CN101208263B - 制氢系统和方法 - Google Patents

制氢系统和方法 Download PDF

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CN101208263B
CN101208263B CN2006800231688A CN200680023168A CN101208263B CN 101208263 B CN101208263 B CN 101208263B CN 2006800231688 A CN2006800231688 A CN 2006800231688A CN 200680023168 A CN200680023168 A CN 200680023168A CN 101208263 B CN101208263 B CN 101208263B
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fuel
steam
reformate
zone
hydrogen
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CN101208263A (zh
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刘科
帕拉格·P·库尔卡尼
格雷格·A·德卢加
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General Electric Co
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General Electric Co
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Abstract

本发明披露一种系统，该系统包括接收第一燃料蒸汽混合物和氧化剂的混合重整区，以提供包含氢气的第一重整产物流。该系统还包括接收第一重整产物流、第一部分蒸汽和第二燃料的至少一个蒸汽重整区，以产生包含氢气的第二重整产物流。第一重整产物流在进入蒸汽重整区之前与第一部分蒸汽和第二燃料混合。

Description

制氢系统和方法
发明背景
本发明涉及从不同的烃类燃料例如天然气、汽油、柴油和醇类(例如甲醇和乙醇)制造氢气。
目前，最具成本效益的制氢方法为燃料例如天然气的集中蒸汽重整(centralized steam reforming of fuels)。能源价格的上涨和对环境的担忧促使对氢气作为能源的关注日益增加。已提出将氢气作为未来具有多种应用(包括车辆和固定电源(stationary power)(电力))的清洁燃料。
在合成氨厂、精炼和甲醇生产中消耗的商品氢气量最大。目前仅有一小部分氢气用于能量用途。然而，氢气在能量市场中的份额正在随着燃料电池的实用化和对低排放或无排放燃料需求的增长而增加。
对于从天然气(NG)分散制氢(distributed hydrogen production)用于燃料电池应用，研究了蒸汽甲烷重整(SMR)、自动热重整(ATR)(autothermalreforming)和催化部分氧化(CPO)(catalytic partial oxidation)。SMR利用重整催化剂例如Ni对NG进行转化并利用蒸汽合成气体(合成气)。常规ATR通常包括催化剂以加速SMR和CPO反应。这些催化剂对于所述两种不同类型的反应通常不是最佳的，因而没有达到最大效率。由于需要大的热交换表面面积以向吸热的蒸汽甲烷重整反应提供热量，所以常规的SMR系统并不是紧凑型的。
CPO(没有SMR催化剂)为紧凑型系统。然而，CPO产生的合成气具有相对较低的氢气(H2)/一氧化碳(CO)比(约为2)，因而更适于费-托或甲醇合成而不是制造纯氢。
因此，需要通过有效集热而具有成本效益的紧凑型制氢系统。
发明内容
一方面，系统包括混合重整区，接收第一燃料蒸汽混合物和氧化剂，以产生包含氢气的第一重整产物流(refomate stream)。该系统还包括至少一个接收第一重整产物流、第一部分蒸汽和第二燃料的蒸汽重整区，以严生包含氢气的第二重整产物流。第一重整产物流在进入蒸汽重整区之前与第一部分蒸汽和第二燃料混合。
另一方面，含氢气流的制造方法包括在催化部分氧化区或ATR区部分氧化第一燃料和氧化剂，以产生包含氢气的第一重整产物流。该方法还包括使第一重整产物流与第二燃料和蒸汽混合以产生混合流，并在蒸汽重整装置中对所述混合流进行蒸汽重整以产生包含氢气的第二重整产物流。
另一方面，系统包括：接收第一燃料与蒸汽和氧化剂的混合重整区，以产生第一重整产物流；接收第一部分蒸汽和第二燃料的预重整装置，以产生包含氢气的预重整流。该系统还包括：第一重整区，以接收预重整蒸汽并产生包含氢气的排放重整流；接收第一重整产物流和排放重整产物流的第二重整区，以产生包含氢气的第二重整产物流。第一重整产物流在进入第二蒸汽重整区之前与排放重整产物流混合。
附图说明
参考附图阅读下述详细说明时，将更好地理解本发明的这些和其它特征、方面和优势，其中相同的标记始终表示相同的部分，其中：
图1示例示范性制氢系统；
图2示例示范性紧凑型制氢系统；
图3示例在反应器中逆向流动的另一示范性紧凑型制氢系统；
图4示例在反应器中逆向流动的另一示范性紧凑型制氢系统；和
图5示例具有预重整装置的另一示范性紧凑型制氢系统。
具体实施方式
图1表示包括混合重整区16和至少一个蒸汽重整区18的示范性制氢系统10。设置混合重整区16来接收第一燃料12和氧化剂34，以产生第一重整产物流20。设置蒸汽重整区18来接收第一重整产物流20、第一部分蒸汽46和第二燃料14，以产生富含氢气的第二重整产物流22。在一种实施方案中，第一重整产物流20和蒸汽46混合形成混合流，将所述混合流引入蒸汽重整区18。混合重整区16包括加速催化部分氧化反应的催化剂。在一种实施方案中，混合重整区16同时加速催化部分氧化(CPO)和蒸汽重整反应。设置混合重整区16来接收第二部分蒸汽48，以产生包含氢气的第一重整产物气流20。在一种实施方案中，第二部分蒸汽48与氧化剂34混合形成混合流38，将所述混合流38引入混合重整区16。在一些实施方案中，所述系统10还包括热交换区28。设置热交换区28，来接收第二重整产物流22、氧化剂24和燃料26并加热氧化剂24和燃料26，以产生经加热氧化剂流34和经加热燃料流36。在此过程中，冷却第二重整产物流22以产生包含氢气的冷却重整产物流58。在一些实施方案中，热交换区28包括燃料热交换器30和氧化剂热交换器32。设置燃料热交换器32来接收燃料26并输出经加热燃料36。将经加热燃料36的第一部分12引入混合重整区16并将经加热燃料36的第二部分14引入蒸汽重整区18。在另一些实施方案中，在将经加热燃料36引入混合重整区16和蒸汽重整区18之前在压缩器68中对其进行压缩。
所述示范性系统10还可包括变换反应区54。将来自热交换区28的冷却第二重整产物流58送至变换反应区54，在此，在变换催化剂存在的条件下将流58中的一氧化碳转化为二氧化碳和氢气，并产生富含氢气的第三重整产物流60。变换催化剂可包括高温变换催化剂(HTS)或低温变换催化剂(LTS)或HTS和LTS催化剂的组合。在净化系统62中对富含氢气的第三重整产物气流60进行进一步处理，以产生富氢成品流64和废气66。在一种实施方案中，将包括未转化的燃料、一氧化碳、氢气和二氧化碳的废气66送进蒸汽发生器40，所述蒸汽发生器40利用废气流66的热含量由水42生成蒸汽44。经过适当的处理后将冷却废气70排放到大气中，或者使冷却废气70燃烧，从而产生热量来满足任何其它过程的需要。在一些实施方案中，蒸汽重整区18包括燃烧器(未在图1中示出)，所述燃烧器使来自氢气净化装置62的废气66与氧化剂一起燃烧，来为蒸汽重整区18中的重整反应提供热量。应当注意的是，在燃烧器中还可使用任何其它燃料，来为蒸汽重整区18中的重整反应提供热量。
运行中，图1所示示范性制氢系统10采用以下构思：利用催化部分氧化产生的热量来增进蒸汽重整反应，该反应是吸热的并且需要外部热量输入。使用于本申请混合重整区的催化剂应对极高的气时空速(GHSV)，例如约72,000hr-1～约7,200,000hr-1。在一种实施方案中，CPO催化剂中的GHSV为约250,000hr-1～约3,000,000hr-1。
CPO催化剂上发生的主要反应如以下反应1-3所示：
CH4+1/2O2＝CO+2H2(1)
CH4+3/2O2＝CO+2H2O(2)
CH4+2O2＝CO2+2H2O(3)
混合重整区、蒸汽重整区和变换区中的催化剂的这种组合和最佳集成显著降低了重整装置的大小和成本。
回到图1，在混合重整区16中，使经加热氧化剂34与第一燃料12和蒸汽48混合并在CPO催化剂上对所述混合流38进行处理。进行CPO反应直到将混合蒸汽38中的氧气含量基本耗尽，并且通过放热CPO反应(1-3)使温度升高。随后，利用放热CPO反应产生的热量，在混合重整区16中，起动蒸汽重整反应。使混合重整区16在约700℃～约1400℃运行，以实现高的燃料转化并使H2产量最大化。
常规的蒸汽重整过程需要消耗大量能源，并且在整个重整过程中需要大量热量。天然气的主要组成为甲烷(CH4)，甲烷以两步反应与蒸汽反应生成氢气。根据图1所示的本发明，按照下述反应(4)和(5)，将天然气转化为氢气。
CH4+H2O
Figure 2006800231688_0
CO+3H2(4)
CO+H2OCO2+H2(5)
在蒸汽重整区18中，通过蒸汽重整过程，对引入的第二部分燃料14的至少一部分进行转化以产生氢气。上述第一反应(4)通常发生在蒸汽重整区18中，其中燃料例如甲烷与蒸汽反应，从而生成一氧化碳和氢气。在一种实施方案中，蒸汽重整区18产生的第二重整产物气流22包括一氧化碳(CO)、二氧化碳(CO2)、氢气(H2)、未使用的燃料和水。第二反应(5)为变换反应，其中一氧化碳被转化为二氧化碳，并且该反应主要发生在低温变换反应区54。
蒸汽重整区18包括在约200℃～约1200℃对第二燃料14和蒸汽进行重整的蒸汽重整(SR)催化剂，所述温度取决于蒸汽重整区18中所用燃料的类型。当天然气用作第二燃料14时，在一种实施方案中，蒸汽重整区18的温度为约550℃～约1200℃，在另一实施方案中，蒸汽重整区18的温度为约700℃～约900℃。当乙醇用作第二燃料14时，在一种实施方案中，蒸汽重整区18的温度为约350℃～约850℃，在另一实施方案中，蒸汽重整区18的温度为约400℃～约600℃。当甲醇用作第二燃料14时，在一种实施方案中，蒸汽重整区18的温度为约200℃～约900℃。由于蒸汽重整反应在混合重整区16中开始，所以与常规蒸汽重整反应器相比，蒸汽重整区18的体积可明显减小。运行中，蒸汽重整区18可作为热交换器，其中所述重整区热的一侧包括燃烧器(未在图1-2中示出)，该燃烧器用于使氧化剂和燃料(来自氢气净化系统的废气)燃烧。
本申请披露的制氢系统中所用的燃料可包括任何合适的气体或液体，例如天然气、包括一氧化碳或氢气的物流、石脑油、丁烷、丙烷、柴油、煤油、乙醇、甲醇、航空燃料、煤成燃料、生物燃料、氧化处理烃进料(oxygenated hydrocarbon feedstock)和它们的混合物。在一些实施方案中，燃料可优选包括天然气(NG)。应当注意的是，第一燃料12和第二燃料14可各自选自本申请所述的这些燃料实例。在一种实施方案中，第一燃料12和第二燃料14相同。所披露的系统中所用的氧化剂可包括任何合适的含氧气体，例如空气、富氧空气、贫氧空气或纯氧气。
图2表示示范性紧凑型制氢系统80，其中将所有前述催化剂区设置在一个容器82内。如图2所示，所述系统80包括混合重整区84和蒸汽重整区86。设置混合重整区84来接收第一燃料144和氧化剂146以产生第一重整产物流150。设置蒸汽重整区86来接收第一重整产物流150、第一部分蒸汽130和第二燃料142，以产生包含氢气的第二重整产物流152。在一种实施方案中，第一部分燃料144和蒸汽146混合形成混合流148，将所述混合流148引入混合重整区84。如先前部分所述，混合重整区84同时有助于催化部分氧化过程和蒸汽重整过程。混合重整区84产生的第一重整产物流150包含包括一氧化碳、二氧化碳、未转化的燃料、氢气和水的气体。使第一重整产物流150与第二部分燃料和蒸汽142在静态混合器88中混合并将其送进蒸汽重整区86。如先前部分所述，将包含氢气的第二重整产物流152引入热交换区153。将来自热交换区153的冷却重整产物流158送至变换区164，在此，在变换催化剂存在的条件下，使流158中的一氧化碳转化为二氧化碳和氢气，并产生富含氢气的第三重整产物流166。变换催化剂可包括高温变换催化剂(HTS)或低温变换催化剂(LTS)或HTS和LTS催化剂的组合。应当注意的是，如图1-2所示加经加热氧化剂100以及第一和第二燃料的配置是非限制性的，可利用在本申请所述制氢系统的任意部分能够获得的热量，来实现对氧化剂100或第一和第二燃料的加热。
运行中，如图2所示的紧凑型制氢系统80采用以下构思：利用催化部分氧化产生的热量增进吸热的蒸汽重整反应。
回到图2，在混合重整区84中，使经加热氧化剂146与第一燃料144和蒸汽混合，并在CPO催化剂上对所述混合流148进行处理。进行CPO反应直到将混合蒸汽148中的氧气含量基本耗尽，并且通过放热CPO反应(1-3)使温度升高。随后，利用放热CPO反应产生的热量，在混合重整区84中，起动蒸汽重整反应。使混合重整区84在约700℃～约1200℃运行，以实现高的燃料转化并使H2产量最大化。
在蒸汽重整区86中，通过蒸汽重整过程，对引入的第二部分燃料142和混合流148的至少一部分进行转化以产生氢气。上述第一反应(4)通常发生在蒸汽重整区86中，其中燃料例如甲烷与蒸汽反应，从而生成一氧化碳和氢气。在一种实施方案中，蒸汽重整区86产生的第二重整产物气流152包括一氧化碳(CO)、二氧化碳(CO2)、氢气(H2)、未使用的燃料和水。第二反应(5)为变换反应，其中将一氧化碳转化为二氧化碳，并且该反应主要发生在低温变换反应区164。
在将第二重整产物气流152引至变换区164的变换催化剂之前，在热交换区153中对其进行冷却，所述第二重整产物气流152包括蒸汽重整区86产生的富氢合成气。设置变换区164来促进变换反应(5)，以减小CO浓度并生成更多氢气，从而产生富含更多氢气的第三重整产物流166。变换区164中的变换催化剂中的GHSV保持在约720hr-1～约360,000hr-1。在一种实施方案中，变换催化剂中的GHSV为约10,000hr-1～约150,000hr-1。
在净化系统174中对富含氢气的第三重整产物流166进行进一步处理，以产生氢气成品流176和废气178。如先前所述，可使包括未转化的燃料、一氧化碳和二氧化碳的废气178与空气或O2燃烧，从而为蒸汽重整区86中的吸热重整反应(4)提供热量(未在图1-2中示出)。或者可使废气在蒸汽发生器108的蒸发器中燃烧，从而产生蒸汽。净化过程可应用本领域已知的各种技术，包括但不限于变压吸附(pressure swing adsorption)、化学吸附和膜分离，以产生氢气成品气流176。
将氢气从其它气体中分离出来以产生富氢成品流176的方法包括变压吸附(PSA)和膜分离。变压吸附(PSA)可用于将氢气从包含氢气的气体混合物中分离出来。在PSA技术中，在高分压下，与对氢气的吸附相比，固体分子筛可更强烈地吸附例如二氧化碳等气体。因而，在高压下，当包含氢气的气体混合物经过吸附床时，从中选择性地除去氢气以外的气体。通过减压和清洗实现吸附床的再生。通常对于临界操作，使用多个吸附容器用于连续分离氢气，其中使用一个吸附床的同时对其它吸附床进行再生。
在一种实施方案中，净化系统中可使用膜分离装置。各种聚合物可用于氢气选择性膜，所述膜在相对较低的温度下工作。在一种实施方案中，可通过组合PSA装置和CO2分离膜，提高氢气的分离效率。在第一步中，通过PSA技术分离H2。在下一步中，通过CO2选择性膜分离CO2。一些聚合物膜表现出良好的渗透性并且在相对较低的温度下表现出对CO2分离的选择性。
在另一实施方案中，对于不含N2的富H2气体，例如通过SMR制得的那些气体，氢气分离器可采用深冷分离技术(cryogenic separation technique)。在一种实施方案中，将来自变换反应器的第三重整产物气流49压至约900psia，然后利用冷凝器将其冷却至室温，所述冷凝器使CO2液化。可从该过程回收气态氢气，同时将液态CO2从冷凝器的底部除去。
另一种净化第三重整产物气流49的技术包括：通过使用氧化物例如氧化钙(CaO)和氧化镁(MgO)或它们的组合进行化学吸附，将二氧化碳从第三重整产物气流49中分离出来。在一种实施方案中，在高压和高温下，CaO吸附CO2形成碳酸钙(CaCO3)，从而从气体混合物中除去CO2。通过煅烧CaCO3生成CaO和CO2，使吸附剂CaO再生。
用于从第三重整产物气流166中分离CO2的另一种技术可包括但不限于使用胺对CO2进行化学吸附。将第三重整产物气流49冷却至合适的温度，以使用胺对CO2进行化学吸附。该技术基于烷醇胺溶剂，所述溶剂在相对较低的温度下具有吸收二氧化碳的能力，并且易于通过升高富溶剂的温度再生。该技术所用的溶剂可包括例如三乙醇胺、单乙醇胺、二乙醇胺、二异丙醇胺、二甘醇胺和甲基二乙醇胺。
回到图2，系统80还包括第四热交换器168。将水102引入第四热交换器168，以吸取来自变换区164的第三重整产物流166中的热量。在第四热交换器168中使水部分蒸发，从而产生蒸汽和水的混合物104。将所述混合物104的一部分106送进蒸汽发生器108。将一部分燃料94和一部分空气110引入蒸汽发生器108，其中使燃料94在蒸发器中燃烧，从而产生用于重整过程的蒸汽。将该蒸汽的第一部分130引入蒸汽重整区86，并使该蒸汽的第二部分124与燃料92混合。如先前部分所述，将燃料和蒸汽的混合流98的第一部分144送进混合重整区84，并将蒸汽和燃料的混合流98的第二部分142送进蒸汽重整区86。
系统80的热交换区153包括至少一个热交换器。设置第一热交换器132来接收第一部分蒸汽130和第二重整产物流152，其中使热量从第二重整产物流152传递至第一部分蒸汽130，从而产生热蒸汽138和第一冷却第二重整产物流154。热交换区还包括第二和第三热交换器。设置第二热交换器134来接收混合流98和第一冷却重整产物流154，其中使热量从第一冷却重整产物流传递至混合流98，从而产生热混合流140和第二冷却第二重整产物。随后将热混合流140分到第一燃料144和第二燃料142中。设置第三热交换器136来接收氧化剂100和第二冷却第二重整产物流156，其中使热量从第二冷却第二重整产物流156传递至氧化剂100，从而产生经加热氧化剂146和第三冷却第二重整产物流158。
使第三冷却第二重整产物流158与来自蒸汽发生器108的一部分蒸汽114以及水118混合，在引入变换区164之前，在静态混合器162中进行混合。使水118与蒸汽114混合，所述混合流120用于进一步冷却第三冷却第二重整产物流158以促进变换反应。在一些实施方案中，通过分配器160将混合流120引入静态混合器162。应当注意的是，可对本申请所述的热交换器进行改进以在不同的温度下工作。例如，第一热交换器132的一部分和第二热交换器134可组合为一个单独的热交换器。同样地，第一热交换器132的一部分可与第二热交换器134和第三热交换器136组合。在另一实施方案中，可将全部三个热交换器132、134和136组合成一个热交换器，使该热交换器具有所要求的入口和出口数，相应用于加热燃料、蒸汽和氧化剂。
应当注意的是，通常CPO区的所有蒸汽与碳的比小于约2.0。常规蒸汽重整或ATR方法采用的蒸汽与碳的比为约3.0。
在图1-2中，净化系统62或174产生富氢成品气，该富氢成品气可用于要求纯氢气的应用。然而来自变换区164的第三重整产物气流166还包含大量氢气并可用于不要求高纯氢气的应用。
图3-4示例单一反应器202中的示范性紧凑型制氢系统。如图3所示，制氢系统200包括单一反应器202。反应器202包括蒸汽重整区222、混合重整区220、热交换区225和变换区248。紧凑型单一反应器202包括下述催化剂：置于蒸汽重整区222中的蒸汽重整催化剂、混合重整区220中的CPO催化剂和变换区248中的变换催化剂。将所有这些催化剂集成在反应器202中(如图3-4所示)使投资费用最小化并减小系统占地。如图3-4所示的示范性实施方案能够集成并简化重整装置，使得优于独立反应器装置用于各反应的常规系统。
回到图3，将燃料214分为两股物流。第一燃料218与蒸汽215和氧化剂228混合形成混合流242，将所述混合流242引入混合重整区220。为了便于理解，在本申请所述的实施方案中将氧化剂描述为空气。应当注意的是，也可使用先前部分中所列举的任何其它氧化剂。在一些实施方案中，设置第一混合器240，从而在将空气和第一部分燃料218送进混合重整区220之前对它们进行混合。使来自混合重整区220的第一重整产物流221与高温蒸汽234在混合器236中混合并引入蒸汽重整区222。将第二部分燃料216引入紧凑型重整装置202壁204与蒸汽重整区222之间的环状空间232，所述环状空间232起到交换器的作用，从而将来自进给燃料216的热量供给蒸汽重整区222。可由蒸发器提供高温蒸汽234，使来自净化装置的废气在所述蒸发器中燃烧(未在图3中示出)。蒸汽重整区222中经过催化剂床的流与混合重整区220中的流方向相反。来自蒸汽重整区222的第二重整产物流227有助于加热热交换器224中引入的第一部分燃料218并且同时有助于加热另一热交换器226中引入的空气。由于热量取自热交换区225中的第二重整产物流227，所以对进给燃料218和空气228的加热使得第二重整产物流227冷却下来，并在冷却第二重整产物流进入变换区248之前将其与蒸汽216混合。将蒸汽244引入变换区248和重整装置202壁204之间的环状空间。由于变换反应为放热反应，所以利用变换区248中产生的热量提升变换反应的蒸汽温度。利用来自变换区248的第三重整产物流加热水208从而产生蒸汽212，并同时加热交换器206中引入的燃料210。将冷却第三重整产物流250送至净化装置(未在图3中示出)，以产生基本纯净的氢气。
图4示例单一反应器202中的另一示范性紧凑型制氢系统260。图4所示的系统包括置于蒸汽重整区266中的多个管262。将氧化剂例如空气以及来自净化装置(未在图4中示出)的废气引入所述多个管262，其中使所述混合物燃烧，来为蒸汽重整区266中的吸热蒸汽重整反应提供热量。任何其它燃料也可与空气一起使用，来为蒸汽重整反应提供热量。将来自所述多个管264的废气270送至交换器272，在此吸取热量来加热引入的蒸汽212，从而为蒸汽重整反应提供热蒸汽230。经过适当的处理后可将冷却废气274排放到大气中。
图5示例另一紧凑型制氢重整装置280，其中将先前所述的所有催化剂区设置在一个容器282中。如图5所示，系统280包括混合重整区290、第一蒸汽重整区288和第二蒸汽重整区294。设置混合重整区290来接收第一燃料307和氧化剂306，以产生第一重整产物流309。示范性紧凑型重整装置280还包括预重整装置284，从而在将第二部分燃料334引入第一蒸汽重整区288之前对其进行预重整。第二部分燃料334为燃料338的一部分和蒸汽350的混合物。同样地，第一燃料307为燃料338的一部分、蒸汽348和空气306的混合物。预重整装置284对第二部分燃料334进行部分重整，以产生预重整流305。预重整装置284在低于约800℃的温度运行。设置第一蒸汽重整区288，来接收来自预重整装置284的预重整流305并由该第一蒸汽重整区产生排放重整产物流311。设置混合重整区290来接收第一部分燃料307并产生包含氢气的第一重整产物流309。如先前部分所述，混合重整区290同时有助于催化部分氧化过程和蒸汽重整过程。运行中，如图5所示的紧凑型制氢系统280采用以下构思：利用由混合重整区290中的催化部分氧化或自动热重整(ATR)产生的热量，增进吸热的蒸汽重整反应。混合重整区290产生的第一重整产物流309包含包括一氧化碳、二氧化碳、未转化的燃料、氢气和水的气体。使第一重整产物流309与来自第一蒸汽重整区288的排放重整产物流311混合，并在引入第二蒸汽重整区294之前将其引入混合器292。设置第二蒸汽重整区292，来完成蒸汽重整反应并产生第二重整产物流313。
回到图5，将包含氢气的第二重整流313引入蒸汽分配器296，设置所述蒸汽分配器296来利用蒸汽342降低第二重整产物流313的温度。经过蒸汽分配器296之后，如先前部分所述将第二重整产物流313引入热交换区295。热交换区295包括第一热交换器298和第二热交换器299。设置第一热交换器298，来利用第二重整产物流313的热含量加热引入的第二部分燃料360并产生热的第二部分燃料334。设置第二热交换器299，来加热引入的第一部分燃料342并产生热的第一部分燃料332和冷却重整产物流315。将来自热交换区295的冷却重整产物流315送至变换区300，在此，在变换催化剂存在的条件下，使冷却重整产物流315中的一氧化碳转化为二氧化碳和氢气，并产生富氢的第三重整产物流317。变换催化剂可包括高温变换催化剂(HTS)或低温变换催化剂(LTS)或HTS和LTS催化剂的组合。将第三重整产物流317送至第三热交换器302。将水320引入第三热交换器302，以从第三重整产物流317吸取热量，从而产生冷却第三重整产物310和蒸汽326。将冷却第三重整产物流310送至净化装置314，以产生基本纯净的氢气312。利用空气321使自净化装置产生的废气流316在燃烧器318中燃烧，从而产生热气322。在一种实施方案中，使废气在存在催化剂的催化燃烧器中燃烧。在蒸汽发生器324中，利用热气322生成蒸汽346和部分冷却的热气328。这种气流328的温度为约750～800℃。运行中，利用这种气流328的热含量引发预重整装置284中的蒸汽重整反应，在一种实施方案中所述预重整装置284可为气流328在所述管286热的一侧中流动的管壳式热交换器。在预加热器308中，采用来自预重整装置284的排放热气330对氧化剂(空气)304进行预加热。设置预加热器308来产生经加热氧化剂306，在将所述经加热氧化剂306引入混合重整区290之前，使其与经加热燃料和蒸汽332混合。
本申请描述的制氢系统具有许多优点。在所披露的紧凑型制氢系统中，在本申请所述集热过程高的总效率使反应器尺寸减少的情况下，资金和O&M成本明显降低，并有利于减少燃料和耗材。利用来自净化系统的废气为预重整、蒸汽生成和燃料的预加热提供热量，也使得整个过程的效率提高。因而，所披露的系统有效回收了来自废气的过剩热量，从而可使整个过程的效率明显高于常规制氢过程。这种系统设计提供了使催化剂对于各单独反应例如CPO或SMR最佳化的可能，并使用最适合各反应的催化剂。为获得最佳产率，还可对引入两个区的蒸汽量进行最优化。
为实现本发明满足的各种需要，对本发明的各种实施方案进行了描述。应当理解的是，这些实施方案仅是示例性的。在不脱离本发明精神和范围的情况下，对所述实施方案的各种改进和改变对于本领域技术人员是显而易见。因而，本发明意图覆盖所附权利要求及其等价物范围内所有适当的改进和改变。

Claims (22)

1.一种系统，其包括：
混合重整区，其接收第一燃料蒸汽混合物和氧化剂，以产生包含氢气的第一重整产物流；和
至少一个蒸汽重整区，其接收所述第一重整产物流、第一部分蒸汽和第二燃料，以产生包含氢气的第二重整产物流；
其中在所述第一重整产物流进入所述至少一个蒸汽重整区之前使其与所述第一部分蒸汽和第二燃料混合，
该系统还包括热交换区和变换反应区，
其中所述热交换区包括接收所述第一部分蒸汽和所述第二重整产物流的第一热交换器，在所述第一热交换器中热量从所述第二重整产物气流传递至所述第一部分蒸汽，从而产生热蒸汽和第一冷却第二重整产物流。
2.权利要求1的系统，其中所述混合重整区包括催化部分氧化(CPO)或自动热重整(ATR)区。
3.权利要求1的系统，其中所述热交换区包括接收所述第一燃料、所述第二燃料和所述第一冷却第二重整产物流的第二热交换器，在所述第二热交换器中热量从所述第一冷却第二重整产物流传递至所述第一和第二燃料，从而产生经加热的第一和第二燃料以及第二冷却第二重整产物。
4.权利要求3的系统，其中所述热交换区包括接收所述氧化剂和所述第二冷却第二重整产物气流的第三热交换器，在所述第三热交换器中热量从所述第二冷却第二重整产物气流传递至所述氧化剂，从而产生经加热的氧化剂和第三冷却第二重整产物流。
5.权利要求4的系统，其中设置所述变换反应区来接收所述第三冷却第二重整产物流和蒸汽，以产生富氢的第三重整产物流。
6.权利要求1的系统，该系统还包括净化系统，其中所述净化系统产生废气和富氢成品气。
7.权利要求6的系统，其中该系统还包括蒸汽发生器，其中将所述废气循环至蒸汽发生器以生成蒸汽并产生冷却废气。
8.权利要求6的系统，该系统还包括接收所述第三重整产物流和水的第四热交换器，在所述第四热交换器中从所述第三重整产物流中吸取热量，以产生蒸汽和冷却的第三重整产物气流。
9.权利要求6的系统，其中所述第一燃料和第二燃料选自天然气、甲烷、甲醇、乙醇、包括石脑油的物流、丁烷、丙烷、柴油、航空燃料、生物燃料、氧化处理烃进料和它们的混合物。
10.权利要求1的系统，其中所述第一燃料和所述第二燃料包括天然气。
11.权利要求1的系统，其中使所述蒸汽重整区在500℃～1200℃工作。
12.权利要求1的系统，其中使所述至少一个蒸汽重整区在350℃～850℃工作，并且所述第二燃料为乙醇。
13.权利要求1的系统，其中使所述至少一个蒸汽重整区在200℃～400℃工作，并且所述第二燃料包括甲醇。
14.权利要求1的系统，其中所述系统还包括催化部分氧化区、热交换区和变换反应区，以及其中将所述蒸汽重整区、催化部分氧化区、热交换区和变换反应区放在容器中。
15.权利要求6的系统，其中所述净化系统包括选自至少一个化学吸附器、变压吸附器、深冷分离器、膜分离器和液化器的装置。
16.权利要求1的系统，其中所述氧化剂选自空气、富氧空气、贫氧空气和纯氧气。
17.权利要求1的系统，其中所述氧化剂为空气。
18.权利要求1的系统，该系统还包括将所述第二燃料引入所述至少一个重整区之前对所述第二燃料进行重整的预重整装置。
19.权利要求18的系统，其中所述预重整装置利用来自所述废气的热量对所述第二燃料进行重整。
20.权利要求1的系统，其中所述第一燃料和第二燃料为煤油。
21.一种系统，其包括：
混合重整区，其接收第一燃料以及蒸汽和氧化剂，以产生第一重整产物流；
预重整装置，其接收第一部分蒸汽和第二燃料，以产生包含氢气的预重整流；
第一重整区，其接收所述预重整流并产生包含氢气的排放重整流；和
第二重整区，其接收所述第一重整产物流和排放重整产物流，以产生包含氢气的第二重整产物流；
其中在所述第一重整产物流进入所述第二蒸汽重整区之前使其与所述排放重整产物流混合。
22.权利要求21的系统，其中所述混合重整区包括催化部分氧化(CPO)或自动热重整(ATR)区，并且所述第二蒸汽重整区为反应器，在该反应器中，推动吸热蒸汽重整反应的热量由所述CPO或ATR区提供。
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US8216323B2 (en) 2012-07-10
US20070000176A1 (en) 2007-01-04
WO2007005255A2 (en) 2007-01-11
CN101208263A (zh) 2008-06-25
JP5148489B2 (ja) 2013-02-20
JP2009500274A (ja) 2009-01-08
WO2007005255A3 (en) 2007-03-22

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