CN113710611A - 几乎零温室气体排放的烃类制氢 - Google Patents
几乎零温室气体排放的烃类制氢 Download PDFInfo
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- CN113710611A CN113710611A CN202080027161.3A CN202080027161A CN113710611A CN 113710611 A CN113710611 A CN 113710611A CN 202080027161 A CN202080027161 A CN 202080027161A CN 113710611 A CN113710611 A CN 113710611A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 15
- 239000005431 greenhouse gas Substances 0.000 title claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000006227 byproduct Substances 0.000 claims abstract description 47
- 239000011435 rock Substances 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000000047 product Substances 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 56
- 239000007924 injection Substances 0.000 claims description 29
- 238000002347 injection Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 238000000629 steam reforming Methods 0.000 claims description 8
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 56
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
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- 239000011575 calcium Substances 0.000 description 7
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- 238000003786 synthesis reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
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- 238000007670 refining Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
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- 229910052612 amphibole Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000008398 formation water Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000005374 membrane filtration Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
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Abstract
用于制氢且基本无温室气体排放的方法和系统,所述方法包括由烃燃料源产生包含氢气和二氧化碳的产物气体;从产物气体中分离出氢气以产生氢气产物流和副产物流;将副产物流注入含有镁铁质岩石的储层中;以及使副产物流的组分与镁铁质岩石的组分发生原位反应以使副产物流的组分沉淀并封存在储层中。
Description
技术领域
本公开的实施方案涉及协同进行制氢和碳捕获。特别地,本公开的实施方案涉及基本无温室气体排放的石油燃料制氢,这种基本无温室气体排放是由于经由镁铁质岩石(例如玄武岩)进行的碳捕获而实现的。
背景技术
氢气或H2是一种环境友好的燃料,其具有替代排放温室气体的烃燃料的潜力。例如,氢气可用于为燃料电池供能。目前生产的几乎所有H2(超过约95%)都来自烃类,并且主要来自天然气。排放到大气中的废CO2(每生产一吨H2伴随大约7吨至12吨CO2)部分抵消了H2的“清洁燃料”优势。为了减轻制H2时伴随的碳足迹,已经提出了经济上不切实际的制H2方法和系统,该方法和系统将捕获共同产生的CO2、将其压缩成液体并注入深部(深度大于地下约800米至850米)沉积岩储层中组合于一个工艺中,这一工艺被称为碳捕获与封存(“CCS”)。然而,常规的CCS会显著增加本已高耗能的制H2方法的成本,从而使该组合技术在当前市场和监管条件下不可行。
对于先前提出的烃类制H2与CO2的常规CCS的组合,例如在枯竭的含烃储层或含盐地下水含水层中的CO2的CCS,增加了与CO2的纯化、压缩、运输和注入相关的高昂成本。采用了许多耗能步骤来确保满足常规CCS要求所需的高纯度CO2(大于约98mol%)。而且,由于标准变压吸附(“PSA”)H2-CO2分离技术本身并不能为CCS生产质量和纯度足够高的CO2,因此需要进一步纯化,该纯化涉及酸性气体吸收试剂,例如SelexolTM(用于重质烃类和固体烃类)和甲基二乙醇胺(MDEA)。
常规的CCS中CO2的安全且经济的运输、以及注入和长期封存都依赖于将CO2压缩到超临界(液体)状态,这也显著增加了成本。因此,地下CO2封存储层必须位于地表以下垂直距离至少约850米处,以确保有足够的压力使CO2保持液态,从而增加了注入井和处置井的成本。
由于常规的CCS中的CO2会保持液体状态和/或压缩气体状态达数百年或数千年,因此需要复杂的长期监测程序,以确保将CO2真正限制在给定的CCS储层中并且不会迁移到覆岩(overlying)含水层或地表。
发明内容
本公开提供了由烃化石燃料有效制氢且很少或没有温室气体排放的系统和方法。在一些实施方案中,该方法的第一步骤是由气态、液态或固态烃类同时产生H2和废物或副产物CO2(例如天然气蒸汽重整)。由烃类同时产生H2和CO2可以通过多种工艺完成。在该方法的第二步骤中,将CO2注入反应性镁铁质岩石或超镁铁质岩石中,CO2和/或其他废气在反应性镁铁质岩石或超镁铁质岩石中作为沉淀的碳酸盐矿物质而永久固定。术语镁铁质岩概括性地描述富含镁和铁的硅酸盐矿物岩或火成岩。镁铁质矿物质颜色可能较深,而形成岩石的镁铁质矿物质包括橄榄石、辉石、角闪石和黑云母。镁铁质岩石的实例包括玄武岩、辉绿岩和辉长岩。超镁铁质岩石的实例包括纯橄榄岩、橄榄岩和辉石岩。在化学上,镁铁质岩石和超镁铁质岩石可以富含铁、镁和钙。
在系统和方法的实施方案中,产生的氢气能够可逆地转化为氨,以便于以更小的体积安全储存和运输。本发明的碳捕获与封存(“CCS”)系统和方法的用途广泛,还能够使来自诸如精炼、发电和脱盐之类的其他来源的CO2经济地固定在例如玄武岩中。
为了提高协同进行的制H2和CO2去除的效率,制H2在可供选择的CCS工艺之前进行,在该CCS工艺中,将溶解于水的CO2注入由反应性玄武岩和超镁铁质岩石组成的天然地质宿体(geological sink)中,在该天然地质宿体中,CO2迅速反应以形成稳定的矿物相,例如沉淀的碳酸盐。与其他CCS系统和工艺相比,玄武岩中的碳封存(“CSB”)消耗的能源明显更少,有利地对酸性气体杂质(即H2S)具有较高的耐受性,不需要深井,例如850m深或更深的井,并且不需要长期的储层监测。
与常规的CCS相比,玄武岩和超镁铁质岩石中的CO2封存是独特的,因为它在某种程度上依赖于快速进行将CO2气体转化为固体的化学反应,而不是依赖于随时间推移的CO2本身(作为气态或液态)的物理封存。经济估算表明,与常规的CCS相比,本公开的系统和方法捕获一公吨CO2的成本要低得多。
在一些实施方案中,在将CO2气体注入含玄武岩的储层之前或在此期间,将CO2气体溶解在水中,这避免了包括压缩和保持CO2为液体状态在内的一些困难。通过将CO2溶解在水相中,有助于避免如常规CCS所要求的钻探地表以下深度大于约850m的深的处置井。换句话说,CSB需要远远更低的压力就能使足够量的CO2保持溶解于水中,并且对于本公开的实施方案,注入区可以浅至地表以下垂直距离350米。
将CO2快速固定为稳定的固体碳酸盐矿物质,不仅确保从环境中永久去除CO2,而且排除了对于常规CCS现场所需的复杂监测程序的需要。本技术的对存在高达约40mol%的诸如H2S之类的其他水溶性废气的极端耐受性也对效率具有重要的影响,这些水溶性废气能够像CO2一样,在玄武岩和超镁铁质岩中迅速且基本完全地矿化。
CSB不需要昂贵且耗能的步骤来从制H2过程中产生的CO2和其他气体中去除硫/H2S杂质。另一个重要的优点是,与液态CO2(液态CO2密度低于储层水,因此具有浮力)不同的是,富含CO2的水的密度高于环境地下水。因此,当注入富含CO2的水时,其将沉入储层而不是向上移动,这在一些实施方案中消除了对冠岩的需要,而冠岩是所有常规CCS储层的极其重要的地质特征。在本公开的实施方案中,在玄武岩和镁铁质岩石中注入并封存CO2对存在于那些岩石中的地下水的质量没有影响。当将这些含水层用于供应饮用水或其他目的用水时,这一点尤为重要。
因此,本文公开了一种用于制氢且基本无温室气体排放的方法,该方法包括由烃燃料源产生包含氢气和二氧化碳的产物气体;从产物气体中分离出氢气以产生氢气产物流和副产物流;将副产物流注入含有镁铁质岩石的储层中;以及使副产物流的组分与镁铁质岩石的组分发生原位反应,以使副产物流的组分沉淀并封存在储层中。
在一些实施方案中,镁铁质岩石包括玄武岩。在其他实施方案中,在将副产物流注入储层的步骤之前,进一步处理副产物流以将CO2与其他组分分离并纯化,以提高用于注入储层中的副产物流的CO2浓度。该方法的其他实施方案还包括将用于注入储层中的副产物流中的CO2液化的步骤。在一些实施方案中,该方法包括将副产物流与水混合的步骤,该副产物流包含H2S。在一些实施方案中,该方法包括使分离出的氢气与氮气反应以形成压缩液氨的步骤。其他实施方案包括运输压缩液氨的步骤、以及通过电解法使压缩液氨再次转变为氢气和氮气以将氢气用作氢燃料源的步骤。
在其他的实施方案中,产生产物气体的步骤包括蒸汽重整或部分氧化。在某些实施方案中,包括使副产物流的组分与镁铁质岩石的组分发生原位反应,以沉淀产生选自由碳酸钙、碳酸镁、碳酸铁以及它们的组合组成的组中的沉淀物的步骤。还在其他实施方案中,储层在地表以下约250m和约700m之间,或在约400m和约500m之间,并且在约150℃和约280℃之间,或更低。合适的储层中的温度可低至约30℃。在其他实施方案中,储层在地表以下约700m和约2,200m之间并且低于约325℃。
本文还公开了一种用于制氢且基本无温室气体排放的系统,该系统包括:具有烃燃料入口的制氢单元,该制氢单元能够由烃燃料产生包含氢气和二氧化碳的产物气体;氢气分离单元,该氢气分离单元能够从产物气体中分离出氢气以产生氢气产物流和副产物流;和注入井,该注入井能够将副产物流注入包含镁铁质岩石的储层,以使副产物流的组分与镁铁质岩石的组分发生原位反应,从而将副产物流的组分沉淀并封存在储层中。在一些实施方案中,镁铁质岩石包括玄武岩。在其他实施方案中,该系统包括副产物处理单元以处理副产物流,从而将CO2与其他组分分离并纯化,并且提高用于注入储层中的副产物流的CO2浓度。
还在其他实施方案中,该系统包括压缩机,以液化用于注入储层中的副产物流中的CO2。在某些实施方案中,该系统包括混合单元以混合副产物流和水,该副产物流包含H2S。还在其他实施方案中,该系统包括反应单元,以使分离出的氢气与氮气反应从而形成压缩液氨。在某些实施方案中,该系统包括运输单元,以运输压缩液氨并通过电解法使压缩液氨再次转变为氢气和氮气,以将氢气用作氢燃料源。
还在其他实施方案中,制氢单元包括蒸汽重整器或部分氧化反应器。在一些实施方案中,所产生的副产物流的组分与镁铁质岩石的组分发生原位反应,以沉淀选自由碳酸钙、碳酸镁、碳酸铁以及它们的组合组成的组中的产物。另外在其他实施方案中,储层在地表以下约250m和约700m之间,或在约400m和约500m之间,并且在约150℃和约280℃之间,或更低。合适的储层中的温度可低至约30
℃。在其他实施方案中,储层在地表以下约700m和约2,200m之间并且低于约325℃。
附图说明
参照以下说明书、权利要求和附图,将更好地理解本公开的这些和其他特征、方面和优点。然而,需要注意的是,附图仅示出了本公开的几个实施方案,因此不应被视为对本公开范围的限制,因为本公开可以容许其他同样有效的实施方案。
图1示出用于同时进行制H2、H2运输和CO2封存的系统的示例性实施方案的示意流程图,该系统用于由烃类制H2且几乎零温室气体排放。
具体实施方式
因此,通过参考构成本说明书的一部分的附图中示出的实施方案,可对之前简要概括的本公开的实施方案进行更具体的描述,从而可更详细地理解将变得明显的用于由烃类制H2且几乎零温室气体排放的系统和方法的实施方案的特征和优点以及其他特征和优点的方式。然而,需要注意的是,附图仅示出了本公开的各种实施方案,因此不应被认为是对本公开范围的限制,因为本公开还可以包括其他有效的实施方案。
通过使用诸如蒸汽重整或部分氧化/气化的技术由烃类制H2包括三个步骤。在蒸汽重整中,在H2O(蒸汽)和催化剂的存在下加热烃(例如甲烷),以释放由氢气(H2)、一氧化碳(CO)、少量二氧化碳(CO2)和/或其他杂质组成的粗合成气,如方程式1和2所示:
和/或
然后处理粗合成气以除去硫化合物并且/或者进一步纯化。然后,根据方程式3,通过使粗合成气与H2O蒸汽在催化剂的存在下反应以产生H2和CO2,从而使H2产率最大化:
CO+H2O→CO2+H2 方程式3
这被称为水煤气变换反应,因此产物被称为“变换”合成气。在部分氧化中,根据方程式4,烃与少量(非化学计量)的氧气(O2)反应,以产生由H2和CO组成的粗合成气:
CH4+1/2O2→CO+2H2 方程式4
该粗合成气还包含少量的CO2和/或氮气(N2,如果使用空气代替纯O2的话)。然后纯化粗合成气,并通过方程式3的反应使其H2含量最大化。表1列出了由两种方法(蒸汽重整和部分氧化)生产的示例性变换合成气的组成:
表1.来自蒸汽重整或部分氧化的示例性变换合成气的组成。
组分 | H<sub>2</sub> | CO | CO<sub>2</sub> | N<sub>2</sub> | O<sub>2</sub> | Ar | H<sub>2</sub>S | H<sub>2</sub>O | 其他 |
Mol.% | 40.9 | 1 | 29.8 | 2.4 | 0 | 0.4 | 0.01 | 25.4 | 0.11 |
在水煤气变换之后,通过采用吸附、吸收和/或膜过滤的方法使H2与CO2和其他杂质分离,从而纯化H2。一个示例性的方法是变压吸附(“PSA”),该方法利用了诸如活性炭、二氧化硅和沸石等材料的压力相关的选择性吸附特性。在PSA过程中,与H2分离的废物或副产物CO2和其他杂质随后被排放到大气中。遗憾的是,如果要使用常规的CCS方案来封存CO2,则必须进一步纯化CO2并将其压缩成液体(超临界)状态,以便运输和注入深部储层中。然而在本文中,当改为采用CSB时,这两个步骤都可以被避免(或显著简化)。
常规CCS主要依赖于物理过程,例如将单相液态CO2注入并封存在非反应性岩石储层(例如砂岩、石灰岩)中,而CSB依赖于CO2与镁铁质岩石和超镁铁质岩石之间发生的天然化学反应以沉淀固体碳酸盐。反应包括如下:如方程式5至7所示,首先,CO2溶解到水(地表处的具有CO2气体的水或原位存在于镁铁质岩储层中的水中的任一种水、或者这两种水)中并与水发生反应,以形成弱碳酸:
根据方程式8,酸化水溶解富含Ca、Fe和Mg的硅酸盐相(矿物质和/或火山玻璃),这使得溶液中释放出二价金属离子:
(Mg,Fe,Ca)2SiO4+4H+→2(Mg,Fe,Ca)2++2H2O+SiO2(aq) 方程式8
方程式7所示的反应过程中形成的CO3 2-与二价金属阳离子反应,使得碳酸盐矿物质沉淀,如方程式9中所示:
(Ca,Mg,Fe)2++CO3 2-→(Ca,Mg,Fe)CO3 方程式9
地球化学反应-运输模型表明,矿物相(例如方解石、菱铁矿和菱镁矿)在一般的地下条件下将保持稳定,因此可以从大气中安全地去除CO2达数十万至数百万年。其他碳酸盐矿物质包括铁白云石Ca[Fe,Mg,Mn](CO3)2。此外,CSB对其他水溶性酸性气体杂质(例如H2S,其也可矿化为硫化物)具有极高的耐受性。这种有利的品质不仅进一步简化了工艺,消除了从离开制H2过程的气体混合物中去除这些杂质的需要,而且还同时封存了所有其他能够通过与玄武岩/超镁铁质岩反应而形成稳定矿物相的H2O可溶性气体污染物。
CSB在水中的CO2溶解可以通过以下任一方式实现:a)将CO2和水分别注入到注入井的管道和环形空间中,并在进入储层之前使它们在井筒中约350m深度处或更深处混合;或b)在加压容器中、在地表溶解CO2和水,然后将溶液注入玄武岩/超镁铁质岩储层中。前一种方法通常适用于纯CO2和/或CO2与其他水溶性酸性气体的混合物,而后一种方法用于有效地将CO2(和其他水溶性气体)与不溶性或微溶性杂质分离,因此可以用于处理复杂的烟气混合物(例如变换合成气)。
由于CO2在水中的溶解存在某些热力学限制,因此这两种方法每封存1吨的CO2都需要约27吨的H2O。在水供给短缺的地区,可以通过在玄武岩或超镁铁质岩中注入超临界(液态)CO2来进行CSB;然而,由于需要通过压缩使CO2液化,因此这会增加能源需求。
关于制得的H2,常规来说H2以温度约-253℃的液体形式储存和运输,这除了需要持续制冷外,还需要特殊的双壁隔离容器,或者需要特殊的双壁隔离容器以替代持续制冷。然而,通过H2向液氨(NH3)的可逆化学转化,使得H2的储存和运输可在低压和环境温度下以大大减少的体积进行。H2到NH3的可逆储存和运输方法本质上是更安全且有利的,特别是在要储存和运输大量H2的情况下。
由于CSB对CO2流中的杂质(例如H2S和其他气体)的高度耐受性,因此来自诸如精炼、发电和脱盐之类的其他来源的富含CO2的尾气可以在有限的处理后添加到主要废物流中,或者独立注入反应性岩石中,以便永久固定和处置。
对于在使用CSB在玄武岩和超镁铁质岩中永久固定CO2的同时由烃类制H2,其意外且令人惊讶的优势包括显著降低的预计能源用量和成本,原因在于:因为不需要压缩和液化CO2,使得能源消耗较低且井成本较低;由于对CO2流中的杂质的耐受性高,因此操作复杂性较低;通过沉淀为固体,同时在储层中去除了H2S和CO2;不需要储层冠岩;并且不需要复杂的长期监测程序。当在地表或井筒中将CO2溶解于水中时,无需将CO2液化,但如果将CO2作为超临界流体直接注入地下,则要使CO2液化。
图1示出用于同时进行制H2、H2运输和CO2封存的系统的示例性实施方案的示意流程图,该系统用于由烃类制H2而几乎零温室气体排放。在系统100中,烃入口102向制氢系统104提供烃源,例如天然气。制氢系统104可以包括蒸汽重整或部分氧化、以及水煤气变换反应,例如如方程式1至4中所示。产生的气体经由出口106离开并进入分离单元108。分离单元108能够将氢气与CO2和其他副产物分离,并且分离单元108可包括(例如)一个或以上吸附单元、吸收单元、膜分离单元、或者用于将H2与CO2和其他产物气体(例如酸性气体)分离的任何合适的分离技术。
CO2和另外的气体(例如酸性气体)经由出口110离开分离单元108,并且可以任选地行进到进一步的CO2纯化和液化单元112,但并不是必须的。在具有进一步的CO2纯化和液化单元112的情况下,将液化的CO2通过注入井114注入玄武岩地层116中,从而根据方程式5至9形成固体沉淀金属碳酸盐。在没有任选的进一步CO2纯化和液化单元112的情况下,CO2和诸如酸性气体之类的其他气体经由出口110离开分离单元108,并且经由注入井114直接进入玄武岩地层116中,从而根据方程式5至9形成固体沉淀金属碳酸盐。CO2可以在地表处以气体形式与水混合,或者以气体形式在玄武岩地层116中原位与水混合,或者这两种方式兼有。在注入井周围的玄武岩的溶洞和岩脉中形成固体碳酸盐结核,并由注入井向外延伸。
玄武岩溶解和矿物碳酸化反应的速率可以随着温度升高而增加,因此更高温度的玄武岩储层可能是有利的,而并不需要超过约350m的深储层,因为不需要用高压来使CO2保持在加压状态或液体状态。储层温度可低至约30℃并高达约280℃,但是通常不高于约325℃,当温度超过325℃时,某些碳酸盐矿物质会变得热力学不稳定。示例性的合适的储层温度为约185℃,或者例如在约150℃和约280℃之间。如所解释的,注入的CO2本身或者CO2和其他气体(可任选地溶解于水中)在注入井(例如注入井114)附近形成酸性环境。注入井114附近的酸性流体对于玄武岩矿物质和火山玻璃保持不饱和状态。
不饱和以及酸性导致注入井(例如注入井114)附近的主体岩石玄武岩溶解。在主体玄武岩的充分溶解中和了酸性水并使地层水中的碳酸盐和含硫矿物质饱和后,矿化主要发生在远离注入井一定距离处(这使得能够在例如玄武岩地层116之类的储层中连续注入CO2)。
氢气以出口流118离开分离单元108并行进至反应单元120,氢气在反应单元120中与氮气反应以形成氨(NH3)。氨在出口122处离开反应单元120,从而使H2以NH3的形式以更小的体积运输。反应单元120可包括加压多级氨生产系统(PMAPS),以生产加压液相形式的氨。加压液态NH3可以通过加压罐车运输,并且在需要氢气的地方,通过使用NH3电解槽,NH3能够可逆地再次转变为N2和H2。
除非上下文另外明确指出,否则单数形式“一(a)”、“一个(an)”和“该(the)”包括复数指示物。
术语“约”在用于值或范围时是指包括给定值或范围的正负5%的值。
在附图和说明书中,已经公开了本公开的系统和方法的实施方案,该系统和方法用于烃类制氢而温室气体排放几乎为零,并且尽管采用了具体术语,但这些术语仅用于描述性意义而不是用于限制目的。具体参考这些示出的实施方案,已经相当详细地描述了本公开的实施方案。然而,显而易见的是,在如前述说明书中描述的本公开的精神和范围内可以进行各种修改和改变,并且认为这样的修改和改变为本公开的等同形式并且是本公开的一部分。
Claims (22)
1.一种用于制氢且基本无温室气体排放的方法,该方法包括以下步骤:
由烃燃料源产生包含氢气和二氧化碳的产物气体;
从所述产物气体中分离出氢气以产生氢气产物流和副产物流;
将所述副产物流注入含有镁铁质岩石的储层中;以及
使所述副产物流的组分与所述镁铁质岩石的组分发生原位反应,以使所述副产物流的组分沉淀并封存在所述储层中。
2.根据权利要求1所述的方法,其中所述镁铁质岩石包括玄武岩。
3.根据权利要求1或权利要求2所述的方法,其中在将所述副产物流注入所述储层的步骤之前,进一步处理所述副产物流以将CO2与其他组分分离并纯化,从而提高用于注入所述储层中的所述副产物流的CO2浓度。
4.根据权利要求1至3中任一项所述的方法,还包括将用于注入所述储层中的所述副产物流中的CO2液化的步骤。
5.根据权利要求1至4中任一项所述的方法,还包括混合所述副产物流和水的步骤,所述副产物流包含H2S。
6.根据权利要求1至5中任一项所述的方法,还包括使分离出的氢气与氮气反应以形成压缩液氨的步骤。
7.根据权利要求6所述的方法,还包括运输所述压缩液氨,并通过电解法使所述压缩液氨再次转变为氢气和氮气以将氢气用作氢燃料源的步骤。
8.根据权利要求1至7中任一项所述的方法,其中产生产物气体的步骤包括蒸汽重整或部分氧化。
9.根据权利要求1至8中任一项所述的方法,其中使所述副产物流的组分与所述镁铁质岩石的组分发生原位反应的步骤产生选自由碳酸钙、碳酸镁、碳酸铁以及它们的组合组成的组中的沉淀物。
10.根据权利要求1至9中任一项所述的方法,其中所述储层在地表以下250m和2,200m之间并且在30℃和325℃之间。
11.根据权利要求1至9中任一项所述的方法,其中所述储层在地表以下350m和1,500m之间并且低于325℃。
12.一种用于制氢且基本无温室气体排放的系统,该系统包括:
具有烃燃料入口的制氢单元,该制氢单元能够由烃燃料产生包含氢气和二氧化碳的产物气体;
氢气分离单元,该氢气分离单元能够从所述产物气体中分离出氢气以产生氢气产物流和副产物流;以及
注入井,该注入井能够将所述副产物流注入包含镁铁质岩石的储层中,以使所述副产物流的组分与所述镁铁质岩石的组分发生原位反应,从而使所述副产物流的组分沉淀并封存在所述储层中。
13.根据权利要求12所述的系统,其中所述镁铁质岩石包括玄武岩。
14.根据权利要求12或权利要求13所述的系统,还包括副产物处理单元以处理所述副产物流,从而将CO2与其他组分分离并纯化,并且提高用于注入所述储层中的所述副产物流的CO2浓度。
15.根据权利要求12至14中任一项所述的系统,还包括压缩机,以液化用于注入所述储层中的所述副产物流中的CO2。
16.根据权利要求12至15中任一项所述的系统,还包括混合单元以混合所述副产物流和水,所述副产物流包含H2S。
17.根据权利要求12至16中任一项所述的系统,还包括反应单元,以使分离出的氢气与氮气反应从而形成压缩液氨。
18.根据权利要求17所述的系统,还包括运输单元,以运输所述压缩液氨并通过电解法使所述压缩液氨再次转变为氢气和氮气,以将氢气用作氢燃料源。
19.根据权利要求12至18中任一项所述的系统,其中所述制氢单元包括蒸汽重整器或部分氧化反应器。
20.根据权利要求12至19中任一项所述的系统,其中所产生的副产物流的组分与所述镁铁质岩石的组分发生原位反应,以沉淀选自由碳酸钙、碳酸镁、碳酸铁以及它们的组合组成的组中的产物。
21.根据权利要求12至20中任一项所述的系统,其中所述储层在地表以下250m和2,200m之间并且在30℃和325℃之间。
22.根据权利要求12至20中任一项所述的系统,其中所述储层在地表以下350m和1,500m之间并且低于325℃。
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US11491439B2 (en) | 2019-04-08 | 2022-11-08 | Saudi Arabian Oil Company | Method for reducing energy and water demands of scrubbing CO2 from CO2-lean waste gases |
US11167732B1 (en) * | 2020-12-17 | 2021-11-09 | Air Products And Chemicals, Inc. | Hydrogen fueling station with integrated ammonia cracking unit |
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US11707708B2 (en) | 2021-03-12 | 2023-07-25 | Saudi Arabian Oil Company | Systems and methods for capturing carbon dioxide |
US20230050823A1 (en) * | 2021-07-30 | 2023-02-16 | Ohio State Innovation Foundation | Systems and methods for generation of hydrogen by in-situ (subsurface) serpentinization and carbonization of mafic or ultramafic rock |
US11982165B2 (en) * | 2021-11-16 | 2024-05-14 | Lion Fuel Resources, LLC | System and method for enhanced petroleum product recovery |
US11598187B1 (en) | 2022-01-11 | 2023-03-07 | Saudi Arabian Oil Company | Membrane-based systems and methods for increasing the mass transfer rate of dissolved gases |
US11982160B1 (en) | 2022-10-24 | 2024-05-14 | Saudi Arabian Oil Company | Systems for waste gas sequestration in geological formations and methods of gas sequestration of waste gases in geological formations |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090117024A1 (en) * | 2005-03-14 | 2009-05-07 | Geoffrey Gerald Weedon | Process for the Production of Hydrogen with Co-Production and Capture of Carbon Dioxide |
US20090255181A1 (en) * | 2008-04-10 | 2009-10-15 | Rhinesmith R Bret | Method and system for generating hydrogen-enriched fuel gas for emissions reduction and carbon dioxide for sequestration |
CN102159473A (zh) * | 2008-06-24 | 2011-08-17 | Ifp新能源公司 | 处理酸性气体贮藏井周围区域的方法 |
CN102300803A (zh) * | 2008-12-11 | 2011-12-28 | 英国石油有限公司 | 联合式气体精炼 |
US20160082387A1 (en) * | 2014-09-23 | 2016-03-24 | Blue Planet, Ltd. | Carbon sequestration methods and systems |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1843063A (en) | 1932-01-26 | Of cabbon monoxide anj | ||
US1904592A (en) | 1929-08-30 | 1933-04-18 | Standard Oil Dev Co | Process for the manufacture of hydrogen |
JP5717257B2 (ja) * | 2010-03-25 | 2015-05-13 | 国立大学法人広島大学 | 水素の発生方法、水素の利用方法及び発電システム |
DE102015015524A1 (de) * | 2015-12-01 | 2017-06-01 | Linde Aktiengesellschaft | Verfahren zur Erzeugung von Harnstoff |
-
2019
- 2019-07-08 US US16/505,378 patent/US11155462B2/en active Active
-
2020
- 2020-04-05 EP EP20722131.8A patent/EP3947264A1/en active Pending
- 2020-04-05 CN CN202080027161.3A patent/CN113710611A/zh active Pending
- 2020-04-05 WO PCT/US2020/026783 patent/WO2020210137A1/en active Application Filing
-
2021
- 2021-09-21 US US17/480,444 patent/US20220002153A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090117024A1 (en) * | 2005-03-14 | 2009-05-07 | Geoffrey Gerald Weedon | Process for the Production of Hydrogen with Co-Production and Capture of Carbon Dioxide |
US20090255181A1 (en) * | 2008-04-10 | 2009-10-15 | Rhinesmith R Bret | Method and system for generating hydrogen-enriched fuel gas for emissions reduction and carbon dioxide for sequestration |
CN102159473A (zh) * | 2008-06-24 | 2011-08-17 | Ifp新能源公司 | 处理酸性气体贮藏井周围区域的方法 |
CN102300803A (zh) * | 2008-12-11 | 2011-12-28 | 英国石油有限公司 | 联合式气体精炼 |
US20160082387A1 (en) * | 2014-09-23 | 2016-03-24 | Blue Planet, Ltd. | Carbon sequestration methods and systems |
Non-Patent Citations (2)
Title |
---|
INGVI GUNNARSSON 等,: "The rapid and cost-effective capture and subsurface mineral storage of carbon and sulfur at the CarbFix2 site", 《INTERNATIONAL JOURNAL OF GREENHOUSE GAS CONTROL》, vol. 79, pages 117 - 126, XP085548920, DOI: 10.1016/j.ijggc.2018.08.014 * |
NOBUKO HANNADA 等,: "Hydrogen generation by electrolysis of liquid ammonia", 《CHEMCOMM》, vol. 46, pages 7775 - 7777 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117819119A (zh) * | 2024-03-06 | 2024-04-05 | 太原理工大学 | 一种烟道气地下岩层捕集封存分离连续一体化装置及方法 |
CN117819119B (zh) * | 2024-03-06 | 2024-05-10 | 太原理工大学 | 一种烟道气地下岩层捕集封存分离连续一体化装置及方法 |
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