦油破坏小于50mg/m3以下并且将大于90%的生物质颗粒完全气化成包括氢和一氧化碳气体的反应产物。
焦油的至少完全气化和裂解的步骤在化学反应器反应区中在0.01和5秒之间范围的生物质颗粒停留时间内开始和完成。热解可以以300℃或更低的温度开始,在进入反应器管前通过载气预热。
太阳热+C6H10O5(纤维素)+H2O(蒸汽)→6CO+6H2
太阳热+C10H12O3(木质素)+7H2O(蒸汽)→10CO+13H2
该热化学过程允许整个生物质原料(纤维素、半纤维素和木质素)转化,由此降低了反应产物中存在的灰分量并且产生了可变通(flexible)的合成气体。在一些实施方式中,发生以上反应中的至少两个,并且通常在实施方式中所有三个反应同时在反应器管中发生。
一些实施方式可利用含碳燃料(例如生物质)的固定床,气化剂例如蒸汽、氧气、空气和/或任意组合通过固定床流入与向下的燃料共流的构造中。另外,蒸汽鼓风流化床气化器可用于产生具有高能值的不含CO2的气体。可选地,生物质的小颗粒可被夹带在天然气和/或气化剂的气体流中,以在生物质气化过程中进行混合。任一种方法,气化区域可具有蒸汽、生物质并且可能有甲烷类反应物,该反应物产生本文描述的生物质气化反应。
接收器通常包括多个反应器管。在一个实施方式中,反应器管允许甲烷或天然气以及蒸汽通过传热辅助设备以发生太阳能驱动蒸汽甲烷反应。该传热辅助设备用于加热反应物气体。该传热辅助设备可为以下位于每个反应器管中的一种或多种:惰性颗粒的流化床,网眼多孔陶瓷(RPC)泡沫、陶瓷整料、陶瓷管或气凝胶、开放结构填料环例如腊希格环,或由耐高温材料构成的线网或金属丝。辐射是将热从反应器管壁传到传热辅助设备的主要模式,传导、对流或两者的一些结合是传热的次要模式。
一些实施方式可将甲烷加入生物质。当与不添加甲烷的系统相比时可包括以下方面:
(1)太阳能反应器产生等当量的合成气的能量要求为低于33%,因此降低了太阳能基本组件的成本。在从H2∶CO为1∶1的合成气至H2∶CO为2∶1的合成气释放的能量可被包含在气体流中(作为显能)。实际上,在纯生物质气化情况中,可吸收更多太阳能,以得到相同量的合成气,但仅仅是因为在气化前实际上不能使显热回到进料流中;以及
(2)以上结果证实了不同的生物质源(“肯塔基蓝草(KentuckyBluegrass)”、木质素、玉米秸秆、高粱)可在高温下、几秒钟内利用太阳能加热的运输管反应器气化,并且可大大降低或消除焦油形成。
图2说明了可用于太阳能驱动系统的实例多管化学反应器200的图。反应器200具有多个反应器管202、204、206、208,单独的夹带线可用于化学反应器200中气化器反应器管202、204、206、208的每一个。这可允许独立的温度控制和流动在多管太阳能驱动化学反应器200的每个反应器管202、204、206、208中的生物质颗粒量的平衡。生物质进料颗粒可通过闭锁料斗旋转进料系统例如Rotofeed
Figure BPA00001447480800071
闭锁料斗旋转进料系统分配到反应器管202、204、206、208中。这样的系统可允许对单个反应器管202、204、206、208的平衡进料,并且颗粒的进料速率由重量测量计量设备例如测力仪控制。也可允许控制螺杆或螺旋钻的旋转速率,其可沿螺旋钻的旋转轴移动一定量的生物质。螺旋钻可位于闭锁料斗的底部并可由计算机化控制系统如可编程逻辑控制器、PC、MAC、CNC等控制,以响应系统的进料要求。在一个实施方式中,计算机化控制系统基于由包括温度传感器和/或照度计的传感器指示的可用太阳能的量控制太阳能驱动化学反应器中原料生物质颗粒的进料速率。
太阳能驱动的生物炼制设备可包括具有周期运行而不是连续稳定状态运行的太阳能驱动化学反应器。另外,具有传感器的计算机化控制系统可以用良好控制的进料速率来控制进入多个反应器管的生物质材料的进料速率,该良好控制的进料速率可基于改变太阳能的可利用度,通过改变生物质材料的进料速率进行响应。
在一些实施方式中,太阳能驱动化学反应器可具有位于太阳热接收器腔体内的多个反应器管。化学反应可由辐射热驱动。该反应可发生在多个反应器管中,以便生物质的颗粒在蒸汽(H2O)载气和甲烷(CH4)的存在下气化。这可发生在同时发生的蒸汽重整和蒸汽生物质气化反应中,以便利用来自多个反应器管中所吸收的会聚太阳能的太阳热能,产生包括氢和一氧化碳气体的反应产物。
在一些实施方式中,太阳热化学反应器通过将生物质材料的原料颗粒与蒸汽反应(生物质气化)和蒸汽,将含碳生物质材料转化成一氧化碳和氢。例如,这可与补充甲烷蒸汽重整在高温700~1500℃下以控制量的蒸汽、氧气、空气和/或任何组合一起发生,这产生了合成气体的气体混合物。另外,蒸汽同时与生物质和甲烷发生反应,但生物质和甲烷相互不发生反应。较低量的蒸汽(H2O)与碳的比率可能更好。在一些实施方式中,该比率可为1∶1至1∶4。
另外,在700~1500℃高温下的蒸汽重整过程可提供避免在较低温度下发生的水煤气变换反应的反应。这可避免CO2产生并仍然提供了2∶1的H2∶CO比率。例如,利用甲烷与蒸汽的重整反应的反应可允许反应器中的反应产生正确的摩尔比,而不发生水煤气变换反应。
在一些实施方式中,由于发生水煤气变换反应,特别是随着水进料,CO2可通常在反应产物气体流中形成,并且WGS可用于实现H2∶CO=2的期望摩尔比。然而,通过材料平衡天然气的蒸汽重整,可实现H2∶CO=2的期望摩尔比,而不利用也生成CO2的第二WGS。
(2)能量+CO+H2O→CO2+H2(水煤气变换反应)
其中蒸汽重整反应产生3∶1的H2∶CO比率,生物质产生1∶1比率,因此需要较少的生物质来实现2∶1的比率。在一些实例中,需要较少的能量,因为所有这些反应都是吸热的,由会聚太阳能同时驱动。
如图2中所说明的,控制系统可用于平衡生物质气化反应、流重整反应和干重整反应。例如,用有效引向太阳热接收器和太阳能化学反应器处的会聚太阳能量平衡气化,以保持化学反应器运行的温度足够高,以维持H2与CO比率的摩尔比。
在一些实施方式中,控制系统可用于保持反应温度足够高,以基本上完全转化生物质为产物气体和消除焦油产物。例如,温度可为至少1100~1300℃。这可提供小于200mg/m3的反应,同时保持温度足够低,以便反应器管壁温度可小于1600℃,使得壁不在结构上变弱。这样的温度也可显著降低接收器效率。另外,控制系统可控制H2O、天然气和生物质颗粒的量,以保持生成的合成气处于期望的H2∶CO比率内,同时化学反应可为基本无焦油的,并且在生成的合成气中具有以体积计小于7%的CO。例如,控制系统可在多方面(verses)可利用太阳能中平衡质量。这可提供吸热反应,该反应消耗一定量的可用能量,并控制进入化学反应器的每个反应产物的浓度和量,以控制进入反应的反应物的摩尔浓度和比率,以便控制由反应产生的产物。
一些实施方式可包括合成反应器,该反应器可利用在烃燃料合成过程中所得的氢分子和一氧化碳分子(合成气)。这可利用已知方法,通过催化进行重整,产生化学品,包括液体烃燃料。例如,可生产燃料例如合成气,并且燃料也可用于驱动燃气轮机,以通过有效的燃气轮机产生电力,或者可通过催化将其重整为有价值的化学品或液体燃料。在一些实施方式中,一个或多个管可以是具有在高达1500℃下操作的外部SiC涂层的石墨反应管。
图3说明了具有接收器302和定日镜区域304的实例太阳能塔300的图。在一些实施方式中,太阳能塔300可用于形成具有气动生物质进料系统的太阳能驱动生物炼制设备。该进料系统可通过例如生物质的颗粒大小控制进行灵活给料。
化学反应器306从定日镜304阵列接收会聚太阳热能。化学反应器306可以是例如多个反应器管、下行式装置(downdraft)、太阳能驱动化学反应器,其从定日镜304阵列接收会聚太阳热能。
太阳能塔300可形成太阳能驱动生物炼制设备的一部分,该生物炼制设备也可包括生物质进料系统,该生物进料系统具有对多管化学反应器中每个反应器管的进料线的平衡。例如,可在包括三部分的操作中将生物质送入太阳能反应器:用于向太阳能塔反应器给料的生物质运输和准备,向例如500+英尺的塔顶部的生物质运输,以及向具体反应器下行式管的分配。该分配可通过多阶段进行。
在一些实施方式中,太阳能驱动化学设备可包括具有带有内壁的腔体的太阳热接收器,其中对准该太阳热接收器,以便从以下的一种或多种吸收会聚太阳能:1)定日镜阵列,2)聚太阳能盘,以及3)两者的任何组合。所述太阳能驱动化学反应器可以包括多个反应器管垂直取向并位于太阳热接收器内部的下行式几何形状。
在一些实施方式中,会聚太阳能可与水发生相互作用,以将水转化为蒸汽,为反应物气体供应能量,和/或与其它源发生相互作用,为传热设备提供热,用于生物质气化过程。另外,太阳能可被传导到接收器的壁和反应器管的壁上,以便该热被辐射传递到生物质颗粒上。生物质颗粒具有很多表面区域,以吸收辐射热,并且颗粒将该热传递到甲烷分子上。
图4说明了生物质与甲烷的太阳热气化模拟的结果。在存在或不存在添加的甲烷的情况下,对生物质气化进行模拟,以评估补充的甲烷对太阳热过程的影响。
如在图4中所说明的,生物质到合成气的反应实例可以是:
(1)太阳热+C6H10O5(纤维素)+H2O(蒸汽)→6CO+6H2
(2)太阳热+C10H12O3(木质素)+7H2O(蒸汽)→10CO+13H2
(3)太阳热+CH4(甲烷)+H2O(蒸汽)→CO+3H2
合成气体=nCO+mH2,其中n和m为可变摩尔量。
即使一些CO2存在于主要由上述甲烷组成的天然气中,CO2和CH4也与高热通过干重整发生反应,产生氢和一氧化碳。
(4)CH4+CO2==>2H2+2CO
图4中的甲烷添加消除了不存在甲烷的反应中的水煤气变换反应,以便得到期望摩尔的H2/CO=2。注意,当用会聚太阳辐射运行重整过程时,太阳能被转化为化学能,因此,其增加了气体的能量含量。
在不存在甲烷的情况下,生物质到合成气的例子反应可以是:
(1)太阳热+C6H10O5(纤维素)+H2O(蒸汽)→6CO+6H2
(2)太阳热+C10H12O3(木质素)+7H2O(蒸汽)→10CO+13H2
(3)太阳热+CO+H2O(蒸汽)<——>CO2+H2
合成气体=nCO+mH2,其中n和m为可变摩尔量。
图5说明了具有气化器管502的太阳热接收器500的图。根据本文描述的系统和方法,太阳热接收器500可形成太阳能驱动生物炼制设备的一部分。太阳能驱动生物炼制设备可包括太阳能驱动化学反应器、太阳热接收器例如接收器500,或两者。在一些实施方式中,太阳热接收器500可为多个反应管下行式太阳热接收器和太阳能驱动化学反应器。另外,进料系统可将生物质颗粒送入多个反应管502,其中该生物质的颗粒可以在蒸汽的存在下、在反应器管气化反应区出口、超过950℃的温度下被气化。
在一些实施方式中,太阳能驱动化学设备可利用来自天然气的甲烷。另外,生物质和天然气可与由太阳能加热的蒸汽共进料,以干重整经加热的含CH4的CO2、含CO2的甲烷成为合成气,以便即使一些CO2存在于主要由甲烷组成的天然气中,CO2和CH4也与高热通过干重整发生反应,产生了基本不含CO2的氢和一氧化碳。
例如,该反应可包括:
来自H2O的能量+CH4+CO2==>2H2+2CO+H2O。
在一些情况,天然气中少量的CO2可与甲烷发生反应,以产生额外的合成气体。另外,热力学表明,当生物质和甲烷与蒸汽在1200℃下、在产生摩尔比H2∶CO=2(每升2摩尔的氢气-一氧化碳)的化学计量比下共进料时,可产生不含CO2的合成气。存在于反应器所产生的合成气中的二氧化碳的大部分减少源于会聚太阳能,其可从外部驱动生物质反应中甲烷的蒸汽重整和碳的生物质气化。通过反应器产物的快速淬火以避免水煤气变换反应以及与蒸汽重整同时发生的甲烷反应的干重整,以消耗在反应器管中的反应期间存在和/或产生的CO2,可进行额外的CO2减少。2∶1的H2∶CO摩尔比也可为在2.0至2.8的范围内。
在一些实例中,当使用天然气时,设备有可能就在下游合成气催化重整合成之前,使用基本上装配成T字形(T)的高温氧化器(O2,不是空气)、通过NG的氧化、根据需要产生5%至10%的合成气。因此,在部分氧化系统中,该系统可具有催化氧化器。可发生的反应为:CH4+0.5O2=CO+2H2(部分氧化重整)。另外,该补充源可用于提高存在于H2∶CO合成气中H2的量。该过程可与主要太阳能驱动反应器并行运行。
在一些实例中,潜在地存在于天然气中的甲烷与水和生物质的共进料产生了不含CO2的合成气体。在这样的实例中,CO2水平可小于合成气流的7%(以体积计),并具有H2∶CO=2的期望摩尔比。这样的反应也可避免否则可产生CO2的水煤气变换反应。在大约1100~1300℃操作温度下,也可避免焦油形成。在一些实例中,生物质碳的使用可产生不含CO2的合成气。基本上100%的生物质碳都可产生有用的合成气CO组分。另外,由于CO2水平小于合成气流的7%(以体积计),在合成气的催化重整前去除CO2的下游胺系统可能不再是必要的。可使用在可消除焦油以及由于辐射传热而可极大加速反应的温度体系下的操作。
在一些实施方式中,可使用甲烷(CH4)与生物质的共进料,以使生物质的颗粒促进辐射传热。这可将管内温度提高至重整甲烷并引起生物质气化反应的水平。在其它系统中,完成这个过程可能要求单独的流并且可能需要单独添加固体颗粒,以便利用由太阳能加热的蒸汽使甲烷的转化与生物质气化相结合,生成合成气体。
在一些实施方式中,太阳能驱动反应器可位于接收器内部。接收器是将太阳辐射能转变为热能的腔体。接收器可包括多个反应器管。反应器管可允许甲烷或天然气以及蒸汽穿过惰性颗粒的流化床,以引起蒸汽甲烷反应。天然气可通过流,以使甲烷反应与甲烷和CO2的干重整一起发生。另外,多个反应器可并入接收器。为了增加设备的尺寸,可加入更多的接收器。每个反应器都可为下行式管。
图6说明了进料系统600的框图。研磨系统603具有用于将生物质研磨成初级颗粒的机械切割设备,所述颗粒将被送入太阳能驱动化学反应器。研磨系统系统向具有标准带式输送装置的闭锁料斗系统604供应具有平均最小尺寸大小在200微米(μm)和2000μm之间、通常范围在500μm和1000μm之间的初级颗粒。生物质颗粒随后穿过压力边界被送入加压夹带气体,以便向太阳能驱动化学反应器中进料。进料容器可使用螺旋钻式/螺杆式进料器或气闸型旋转固体进料设备/测速设备。
夹带流生物质进料系统600可包括加压闭锁料斗604,其将生物质送入旋转螺杆式输送设备602和测量设备,并随后送入闭锁料斗出口606处的夹带气体管。分流器将生物质的颗粒分配到多个夹带气体管线中,以便向组成太阳能驱动化学反应器的多个反应器管中的至少两个或多个进料。用于气动生物质进料系统的夹带气体可以是从以下方面中回收的废热产生的加压干蒸汽:1)烃燃料合成过程中的甲醇/甲醇制汽油(Methanol-To-Gasoline(MTG))单元,或2)来自太阳能驱动化学反应器中气化反应的产物。夹带气体也可以是CO2、天然气、惰性气体、以任何方式产生的蒸汽或其它相似的夹带气体。
另外,夹带流生物质进料系统具有一条或多条进料线以将生物质颗粒送入多个反应器管,其中夹带流生物质进料系统的单独的夹带线和测量设备用于化学反应器中的每个气化器反应器管。这可允许以下量的平衡:1)流过到达每个反应器管的进料线的生物质颗粒的量与2)可由多管太阳能驱动化学反应器中反应器管利用的太阳能的量。生物质颗粒的进料速率可由测量设备以及通过控制在闭锁料斗604底部的螺杆602的旋转速率来控制,该旋转速率响应于从控制系统收到的进料要求信号。
因此,控制螺杆或螺旋钻602旋转速率可沿螺旋钻602的旋转轴移动一定量的生物质。螺旋钻602可位于闭锁料斗604底部并可由控制系统进行控制,以响应系统的进料要求。如所讨论的,该控制系统基于由包括温度传感器和/或照度计的传感器指示的可用太阳能的量,控制太阳能驱动化学反应器中生物质颗粒的进料速率。
在一些实施方式中,与生物质气化相比,额外的生物质可用于生物质甲烷气化重整。例如,在一些生产规定量的期望H2/CO=2的摩尔比率的实施方式(大约2.5倍)中。在该实例实施方式中,该反应用天然气中的碳替代源自生物质碳的碳。另外,对于直接生物质气化路线,反应器中可能有过量的水。因此,反应器材料可以是抗氧化的和耐蒸汽的。
一些实施方式包括夹带气体生物质进料系统,其使用包括天然气、蒸汽、氧气、空气和/或这些的任何组合的夹带载气,并供应各种原料生物质源,作为颗粒送入太阳能驱动化学反应器。夹带载气可为天然气、蒸汽或天然气和蒸汽的任意组合。另外,夹带气生物质进料系统可接受研磨和粉碎的生物质,该生物质的颗粒大小在150和300微米之间。该颗粒大小的直径具有在200微米(μm)和2000μm之间、通常范围在500μm和1000μm之间的平均最小尺寸大小,以适合通过过滤器中的孔。相似的颗粒大小和具有驱动生物质气化反应、蒸汽重整反应和干重整反应的外部会聚太阳热能的多管设计的使用可用于允许该过程给料灵活,不需要重新设计主要设备以改变给料。
在一些实施方式中,可加进两种或多种生物质类型。这些生物质可单独给料或以组合的混合物给料,这些生物质选自纤维素、木质素、松树锯末、稻米杆、玉米秸秆、柳枝稷草、能源作物、从绿色废弃物中分离的来源、高粱、藻类和其它类似的生物质源。只要控制一些参数,例如原料生物质的颗粒大小和反应器管的操作温度范围,就可以进行操作。
图7说明了根据本文描述的系统和方法的太阳能驱动生物炼制设备700的图。定日镜702阵列可用于使光聚焦到反应器706的窗口704上。在反应器706中,生物质颗粒可被还原成合成气,合成气又可以在液体燃料合成器708中被合成为液体燃料。
例如,在一些实施方式中,原位燃料合成反应器708可接收来自气化反应的氢和一氧化碳产物并在烃燃料合成过程中利用氢和一氧化碳产物产生液体烃燃料。燃料合成反应器706可与化学反应器在地理上位于相同的位置,并且被整合到该过程中以利用来自气化反应的氢和一氧化碳产物。
在一些实施方式中,可在太阳热操作温度下添加甲烷(CH4,即天然气的主要成分),以延伸利用生物质碳,通过甲烷与二氧化碳的干重整,产生基本上不含CO2的合成气(比小于合成气流的7%(以体积计)的CO2水平低)。生物质和补充的天然气快速气化并与蒸汽重整,全部都由会聚到太阳热气化器的太阳能加热,该太阳热气化器主要利用辐射热驱动化学反应。
在一些实施方式中,可使用原位化学设备,其与化学反应器在地理上位于相同的位置,并且将其整合以接收来自气化反应的氢和一氧化碳产物。原位化学设备可具有接收氢和一氧化碳产物的入口并在烃燃料合成过程中使用它们产生液体烃燃料或其它化学产物。
另外,反应器的下游可存在一个或多个分离罐,以从生成的合成气中去除过量的水。对于生物质/甲烷,形成了小于CO2的2~5%的量。
图8说明了根据本文描述的系统和方法的流程图。在步骤800中,可进行生物质研磨。通常用于研磨生物质的设备包括冲击式磨机例如锤磨机)、磨盘式磨机和动力粉碎机(例如甩刀式粉碎机)。锤磨机系统可用于将捆包(由输送机装载)研磨成初级颗粒,该初级颗粒将被送入太阳热气化器。再次研磨的颗粒具有在500μm和1000μm之间的平均大小,并被装入具有标准带式输送机的闭锁料斗系统。
在步骤802中,进行生物质进料。在一些实施方式中,可使用高压进料。由于在一些这样的系统中能够使用较小的压缩机,在压力下气化的生物质固体的高压进料可降低资金成本。另外,因为加压载气的能量来自太阳,而不是来自电,所以可以降低操作成本。闭锁料斗系统可在压力下向反应器工序进料。例如,进料系统可在高压下的蒸汽中夹带的生物质材料,在旋风系统中成功分离微粒,并适当地向反应器管分配流量。
在步骤804中,进行气化。例如,在一些实施方式中,会聚太阳热能驱动原料生物质颗粒的气化,以从气化反应生成至少氢和一氧化碳产物。
在步骤806中,进行燃料合成。原位燃料合成反应器可接收来自气化反应的氢和一氧化碳产物并在烃燃料合成过程中利用氢和一氧化碳产物产生液体烃燃料。燃料合成反应器可与化学反应器在地理上位于相同的位置,并且被整合到该过程中以利用来自气化反应的氢和一氧化碳产物。
权利要求书(按照条约第19条的修改)
1.一种由辐射热驱动的化学反应器,其产物气体出口温度大于900℃,所述化学反应器包括:
辐射热驱动化学反应器,其具有位于热接收器的腔体内的多个反应器管,其中生物质的颗粒在同时发生的蒸汽重整和蒸汽生物质气化反应中、在蒸汽(H2O)载气和甲烷(CH4)的存在下被气化,以便利用来自所述多个反应器管中的辐射热的热能,产生包括氢和一氧化碳气体的反应产物。
2.根据权利要求1所述的化学设备,其中所述热接收器是太阳热接收器,其被对准以便从包括以下的一种或多种太阳能会聚区域吸收会聚太阳能:1)定日镜阵列,2)聚太阳能盘,以及3)两者的任意组合;
其中所述太阳热接收器具有腔体壁;和
其中所述辐射热驱动化学反应器由会聚太阳能驱动,因而是具有多个反应器管的太阳能驱动化学反应器。
3.根据权利要求2所述的化学设备,其中所述蒸汽与所述生物质和所述甲烷发生反应,但生物质和甲烷相互不发生反应,并且其中蒸汽(H2O)与碳的摩尔比在1∶1至1∶4的范围内,并且其中多个反应器被并入接收器中,以及其中所述太阳能驱动化学反应器具有所述多个反应器管为垂直取向并位于所述太阳热接收器内部的下行式几何形状,并且其中,通过在高温700~1500℃下以控制量的蒸汽、天然气和/或任何组合,使所述生物质材料的原料颗粒与蒸汽发生生物质气化反应和使蒸汽与补充甲烷发生蒸汽重整反应,所述太阳热化学反应器将含碳生物质材料转化成一氧化碳和氢,这然后产生合成气体的气体混合物。
4.根据权利要求2所述的化学设备,
其中所述甲烷来源于天然气,所述生物质和天然气与由所述太阳能加热的蒸汽一起共进料,以干重整或者包含在所述天然气内或者作为单独的原料供应的甲烷和CO2,以便即使一些CO2存在于主要由甲烷组成的所述天然气中,所述CO2和CH4也与高热通过干重整反应,产生氢和一氧化碳,以及
其中当生物质和甲烷在产生1.0至3.0范围内的H2∶CO摩尔比的化学计量比下、在750~1300℃的温度范围下与蒸汽共进料时,产生了具有小于合成气的以体积计7%的CO2的合成气体。
5.根据权利要求1所述的化学设备,进一步包括:
在700~1500℃高温下的蒸汽重整过程,以便所述反应避免在较低温度下对平衡有利的水煤气变换反应,并且因此避免来自所述水煤气变换反应的额外CO2产生,所述反应利用甲烷和蒸汽重整反应,以允许在所述反应器中的所述反应产生用于液体燃料或化学合成的期望摩尔比,而不发生水煤气变换反应。
6.根据权利要求1所述的化学设备,
其中所述天然气中的甲烷与水和生物质一起的共进料,产生了在合成气流中具有以体积计小于7%的CO2水平的低CO2合成气体,并且其具有H2∶CO=2.0~3.0的摩尔比,也避免了否则可产生CO2的水煤气变换反应,以及
其中在大约1100~1300℃操作温度下减轻了焦油形成,并且对于具有在30和1000之间的分子量的烃来说,产生了具有小于200mg/m3焦油的合成气体。
7.根据权利要求1所述的化学设备,
其中所述反应器管材料是抗氧化和耐蒸汽的;以及
其中所述蒸汽重整反应产生3∶1的H2∶CO比率,所述生物质产生1∶1的H2∶CO比率,需要较少的生物质来实现具有大约2.1~2.8∶1的H2∶CO比率的合成气产物,与如果在没有所述甲烷存在下气化所述生物质相比,所述大约2.1~2.8∶1的H2∶CO比率适合于液体燃料和化学合成。
8.根据权利要求2所述的化学设备,进一步包括:
其中在反应器管中,进行甲烷(CH4)和所述生物质的共进料,以便所述生物质的颗粒利于辐射传热,以将所述管中的温度升高至重整所述甲烷并引起所述生物质气化反应的水平,以便利用由所述太阳能加热的蒸汽使所述甲烷的蒸汽重整和甲烷的干重整与生物质气化相结合,生成所述合成气体;以及
其中所述会聚太阳能被传递到所述接收器的壁和所述反应器管的壁上,以便所述热辐射传递到所述生物质颗粒上,所述生物质颗粒具有很多表面区域,以吸收所述辐射热,随后所述生物质的颗粒有效地将热传递到所述甲烷和蒸汽分子上。
9.根据权利要求1所述的化学设备,进一步包括:
夹带气体生物质进料系统,其使用包括天然气、蒸汽、空气和/或这些的任意组合的夹带载气,并供应作为颗粒的各种给料生物质源到所述辐射热驱动化学反应器中;
其中所述夹带载气为天然气、蒸汽或天然气和蒸汽的任意组合;
其中所述生物质给料的颗粒大小分布具有直径为200微米(μm)和2000μm之间、通常在500μm和1000μm之间的平均最小尺寸大小;并且利用简单多管设计,以所述辐射热能驱动所述生物质气化反应、蒸汽重整反应和干重整反应,以允许所述过程给料灵活,不需要重新设计主要设备以改变给料;以及
其中种类包括两种或更多种类型的生物质类型,其可通过控制原料生物质的颗粒大小和所述反应器管的操作温度范围,从下述进行单独进料或以组合的混合物进料:纤维素、木质素、松树锯末、稻米杆、玉米秸秆、柳枝稷草、能源作物、从绿色废弃物中分离的源、林业废弃物、林业间伐物、高粱和藻类。
10.根据权利要求2所述的化学设备,进一步包括:
控制系统,其被配置为,通过针对可用太阳能平衡所述生物质和天然气或甲烷进料速率,控制所述接收器的温度,以便通过平衡进入孔的太阳能、由化学反应消耗的能量和反应物/产物显热、以及由辐射、对流和/或传导产生的接收器的热损失,使所述接收器中的温度维持在800°~1600℃范围内的期望设定点;以及
其中所述控制系统:1)保持温度在对所述生物质的基本全部转化而言足够高的温度(1000°~1300℃),以产生气体并将焦油产物减少至小于200mg/m3的浓度;和2)保持反应器管壁足够低的温度(<1600℃),以便所述反应器管壁不在结构上变弱或显著降低接收器效率,并且控制H2O、天然气和生物质颗粒的量,以保持生成的合成气处于期望H2∶CO比率并维持所生成的合成气中CO2以体积计小于7%。
11.根据权利要求1所述的化学设备,进一步包括:
合成反应器,其具有供应入口,以接收来自所述辐射热驱动化学反应器的、包含所得氢分子和一氧化碳分子的合成气,其中所述合成反应器在烃燃料合成过程中利用合成气,催化重整所述合成气以产生化学品。
12.位于接收器内的辐射热驱动反应器,包括:
腔体,其将辐射能转变为热能,所述接收器包围所述辐射热驱动反应器的多个反应器管,所述反应器管被配置用于使1)甲烷,2)天然气,3)蒸汽以及4)三者的结合穿过传热辅助设备,利用来自所述辐射能的所述热能引起蒸汽甲烷反应;
其中传热辅助设备用于加热反应物气体,其中所述传热辅助设备为以下位于每个反应器管中的一种或多种:惰性颗粒的流化床、网眼多孔陶瓷(RPC)泡沫、陶瓷整料、陶瓷管或气凝胶、开放结构填料环包括腊希格环、由耐高温材料构成的线网或金属丝以及这些的任意组合;以及
其中,辐射是将热从反应器管壁传到传热辅助设备的主要模式,传导、对流或两者的一些结合是传热的次要模式。
13.根据权利要求12所述的化学设备,进一步包括:
含碳给料的活动床,通过所述活动床,气化剂在并流或逆流构造中流动,以实现气化,并且所述床由辐射热能加热。
14.根据权利要求12所述的化学设备,进一步包括:
其中所述辐射热驱动化学反应器由会聚太阳能驱动,因而是太阳能驱动化学反应器,以及
第一管,其是具有在高达1500℃下运行的外部SiC涂层的石墨反应管,并且其中将甲烷加到生物质中,以便产生等当量合成气的太阳能反应器的能量要求更低,以及其中可以利用太阳加热的运输管反应器在高温下气化生物质源,以便将焦油形成可以大大降低至小于200mg/m3
15.根据权利要求12所述的化学设备,其中,当使用天然气时,所述设备就在下游合成气催化重整合成前,通过用与来自生物质气化的合成气相结合的高温氧化器的天然气氧化,根据需要产生5%至10%的高H2合成气(>2∶1的H2∶CO比率),以便所述高H2合成气用于将存在于组合合成气中的H2量提高至期望的H2∶CO比率。
16.一种生产化学品的方法,包括:
提供化学反应器,其具有位于所述热接收器的腔体内的多个反应器管,其中由辐射热驱动的化学反应发生在所述多个反应器管中,并且其中生物质的颗粒在蒸汽(H2O)载气和甲烷(CH4)的存在下进行气化,用于同时发生的生物质气化反应和蒸汽甲烷重整反应;以及
向所述反应器管提供生物质源,其包括纤维素、木质素、松树锯末、稻米杆、玉米秸秆、柳枝稷草、能源作物、从绿色废弃物中分离的源、高粱、林业间伐物、林业废弃物和藻类中的至少一种;以及
引起所述同时发生的蒸汽甲烷重整和生物质气化反应,以利用来自所述多个反应器管中的热能,产生包括氢和一氧化碳气体的反应产物。
17.根据权利要求16所述的方法,进一步包括:
提供太阳热接收器,其具有带有内壁的腔体,其中对准所述太阳热接收器,以便从以下的一种或多种吸收会聚太阳能:1)定日镜阵列,2)聚太阳能盘,以及3)两者的任意组合,其中所述辐射热驱动化学反应器由会聚太阳能驱动,因而是太阳能驱动化学反应器;和
其中,通过在高温700~1500℃下,以控制量的蒸汽、天然气和/或任何组合,使生物质材料的原料颗粒与蒸汽反应(生物质气化)以及使蒸汽与补充的甲烷反应,所述太阳热化学反应器将含碳生物质材料转化成一氧化碳和氢,这产生了合成气体的气体混合物。
18.根据权利要求16所述的方法,进一步包括:
提供来自天然气的甲烷;
将所述生物质和天然气与由所述辐射热能加热的蒸汽共进料,以干重整或者包含在所述天然气内或者作为单独的原料供应的甲烷和CO2,以便即使一些CO2存在于主要由甲烷组成的所述天然气中,所述CO2和CH4也与高热通过干重整反应,产生氢和一氧化碳,以及
其中当生物质和甲烷在产生1.0至3.0范围内的H2∶CO摩尔比的化学计量比下、在750~1300℃温度范围下与蒸汽共进料时,产生了具有小于合成气的以体积计7%的CO2的合成气体。
19.根据权利要求16所述的方法,
其中所述天然气中的甲烷与水和生物质的共进料,产生了在合成气流中具有以体积计小于7%的CO2水平的低CO2合成气体,并且其具有H2∶CO=2.0~3.0的摩尔比,也避免了否则可产生CO2的水煤气变换反应,以及
其中在大约1100~1300℃操作温度下将焦油形成减少至200mg/m3,其中基本上100%的生物质碳都产生有用的合成气CO组分。
20.根据权利要求16所述的方法,进一步包括:
原位化学设备,其与所述化学反应器在地理上位于相同的位置,并且将其整合以接收合成气,所述合成气包含来自所述同时发生的生物质气化反应和蒸汽甲烷重整反应的氢和一氧化碳产物,其中所述原位化学设备具有接收包含所述氢和一氧化碳产物的合成气的入口,并在烃燃料合成过程中使用所述它们产生液体烃化学产物。

Claims (20)

1.一种太阳能驱动化学设备,包括:
太阳热接收器,其具有带有内壁的腔体,其中对准所述太阳热接收器,以便从以下的一种或多种吸收会聚太阳能:1)定日镜阵列,2)聚太阳能盘,以及3)两者的任意组合;以及
太阳能驱动化学反应器,其具有位于所述太阳热接收器的腔体内的多个反应器管,其中由辐射热驱动的化学反应发生在所述多个反应器管中,并且其中生物质的颗粒在同时发生的蒸汽重整和蒸汽生物质气化反应中、在蒸汽(H2O)载气和甲烷(CH4)的存在下被气化,以便利用来自所述多个反应器管中所吸收的会聚太阳能的太阳热能,产生包括氢和一氧化碳气体的反应产物。
2.根据权利要求1所述的太阳能驱动化学设备,其中所述太阳能驱动化学反应器具有所述多个反应器管为垂直取向并位于所述太阳热接收器内部的下行式几何形状,并且其中,通过在高温700~1500℃下以控制量的蒸汽、天然气和/或任何组合,使所述生物质材料的原料颗粒与蒸汽发生生物质气化反应和使蒸汽与补充甲烷发生蒸汽重整反应,所述太阳热化学反应器将含碳生物质材料转化成一氧化碳和氢,这然后产生合成气体的气体混合物。
3.根据权利要求1所述的太阳能驱动化学设备,其中所述蒸汽与所述生物质和所述甲烷发生反应,但生物质和甲烷相互不发生反应,并且其中蒸汽(H2O)与碳的摩尔比在1∶1至1∶4的范围内,并且其中多个反应器被并入接收器中。
4.根据权利要求1所述的太阳能驱动化学设备,
其中所述甲烷来源于天然气,所述生物质和天然气与由所述太阳能加热的蒸汽一起共进料,以干重整或者包含在所述天然气内或者作为单独的原料供应的甲烷和CO2,以便即使一些CO2存在于主要由甲烷组成的所述天然气中,所述CO2和CH4也与高热通过干重整反应,产生氢和一氧化碳,以及
其中当生物质和甲烷在产生1.0至3.0范围内的H2∶CO摩尔比的化学计量比下、在750~1300℃的温度范围下与蒸汽共进料时,产生了具有小于合成气的以体积计7%的CO2的合成气体。
5.根据权利要求1所述的太阳能驱动化学设备,进一步包括:
在700~1500℃高温下的蒸汽重整过程,以便所述反应避免在较低温度下对平衡有利的水煤气变换反应,并且因此避免来自所述水煤气变换反应的额外CO2产生,所述反应利用甲烷和蒸汽重整反应,以允许在所述反应器中的所述反应产生用于液体燃料或化学合成的期望摩尔比,而不发生水煤气变换反应。
6.根据权利要求1所述的太阳能驱动化学设备,
其中所述天然气中的甲烷与水和生物质一起的共进料,产生了在合成气流中具有以体积计小于7%的CO2水平的低CO2合成气体,并且其具有H2∶CO=2.0~3.0的摩尔比,也避免了否则可产生CO2的水煤气变换反应,以及
其中在大约1100~1300℃操作温度下减轻了焦油形成,并且对于具有在30和1000之间的分子量的烃来说,产生了具有小于200mg/m3焦油的合成气体。
7.根据权利要求1所述的太阳能驱动化学设备,
其中所述反应器管材料是抗氧化和耐蒸汽的;以及
其中所述蒸汽重整反应产生3∶1的H2∶CO比率,所述生物质产生1∶1的H2∶CO比率,需要较少的生物质来实现具有大约2.1~2.8∶1的H2∶CO比率的合成气产物,与如果在没有所述甲烷存在下气化所述生物质相比,所述大约2.1~2.8∶1的H2∶CO比率适合于液体燃料和化学合成。
8.根据权利要求1所述的太阳能驱动化学设备,进一步包括:
其中在反应器管中,进行甲烷(CH4)和所述生物质的共进料,以便所述生物质的颗粒利于辐射传热,以将所述管中的温度升高至重整所述甲烷并引起所述生物质气化反应的水平,以便利用由所述太阳能加热的蒸汽使所述甲烷的蒸汽重整和甲烷的干重整与生物质气化相结合,生成所述合成气体;以及
其中所述会聚太阳能被传递到所述接收器的壁和所述反应器管的壁上,以便所述热辐射传递到所述生物质颗粒上,所述生物质颗粒具有很多表面区域,以吸收所述辐射热,随后所述生物质的颗粒有效地将热传递到所述甲烷和蒸汽分子上。
9.根据权利要求1所述的太阳能驱动化学设备,进一步包括:
夹带气体生物质进料系统,其使用包括天然气、蒸汽、空气和/或这些的任意组合的夹带载气,并供应作为颗粒的各种给料生物质源到所述太阳能驱动化学反应器中;
其中所述夹带载气为天然气、蒸汽或天然气和蒸汽的任意组合;
其中所述生物质给料的颗粒大小分布具有直径为200微米(μm)和2000μm之间、通常在500μm和1000μm之间的平均最小尺寸大小;并且利用简单多管设计,以所述外部会聚太阳热能驱动所述生物质气化反应、蒸汽重整反应和干重整反应,以允许所述过程给料灵活,不需要重新设计主要设备以改变给料;以及
其中种类包括两种或更多种类型的生物质类型,其可通过控制原料生物质的颗粒大小和所述反应器管的操作温度范围,从下述进行单独进料或以组合的混合物进料:纤维素、木质素、松树锯末、稻米杆、玉米秸秆、柳枝稷草、能源作物、从绿色废弃物中分离的源、林业废弃物、林业间伐物、高粱和藻类。
10.根据权利要求1所述的太阳能驱动化学设备,进一步包括:
控制系统,其被配置为,通过针对可用太阳能平衡所述生物质和天然气或甲烷进料速率,控制所述接收器的温度,以便通过平衡进入孔的太阳能、由化学反应消耗的能量和反应物/产物显热、以及由辐射、对流和/或传导产生的接收器的热损失,使所述接收器中的温度维持在800°~1600℃范围内的期望设定点;以及
其中所述控制系统:1)保持温度在对所述生物质的基本全部转化而言足够高的温度(1000°~1300℃),以产生气体并将焦油产物减少至小于200mg/m3的浓度;和2)保持反应器管壁足够低的温度(<1600℃),以便所述反应器管壁不在结构上变弱或显著降低接收器效率,并且控制H2O、天然气和生物质颗粒的量,以保持生成的合成气处于期望H2∶CO比率并维持所生成的合成气中CO2以体积计小于7%。
11.根据权利要求1所述的太阳能驱动化学设备,进一步包括:
合成反应器,其具有供应入口,以接收来自所述太阳能驱动化学反应器的、包含所得氢分子和一氧化碳分子的合成气,其中所述合成反应器在烃燃料合成过程中利用合成气,催化重整所述合成气以产生化学品。
12.位于接收器内的太阳能驱动反应器,包括:
腔体,其将太阳辐射能转变为热能,所述接收器包围所述太阳能驱动反应器的多个反应器管,所述反应器管被配置用于使1)甲烷,2)天然气,3)蒸汽以及4)三者的结合穿过传热辅助设备,利用来自所述太阳辐射能的所述热能引起蒸汽甲烷反应;
其中传热辅助设备用于加热反应物气体,其中所述传热辅助设备为以下位于每个反应器管中的一种或多种:惰性颗粒的流化床、网眼多孔陶瓷(RPC)泡沫、陶瓷整料、陶瓷管或气凝胶、开放结构填料环包括腊希格环、由耐高温材料构成的线网或金属丝以及这些的任意组合;以及
其中,辐射是将热从反应器管壁传到传热辅助设备的主要模式,传导、对流或两者的一些结合是传热的次要模式。
13.根据权利要求12所述的太阳能驱动化学设备,进一步包括:
含碳给料的活动床,通过所述活动床,气化剂在并流或逆流构造中流动,以实现气化,并且所述床由太阳热能加热。
14.根据权利要求12所述的太阳能驱动化学设备,进一步包括:
第一管,其是具有在高达1500℃下运行的外部SiC涂层的石墨反应管,并且其中将甲烷加到生物质中,以便产生等当量合成气的太阳能反应器的能量要求更低,以及其中可以利用太阳加热的运输管反应器在高温下气化生物质源,以便将焦油形成可以大大降低至小于200mg/m3
15.根据权利要求12所述的太阳能驱动化学设备,其中,当使用天然气时,所述设备就在下游合成气催化重整合成前,通过用与来自太阳能生物质气化的合成气相结合的高温氧化器的天然气氧化,根据需要产生5%至10%的高H2合成气(>2∶1的H2∶CO比率),以便所述高H2合成气用于将存在于组合合成气中的H2量提高至期望的H2∶CO比率,并且当太阳能流量低时,可根据需要利用合成气。
16.一种利用太阳能生产化学品的方法,包括:
提供太阳能驱动化学设备,包括:
太阳热接收器,其具有带有内壁的腔体,其中对准所述太阳热接收器,以便从以下的一种或多种吸收会聚太阳能:1)定日镜阵列,2)聚太阳能盘,以及3)两者的任意组合;和
太阳能驱动化学反应器,其具有位于所述太阳热接收器的腔体内的多个反应器管,其中由辐射热驱动的化学反应发生在所述多个反应器管中,并且其中生物质的颗粒在蒸汽(H2O)载气和甲烷(CH4)的存在下进行气化,用于同时发生的生物质气化反应和蒸汽甲烷重整反应;以及
向所述反应器管提供生物质源,其包括纤维素、木质素、松树锯末、稻米杆、玉米秸秆、柳枝稷草、能源作物、从绿色废弃物中分离的源、高粱、林业间伐物、林业废弃物和藻类中的至少一种;以及
引起所述同时发生的蒸汽甲烷重整和生物质气化反应,以利用来自所述多个反应器管中所吸收的会聚太阳能的太阳热能,产生包括氢和一氧化碳气体的反应产物。
17.根据权利要求16所述的方法,其中,通过在高温700~1500℃下,以控制量的蒸汽、天然气和/或任何组合,使生物质材料的原料颗粒与蒸汽反应(生物质气化)以及使蒸汽与补充的甲烷反应,所述太阳热化学反应器将含碳生物质材料转化成一氧化碳和氢,这产生了合成气体的气体混合物。
18.根据权利要求16所述的方法,进一步包括:
提供来自天然气的甲烷;
将所述生物质和天然气与由所述太阳能加热的蒸汽共进料,以干重整或者包含在所述天然气内或者作为单独的原料供应的甲烷和CO2,以便即使一些CO2存在于主要由甲烷组成的所述天然气中,所述CO2和CH4也与高热通过干重整反应,产生氢和一氧化碳,以及
其中当生物质和甲烷在产生1.0至3.0范围内的H2∶CO摩尔比的化学计量比下、在750~1300℃温度范围下与蒸汽共进料时,产生了具有小于合成气的以体积计7%的CO2的合成气体。
19.根据权利要求16所述的方法,
其中所述天然气中的甲烷与水和生物质的共进料,产生了在合成气流中具有以体积计小于7%的CO2水平的低CO2合成气体,并且其具有H2∶CO=2.0~3.0的摩尔比,也避免了否则可产生CO2的水煤气变换反应,以及
其中在大约1100~1300℃操作温度下将焦油形成减少至200mg/m3,其中基本上100%的生物质碳都产生有用的合成气CO组分。
20.根据权利要求16所述的方法,进一步包括:
原位化学设备,其与所述化学反应器在地理上位于相同的位置,并且将其整合以接收合成气,所述合成气包含来自所述同时发生的生物质气化反应和蒸汽甲烷重整反应的氢和一氧化碳产物,其中所述原位化学设备具有接收包含所述氢和一氧化碳产物的合成气的入口,并在烃燃料合成过程中使用所述它们产生液体烃化学产物。
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