CN114249297A - 一种利用太阳能的甲醇重整制氢系统 - Google Patents
一种利用太阳能的甲醇重整制氢系统 Download PDFInfo
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- CN114249297A CN114249297A CN202111661722.8A CN202111661722A CN114249297A CN 114249297 A CN114249297 A CN 114249297A CN 202111661722 A CN202111661722 A CN 202111661722A CN 114249297 A CN114249297 A CN 114249297A
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- heat exchange
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 174
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 64
- 239000001257 hydrogen Substances 0.000 title claims abstract description 64
- 238000002407 reforming Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000007789 gas Substances 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims abstract description 73
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000006057 reforming reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000012782 phase change material Substances 0.000 claims description 49
- 238000012546 transfer Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 16
- 238000009792 diffusion process Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 7
- 238000005338 heat storage Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000011161 development Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical class [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
本发明公开了一种利用太阳能的甲醇重整制氢系统,包括装有甲醇水溶液的储放箱、换热器、预热器、蒸发器、反应器和气体分离器;还包括水箱和太阳能高温集热管;太阳能高温集热管将水箱内的水加热成高温水或水蒸气,高温水或水蒸气通入反应器和/或蒸发器和/或预热器的换热管道中,与甲醇水溶液进行热交换,降温后的水回流入水箱;甲醇水溶液经换热器、预热器、蒸发器逐级加热后,在反应器中发生甲醇重整反应,生成的氢气和二氧化碳混合气体经换热器与甲醇水溶液进行热交换后,在气体分离器中被分离成氢气和二氧化碳;反应器内涂覆有催化剂层。本发明利用太阳能作为热能进行甲醇重整制氢反应,有效降低了产氢成本。
Description
技术领域
本发明涉及一种利用太阳能的甲醇重整制氢系统。
背景技术
在气候变化、能源资源减少和空气污染的大背景下,实现能源的可持续、低二氧化碳排放的交通运输显得尤为重要。交通运输业是国民经济的重要组成部分,然而石油资源的高度消耗,能源和环境危机的加剧,迫切要求发展新能源汽车以解决环境和能源问题。发展新能源汽车被认为是实现清洁能源转型的有效途径,新能源汽车产业的发展众望所归。
氢能因为其燃烧性能好、燃烧值高、利用率高、无毒无污染等优点成为新能源汽车燃料的选择之一。目前已工业化的制氢技术主要有烃类水蒸汽转化、水电解、甲醇重整、重油部分氧化等。而烃类水蒸汽转化要求温度高(500℃~850℃),水电解能耗高、效率低,重油部分氧化成本高,甲醇重整制氢具有原料要求简单(仅需甲醇与水),效率高,工作温度要求低的优势,因此成为制氢技术的首选。
随着燃料电池汽车的发展,加氢站的建设成为限制燃料电池汽车发展的关键因素。然而由于氢气储存和运输都比较难,因此利用甲醇重整制氢即产即用的加氢站,避免了氢气的储存和运输,成为当今的研究热点。甲醇重整制氢过程是吸热反应,传统做法是燃烧部分甲醇为甲醇重整制氢提供必要的热量,上述方式一方面降低了系统的产氢率,另一方面也提高了产氢成本。
发明内容
发明目的:本发明目的在于提供一种利用太阳能作为热能的甲醇重整制氢系统,该系统能够有效降低产氢成本。
技术方案:本发明所述的利用太阳能的甲醇重整制氢系统,包括装有甲醇水溶液的储放箱、换热器、预热器、蒸发器、反应器和气体分离器;还包括水箱和太阳能高温集热管;太阳能高温集热管将水箱内的水加热成高温水或水蒸气,高温水或水蒸气通入反应器和/或蒸发器和/或预热器的换热管道中,与甲醇水溶液进行热交换,降温后的水回流入水箱;甲醇水溶液经换热器、预热器、蒸发器逐级加热后,在反应器中发生甲醇重整反应,生成的氢气和二氧化碳混合气体经换热器与甲醇水溶液进行热交换后,在气体分离器中被分离成氢气和二氧化碳;反应器内涂覆有催化剂层。
其中,所述太阳能高温集热管出口处设有热电偶,所述太阳能高温集热管出口连有三个支路,分别为第一支路、第二支路和第三支路,三个支路上均设有阀门;太阳能高温集热管通过第一支路与预热器、水箱形成闭环回路连接;太阳能高温集热管通过第二支路与蒸发器、预热器、水箱形成闭环回路连接;太阳能高温集热管通过第三支路与反应器、蒸发器、预热器、水箱形成闭环回路连接;反应器和蒸发器之间的换热连接管路以及蒸发器和预热器之间的换热连接管路上也设有阀门。
其中,还包括PLC控制箱,热电偶与各支路、各换热连接管路上的阀门分别通过电缆与PLC控制箱连接。根据太阳能高温集热管出口水的温度开启不同支路上的阀门,当热电偶检测到出口温度为T1时,T1为250℃~300℃,开启第三支路上、反应器和蒸发器之间换热连接管路以及蒸发器和预热器之间换热连接管路上的阀门,第一支路和第二支路上的阀门关闭;温度在T2时,T2为100℃~250℃,开启第二支路上以及蒸发器和预热器之间换热连接管路上的阀门,第一支路和第三支路上的阀门关闭;温度在T3时,T3为50℃~100℃,开启第一支路上的阀门,第二支路、第三支路以及反应器和蒸发器之间换热连接管路以及蒸发器和预热器之间换热连接管路上的阀门全部关闭;温度在T4时,T4低于50℃,不开启任何阀门。
其中,所述反应器包括水蒸气进气口、水蒸气出气口、混合气体进气口和混合气体出气口;还包括换热室、位于换热室上方的气体扩散室以及位于换热室下方的气体汇流室;换热室内设有换热管道,换热管道外包覆有相变材料I;换热管道和相变材料I外涂覆有催化剂层;水蒸气从水蒸气进气口进入反应器,经分离管道后均匀分散至多根换热管道中,水蒸气将热量传递至换热管道和相变材料I后汇流到汇流管道,经汇流管道汇流后从水蒸气出气口流出反应器;甲醇和水蒸气混合气体经混合气体进气口进入气体扩散室中;经气体扩散室流进换热室,在换热室相变材料I表面催化剂的作用下发生甲醇重整反应生成氢气与二氧化碳,氢气与二氧化碳混合气体向下移动至气体汇流室,由混合气体出气口流出反应器。
其中,所述相变材料I对应的相变材料的熔点为250℃~300℃。甲醇重整制氢的反应温度为250℃~300℃;相变材料I可以为由质量百分数30.7%Na2CO3、26.8%K2CO3以及42.5%Li2CO3构成的熔融盐。
其中,所述气体扩散室内设有多层多孔介质板,每层多孔介质板的孔径为0.5mm。
其中,所述蒸发器包括换热腔以及位于换热腔上方的汇流腔;换热腔侧壁设有水蒸气流入口、水蒸气流出口和混合液流入口;汇流腔顶部设有混合气排出口;换热腔内设有换热支管,换热支管外包覆有相变材料II;水蒸气从水蒸气流入口进入蒸发器,经分离管道后均匀分散至多根换热支管中,水蒸气将热量传递至换热支管和相变材料II后汇流到汇流管道,经汇流管道汇流后从水蒸气流出口流出蒸发器;甲醇水溶液从混合液流入口进入换热腔中,每层换热支管上均设置有喷头,甲醇水溶液从每层换热支管上的喷头喷出,接触到换热支管和储热后的相变材料II后汽化,混合气体经汇流腔汇流后从混合气排出口流出蒸发器。
其中,所述相变材料II的熔点(相变温度)为100℃~250℃。相变材料II可以为由质量百分数60%NaNO3和40%KNO3构成的太阳盐。
其中,所述预热器包括反应箱体,反应箱体内设有加热板和流道板;加热板和流道板上均设有S型流道;加热板和流道板依次交替排布,加热板和流道板之间设有换热层,换热层由相变材料III和肋片依次交替排布组成;反应箱体内还设有水蒸气中转管道、水蒸气汇流管道、溶液中转管道和溶液汇流管道;水蒸气中转管道上设有水蒸气入口,水蒸气汇流管道上设有水蒸气出口,溶液中转管道上设有溶液入口,溶液汇流管道上设有溶液出口;水蒸气中转管道和水蒸气汇流管道分别通过水蒸气支管与加热板上S型流道的首尾连接;溶液中转管道和溶液汇流管道分别通过溶液支管与流道板上S型流道的首尾连接;水蒸气从水蒸气入口流入水蒸气中转管道,经多个水蒸气支管把水蒸气中转管道里的水蒸气输送到加热板;水蒸气在加热板中沿着S型流道流动后从多个支管流进水蒸气汇流管道,再从水蒸气汇流管道的水蒸气出口流出预热器,甲醇水溶液从预热器的溶液入口流入溶液中转管道,经多个溶液支管把溶液中转管道里的溶液输送到流道板;溶液在流道板中沿着S型流道流动后从多个支管流进溶液汇流管道,再从溶液汇流管道的溶液出口流出预热器,流向蒸发器。
其中,S型流道为热端到冷端的距离渐变(逐渐变低)。
其中,所述相变材料III的熔点为50℃~100℃。相变材料Ⅲ可以为由质量百分数53%KNO3、40%NaNO2和7%NaNO3构成的Hitec盐。
其中,所述气体分离器包括密封腔体,密封腔体设有混合气体进口管道、二氧化碳出口管道以及氢气出口;在混合气体进口管道与二氧化碳出口管道之间设有气体分离膜。
有益效果:相比于现有甲醇重整制氢技术,本发明具有的显著效果为:(1)本发明利用太阳能为甲醇重整制氢提供必要的热量,另外一部分热量存储于相变材料中以便于太阳能微弱时为系统提供热量,整个系统不需要额外的能量供给,有效降低了产氢成本;(2)本发明根据预热、蒸发、重整反应的不同温度需求,选取不同相变温度的相变储热材料,进而实现不同换热的热量需求;(3)本发明蒸发器和反应器内均采用逐级一分为二的分离管道确保水蒸气在各换热支管中分布更加均匀;(4)本发明的预热器流道采用渐变距离S型流道,加强了热端处的换热,在甲醇水溶液流道板与加热板之间设置肋片,加强了流道板与加热板、流道板与相变材料、加热板与相变材料之间的换热;(5)本发明气体分离器通过膜分离氢气与二氧化碳,分离效率高。
附图说明
图1为本发明系统的系统原理图;
图2为反应器的结构示意图;
图3为蒸发器的结构示意图;
图4为预热器的结构示意图;
图5为预热器的爆炸图;
图6为气体分离器的结构示意图;
图7为分离管道的结构示意图;
图8为渐变距离的S型流道的结构示意图;
图9为气体扩散室的结构示意图。
具体实施方式
如图1~9所示,本发明利用太阳能的甲醇重整制氢系统,包括装有甲醇水溶液的储放箱10、换热器11、预热器8、蒸发器7、反应器6和气体分离器14;本发明利用太阳能的甲醇重整制氢系统还包括水箱1和太阳能高温集热管3;太阳能高温集热管3将水箱1内的水加热成高温水或水蒸气,高温水或水蒸气通入反应器6和/或蒸发器7和/或预热器8的换热管道中,与甲醇水溶液进行热交换,降温后的水回流入水箱1;甲醇水溶液经换热器11、预热器8、蒸发器7逐级加热后,在反应器6中发生甲醇重整反应,生成的氢气和二氧化碳混合气体经换热器11与甲醇水溶液进行热交换后,在气体分离器14中被分离成氢气和二氧化碳;分离出的氢气进入储氢罐12中,分离出的二氧化碳进入二氧化碳储罐13中。
其中,太阳能高温集热管3出口处设有热电偶4,太阳能高温集热管3出口连有三个支路,分别为第一支路15、第二支路16和第三支路17,三个支路上均设有阀门;太阳能高温集热管3通过第一支路15与预热器8和水箱1形成闭环回路;太阳能高温集热管3通过第二支路16与蒸发器7、预热器8以及水箱1形成闭环回路;太阳能高温集热管3通过第三支路17与反应器6、蒸发器7、预热器8以及水箱1形成闭环回路;反应器6和蒸发器7之间的换热连接管路以及蒸发器7和预热器8之间的换热连接管路上也设有阀门。
本发明利用太阳能的甲醇重整制氢系统还包括PLC控制箱,热电偶4与各支路、各换热连接管路上的阀门分别通过电缆与PLC控制箱连接。根据太阳能高温集热管3出口水的温度开启不同支路上的阀门,水箱1中的水经泵2输送至太阳能高温集热管3后在串联的太阳能高温集热管3中不断加热,热电偶4检测到出口温度,当太阳能高温集热管出口水的温度为T1时,T1为250℃~300℃,开启第三支路17上、反应器6和蒸发器7之间换热连接管路以及蒸发器7和预热器8之间换热连接管路上的阀门(即开启阀门51、52、58、56),第一支路15和第二支路16上的阀门关闭(即关闭阀门53、55、54、57);水蒸气从反应器6的水蒸气进气口61流进反应器6后经分离管道62均匀分离至换热管道63,水蒸气在换热管道63流动时,其中部分热量加热换热管道63用于甲醇重整反应,部分热量传递到相变材料I64中储存起来;经过热交换的水蒸气从换热管道63流到一级汇流管道65,然后从一级汇流管道65流到二级汇流管道66,最后从水蒸气出气口67流出反应器6,然后流向蒸发器7,水蒸气从蒸发器7的水蒸气流入口711流进蒸发器7,进入蒸发器7后经分离管道62均匀分离至换热支管72,水蒸气在换热支管72流动时,其中部分热量加热换热支管72用于蒸发甲醇水溶液,部分热量传递到相变材料II76中储存起来;传热后的水蒸气从换热支管72流到一级汇流管道65,然后从一级汇流管道65流到二级汇流管道66,最后从水蒸气流出口75流出蒸发器7,然后流向预热器8;水蒸气从预热器8的水蒸气入口813流入预热器8后先汇集到水蒸气中转管道81,再经多个水蒸气支管82把水蒸气中转管道81里的水蒸气输送到加热板88;水蒸气在加热板88中以渐变距离S型流道814流动后从多个水蒸气支管流进水蒸气汇流管道83,再从水蒸气汇流管道83的水蒸气出口84流出预热器8,然后流回水箱1。当太阳能高温集热管出口水的温度为T2时,T2为100℃~250℃,开启第二支路16上以及蒸发器7和预热器8之间换热连接管路上的阀门(即开启阀门51、54、57、56),第一支路15和第三支路17上的阀门关闭(即关闭阀门52、58、53、55),水蒸气通过蒸发器7与预热器8后流回水箱1;当温度在T3时,T3为50℃~100℃,开启第一支路15上的阀门(即开启阀门53、55),第二支路16、第三支路17以及反应器6和蒸发器7之间换热连接管路以及蒸发器7和预热器8之间换热连接管路上的阀门全部关闭(即关闭阀门51、52、54、58、57、56),水蒸气仅通过预热器8后流回水箱1;当温度在T4时,T4低于50℃,不开启任何阀门,从而实现不同光照条件下太阳能的分类利用。
其中,反应器6包括水蒸气进气口61、水蒸气出气口67、混合气体进气口613和混合气体出气口611;反应器6还包括换热室612、位于换热室612上方的气体扩散室68以及位于换热室612下方的气体汇流室610;水蒸气进气口61和水蒸气出气口67设置在换热室612侧壁上,混合气体进气口613设置在气体扩散室68顶部,混合气体出气口611位于气体汇流室610底部;换热室612内设有换热管道63,换热管道63外包覆有相变材料I64;相变材料I64外还涂覆有催化剂;换热管道63外以一定间隔覆盖相变材料I64,相变材料I64熔点为T1,在没有覆盖相变材料I64的换热管道63外表面和相变材料I64外表面覆盖催化剂涂层;水蒸气在换热管道63内流动时,其中部分热量加热换热管道63用于甲醇重整反应,部分热量传递到相变材料I64中储存起来,实现不同光照条件下,都可以为甲醇重整反应提供充足的热量,确保反应的正常进行。
水蒸气从水蒸气进气口61进入反应器6,经分离管道62后均匀分散至多根换热管道63中,水蒸气将热量传递至换热管道63和相变材料I64后汇流至一级汇流管道65,再经一级汇流管道65汇流至二级汇流管道68,最后从水蒸气出气口67流出反应器6,进入蒸发器7中;甲醇和水蒸气混合气体经混合气体进气口613进入气体扩散室68中,气体扩散室68内设有多层多孔介质板69;流入反应器6的混合气体经气体扩散室68内的多孔介质板69均匀扩散后向下方移动,接触到覆盖在换热管道63和相变材料I64表面的催化剂时发生甲醇重整反应生成氢气与二氧化碳,氢气与二氧化碳混合气体向下方移动,经气体汇流室610汇流后由混合气体出气口611流出反应器6,然后流向换热器11。气体汇流室610和气体扩散室68形状为漏斗形或其他开口逐渐减小的形状。
其中,蒸发器7包括换热腔713以及位于换热腔713上方的汇流腔79;换热腔713侧壁设有水蒸气流入口711、水蒸气流出口75和混合液流入口712;汇流腔79顶部设有混合气排出口710;换热腔713内设有换热支管72,换热支管72外包覆有相变材料II76,换热支管72外以一定间隔覆盖相变材料II76,相变材料II的熔点为T2(100℃~250℃);甲醇水溶液经过喷头77雾化,蒸发更快;水蒸气从水蒸气流入口711进入蒸发器7,经分离管道62后均匀分散至多根换热支管72中,水蒸气将热量传递至换热支管72和相变材料II76后汇流到一级汇流管道65,经一级汇流管道65汇流至二级汇流管道68,最后从水蒸气流出口75流出蒸发器7,进入预热器8中;甲醇水溶液从混合液流入口712进入换热腔713中,每层换热支管72上均架设有喷头77,甲醇水溶液从每层换热支管72上的喷头77喷出,接触到加热后的换热支管72和储热后的相变材料II76后汽化,混合气体经汇流腔79汇流后从混合气排出口710流出蒸发器7,然后流向反应器6。
预热器8包括反应箱体815,反应箱体815内设有加热板88和流道板87;加热板88和流道板87上均设有S型流道814;加热板88和流道板87依次交替排布,加热板88和流道板87之间设有换热层,换热层由相变材料III86和肋片85依次交替组成;反应箱体815内还设有水蒸气中转管道81、水蒸气汇流管道83、溶液中转管道810和溶液汇流管道811;水蒸气中转管道81上设有水蒸气入口813,水蒸气汇流管道83上设有水蒸气出口84,溶液中转管道810上设有溶液入口89,溶液汇流管道811上设有溶液出口812;水蒸气中转管道81和水蒸气汇流管道83分别通过水蒸气支管82与加热板88上S型流道814的首尾连接;溶液中转管道810和溶液汇流管道811分别通过溶液支管816与流道板87上S型流道814的首尾连接;水蒸气从水蒸气入口813流入水蒸气中转管道81,经多个水蒸气支管82把水蒸气中转管道81里的水蒸气输送到加热板88;水蒸气在加热板88中沿着S型流道814流动后从多个支管流进水蒸气汇流管道83,再从水蒸气汇流管道83的水蒸气出口84流出预热器8,流入水箱1中;水蒸气流过加热板88,将热量传递至加热板88上下的相变材料III86中,其中部分热量用于加热甲醇水溶液,部分热量传递到相变材料III86中储存起来;甲醇水溶液从预热器8的溶液入口89流入溶液中转管道810,经多个溶液支管816把溶液中转管道810里的溶液输送到流道板87;溶液在流道板87中沿着S型流道814流动后从多个支管流进溶液汇流管道811,再从溶液汇流管道811的溶液出口812流出预热器8,流向蒸发器7。S型流道814为热端到冷端的距离渐变(逐渐变低),S型流道814通过延长距离加强换热。相变材料III86的熔点为50℃~100℃。
反应器6和蒸发器7的分离管道62均采用逐级一分为二的分离方式确保水蒸气在各换热管中分布更加均匀。
氢气和二氧化碳混合气体在换热器11中与甲醇水溶液换热后流向气体分离器14,气体分离器14包括密封腔体141,密封腔体141设有混合气体进口管道1401、二氧化碳出口管道1404以及氢气出口1403;在混合气体进口管道1401与二氧化碳出口管道1404之间设有气体分离膜1402;氢气和二氧化碳混合气体从混合气体进口管道1401流入气体分离器14,流经气体分离膜1402时被分离,氢气被分离至膜外,然后从氢气出口1403流入储氢罐12,二氧化碳无法穿过膜,继续在膜内移动,最后从二氧化碳出口管道1404流入二氧化碳储罐13。
本发明系统利用太阳能为甲醇重整制氢提供必要的热量,并将一部分热量存储至相变材料以便太阳能微弱时为甲醇重整反应提供热量,系统不需要额外的能量供给,节省了传统利用电加热或燃料加热的能耗;本系统产出的氢气十分纯净,可直接用于燃料电池汽车加氢,分离出的二氧化碳可以回收再利用。
Claims (10)
1.一种利用太阳能的甲醇重整制氢系统,其特征在于:包括装有甲醇水溶液的储放箱(10)、换热器(11)、预热器(8)、蒸发器(7)、反应器(6)和气体分离器(14);还包括水箱(1)和太阳能高温集热管(3);太阳能高温集热管(3)将水箱(1)内的水加热成高温水或水蒸气,高温水或水蒸气通入反应器(6)和/或蒸发器(7)和/或预热器(8)的换热管道中,与甲醇水溶液进行热交换,降温后的水回流入水箱(1);甲醇水溶液经换热器(11)、预热器(8)、蒸发器(7)逐级加热后,在反应器(6)中发生甲醇重整反应,生成的氢气和二氧化碳混合气体经换热器(11)与甲醇水溶液进行热交换后,在气体分离器(14)中被分离成氢气和二氧化碳;反应器(6)内涂覆有催化剂层。
2.根据权利要求1所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述太阳能高温集热管(3)出口处设有热电偶(4),所述太阳能高温集热管(3)出口连有三个支路,分别为第一支路(15)、第二支路(16)和第三支路(17),三个支路上均设有阀门;太阳能高温集热管(3)通过第一支路(15)与预热器(8)、水箱(1)形成闭环回路;太阳能高温集热管(3)通过第二支路(16)与蒸发器(7)、预热器(8)、水箱(1)形成闭环回路;太阳能高温集热管(3)通过第三支路(17)与反应器(6)、蒸发器(7)、预热器(8)、水箱(1)形成闭环回路;反应器(6)和蒸发器(7)之间的换热连接管路以及蒸发器(7)和预热器(8)之间的换热连接管路上也设有阀门。
3.根据权利要求2所述的利用太阳能的甲醇重整制氢系统,其特征在于:还包括PLC控制箱,热电偶(4)与各支路、各换热连接管路上的阀门分别通过电缆与PLC控制箱连接。
4.根据权利要求1所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述反应器(6)包括水蒸气进气口(61)、水蒸气出气口(67)、混合气体进气口(613)和混合气体出气口(611);还包括换热室(612)、位于换热室(612)上方的气体扩散室(68)以及位于换热室(612)下方的气体汇流室(610);换热室(612)内设有换热管道(63),换热管道(63)外包覆有相变材料I(64);换热管道(63)和相变材料I(64)外涂覆有催化剂层;水蒸气从水蒸气进气口(61)进入反应器(6),经分离管道(62)后均匀分散至多根换热管道(63)中,水蒸气将热量传递至换热管道(63)和相变材料I(64)后汇流到汇流管道,经汇流管道汇流后从水蒸气出气口(67)流出反应器(6);甲醇和水蒸气混合气体经混合气体进气口(613)进入气体扩散室(68)中;经气体扩散室(68)流进换热室(612),在换热室(612)相变材料I(64)表面催化剂的作用下发生甲醇重整反应生成氢气与二氧化碳,氢气与二氧化碳混合气体向下移动至气体汇流室(610),由混合气体出气口(611)流出反应器(6)。
5.根据权利要求4所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述相变材料I(64)对应的相变材料的熔点为250℃~300℃。
6.根据权利要求4所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述气体扩散室(68)内设有多层多孔介质板(69),每层多孔介质板(69)的孔径为0.5mm。
7.根据权利要求1所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述蒸发器(7)包括换热腔(713)以及位于换热腔(713)上方的汇流腔(79);换热腔(713)侧壁设有水蒸气流入口(711)、水蒸气流出口(75)和混合液流入口(712);汇流腔(79)顶部设有混合气排出口(710);换热腔(713)内设有换热支管(72),换热支管(72)外包覆有相变材料II(76);水蒸气从水蒸气流入口(711)进入蒸发器(7),经分离管道(62)后均匀分散至多根换热支管(72)中,水蒸气将热量传递至换热支管(72)和相变材料II(76)后汇流到汇流管道,经汇流管道汇流后从水蒸气流出口(75)流出蒸发器(7);甲醇水溶液从混合液流入口(712)进入换热腔(713)中,每层换热支管(72)上均架设有喷头(77),甲醇水溶液从每层换热支管(72)上的喷头(77)喷出,接触到换热支管(72)和储热后的相变材料II(76)后汽化,混合气体经汇流腔(79)汇流后从混合气排出口(710)流出蒸发器(7)。
8.根据权利要求7所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述相变材料II(76)的熔点为100℃~250℃。
9.根据权利要求1所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述预热器(8)包括反应箱体(815),反应箱体(815)内设有加热板(88)和流道板(87);加热板(88)和流道板(87)上均设有S型流道(814);加热板(88)和流道板(87)依次交替排布,加热板(88)和流道板(87)之间设有换热层,换热层由相变材料III(86)和肋片(85)依次交替排布组成;反应箱体(815)内还设有水蒸气中转管道(81)、水蒸气汇流管道(83)、溶液中转管道(810)和溶液汇流管道(811);水蒸气中转管道(81)上设有水蒸气入口(813),水蒸气汇流管道(83)上设有水蒸气出口(84),溶液中转管道(810)上设有溶液入口(89),溶液汇流管道(811)上设有溶液出口(812);水蒸气中转管道(81)和水蒸气汇流管道(83)分别通过水蒸气支管(82)与加热板(88)上S型流道(814)的首尾连接;溶液中转管道(810)和溶液汇流管道(811)分别通过溶液支管(816)与流道板(87)上S型流道(814)的首尾连接;水蒸气从水蒸气入口(813)流入水蒸气中转管道(81),经多个水蒸气支管(82)把水蒸气中转管道(81)里的水蒸气输送到加热板(88);水蒸气在加热板(88)中沿着S型流道(814)流动后从多个支管流进水蒸气汇流管道(83),再从水蒸气汇流管道(83)的水蒸气出口(84)流出预热器(8),甲醇水溶液从预热器(8)的溶液入口(89)流入溶液中转管道(810),经多个溶液支管(816)把溶液中转管道(810)里的溶液输送到流道板(87);溶液在流道板(87)中沿着S型流道(814)流动后从多个支管流进溶液汇流管道(811),再从溶液汇流管道(811)的溶液出口(812)流出预热器(8)。
10.根据权利要求1所述的利用太阳能的甲醇重整制氢系统,其特征在于:所述气体分离器(14)包括密封腔体(141),密封腔体(141)设有混合气体进口管道(1401)、二氧化碳出口管道(1404)以及氢气出口(1403);在混合气体进口管道(1401)与二氧化碳出口管道(1404)之间设有气体分离膜(1402)。
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CN114249297B (zh) * | 2021-12-30 | 2023-01-31 | 江苏科技大学 | 一种利用太阳能的甲醇重整制氢系统 |
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WO2023124030A1 (zh) * | 2021-12-30 | 2023-07-06 | 江苏科技大学 | 一种利用太阳能的甲醇重整制氢系统 |
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CN114538375B (zh) * | 2022-04-22 | 2022-08-09 | 河北氢联新能源科技有限公司 | 甲醇液相重整制氢装置和方法以及供电系统 |
CN115650163A (zh) * | 2022-10-17 | 2023-01-31 | 佛山仙湖实验室 | 一种陶瓷储热的甲醇重整制氢系统及方法 |
CN115650163B (zh) * | 2022-10-17 | 2024-06-25 | 佛山仙湖实验室 | 一种陶瓷储热的甲醇重整制氢系统及方法 |
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