CN114214637A - 一种电解水制氢氧综合利用的装置和方法 - Google Patents
一种电解水制氢氧综合利用的装置和方法 Download PDFInfo
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- CN114214637A CN114214637A CN202111507735.XA CN202111507735A CN114214637A CN 114214637 A CN114214637 A CN 114214637A CN 202111507735 A CN202111507735 A CN 202111507735A CN 114214637 A CN114214637 A CN 114214637A
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- hydrogen
- oxygen
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- pipeline
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 296
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 296
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 239000001301 oxygen Substances 0.000 title claims abstract description 191
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 191
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 189
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000000034 method Methods 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 137
- 238000000926 separation method Methods 0.000 claims abstract description 89
- 238000000746 purification Methods 0.000 claims abstract description 74
- 238000010248 power generation Methods 0.000 claims abstract description 70
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 68
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 44
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000446 fuel Substances 0.000 claims abstract description 31
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 24
- 239000002918 waste heat Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 16
- 238000007906 compression Methods 0.000 claims description 15
- 238000005057 refrigeration Methods 0.000 claims description 15
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000006835 compression Effects 0.000 claims description 12
- 238000004146 energy storage Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 238000002309 gasification Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 2
- 230000020169 heat generation Effects 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
本发明公开了一种电解水制氢氧综合利用的装置和方法,解决了现有技术中通过电解水生产高纯氢气和/或氧气,存在产品单一、得到的电子氢纯度低的技术问题。它包括发电单元(1)、电解水单元(2)、氢气纯化单元(3)、氧气纯化单元(4)、氢气液化冷箱(5)、氧氮液化冷箱(6)以及将空气分离成氮气和氧气的空气分离单元(7)。本发明的电解水制氢氧综合利用的装置和方法,可以利用空气和水生产燃料氢、电子氢、液氢、液氧、液氮、气氧、液氨和中压蒸汽,实现了能源的综合利用。
Description
技术领域
本发明涉及电能、氢能、储能、碳中和电子等领域,具体涉及一种电解水制氢氧综合利用的装置和方法。
背景技术
为实现“2030碳达峰,2060碳中和”,减少对化石能源的依赖,我国一直大力发展光伏、风力、水力等清洁能源发电,截止2021年一季度,光伏发电装机259GW,风力发电装机287GW,水力发电装机371GW,但光伏、风力发电不稳定,偏远地区水力发电不便上网,2021年一季度,弃光电量1700 GW·h、弃风电量7200 GW·h、弃水电量1249GW·h。根据国家发改委、国家能源局发布《关于加快推动新型储能发展的指导意见》,氢能被纳入新型储能,氢电耦合进入示范阶段。氢是一种高效、洁净的二次能源,可从多种途径获取的理想能源载体,是化石能源向可再生能源过渡的重要桥梁之一。
因此,可利用电解水制氢氧综合利用装置来解决以上问题,近年来电解水制氢氧综合利用大多集中在制甲醇及氨。
中国发明专利CN 106977369 A“一种综合利用电能联合制甲醇及氨的装置及方法”,生产甲醇和氨,存在产品单一,市场竞争激烈,经济性不够高,且仍然结合了煤化工,带来碳排放,不利于碳中和等不足。
中国发明专利CN 110965069 A“电解水生产高纯氢气和/或氧气的装置和方法”生产高纯氢气/氧氢,存在产品单一,未能达到超纯电子氢99.9999%以上纯度标准等不足。
发明内容
本发明的目的在于提供一种电解水制氢氧综合利用的装置和方法,以解决现有技术中通过电解水生产高纯氢气和/或氧气,存在产品单一、得到的电子氢纯度低的技术问题。
为实现上述目的,本发明提供了以下技术方案:
本发明提供的一种电解水制氢氧综合利用的装置,包括发电单元、电解水单元、氢气纯化单元、氧气纯化单元、氢气液化冷箱、氧氮液化冷箱以及将空气分离成氮气和氧气的空气分离单元;其中,
所述发电单元的电能输出端分别与电解水单元以及空气分离单元的电能输入端相连;
所述电解水单元的氢气出口端与氢气纯化单元相接;
所述氢气纯化单元的纯化氢气出口端分别连接有纯化氢气管道一和纯化氢气管道二,所述纯化氢气管道一和纯化氢气管道二分别与外部的燃料氢管道和氢气液化冷箱连接;
所述电解水单元的氧气出口端与氧气纯化单元相接;
所述氧气纯化单元的氧气出口端分别连接有纯化氧气管道一和纯化氧气管道二,所述纯化氧气管道一和纯化氧气管道二分别与氧氮液化冷箱和外部的气氧管道连接;
所述空气分离单元的氧气出口端连接有分离氧气管道,所述分离氧气管道与纯化氧气管道一相接;
所述空气分离单元的氮气出口端连接有分离氮气管道一,所述分离氮气管道一与氧氮液化冷箱连接;
所述氧氮液化冷箱的LN2出口与氢气液化冷箱的入口相连,所述氢气液化冷箱的N2出口与氧氮液化冷箱入口相连。
进一步的,还包括合成氨单元,所述合成氨单元与氢气纯化单元的纯化氢气出口端通过纯化氢气管道三相接;所述空气分离单元的氮气出口端通过分离氮气管道二与合成氨单元连接。
进一步的,所述氧氮液化冷箱上设有液氧出口和液氮出口,所述液氧出口和液氮出口分别与外部的液氧管道和液氮管道连接。
进一步的,所述纯化氢气管道一、纯化氢气管道二、纯化氢气管道三上分别设有阀门一、阀门二、阀门三;
所述纯化氧气管道一、纯化氧气管道二上分别设有阀门四和阀门五;
所述分离氧气管道上设有阀门六;
所述分离氮气管道一、分离氮气管道二上分别设有阀门七、阀门八。
进一步的,还包括控制系统;所述阀门一、阀门二、阀门三、阀门四、阀门五、阀门六、阀门七和阀门八均为电磁阀;所述控制系统分别与发电单元、电解水单元、氢气纯化单元、氧气纯化单元、氢气液化冷箱、氧氮液化冷箱、空气分离单元、合成氨单元、阀门一、阀门二、阀门三、阀门四、阀门五、阀门六、阀门七和阀门八电连接。
进一步的,所述的发电单元为水力发电装置、光伏发电装置、风力发电装置、核能发电装置、生物质发电装置、地热能发电装置、潮汐能发电装置、余热发电装置中的一种或多种组合;
所述的电解水单元为碱性水电解制氢装置、质子交换膜电解水制氢装置、固体氧化物电解水制氢装置中的一种或多种组合;
所述的氢气纯化单元为催化脱氧装置、变压吸附装置或膜分离装置中的一种或多种组合;
所述的氧气纯化单元为催化脱氢装置、变压吸附装置或膜分离装置中的一种或多种组合;
所述的氢气液化冷箱包括预冷装置、低温吸附装置、正仲氢转化装置和深冷液化装置;其中,
所述预冷装置包括低温冰机预冷、低温氮气预冷中的一种或两种组合;
所述深冷液化装置包括MRC制冷、氦气循环制冷、氢气循环制冷中的一种或多种组合;
所述的氧氮液化冷箱包括压缩装置、预冷装置和液化装置;
所述的空气分离单元为深冷分离装置、变压吸附装置或膜分离装置中的一种或多种组合;
所述的合成氨单元包括压缩装置、催化合成装置、精馏装置和余热回收装置。
本发明提供的一种电解水制氢氧综合利用的方法,应用上述的装置进行电解水单元制氢氧综合利用,包括以下步骤:
S1、发电单元为电解水单元和空气分离单元提供电能;
S2、水进入电解水单元中,电解产生含少量水、氧气的氢气以及含少量水、氢气的氧气;含少量水、氧气的氢气从电解水单元的氢气出口端进入氢气纯化单元中,通过氢气纯化单元进行脱氧、脱水、加压,生产用于燃料电池或储能的燃料氢,此时阀门一开启,阀门二关闭,阀门三关闭;
S3、氢气纯化单元处理后的高纯氢气,进入氢液化冷箱中进行处理,此时阀门一关闭,阀门二开启,阀门三关闭;处理过程如下:
①氢气液化冷箱进行预冷;
②然后采用低温吸附装置进行低温吸附,进一步除去含有的少量水和氧气;
③接着采用正仲氢转化装置进行正仲氢转化;
④最后经过深冷液化装置进行深冷液化工艺处理,生产超纯电子氢以及用于氢燃料电池或储能的液氢;
S4、含少量水、氢气的氧气从电解水单元的氧气出口端进入氧气纯化单元中,进行脱氢、脱水,生产富氧燃烧或煤气化的气氧,此时阀门四关闭,阀门五开启;
S5、空气进入空气分离单元中,分离产生氮气和氧气,氧气与氧气纯化单元处理后的高纯氧气,一起进入氧氮液化冷箱中,通过压缩装置、预冷装置和液化装置进行深冷液化处理,生产液氧和液氮,氧氮液化冷箱出口的LN2进入氢液化冷箱中,为氢气液化提供冷量;
S6、氢气纯化单元出口的高纯氢气与空气分离单元出口的氮气一起进入合成氨单元中进行处理,依次经压缩装置进行加压、催化合成装置进行催化合成、精馏装置进行精馏、余热回收装置进行余热回收生产液氨,余热回收过程中产生中压蒸汽,生产的中压蒸汽为发电单元及各单元压缩工艺提供动力,生产的液氨为各制冷单元提供冷量或者作为储氢储能的载体。
进一步的,所述步骤S2中,电解水单元的操作压力为0.15MPa-8.0MPa。
进一步的,所述步骤S6中,合成氨单元中的催化合成装置进行催化合成时的操作压力在15MPa-30MPa。
基于上述技术方案,本发明实施例至少可以产生如下技术效果:
(1)本发明提供的电解水制氢氧综合利用的装置和方法,以空气和水为原料,可以生产燃料氢、液氢、电子氢、液氧、液氮、气氧、液氨和中压蒸汽,实现了能源的综合利用。生产的燃料氢、液氢可以用于新型储能,解决弃光、弃风、弃水等问题;生产的燃料氢和液氢可以可以燃料电池汽车,解决化石燃料碳排放问题,有利于实现“2030碳达峰,2060碳中和”目标;本发明装置可达到超纯电子氢99.9999%以上纯度标准,生产的电子氢解决半导体超纯氢“掐脖子”问题;
(2)本发明提供的电解水制氢氧综合利用的装置和方法,结合空气分离联产液氮、液氨,为各液化冷箱提供冷量;并回收液氨生产过程的余热,生产中压蒸汽,用于发电或驱动压缩机,实现能源综合利用,具有良好的经济效益;并且,生产的液氨是一种无碳储氢载体。
(3)本发明提供的电解水制氢氧综合利用的装置和方法,本发明合成氨,相较煤化工合成氨,减少了碳排放。
(4)本发明提供的电解水制氢氧综合利用的装置和方法,发电单元可以为电解水单元和空气分离单元提供绿色电能;在应用中发电单元还可以为氢气纯化单元、氧气纯化单元、氢气液化冷箱、氧氮液化冷箱、空气分离单元、合成氨单元提供绿色电能。
附图说明
图1是本发明实施例1的结构示意图;
图2是本发明实施例3的结构示意图;
图中:1、发电单元;2、电解水单元;3、氢气纯化单元;4、氧气纯化单元;5、氢气液化冷箱;6、氧氮液化冷箱;7、空气分离单元;8、合成氨单元;9、纯化氢气管道一;10、纯化氢气管道二;11、纯化氢气管道三; 12、纯化氧气管道一;13、纯化氧气管道二;14、分离氧气管道;15、分离氮气管道一;16、分离氮气管道二;17、阀门一;18、阀门二;19、阀门三;20、阀门四;21、阀门五;22、阀门六;23、阀门七;24、阀门八。
具体实施方式
实施例1:
如图1所示,本发明提供了一种电解水制氢氧综合利用的装置,包括发电单元1、电解水单元2、氢气纯化单元3、氧气纯化单元4、氢气液化冷箱5、氧氮液化冷箱6以及将空气分离成氮气和氧气的空气分离单元7;其中,
所述发电单元1的电能输出端分别与电解水单元2以及空气分离单元7的电能输入端相连;
所述电解水单元2的氢气出口端与氢气纯化单元3相接;
所述氢气纯化单元3的纯化氢气出口端分别连接有纯化氢气管道一9和纯化氢气管道二10,所述纯化氢气管道一9和纯化氢气管道二10分别与外部的燃料氢管道和氢气液化冷箱连接;
所述电解水单元2的氧气出口端与氧气纯化单元4相接;
所述氧气纯化单元4的氧气出口端分别连接有纯化氧气管道一12和纯化氧气管道二13,所述纯化氧气管道一12和纯化氧气管道二13分别与氧氮液化冷箱6和外部的气氧管道连接;
所述空气分离单元7的氧气出口端连接有分离氧气管道14,所述分离氧气管道14与纯化氧气管道一12相接;
所述空气分离单元7的氮气出口端连接有分离氮气管道一15,所述分离氮气管道一15与氧氮液化冷箱6连接;
所述氧氮液化冷箱6的LN2出口与氢气液化冷箱5的入口相连,所述氢气液化冷箱5的N2出口与氧氮液化冷箱6入口相连。
本发明提供的电解水制氢氧综合利用的装置,以空气和水为原料,可以生产燃料氢、液氢、电子氢、液氧、液氮和气氧,实现了能源的综合利用。生产的燃料氢、液氢可以用于新型储能,解决弃光、弃风、弃水等问题;生产的燃料氢和液氢可以作为燃料用于电池汽车,解决化石燃料碳排放问题,有利于实现“2030碳达峰,2060碳中和”目标;本发明装置可达到超纯电子氢99.9999%以上纯度标准,生产的超纯电子氢解决半导体超纯氢“掐脖子”问题;本发明提供的电解水制氢氧综合利用的装置,结合空气分离联产液氮、液氨,为各液化冷箱提供冷量;并回收液氨生产过程的余热,生产中压蒸汽,用于发电或驱动压缩机,实现能源综合利用,具有良好的经济效益;并且,生产的液氨是一种无碳储氢载体;本发明提供的电解水制氢氧综合利用的装置,可以合成氨,相较煤化工合成氨,减少了碳排放;发电单元1可以为电解水单元2和空气分离单元7提供绿色电能;在应用中发电单元1还可以为氢气纯化单元、3氧气纯化单元4、氢气液化冷箱5、氧氮液化冷箱6、空气分离单元7、合成氨单元提8供绿色电能。
作为可选的实施方式,所述氧氮液化冷箱6上设有液氧出口和液氮出口,所述液氧出口和液氮出口分别与外部的液氧管道和液氮管道连接。
作为可选的实施方式,所述纯化氢气管道一9、纯化氢气管道二10、纯化氢气管道三11上分别设有阀门一17、阀门二18、阀门三19;
所述纯化氧气管道一12、纯化氧气管道二13上分别设有阀门四20和阀门五21;
所述分离氧气管道14上设有阀门六22;
所述分离氮气管道一15上分别设有阀门七23。
作为可选的实施方式,还包括控制系统;所述阀门一17、阀门二18、阀门三19、阀门四20、阀门五21、阀门六22、阀门七23和阀门八24均为电磁阀;所述控制系统分别与发电单元1、电解水单元2、氢气纯化单元3、氧气纯化单元4、氢气液化冷箱5、氧氮液化冷箱6、空气分离单元7、合成氨单元8、阀门一17、阀门二18、阀门三19、阀门四20、阀门五21、阀门六22、阀门七23、阀门八24电连接。
作为可选的实施方式,所述的发电单元1为水力发电装置、光伏发电装置、风力发电装置、核能发电装置、生物质发电装置、地热能发电装置、潮汐能发电装置、余热发电装置中的一种或多种组合;
作为可选的实施方式,所述的电解水单元2为碱性水电解制氢装置、质子交换膜电解水制氢装置、固体氧化物电解水制氢装置中的一种或多种组合;
作为可选的实施方式,所述的氢气纯化单元3为催化脱氧装置、变压吸附装置、膜分离装置中的一种或多种;
作为可选的实施方式,所述的氧气纯化单元4为催化脱氢装置、变压吸附装置、膜分离装置中的一种或多种;
所述的氢气液化冷箱5包括预冷装置、低温吸附装置、正仲氢转化装置和深冷液化装置;其中,
作为可选的实施方式,所述预冷装置为低温冰机预冷、低温氮气预冷中的一种或两种组合;
作为可选的实施方式,所述深冷液化装置为MRC制冷、氦气循环制冷、氢气循环制冷中的一种或多种组合;
所述的氧氮液化冷箱6包括压缩装置、预冷装置和液化装置;
作为可选的实施方式,所述的空气分离单元7包括深冷分离装置、变压吸附装置或膜分离装置中的一种或多种组合。
实施例2:
本发明提供的一种电解水制氢氧综合利用的方法,应用上述实施例1中的装置进行电解水单元制氢氧综合利用,包括以下步骤:
S1、发电单元1为电解水单元2和空气分离单元7提供电能;
S2、水进入电解水单元2中,电解产生含少量水、氧气的氢气以及含少量水、氢气的氧气,电解水单元2的操作压力为0.15MPa-8.0MPa;含少量水、氧气的氢气从电解水单元2的氢气出口端进入氢气纯化单元3中,进行脱氧、脱水、加压至35MPa以上,生产用于燃料电池或储能的燃料氢(得到的燃料氢中:氢气摩尔纯度≥99.99%,氧气摩尔纯度≤5ppm,水摩尔纯度≤5ppm),此时阀门一17开启,阀门二18关闭,阀门三19关闭,燃料氢经纯化氢气管道一9从图1中的A出口送出;
S3、氢气纯化单元3处理后的高纯氢气,经纯化氢气管道二10进入氢气液化冷箱5中进行处理,此时阀门一17关闭,阀门二18开启,阀门三19关闭;处理过程如下:
①氢气液化冷箱5中的预冷装置加压至20barA以上,在80K温度下,进行预冷;
②然后采用低温吸附装置(使用硅胶、分子筛等吸附剂)进行低温吸附,进一步除去含有的少量水和氧气(得到的氢气中:氢气摩尔纯度≥99.9999%,氧气摩尔纯度≤0.2ppm,水摩尔纯度≤1ppm);
③接着采用正仲氢转化装置(使用铁基催化剂)进行多级正仲氢转化(仲氢纯度≥95%);
④最后经过深冷液化装置进行深冷液化工艺处理,生产超纯电子氢(得到的超纯电子氢纯度≥99.9999%,从图1中的B出口送出)、用于氢燃料电池或储能的液氢(得到的液氢纯度≥99.9999%,从图1中的C出口送出);
S4、含少量水、氢气的氧气从电解水单元2的氧气出口端进入氧气纯化单元4中,进行脱氢、脱水,生产富氧燃烧或煤气化的气氧,此时阀门四20关闭,阀门五21开启,气氧从图1中的F出口送出;
S5、空气进入空气分离单元7中,分离产生氮气和氧气,氧气与氧气纯化单元4处理后的高纯氧气,一起进入氧氮液化冷箱6中,通过压缩装置、预冷装置和液化装置进行深冷液化处理,生产液氧(从图1中的D出口送出)、液氮(从图1中的E出口送出),氧氮液化冷箱6出口的LN2进入氢液化冷箱5中,为氢气液化提供冷量;
实施例3:
如图2所示,本发明提供了一种电解水制氢氧综合利用的装置,包括发电单元1、电解水单元2、氢气纯化单元3、氧气纯化单元4、氢气液化冷箱5、氧氮液化冷箱6以及将空气分离成氮气和氧气的空气分离单元7;其中,
所述发电单元1的电能输出端分别与电解水单元2以及空气分离单元7的电能输入端相连;
所述电解水单元2的氢气出口端与氢气纯化单元3相接;
所述氢气纯化单元3的纯化氢气出口端分别连接有纯化氢气管道一9和纯化氢气管道二10,所述纯化氢气管道一9和纯化氢气管道二10分别与外部的燃料氢管道和氢气液化冷箱连接;
所述电解水单元2的氧气出口端与氧气纯化单元4相接;
所述氧气纯化单元4的氧气出口端分别连接有纯化氧气管道一12和纯化氧气管道二13,所述纯化氧气管道一12和纯化氧气管道二13分别与氧氮液化冷箱6和外部的气氧管道连接;
所述空气分离单元7的氧气出口端连接有分离氧气管道14,所述分离氧气管道14与纯化氧气管道一12相接;
所述空气分离单元7的氮气出口端连接有分离氮气管道一15,所述分离氮气管道一15与氧氮液化冷箱6连接;
所述氧氮液化冷箱6的LN2出口与氢气液化冷箱5的入口相连,所述氢气液化冷箱5的N2出口与氧氮液化冷箱6入口相连。
本发明提供的电解水制氢氧综合利用的装置,以空气和水为原料,可以生产燃料氢、液氢、电子氢、液氧、液氮、气氧、液氨和中压蒸汽,实现了能源的综合利用。生产的燃料氢、液氢可以用于新型储能,解决弃光、弃风、弃水等问题;生产的燃料氢和液氢可以作为燃料用于电池汽车,解决化石燃料碳排放问题,有利于实现“2030碳达峰,2060碳中和”目标;本发明装置可达到超纯电子氢99.9999%以上纯度标准,生产的超纯电子氢解决半导体超纯氢“掐脖子”问题;本发明提供的电解水制氢氧综合利用的装置,结合空气分离联产液氮、液氨,为各液化冷箱提供冷量;并回收液氨生产过程的余热,生产中压蒸汽,用于发电或驱动压缩机,实现能源综合利用,具有良好的经济效益;并且,生产的液氨是一种无碳储氢载体;本发明提供的电解水制氢氧综合利用的装置,可以合成氨,相较煤化工合成氨,减少了碳排放;发电单元1可以为电解水单元2和空气分离单元7提供绿色电能;在应用中发电单元1还可以为氢气纯化单元、3氧气纯化单元4、氢气液化冷箱5、氧氮液化冷箱6、空气分离单元7、合成氨单元提8供绿色电能。
作为可选的实施方式,还包括合成氨单元8,所述合成氨单元8与氢气纯化单元3的纯化氢气出口端通过纯化氢气管道三11相接;所述空气分离单元7的氮气出口端通过分离氮气管道二16与合成氨单元8连接。
作为可选的实施方式,所述氧氮液化冷箱6上设有液氧出口和液氮出口,所述液氧出口和液氮出口分别与外部的液氧管道和液氮管道连接。
作为可选的实施方式,所述纯化氢气管道一9、纯化氢气管道二10、纯化氢气管道三11上分别设有阀门一17、阀门二18、阀门三19;
所述纯化氧气管道一12、纯化氧气管道二13上分别设有阀门四20和阀门五21;
所述分离氧气管道14上设有阀门六22;
所述分离氮气管道一15、分离氮气管道二16上分别设有阀门七23、阀门八24。
作为可选的实施方式,还包括控制系统;所述阀门一17、阀门二18、阀门三19、阀门四20、阀门五21、阀门六22、阀门七23和阀门八24均为电磁阀;所述控制系统分别与发电单元1、电解水单元2、氢气纯化单元3、氧气纯化单元4、氢气液化冷箱5、氧氮液化冷箱6、空气分离单元7、合成氨单元8、阀门一17、阀门二18、阀门三19、阀门四20、阀门五21、阀门六22、阀门七23和阀门八24电连接。
作为可选的实施方式,所述的发电单元1为水力发电装置、光伏发电装置、风力发电装置、核能发电装置、生物质发电装置、地热能发电装置、潮汐能发电装置、余热发电装置中的一种或多种组合;
作为可选的实施方式,所述的电解水单元2为碱性水电解制氢装置、质子交换膜电解水制氢装置、固体氧化物电解水制氢装置中的一种或多种组合;
作为可选的实施方式,所述的氢气纯化单元3为催化脱氧装置、变压吸附装置、膜分离装置中的一种或多种;
作为可选的实施方式,所述的氧气纯化单元4为催化脱氢装置、变压吸附装置、膜分离装置中的一种或多种;
所述的氢气液化冷箱5包括预冷装置、低温吸附装置、正仲氢转化装置和深冷液化装置;其中,
作为可选的实施方式,所述预冷装置为低温冰机预冷、低温氮气预冷中的一种或两种组合;
作为可选的实施方式,所述深冷液化装置为MRC制冷、氦气循环制冷、氢气循环制冷中的一种或多种组合;
所述的氧氮液化冷箱6包括压缩装置、预冷装置和液化装置;
作为可选的实施方式,所述的空气分离单元7包括深冷分离装置、变压吸附装置或膜分离装置中的一种或多种组合;
所述的合成氨单元8包括压缩装置、催化合成装置、精馏装置和余热回收装置。
实施例4:
本发明提供的一种电解水制氢氧综合利用的方法,应用上述实施例3的装置进行电解水单元制氢氧综合利用,包括以下步骤:
S1、发电单元1为电解水单元2和空气分离单元7提供电能;
S2、水进入电解水单元2中,电解产生含少量水、氧气的氢气以及含少量水、氢气的氧气,电解水单元2的操作压力为0.15MPa-8.0MPa;含少量水、氧气的氢气从电解水单元2的氢气出口端进入氢气纯化单元3中,进行脱氧、脱水、加压至35MPa以上,生产用于燃料电池或储能的燃料氢(得到的燃料氢中:氢气摩尔纯度≥99.99%,氧气摩尔纯度≤5ppm,水摩尔纯度≤5ppm),此时阀门一17开启,阀门二18关闭,阀门三19关闭,燃料氢经纯化氢气管道一9 从图 2 中的 A 出口送出;
S3、氢气纯化单元3处理后的高纯氢气,经纯化氢气管道二 10进入氢气液化冷箱5中进行处理,此时阀门一17关闭,阀门二18开启,阀门三19关闭;处理过程如下:
①氢气液化冷箱 5中的预冷装置加压至20barA以上,在80K温度下,进行预冷,
②然后采用低温吸附装置(使用硅胶、分子筛等吸附剂)进行低温吸附,进一步除去含有的少量水和氧气(得到的氢气中:氢气摩尔纯度≥99.9999%,氧气摩尔纯度≤0.2ppm,水摩尔纯度≤1ppm);
③接着采用正仲氢转化装置(使用铁基催化剂)进行多级正仲氢转化(仲氢纯度≥95%);
④最后经过深冷液化装置进行深冷液化工艺处理,生产超纯电子氢(得到的超纯电子氢纯度≥99.9999%,从图 2 中的 B 出口送出)、用于氢燃料电池或储能的液氢(得到的液氢纯度≥99.9999%,从图 2 中的 C 出口送出);
S4、含少量水、氢气的氧气从电解水单元2的氧气出口端进入氧气纯化单元4中,进行脱氢、脱水,生产富氧燃烧或煤气化的气氧,此时阀门四20关闭,阀门五21开启,气氧从图2 中的 F 出口送出;
S5、空气进入空气分离单元7中,分离产生氮气和氧气,氧气与氧气纯化单元4处理后的高纯氧气,一起进入氧氮液化冷箱6中,通过压缩装置、预冷装置和液化装置进行深冷液化处理,生产液氧(从图 2中的 D 出口送出)、液氮(从图 2 中的 E 出口送出),氧氮液化冷箱6出口的LN2进入氢液化冷箱5中,为氢气液化提供冷量;
S6、氢气纯化单元3出口的高纯氢气与空气分离单元7出口的氮气一起进入合成氨单元8中进行处理,依次经压缩装置进行加压、催化合成装置进行催化合成、精馏装置进行精馏、余热回收装置进行余热回收,生产液氨(从图 2中的 G出口送出),余热回收过程中产生中压蒸汽(从图 2中的 H出口送出),生产的中压蒸汽为发电单元1及各单元压缩工艺提供动力,生产的液氨为各制冷单元提供冷量或者作为储氢储能的载体。合成氨单元8中的催化合成装置进行催化合成时的操作压力在15MPa-30MPa。
Claims (9)
1.一种电解水制氢氧综合利用的装置,其特征在于:包括发电单元(1)、电解水单元(2)、氢气纯化单元(3)、氧气纯化单元(4)、氢气液化冷箱(5)、氧氮液化冷箱(6)以及将空气分离成氮气和氧气的空气分离单元(7);其中,
所述发电单元(1)的电能输出端分别与电解水单元(2)以及空气分离单元(7)的电能输入端相连;
所述电解水单元(2)的氢气出口端与氢气纯化单元(3)相接;
所述氢气纯化单元(3)的纯化氢气出口端分别连接有纯化氢气管道一(9)和纯化氢气管道二(10),所述纯化氢气管道一(9)和纯化氢气管道二(10)分别与外部的燃料氢管道和氢气液化冷箱(5)连接;
所述电解水单元(2)的氧气出口端与氧气纯化单元(4)相接;
所述氧气纯化单元(4)的氧气出口端分别连接有纯化氧气管道一(12)和纯化氧气管道二(13),所述纯化氧气管道一(12)和纯化氧气管道二(13)分别与氧氮液化冷箱(6)和外部的气氧管道连接;
所述空气分离单元(7)的氧气出口端连接有分离氧气管道(14),所述分离氧气管道(14)与纯化氧气管道一(12)相接;
所述空气分离单元(7)的氮气出口端连接有分离氮气管道一(15),所述分离氮气管道一(15)与氧氮液化冷箱(6)连接;
所述氧氮液化冷箱(6)的LN2出口与氢气液化冷箱(5)的入口相连,所述氢气液化冷箱(5)的N2出口与氧氮液化冷箱(6)入口相连。
2.根据权利要求1所述的电解水制氢氧综合利用的装置,其特征在于:还包括合成氨单元(8),所述合成氨单元(8)与氢气纯化单元(3)的纯化氢气出口端通过纯化氢气管道三(11)相接;所述空气分离单元(7)的氮气出口端通过分离氮气管道二(16)与合成氨单元(8)连接。
3.根据权利要求1所述的电解水制氢氧综合利用的装置,其特征在于:所述氧氮液化冷箱(6)上设有液氧出口和液氮出口,所述液氧出口和液氮出口分别与外部的液氧管道和液氮管道连接。
4.根据权利要求1所述的电解水制氢氧综合利用的装置,其特征在于:所述纯化氢气管道一(9)、纯化氢气管道二(10)、纯化氢气管道三(11)上分别设有阀门一(17)、阀门二(18)、阀门三(19);
所述纯化氧气管道一(12)、纯化氧气管道二(13)上分别设有阀门四(20)和阀门五(21);
所述分离氧气管道(14)上设有阀门六(22);
所述分离氮气管道一(15)、分离氮气管道二(16)上分别设有阀门七(23)、阀门八(24)。
5.根据权利要求4所述的电解水制氢氧综合利用的装置,其特征在于:还包括控制系统;所述阀门一(17)、阀门二(18)、阀门三(19)、阀门四(20)、阀门五(21)、阀门六(22)、阀门七(23)和阀门八(24)均为电磁阀;所述控制系统分别与发电单元(1)、电解水单元(2)、氢气纯化单元(3)、氧气纯化单元(4)、氢气液化冷箱(5)、氧氮液化冷箱(6)、空气分离单元(7)、合成氨单元(8)、阀门一(17)、阀门二(18)、阀门三(19)、阀门四(20)、阀门五(21)、阀门六(22)、阀门七(23)和阀门八(24)电连接。
6.根据权利要求2所述的电解水制氢氧综合利用的装置,其特征在于:所述的发电单元(1)为水力发电装置、光伏发电装置、风力发电装置、核能发电装置、生物质发电装置、地热能发电装置、潮汐能发电装置、余热发电装置中的一种或多种组合;
所述的电解水单元(2)为碱性水电解制氢装置、质子交换膜电解水制氢装置、固体氧化物电解水制氢装置中的一种或多种组合;
所述的氢气纯化单元(3)为催化脱氧装置、变压吸附装置或膜分离装置中的一种或多种组合;
所述的氧气纯化单元(4)为催化脱氢装置、变压吸附装置或膜分离装置中的一种或多种组合;
所述的氢气液化冷箱(5)包括预冷装置、低温吸附装置、正仲氢转化装置和深冷液化装置;其中,
所述预冷装置包括低温冰机预冷、低温氮气预冷中的一种或两种组合;
所述深冷液化装置包括MRC制冷、氦气循环制冷、氢气循环制冷中的一种或多种组合;
所述的氧氮液化冷箱(6)包括压缩装置、预冷装置和液化装置;
所述的空气分离单元(7)为深冷分离装置、变压吸附装置或膜分离装置中的一种或多种组合;
所述的合成氨单元(8)包括压缩装置、催化合成装置、精馏装置和余热回收装置。
7.一种电解水制氢氧综合利用的方法,其特征在于:应用权利要求2-7任意一项所述的装置进行电解水单元制氢氧综合利用,包括以下步骤:
S1、发电单元(1)为电解水单元(2)和空气分离单元(7)提供电能;
S2、水进入电解水单元(2)中,电解产生含少量水、氧气的氢气以及含少量水、氢气的氧气;含少量水、氧气的氢气从电解水单元(2)的氢气出口端进入氢气纯化单元(3)中,通过氢气纯化单元(3)进行脱氧、脱水、加压,生产用于燃料电池或储能的燃料氢,此时阀门一(17)开启,阀门二(18)关闭,阀门三(19)关闭;
S3、氢气纯化单元(3)处理后的高纯氢气,进入氢液化冷箱(5)中进行处理,此时阀门一(17)关闭,阀门二(18)开启,阀门三(19)关闭;处理过程如下:
①氢气液化冷箱(5)进行预冷;
②然后采用低温吸附装置进行低温吸附,进一步除去含有的少量水和氧气;
③接着采用正仲氢转化装置进行正仲氢转化;
④最后经过深冷液化装置进行深冷液化工艺处理,生产超纯电子氢以及用于氢燃料电池或储能的液氢;
S4、含少量水、氢气的氧气从电解水单元(2)的氧气出口端进入氧气纯化单元(4)中,进行脱氢、脱水,生产富氧燃烧或煤气化的气氧,此时阀门四(20)关闭,阀门五(21)开启;
S5、空气进入空气分离单元(7)中,分离产生氮气和氧气,氧气与氧气纯化单元(4)处理后的高纯氧气,一起进入氧氮液化冷箱(6)中,通过压缩装置、预冷装置和液化装置进行深冷液化处理,生产液氧和液氮,氧氮液化冷箱(6)出口的LN2进入氢液化冷箱(5)中,为氢气液化提供冷量;
S6、氢气纯化单元(3)出口的高纯氢气与空气分离单元(7)出口的氮气一起进入合成氨单元(8)中进行处理,依次经压缩装置进行加压、催化合成装置进行催化合成、精馏装置进行精馏、余热回收装置进行余热回收生产液氨,余热回收过程中产生中压蒸汽,生产的中压蒸汽为发电单元(1)及各单元压缩工艺提供动力,生产的液氨为各制冷单元提供冷量或者作为储氢储能的载体。
8.根据权利要求7所述的电解水制氢氧综合利用的方法,其特征在于:所述步骤S2中,电解水单元(2)的操作压力为0.15MPa-8.0MPa。
9.根据权利要求7所述的电解水制氢氧综合利用的方法,其特征在于:所述步骤S6中,合成氨单元(8)中的催化合成装置进行催化合成时的操作压力在15MPa-30MPa。
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