CN107074538A - Method for producing liquified hydrogen - Google Patents
Method for producing liquified hydrogen Download PDFInfo
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- CN107074538A CN107074538A CN201580058397.2A CN201580058397A CN107074538A CN 107074538 A CN107074538 A CN 107074538A CN 201580058397 A CN201580058397 A CN 201580058397A CN 107074538 A CN107074538 A CN 107074538A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 91
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 91
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 49
- 230000005611 electricity Effects 0.000 claims abstract description 39
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 230000008929 regeneration Effects 0.000 claims abstract description 16
- 238000011069 regeneration method Methods 0.000 claims abstract description 16
- 230000001172 regenerating effect Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000003860 storage Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010924 continuous production Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 150000007513 acids Chemical class 0.000 claims description 5
- 238000004146 energy storage Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims 2
- 239000011686 zinc sulphate Substances 0.000 claims 2
- 235000009529 zinc sulphate Nutrition 0.000 claims 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 235000011147 magnesium chloride Nutrition 0.000 claims 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims 1
- 235000019341 magnesium sulphate Nutrition 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
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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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/22—Inorganic acids
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
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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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/0002—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the fluid to be liquefied
- F25J1/0005—Light or noble gases
- F25J1/001—Hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0228—Coupling of the liquefaction unit to other units or processes, so-called integrated processes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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- F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
- F25J1/0243—Start-up or control of the process; Details of the apparatus used; Details of the refrigerant compression system used
- F25J1/0244—Operation; Control and regulation; Instrumentation
- F25J1/0245—Different modes, i.e. 'runs', of operation; Process control
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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- F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
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- F25J1/0279—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc.
- F25J1/0281—Compression of refrigerant or internal recycle fluid, e.g. kind of compressor, accumulator, suction drum etc. characterised by the type of prime driver, e.g. hot gas expander
- F25J1/0284—Electrical motor as the prime mechanical driver
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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- F25J2260/00—Coupling of processes or apparatus to other units; Integrated schemes
- F25J2260/30—Integration in an installation using renewable energy
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- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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- F25J2290/00—Other details not covered by groups F25J2200/00 - F25J2280/00
- F25J2290/62—Details of storing a fluid in a tank
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明涉及用于连续生产液态氢的集成方法，其包括：(a)通过电解生产气态氢；和(b)在氢液化单元中使所述气态氢液化，所述液化单元通过基本上来自再生源的能量供电；和，(c)当需要另外的电时，使用在其中通过集成电解方法共同生成电能和氢的方法中生成的电能，所述集成电解方法包括：(d)将金属盐或金属盐的混合物和水电解成相应的一种或多种金属、一种或多种酸和氧(电力储存阶段)，和(e)在步骤(d)的金属和酸的再生反应中产生气态氢并回收电力(再生阶段)；其中步骤(e)中生成的至少部分气态氢用于该方法的步骤(b)。The present invention relates to an integrated process for the continuous production of liquid hydrogen comprising: (a) production of gaseous hydrogen by electrolysis; and (b) liquefaction of said gaseous hydrogen in a hydrogen liquefaction unit, said liquefaction unit being obtained by essentially regenerating and, (c) when additional electricity is required, use the electricity generated in a method in which electricity and hydrogen are co-generated by an integrated electrolysis process comprising: (d) adding a metal salt or The mixture of metal salts and water are electrolyzed to the corresponding metal(s), acid(s) and oxygen (electricity storage stage), and (e) the gaseous state is produced in the metal and acid regeneration reaction in step (d) Hydrogen and electricity recovery (regeneration phase); wherein at least part of the gaseous hydrogen produced in step (e) is used in step (b) of the process.
Description
技术领域technical field
本发明涉及用于生产液态氢的方法和用于所述方法的系统。The present invention relates to a method for producing liquid hydrogen and a system for said method.
背景技术Background technique
氢是炼油和化肥工业以及其他几种化学工艺中使用的重要工业气体。预期氢可能另外起到作为能量载体的重要作用，特别是在运输部门中。Hydrogen is an important industrial gas used in the oil refining and fertilizer industries, as well as in several other chemical processes. It is expected that hydrogen may additionally play an important role as an energy carrier, especially in the transport sector.
在不存在国内管道网络的情况下或用于进口，预期以液体形式的氢将是其供应和分配的最有效方式之一。然而，目前氢液化仍然是昂贵以及能源密集型的。氢的液化涉及进料氢气的压缩，几个冷却步骤，以及最后通过膨胀液化。目前，在改进氢液化方法的经济性方面正在进行大量研究(参见例如，2013年12月报道了最近开发的“优选方法”的欧洲赞助的IDEALHY项目，参见www.idealhy.eu)。In the absence of domestic pipeline networks or for import, hydrogen in liquid form is expected to be one of the most efficient ways of supplying and distributing it. However, currently hydrogen liquefaction remains expensive and energy intensive. Liquefaction of hydrogen involves compression of feed hydrogen, several cooling steps, and finally liquefaction by expansion. Currently, a lot of research is going on in improving the economics of hydrogen liquefaction processes (see eg the European sponsored IDEALHY project reporting a recently developed "preferred process" in December 2013, see www.idealhy.eu).
大多数氢当前经由烃类特别是天然气的蒸汽重整而产生，因为该方法的成本相对较低。蒸汽重整是强吸热过程。该方法所需的热量通常通过在炉中燃烧天然气进料的部分来提供。Most hydrogen is currently produced via steam reforming of hydrocarbons, especially natural gas, due to the relatively low cost of the process. Steam reforming is a strongly endothermic process. The heat required for the process is usually provided by burning a portion of the natural gas feed in the furnace.
生产氢的其他方法也是已知的，例如通过电解。存在三种主要类型的电解槽：固体氧化物电解槽(SOEC)、聚合物电解质膜槽(PEM)和碱性电解槽(AEC)。SOEC在高温下操作，通常在800℃左右。PEM电解槽通常在100℃以下工作，并且变得越来越商购可得。这些槽具有相对简单的优点，并且可被设计成接受广泛变化的电压输入，这使得其对于与再生能源例如太阳能PV一起使用是理想的。AEC在高浓度电解质(KOH或碳酸钾)和高温下(通常接近200℃)下最佳操作。Other methods of producing hydrogen are also known, for example by electrolysis. There are three main types of electrolyzers: solid oxide electrolyzers (SOEC), polymer electrolyte membrane cells (PEM) and alkaline electrolyzers (AEC). SOECs operate at high temperatures, typically around 800°C. PEM electrolysers typically operate below 100°C and are becoming increasingly commercially available. These tanks have the advantage of being relatively simple and can be designed to accept widely varying voltage inputs, making them ideal for use with renewable energy sources such as solar PV. AECs operate optimally with high concentrations of electrolyte (KOH or potassium carbonate) and high temperatures (typically close to 200°C).
另外，已知通过完全电化学方式同时共同生成氢和电能的方法，所述方法例如包括通过在水的存在下，使金属盐电解为金属和酸并且由此释放氧的电力储存阶段，以及由此储存阶段中产生的金属和酸反应以产生氢和任选的电力的发电阶段。可电解金属选自锌、镍、锰。参见例如US 8,617,766。In addition, methods are known for the simultaneous co-generation of hydrogen and electrical energy by purely electrochemical means, for example by electrolysis of metal salts in the presence of water into metals and acids and by an electrical storage stage in which oxygen is released, as well as by The metals and acids produced in this storage phase react to produce hydrogen and optionally a power generation phase of electricity. The electrolyzable metal is selected from zinc, nickel, manganese. See eg US 8,617,766.
在(通常)偏远地区的再生电预期比接近于市场更实惠，主要是由于适当土地的可用性以及能量资源(太阳能、风能等)本身的更好可用性。这种远程再生电可非常良好地适合电解以产生氢，因为它生成可负担的再生能量分子。在再生供电无法充分获得的情况下，也可使用或另外使用来自常规源的电(例如由燃气涡轮生成的并通过电网输送的电)。Renewable electricity in (usually) remote areas is expected to be more affordable than close to the market, mainly due to the availability of suitable land and the better availability of the energy resources (solar, wind, etc.) themselves. This remotely regenerative electricity could be well suited for electrolysis to produce hydrogen because it produces affordable regenerative energy molecules. Electricity from conventional sources (such as electricity generated by gas turbines and delivered through the grid) may also or additionally be used in cases where regenerative power is not adequately available.
特别是由风能和太阳能生成的再生电受到这些自然资源间歇性可用性的困扰。在供电不稳定的这种地区，氢的生产且特别是氢的液化不像在其中生产和液化方法可连续运行并且因此昂贵的液化工厂可被高度利用的地区一样有效。In particular, renewable electricity generated by wind and solar energy suffers from the intermittent availability of these natural resources. In such regions where the power supply is unstable, the production of hydrogen and especially the liquefaction of hydrogen is not as efficient as in regions where production and liquefaction processes can be run continuously and thus expensive liquefaction plants can be highly utilized.
本发明提供了特别是在供电不稳定的偏远地区，氢生产和氢液化工厂利用不足的问题的解决方案。此外，本发明解决了在其中供电至少部分来自再生能源，且特别是来自风能和太阳能的地区的氢生产和液化工厂中的间歇性问题。The present invention provides a solution to the problem of underutilization of hydrogen production and hydrogen liquefaction plants, especially in remote areas with unstable power supplies. Furthermore, the invention solves the problem of intermittency in hydrogen production and liquefaction plants in regions where the power supply comes at least partly from renewable energy sources, and in particular from wind and solar energy.
发明内容Contents of the invention
目前已发现通过在偏远地区集成氢生产和液化方法与允许间歇性氢和电力储存的方法，对上述问题提供了解决方案。相应地，本发明提供了用于连续生产液态氢的集成方法，其包括：It has been found that solutions to the above problems are provided by integrating hydrogen production and liquefaction methods in remote locations with methods that allow intermittent hydrogen and electricity storage. Accordingly, the present invention provides an integrated method for the continuous production of liquid hydrogen comprising:
(a)通过电解生产气态氢；和(a) production of gaseous hydrogen by electrolysis; and
(b)在氢液化单元中使所述气态氢液化，所述液化单元通过基本上(即至少80％，优选至少90％，最优选100％)来自再生源的能量供电；和，(b) liquefying said gaseous hydrogen in a hydrogen liquefaction unit powered by substantially (i.e. at least 80%, preferably at least 90%, most preferably 100%) energy from a renewable source; and,
(c)当需要另外的电时，使用在其中通过集成电解方法共同生成电能和氢的方法中生成的电能，所述集成电解方法包括：(c) when additional electricity is required, using electrical energy generated in a process in which electrical energy and hydrogen are co-generated by an integrated electrolysis process comprising:
(d)将金属盐或金属盐的混合物和水电解成相应的一种或多种金属、一种或多种酸和氧(电力储存阶段)，和(d) electrolysis of a metal salt or mixture of metal salts and water to the corresponding metal or metals, acid or acids and oxygen (electricity storage stage), and
(e)在步骤(d)的金属和酸的再生反应中产生气态氢并回收电力(再生阶段)；(e) producing gaseous hydrogen and recovering electricity (regeneration phase) in the metal and acid regeneration reaction of step (d);
其中步骤(e)中生成的至少部分气态氢用于该方法的步骤(b)。wherein at least part of the gaseous hydrogen produced in step (e) is used in step (b) of the process.
通过允许昂贵的液化单元在连续基础上运行，同时在按需的基础上提供氢和另外的电力，本发明的该方法理想地适合于液态氢制造，尽管基本再生能源仅间歇地可用的事实。By allowing expensive liquefaction units to operate on a continuous basis, while providing hydrogen and additional electricity on an on-demand basis, the method of the present invention is ideally suited for liquid hydrogen production despite the fact that substantially renewable energy is only intermittently available.
此外，电解方法的集成可有利地在生产和液化方法中的一个或多个位置处进行。例如，在电解中生成的电可提供液化循环中所需的电(的部分)。Furthermore, the integration of the electrolysis process may advantageously be performed at one or more locations in the production and liquefaction process. For example, electricity generated in electrolysis can provide (a portion of) the electricity needed in the liquefaction cycle.
附图说明Description of drawings
在图1中，示意性显示了根据本发明的方法。In FIG. 1 , the method according to the invention is schematically shown.
具体实施方式detailed description
根据本发明，该方法包括首先将再生(风能、太阳能等)间歇电力供给到集成电解方法设置。According to the invention, the method comprises first supplying regenerative (wind, solar, etc.) intermittent power to the integrated electrolysis process setup.
集成电解方法定义为包括两个不同步骤的电解方法：An integrated electrolysis method is defined as an electrolysis method comprising two distinct steps:
(d)电力储存步骤，其中金属盐或金属盐的混合物(金属盐选自ZnSO4、MgSO4、MgCl2等等；优选地，金属盐为ZnSO4)与水反应，以将金属沉积在电极上并形成酸(H2SO4、HCl等)，同时释放氧，所述反应由间歇的、任选再生的电力驱动；(d) a power storage step, wherein a metal salt or a mixture of metal salts (the metal salt is selected from ZnSO 4 , MgSO 4 , MgCl 2 , etc.; preferably, the metal salt is ZnSO 4 ) reacts with water to deposit the metal on the electrodes and formation of acids (H 2 SO 4 , HCl, etc.) with simultaneous release of oxygen, the reaction being driven by intermittent, optionally regenerated electricity;
(e)再生步骤，其中电极上沉积的金属与步骤(d)中产生的酸反应以释放氢，并且重新合成原始金属盐，其可在合适催化剂的存在下进行。任选地，在该步骤中，储存的能量(的部分)可作为电力(除氢之外)再生。(e) A regeneration step in which the metal deposited on the electrode reacts with the acid produced in step (d) to release hydrogen and resynthesize the original metal salt, which may be carried out in the presence of a suitable catalyst. Optionally, (part of) the stored energy can be regenerated as electricity (in addition to hydrogen) during this step.
通过如此处所述的两步电解方法共同生成电能和氢的方法是本领域已知的，例如，如US 8,617,766中公开的。Co-generation of electrical energy and hydrogen by a two-step electrolysis process as described herein is known in the art, for example, as disclosed in US 8,617,766.
通过进行上述两步集成电解方法，能够将充电(电力储存)步骤(d)与放电(再生)步骤(e)分开。以这种方式，与由此当向电解器送电时同时释放氢的传统的电解方法相比较，能量和氢储存能力提供了另外的电力和氢源。By performing the two-step integrated electrolysis method described above, it is possible to separate the charging (electricity storage) step (d) from the discharging (regeneration) step (e). In this way, the energy and hydrogen storage capability provides an additional source of power and hydrogen compared to conventional electrolysis methods whereby hydrogen is simultaneously released when power is supplied to the electrolyzer.
另外，作为根据本发明的方法的优点，步骤(e)的氢和电力产物两者可根据需要“按需”个别产生。因此，本发明的方法有利地允许设备可以这样的方式布置，使得可全天产生氢，并且仅在需要时，例如在夜间(例如在太阳能供电系统的情况下)产生电力。Furthermore, as an advantage of the method according to the invention, both the hydrogen and the electricity products of step (e) can be produced individually "on demand" as required. Thus, the method of the invention advantageously allows the plant to be arranged in such a way that hydrogen can be produced throughout the day and electricity only when needed, eg at night (eg in the case of a solar powered system).
在将再生间歇电力供给到集成电解方法设置的第一步之后，随后将所产生的氢和/或电力供给到有利地与集成电解器共同定位的氢液化单元。在氢液化单元中，需要电力作为输入以驱动形成液化方法核心的压缩机和冷却单元。After supplying the regenerative intermittent power to the first step of the integrated electrolysis process setup, the hydrogen and/or electricity produced is then supplied to a hydrogen liquefaction unit which is advantageously co-located with the integrated electrolyser. In a hydrogen liquefaction unit, electricity is required as input to drive the compressor and cooling unit that form the heart of the liquefaction process.
通过使用本发明的集成方法，能够以稳定和连续的操作模式运行昂贵的氢液化单元，这是为了充分利用这一资本投资所需的。否则这只能直接供给间歇电力和/或间歇氢供给。By using the integrated method of the present invention, it is possible to run an expensive hydrogen liquefaction unit in a stable and continuous mode of operation, which is required in order to fully utilize this capital investment. Otherwise this can only be directly supplied with intermittent electricity and/or intermittent hydrogen supply.
通常，氢液化单元将在可用时在再生电力上运行，而在步骤(e)中从电解器再生的电力用作间歇时期的备用电源(即在太阳能发电的情况下，在夜间或恶劣天气条件期间)。Typically, the hydrogen liquefaction unit will run on regenerative electricity when available, while the electricity regenerated from the electrolyser in step (e) is used as backup power for intermittent periods (i.e. in the case of solar power, at night or in bad weather conditions period).
在进一步的实施例中，在再生电力是唯一的电力源的情况下，当再生电源不可用，和/或从电解器再生的电力不足以对氢液化单元供应足够的电时，任选地另外的电力供应源(例如电储存装置如电池)可用作备用电源。In a further embodiment, where regenerative power is the only source of electrical power, when regenerative power is not available, and/or the power regenerated from the electrolyzer is insufficient to supply sufficient power to the hydrogen liquefaction unit, optionally additionally A power supply source (for example, an electrical storage device such as a battery) can be used as a backup power source.
在本发明的一个实施方案中，在包括集成电解方法和氢液化方法的方法中，气态氢任选储存在电解器(即在步骤(e)之后)和氢液化单元(即在使氢液化之前)之间的氢储存单元中，以管理对液化单元的稳定氢供应。In one embodiment of the present invention, in a process comprising an integrated electrolysis process and a hydrogen liquefaction process, gaseous hydrogen is optionally stored in an electrolyser (i.e. after step (e)) and a hydrogen liquefaction unit (i.e. before liquefying the hydrogen ) between hydrogen storage units to manage a steady supply of hydrogen to the liquefaction unit.
氢液化和适合于氢液化的液化循环是本领域已知的。可使用本领域已知的任何合适的液化循环，包括克劳德循环、布雷顿循环、焦耳汤普森循环及其任何修改或组合。Hydrogen liquefaction and liquefaction cycles suitable for hydrogen liquefaction are known in the art. Any suitable liquefaction cycle known in the art may be used, including the Claude cycle, the Brayton cycle, the Joule Thompson cycle, and any modifications or combinations thereof.
本发明的进一步实施例涉及用于连续生产液态氢的集成系统，其包括用于将能量从再生源供给到用于共同生成电能和氢的电解系统的能量入口，所述电解系统包括能量储存部分和再生部分，其中所述电解系统的再生部分具有联接到氢液化单元的氢出口，并且其中所述电解系统的再生部分具有在所述电解系统中产生的电力的出口，所述出口联接到进入所述氢液化单元的能量入口用于供电。该系统可有利地包括用于间歇地储存气态氢的氢储存单元。此外，该系统可有利地包括用于储存电的电池，用于在非常高需求的时刻提供另外的电。A further embodiment of the invention relates to an integrated system for the continuous production of liquid hydrogen comprising an energy inlet for supplying energy from a regenerative source to an electrolysis system for co-generation of electrical energy and hydrogen, the electrolysis system comprising an energy storage section and a regeneration section, wherein the regeneration section of the electrolysis system has a hydrogen outlet coupled to a hydrogen liquefaction unit, and wherein the regeneration section of the electrolysis system has an outlet for electricity generated in the electrolysis system, the outlet being coupled to an incoming The energy inlet of the hydrogen liquefaction unit is used for power supply. The system may advantageously comprise a hydrogen storage unit for intermittently storing gaseous hydrogen. Furthermore, the system may advantageously include batteries for storing electricity for providing additional electricity at moments of very high demand.
应当注意，本领域技术人员将理解，对于指定的液态氢生产设备，需要根据现场位置、基础设施和具体应用来优化上文讨论的电解器方法集成选项。因此，可围绕通过包括根据本发明的集成电解器的方法供给的氢液化设备的基本构建块来构建多个工艺方案。It should be noted that those skilled in the art will understand that for a given liquid hydrogen production facility, the electrolyzer process integration options discussed above need to be optimized based on site location, infrastructure, and specific application. Thus, a number of process schemes can be constructed around the basic building blocks of a hydrogen liquefaction plant supplied by a method comprising an integrated electrolyser according to the invention.
附图的详细描述Detailed description of the drawings
在图1中，示意性显示了根据本发明的方法的示例，其不应被解释为限制本发明：In FIG. 1 , an example of the method according to the invention is schematically shown, which should not be construed as limiting the invention:
基本上来自再生源的能量(e-)经由入口(1)供给到集成电解系统(2)内，所述集成电解系统(2)包括能量储存部分(3)和再生部分(4)；在电解系统的能量储存部分中，金属盐(MX)和水被转化成相应的金属(M)、相应的酸(HX)和氧；需要时(“按需”)，在再生部分(4)中再次形成金属盐，并且经由出口(5)释放气态氢(GH2)，同时任选还产生电力；气态氢经由入口(6)引入氢液化单元(7)内；来自电解系统的电力可按需经由出口(8)释放，以用于氢液化单元(7)中；基本上来自再生源的能量(e-)也用于经由入口(9)对氢液化单元(7)供电；电力还可储存在电池(10)中，用于在高需求情况下供应给氢液化单元(7)，或者在再生源的低可用性的情况下补充；液态氢(LH2)经由管线(11)从系统输出。Basically energy (e − ) from a regenerative source is supplied via the inlet (1) into the integrated electrolysis system (2) comprising an energy storage part (3) and a regenerative part (4); In the energy storage part of the system, the metal salt (MX) and water are converted to the corresponding metal (M), corresponding acid (HX) and oxygen; when needed ("on demand"), again in the regeneration part (4) Metal salts are formed and gaseous hydrogen (GH 2 ) is released via outlet (5), while optionally also generating electricity; gaseous hydrogen is introduced into the hydrogen liquefaction unit (7) via inlet (6); electricity from the electrolysis system can be supplied via The outlet (8) is released to be used in the hydrogen liquefaction unit (7); substantially the energy (e − ) from the regenerative source is also used to power the hydrogen liquefaction unit (7) via the inlet (9); electricity can also be stored in In the battery (10) for supplying the hydrogen liquefaction unit (7) in case of high demand, or replenishing in case of low availability of regeneration sources; liquid hydrogen (LH2) is exported from the system via line ( 11 ).
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| SI25573A (en) * | 2017-12-13 | 2019-06-28 | Univerza V Novi Gorici | Procedure for storing electrical energy in solid matter |
| WO2019190305A1 (en) * | 2018-03-27 | 2019-10-03 | Harit Ecotech Sdn. Bhd. | A hydroxygen generator for reducing carbon emission and increasing fuel efficieny |
| EP4067533A1 (en) * | 2021-03-30 | 2022-10-05 | Linde GmbH | Method and system for the production of liquid hydrogen by means of electrolysis |
| CN114909871B (en) * | 2022-04-22 | 2023-05-09 | 湖南大学 | A method and device for preparing liquid hydrogen by offshore off-grid superconducting wind power |
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| US20170321332A1 (en) | 2017-11-09 |
| ES2643558B1 (en) | 2018-09-19 |
| AU2015340752A1 (en) | 2017-04-20 |
| ES2643558R1 (en) | 2017-12-13 |
| AU2015340752B2 (en) | 2018-02-01 |
| CL2017000975A1 (en) | 2018-01-12 |
| ES2643558A2 (en) | 2017-11-23 |
| BR112017007390A2 (en) | 2018-02-14 |
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