CN113454019A - 用于回收氢并将碳化合物转化为有价值的有机产物的方法和系统 - Google Patents
用于回收氢并将碳化合物转化为有价值的有机产物的方法和系统 Download PDFInfo
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- CN113454019A CN113454019A CN202080014951.8A CN202080014951A CN113454019A CN 113454019 A CN113454019 A CN 113454019A CN 202080014951 A CN202080014951 A CN 202080014951A CN 113454019 A CN113454019 A CN 113454019A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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Abstract
一方面,一种回收氢的方法,该方法包括在催化剂的存在下使烃反应形成碳化合物和氢,其中该碳化合物包括二氧化碳或一氧化碳中的至少一种;将碳化合物与氢分离;将碳化合物引导至电化学电池的阴极侧并将水引导至电化学电池的阳极侧;在阳极侧电解水以形成氧气和质子;向电化学电池中的膜和电极组件施加电压,以使质子从阳极穿过质子交换膜到达阴极侧的阴极;和使质子与碳化合物反应形成有机产物。
Description
相关申请的交叉引用
本申请要求于2019年2月18日提交的美国临时专利申请系列号62/807,004的权益。相关申请通过整体引用并入本文。
背景技术
氢用于整个石化精炼厂的各种加氢处理过程,包括硫氢化,其中硫从燃料中除去并转化为元素硫;加氢异构化,其中正链烷烃转化为异链烷烃;脱芳构化,其中芳烃氢化为环烷烃或烷烃;和加氢裂化,其中长链烃裂化为汽油范围内的较短链。在精炼过程的不同阶段产生的氢可以被收集并输送到工厂的特定加氢处理过程中。然而,随着对更清洁燃烧的燃料的需求持续增长以及精炼操作效率的改善成为必要,氢需求正越来越多地超过精炼过程所提供的生产率。因此,精炼厂不得不通过多种不同的方法补充其氢现场供应,包括:甲烷或其他烃的蒸汽重整;从精炼厂废气中回收;从合成气中回收;和油精炼残余物的气化。
目前,精炼厂经常将包含氢的废气料流排放到大气中,而损失其中所含的氢。氢是形成石化产物的有价值的组分,因此需要新的回收方法来回收所述氢。
发明内容
本文公开了一种用于回收氢并将碳化合物转化为有价值的有机化合物的方法和系统。
在一方面,一种回收氢的方法,该方法包括在催化剂的存在下使烃反应形成碳化合物和氢,其中该碳化合物包括二氧化碳或一氧化碳中的至少一种;将碳化合物与氢分离;将碳化合物引导至电化学电池的阴极侧并将水引导至电化学电池的阳极侧;在阳极侧电解水以形成氧气和质子;向电化学电池中的膜和电极组件施加电压,以使质子从阳极穿过质子交换膜到达阴极侧的阴极;和使质子与碳化合物反应形成有机产物。
在另一方面,一种方法包括将包含碳化合物和氢的来自精炼厂的废气料流引导至电化学氢分离器的阳极侧;向电化学氢分离器中的分离单元膜和电极组件施加电压,以使分离单元阳极处的氢解离成质子和电子,并将质子从分离单元阳极通过分离单元质子交换膜引导至分离单元阴极,其中质子与分离单元阴极处的电子重新结合形成氢;从电化学氢分离器的分离单元阴极侧移除氢;从分离单元阳极侧移除分离的碳料流。
在另一方面,氢回收系统包括:重整器,该重整器通过烃料流和反应物源与烃源流体连通;其中该重整器能够使来自烃源的烃反应以形成氢和包含二氧化碳和一氧化碳中的至少一种的碳化合物;分离单元,其通过重整产物料流与重整器流体连通;其中该分离单元能够使该重整产物料流的氢与碳化合物分离,并且其中通过氢料流从该分离单元中回收氢;电化学电池,其通过包含该碳化合物的分离的碳料流与分离单元流体连通;其中该电化学电池包括在质子交换膜阴极侧处的阴极和在质子交换膜阳极侧处的阳极;其中该分离的碳料流与电化学电池的阴极侧流体连通,且水料流与电化学电池的阳极侧流体连通;其中该电化学电池能够使所述碳化合物与质子反应以在阴极处形成有机产物,所述质子由在阳极处从水料流中分离的质子提供。
上述和其他特征通过以下附图、具体实施方式和权利要求书举例说明。
附图说明
以下附图是示例性的方面,其被提供来说明本公开。附图是对本公开的实施例的说明,这些实施例并不旨在使根据本公开制造的装置限制于本文所述的材料、条件或工艺参数。
图1是用于回收氢并将碳化合物转化为有价值的有机化合物的系统的一个方面的示意图;
图2是用于回收氢并将碳化合物转化为有价值的有机化合物的系统的一个方面的示意图;和
图3是用于回收氢的系统的一个方面的示意图。
具体实施方式
开发了一种回收氢的方法,如图1所示,其中将烃料流2引导至重整器10,将重整产物分离成回收的氢料流12和分离的碳料流14,并将来自重整器的分离的碳料流14引导至电化学电池30以形成有机产物料流34和氧气料流38。该方法具有额外的好处,即如果电化学电池30通过可再生能源如光伏电池供电,则可以收集碳信用。
烃料流2可以包含天然气、生物气或精炼原料中的至少一种。烃料流2可以包含甲烷、乙烷、乙烯、丙烷、丙烯、丁烷、丁二烯、环己烷、苯或甲苯中的至少一种。烃料流2可以进一步包含含硫气体(例如,如硫化氢)、氮气、氦气、二氧化碳、水、气味剂或金属(例如汞)。应注意,可在重整之前除去含硫气体,优选将硫含量降低至小于百万分之一体积的量。基于烃料流2的总摩尔数,烃料流2可以包含大于或等于75摩尔%、或80至97摩尔%的量的甲烷。
可以将烃料流2引导至重整器10,在其中烃料流2可以通过蒸汽重整、部分氧化、CO2重整或通过自热重整反应进行反应以形成包含氢和一氧化碳或二氧化碳中的至少一种的重整产物。重整器10可以包含重整催化剂以催化反应。重整催化剂可以包含镧(La)、钙(Ca)、钾(K)、钨(W)、铜(Cu)、铝(Al)、镍(Ni)或锰(Mn)中的至少一种的氧化物。重整催化剂可以包含锰的氧化物。重整催化剂可以是包含载体的成型催化剂(例如粒料、挤出物、环、球或片)。载体可以包含氧化铝(例如Al2O3)、氧化镁(例如MgO)、二氧化硅、二氧化钛或氧化锆中的至少一种。
重整产物可以在蒸汽甲烷重整器中通过经反应式(1)和(2)转化烃(例如甲烷)而形成。
重整产物可以在自热重整器中通过经反应式(3)和(4)转化烃(例如甲烷)而形成。
2CH4+O2+CO2→3H2+3CO+H2O (3)
4CH4+O2+2H2O→10H2+4CO (4)
可以通过变压吸附(例如用分子筛)从重整产物中分离氢。变压吸附可以从重整产物中吸附杂质以形成氢料流12和分离的碳料流14。
可以使用如图2所示的电化学氢分离器50从重整产物中分离氢。图2示出了可以将重整产物料流16引导至电化学氢分离器50的阳极侧48。在阳极46处,氢通过电化学反应(5)分解为质子和电子。
H2→2H++2e-(5)
由于所施加电压的极性,可以驱动由反应(5)形成的质子穿过质子交换膜44,并且由反应(5)形成的电子可以通过外部电路引出。被驱动通过质子交换膜44的质子然后可以在膜和电极组件的阴极侧40处与从外部电路引出的电子通过电化学反应(6)结合。
2H++2e-→H2(6)
一定量的水可以被氢拖过质子交换膜44。可以通过电化学氢分离器50的阴极侧40上的水导管从系统中回收液体形式的冷凝水。可以将去除的水再循环回至重整器10,或者可以引导至电化学电池30的阳极侧。
图3示出了作为将重整产物料流16引导至电化学氢分离器50的代替或附加,可以将废气料流18引导至电化学氢分离器50。废气料流18可以是从包含一定量待分离氢的过程中回收的任何料流。可以将分离的碳料流14类似地引导至电化学电池30。
可以将分离的碳料流14引导至电化学电池30的阴极侧20。可以将水供给到电化学电池30的阳极侧28,在其中水被电解以形成氧气和质子。质子从阳极26穿过质子交换膜24到达阴极22。在阴极侧20,质子与分离的碳料流14中的碳化合物反应以形成有机产物。有机产物可以包含甲烷、羧酸(例如甲酸)、醇(例如甲醇或乙醇)、甲醛或一氧化碳中的至少一种。有机产物可以通过有机产物料流34从阴极侧20回收。
附图进一步说明了可以使用电源向相应的电化学电池施加电压。所施加的电压可以为小于或等于1伏(V)、或小于或等于0.8伏、小于或等于0.5伏、或0.01至0.2伏。电源可以是太阳能阵列、直流(DC)电源、风车、电池(例如液流电池)、燃料电池等。
电化学电池30和电化学氢分离器50的相应电极可以独立地与质子交换膜24或44直接物理接触,并且可以覆盖质子交换膜24或44的相应表面积的90%至100%。每个电极独立地包含催化剂层。可以选择催化剂层来进行所需的反应。催化剂层可以包含铂、钯、铑、碳、金、钽、钨、钌、铱、锇或银中的至少一种。催化剂可以包含粘合的催化剂。电化学电池30可以包括催化剂层,该催化剂层包括金属(例如,铟、锡、铅或它们的氧化物中的至少一种)、酞菁(例如,包括镍、铁或钴中的至少一种)或金属水合物(例如,包括钯或铜中的至少一种)中的至少一种。粘合剂可以包含含氟聚合物、质子传导离聚物或颗粒碳中的至少一种。催化剂和任选的粘合剂可以直接沉积在质子交换膜的表面上。催化剂可以布置在气体扩散层上,使得它位于整个气体扩散层上或位于与质子交换膜接触的气体扩散层的表面。气体扩散层可以是多孔的。气体扩散层可以是网。气体扩散层可以包含石墨材料。气体扩散层可以包含多根纤维,例如碳纤维。气体扩散层可以是导电的。
相应的质子交换膜可以各自独立地包含电解质,例如质子传导离聚物或离子交换树脂中的至少一种。质子传导离聚物可以包含与碱金属盐、碱土金属盐、质子酸或质子酸盐中的至少一种络合的聚合物。络合的聚合物可以包括聚醚、聚酯、聚酰亚胺或聚氧化烯(例如聚乙二醇、聚乙二醇单醚或聚乙二醇二醚)中的至少一种。
质子交换膜44和24可以包含相同或不同的材料。例如,质子交换膜可以包含离聚物型聚合电解质,该离聚物型聚合电解质在疏水主链上或在疏水主链(例如烃型和氟碳型树脂)的侧基上包含一定量的离子基团。烃型离子交换树脂可以包含酚醛树脂或聚苯乙烯中的至少一种。烃型离子交换树脂可以是磺化的,例如磺化聚氧化二甲苯。烃型离子交换树脂可以包含质子传导分子,例如富勒烯分子、碳纤维或碳纳米管中的至少一种。质子传导分子可以包含质子解离基团,例如-OSO3H、-OPO(OH)2、COOH、-SO3H、-C6H4、-SO3H或-OH中的至少一种。质子传导分子可以单独形成质子交换膜,或可以作为与粘合剂聚合物例如含氟聚合物(例如聚氟乙烯或聚偏二氟乙烯)或聚乙烯醇中的至少一种的混合物存在。电化学电池50可以在质子交换膜中不含大量的氧,对氧化的关注低,并且质子交换膜可以包含烃型离子交换树脂。
氟碳型离子交换树脂可以包含四氟乙烯-全氟磺酰基乙氧基乙烯基醚或四氟乙烯-羟基化全氟乙烯基醚共聚物中至少一种的水合物。氟碳型离子交换树脂可以具有磺酸、羧酸或磷酸官能团中的至少一种。氟碳型离子交换树脂可以是磺化含氟聚合物(例如全氟乙烯磺酸的锂盐)。氟碳型离子交换树脂的一个示例是从DuPont购得的NafionTM。
下文阐述本公开的各种非限制性方面。
方面1:一种回收氢的方法,所述方法包括:在催化剂的存在下使烃反应形成碳化合物和氢,其中所述碳化合物包括二氧化碳或一氧化碳中的至少一种;将碳化合物与氢分离;将碳化合物引导至电化学电池的阴极侧并将水引导至电化学电池的阳极侧;在阳极侧电解水以形成氧气和质子;向电化学电池中的膜和电极组件施加电压,以使质子从阳极穿过质子交换膜到达阴极侧的阴极;和使质子与碳化合物反应形成有机产物。
方面2:方面1所述的方法,其中所述反应包括蒸汽重整、部分氧化、CO2重整或自热重整中的至少一种。
方面3:方面1所述的方法,其中所述反应包括将烃料流和水引导至蒸汽重整器,并且使所述烃与水反应以形成包含碳化合物和氢的重整产物。
方面4:前述方面中任一项或多项所述的方法,其中所述反应包括将烃料流、水和二氧化碳引导至自热重整器,并使所述烃、水和二氧化碳反应以形成包含一氧化碳和氢的重整产物。
方面5:前述方面中任一项或多项所述的方法,其中所述烃包括甲烷、乙烷、乙烯、丙烷、丙烯、丁烷、丁二烯、环己烷、苯或甲苯中的至少一种。
方面6:前述方面中任一项或多项所述的方法,其中所述分离包括变压吸附。
方面7:前述方面中任一项或多项所述的方法,其中所述分离包括将包含碳化合物和氢的重整产物料流引导至电化学氢分离器的阳极侧;向电化学氢分离器中的分离单元膜和电极组件施加电压,以使分离单元阳极处的氢解离成质子和电子,并将质子从分离单元阳极通过分离单元质子交换膜引导至分离单元阴极,其中质子与分离单元阴极处的电子重新结合形成氢;从电化学氢分离器的分离单元阴极侧移除氢;和从分离单元阳极侧移除分离的碳料流。
方面8:方面7所述的方法,其中所述施加电压包括通过可再生能源施加电压。
方面9:方面7至8中任一项或多项所述的方法,其中一定量的水从所述电化学氢分离器的分离单元阴极侧回收并用于反应中和/或引导至电化学电池。
方面10:一种方法,任选地是前述方面中的任一项或多项所述的方法,其包括:将包含碳化合物和氢的来自精炼厂的废气料流引导至电化学氢分离器的阳极侧;向电化学氢分离器中的分离单元膜和电极组件施加电压,以使分离单元阳极处的氢解离成质子和电子,并将质子从分离单元阳极通过分离单元质子交换膜引导至分离单元阴极,其中质子与分离单元阴极处的电子重新结合形成氢;从电化学氢分离器的分离单元阴极侧移除氢;从分离单元阳极侧移除分离的碳料流。
方面11:前述方面中任一项或多项所述的方法,其中所述有机产物包括甲烷、羧酸、醇、甲醛或一氧化碳中的至少一种。
方面12:一种氢回收系统,其包括:重整器,该重整器通过烃料流和反应物源与烃源流体连通;其中所述重整器能够使来自烃源的烃反应以形成氢和包含二氧化碳和一氧化碳中的至少一种的碳化合物;分离单元,其通过重整产物料流与重整器流体连通;其中所述分离单元能够使重整产物料流的氢与所述碳化合物分离,并且其中通过氢料流从所述分离单元中回收氢;电化学电池,其通过包含碳化合物的分离的碳料流与分离单元流体连通;其中所述电化学电池包括在质子交换膜阴极侧的阴极和在质子交换膜阳极侧的阳极;其中所述分离的碳料流与电化学电池的阴极侧流体连通,且水料流与电化学电池的阳极侧流体连通;其中所述电化学电池能够使碳化合物与质子反应以在阴极处形成有机产物,所述质子由在阳极处从水料流中分离的质子提供。
方面13:方面12所述的系统,其中所述重整器是蒸汽重整器,并且其中水源还与所述蒸汽重整器流体连通。
方面14:方面12所述的系统,其中所述重整器是自热重整器,并且水源和二氧化碳源还与所述自热重整器流体连通。
方面15:方面12至14中任一项或多项所述的系统,其中所述烃源包括甲烷、乙烷、乙烯、丙烷、丙烯、丁烷、丁二烯、环己烷、苯或甲苯中的至少一种。
方面16:方面12至15中任一项或多项所述的系统,其中所述分离单元是变压吸附单元。
方面17:方面12至15中任一项或多项所述的系统,其中所述分离单元是电化学氢分离器;其中所述电化学氢分离器的氢分离器阳极侧与重整器流体连通;其中所述电化学氢分离器被配置成在重整器的氢分离器阳极侧解离氢,并在所述电化学氢分离器的氢分离器阴极侧重整氢。
方面18:方面17所述的系统,其中使用可再生能源为所述电化学氢分离器供电。
方面19:方面17至18中任一项或多项所述的系统,其中一定量的水从电化学氢分离器的阴极侧回收并与重整器或电化学电池中的至少一个流体连通。
方面20:方面12至19中任一项或多项所述的系统,其中来自精炼厂的废气料流与电化学氢分离器流体连通。
组合物、方法和制品可以替代地包含本文公开的任何合适的材料、步骤或组分,由其组成或基本上由其组成。组合物、方法和制品可以额外地或替代地被配制成不含或基本上不含对于实现组合物、方法和制品的功能或目的不是必需的任何材料(或物质)、步骤或组分。
术语“一(a)”和“一(an)”不表示对数量的限制,而是表示存在至少一个所引用的项目。术语“或”是指“和/或”,除非上下文另有明确说明。在整个说明书中对“一个方面”、“一个实施方案”、“另一个实施方案”、“一些实施方案”等的引用是指结合该实施方案描述的特定元素(例如,特征、结构、步骤或特性)被包括在本文所述的至少一个实施方案中,并且可以存在于或不存在于其他实施方案中。此外,应当理解,所描述的元素可以在各个实施方案以任何合适的方式组合。
例如层、膜、区域或基底的元件可以在另一个元件“上”,这是指它可以直接在另一个元件上,或者也可以存在中间元件,或者可以“直接在”另一个元件上而不存在中间元件。
术语“……中的至少一种”是指该列表包括每个单独的元素,以及列表的两个或多个元素的组合,以及列表的至少一个元素与未指出的相似元素的组合。术语“组合”包括共混物、混合物、合金、反应产物等。除非另有定义,本文使用的技术和科学术语与本发明所属领域技术人员通常理解的含义相同。
所有引用的专利、专利申请和其他参考文献通过整体引用并入本文。然而,如果本申请中的术语与并入的参考文献中的术语相矛盾或冲突,则来自本申请的术语优先于来自并入的参考文献的冲突术语。
虽然已经描述了特定的实施方案,但是申请人或本领域的其他技术人员可以想到目前未预见到或可能未预见到的替换、修改、变型、改进和实质等同方案。因此,所提交的所附权利要求及其可能的修改旨在包括所有这样的替换、修改、变型、改进和实质等同方案。
Claims (20)
1.一种回收氢的方法,所述方法包括:
在催化剂的存在下使烃反应形成碳化合物和氢,其中所述碳化合物包括二氧化碳或一氧化碳中的至少一种;
将碳化合物与氢分离;
将碳化合物引导至电化学电池的阴极侧并将水引导至电化学电池的阳极侧;
在阳极侧电解水以形成氧气和质子;
向电化学电池中的膜和电极组件施加电压,以使质子从阳极穿过质子交换膜到达阴极侧的阴极;和
使质子与碳化合物反应形成有机产物。
2.如权利要求1所述的方法,其中所述反应包括蒸汽重整、部分氧化、CO2重整或自热重整中的至少一种。
3.如权利要求1所述的方法,其中所述反应包括将烃和水引导至蒸汽重整器,并且使所述烃与水反应以形成包含碳化合物和氢的重整产物。
4.如前述权利要求中任一项或多项所述的方法,其中所述反应包括将烃、水和二氧化碳引导至自热重整器,并使所述烃、水和二氧化碳反应以形成包含一氧化碳和氢的重整产物。
5.如前述权利要求中任一项或多项所述的方法,其中所述烃包括甲烷、乙烷、乙烯、丙烷、丙烯、丁烷、丁二烯、环己烷、苯或甲苯中的至少一种。
6.如前述权利要求中任一项或多项所述的方法,其中所述分离包括变压吸附。
7.如前述权利要求中任一项或多项所述的方法,其中所述分离包括将包含碳化合物和氢的重整产物料流引导至电化学氢分离器的阳极侧;
向电化学氢分离器中的分离单元膜和电极组件施加电压,以使分离单元阳极处的氢解离成质子和电子,并将质子从分离单元阳极通过分离单元质子交换膜引导至分离单元阴极,其中质子与分离单元阴极处的电子重新结合形成氢;
从电化学氢分离器的分离单元阴极侧移除氢;和
从分离单元阳极侧移除分离的碳料流。
8.如权利要求7所述的方法,其中所述施加电压包括通过可再生能源施加电压。
9.如权利要求7至8中任一项或多项所述的方法,其中一定量的水从所述电化学氢分离器的分离单元阴极侧回收并用于反应中和/或引导至电化学电池。
10.如前述权利要求中任一项或多项所述的方法,其中所述有机产物包括甲烷、羧酸、醇、甲醛或一氧化碳中的至少一种。
11.一种方法,其包括:
将包含碳化合物和氢的来自精炼厂的废气料流引导至电化学氢分离器的阳极侧;
向电化学氢分离器中的分离单元膜和电极组件施加电压,以使分离单元阳极处的氢解离成质子和电子,并将质子从分离单元阳极通过分离单元质子交换膜引导至分离单元阴极,其中质子与分离单元阴极处的电子重新结合形成氢;
从电化学氢分离器的分离单元阴极侧移除氢;
从分离单元阳极侧移除分离的碳料流。
12.一种氢回收系统,其包括
重整器,其通过烃料流和反应物源与烃源流体连通;其中所述重整器能够使来自烃源的烃反应以形成氢和包含二氧化碳和一氧化碳中的至少一种的碳化合物;
分离单元,其通过重整产物料流与重整器流体连通;其中所述分离单元能够使所述重整产物料流的氢与碳化合物分离,并且其中通过氢料流从所述分离单元中回收氢;
电化学电池,其通过包含碳化合物的分离的碳料流与分离单元流体连通;其中所述电化学电池包括在质子交换膜阴极侧的阴极和在质子交换膜阳极侧的阳极;
其中所述分离的碳料流与电化学电池的阴极侧流体连通,且水料流与电化学电池的阳极侧流体连通;其中所述电化学电池能够使碳化合物与质子反应以在阴极处形成有机产物,所述质子由在阳极处从水料流中分离的质子提供。
13.如权利要求12所述的系统,其中所述重整器是蒸汽重整器,并且其中水源还与所述蒸汽重整器流体连通。
14.如权利要求12所述的系统,其中所述重整器是自热重整器,并且水源和二氧化碳源还与所述自热重整器流体连通。
15.如权利要求12至14中任一项或多项所述的系统,其中所述烃源包括甲烷、乙烷、乙烯、丙烷、丙烯、丁烷、丁二烯、环己烷、苯或甲苯中的至少一种。
16.如权利要求12至15中任一项或多项所述的系统,其中所述分离单元是变压吸附单元。
17.如权利要求12至15中任一项或多项所述的系统,其中所述分离单元是电化学氢分离器;其中所述电化学氢分离器的氢分离器阳极侧与重整器流体连通;
其中所述电化学氢分离器被配置成在重整器的氢分离器阳极侧解离氢并在所述电化学氢分离器的氢分离器阴极侧重整氢。
18.如权利要求17所述的系统,其中使用可再生能源为所述电化学氢分离器供电。
19.如权利要求17至18中任一项或多项所述的系统,其中一定量的水从电化学氢分离器的阴极侧回收并与重整器或电化学电池中的至少一个流体连通。
20.如权利要求12至19中任一项或多项所述的系统,其中来自精炼厂的废气料流与所述电化学氢分离器流体连通。
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