CN112212610B - 一种lng制备液氢的方法 - Google Patents

一种lng制备液氢的方法 Download PDF

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CN112212610B
CN112212610B CN202011299737.XA CN202011299737A CN112212610B CN 112212610 B CN112212610 B CN 112212610B CN 202011299737 A CN202011299737 A CN 202011299737A CN 112212610 B CN112212610 B CN 112212610B
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hydrogen
lng
section
cooling
natural gas
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CN112212610A (zh
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王秀林
李又武
张瑜
侯海龙
张丹
宋鹏飞
姚辉超
穆祥宇
隋依言
王斯
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China National Offshore Oil Corp CNOOC
CNOOC Gas and Power Group Co Ltd
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Abstract

本发明公开了一种LNG制备液氢的方法。所述方法包括如下步骤：增压后的LNG与H2与He的混合物换热后，进入预冷单元与氮气或混合冷剂进行换热并升温；升温后的天然气经加热后进入天然气转化工段；在天然气转化工段内，天然气经转化、变换和变压吸附提浓得到富氢气体；富氢气体经压缩工段增压后，进入氢气预冷段，与氮气或混合冷剂进行换热冷却；经氢气预冷段冷却后的氢气进入氢气液化段与He/Ne混合物进行换热冷却，经节流阀节流后，制得液氢。本发明直接将LNG气化工艺与氢气液化工艺能量相互利用，制备的液氢可方便进行运输和利用，提高氢气的运输消耗和氢气经济性，流程简单、自动化程度高，所采用的设备可靠，提高氢气的制备成本和液化成本，经济效益显著。

Description

一种LNG制备液氢的方法
技术领域
本发明涉及一种LNG制备液氢的方法。
背景技术
氢能是公认的清洁能源，因具有高能量密度以及零碳排放等优点被认为是未来最有潜力的化石燃料替代者，其被看作是以氢燃料电池汽车为代表的移动能源领域的“终极方案”，绿色的氢气也可以作为化石资源加氢过程的氢气来源，实现碳的减排。预计到2020年氢能将以产业链示范为主，到2030年氢能产业链(包括制氢、氢储运、加氢站、燃料电池车、分布式能源等)将初具规模，建设加氢站1000座，到2050年国内氢能基础设施完善，氢能和燃料电池在交通、分布式能源等领域得到普及应用，建设加氢站10000座，氢能成为我国能源结构的重要组成部分。。
由于燃料电池技术的重大突破和成本的迅速降低，近几年全球氢能产业快速发展，世界主要国家相继出台氢能产业发展战略，对氢能各产业链环节有针对性发布国家型的补贴政策。目前，影响氢能产业发展的关键因素是氢气的价格，氢气价格决定氢气利用的经济性，进而决定了整个产业的经济性和可行性。氢能产业包括制氢、氢气储运和氢气利用三个主要环节，其中高效制氢技术和降低氢气运行成本是实现氢能产业发展的关键。
发明内容
针对氢气液化能耗高、液氢制造成本的问题，本发明提供了一种利用LNG冷能进行氢气液化的方法，得到的氢气浓度大于99.9％；本发明将LNG气化工艺和氢气液化工艺能量相互利用，工艺简单、自动化程度高、操作方便，能够很好地解决氢气液化能耗的问题。
具体地，本发明提供的LNG制备液氢的方法，包括如下步骤：
1)增压后的LNG与H2与He的混合物换热后，进入预冷单元与氮气或混合冷剂进行换热并升温；
2)升温后的天然气经加热后进入天然气转化工段；
3)在所述天然气转化工段内，所述天然气经转化、变换和变压吸附提浓得到富氢气体；
4)所述富氢气体经压缩工段增压后，进入氢气预冷段，与氮气或混合冷剂进行换热冷却；
5)经所述氢气预冷段冷却后的氢气进入氢气液化段与He/Ne混合物进行换热冷却，经节流阀节流后，制得液氢。
上述的方法中，步骤1)中，采用低温LNG增压泵将所述LNG增压至0.3～10MPaG；
所述LNG升温至-100～0℃。
上述的方法中，步骤1)中，所述氮气或所述混合冷剂增压至0.5～5MPAG后与所述LNG换热被冷却至-180～10℃，经冷却后的氮气或混合冷剂节流后与步骤4)中的氢气换热后继续增压而循环使用。
上述的方法中，步骤2)中，将所述天然气加热至600℃～1000℃；
步骤3)中，所述富氢气体中氢气的浓度大于99.9％。
上述的方法中，步骤5)中，所述氢气液化段中，所述He/Ne混合物增压后与低温氮气换热后进行冷却，冷却后的He/Ne混合物节流至0.1～2MPaG后，与氢气换热，将氢气冷却至-254℃～-170℃，压力为0.02～4MPAG。
上述的方法中，步骤5)中，所述He/Ne混合物中Ne的浓度范围为5％～30％。
上述的方法中，所述混合冷剂为N2、C2H4和CH4的混合气，浓度分别为10％～90％、5％～50％和5％～40％。
本发明方法直接将LNG气化工艺与氢气液化工艺能量相互利用，制备的液氢可方便进行运输和利用，提高氢气的运输消耗和氢气经济性，本发明方法流程简单、自动化程度高，所采用的设备可靠，提高氢气的制备成本和液化成本，经济效益显著。
附图说明
图1为本发明LNG制液氢的流程示意图。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
本实施例中LNG增压后进入
氮气(或混合冷剂)冷却单元与低温冷剂氢气换热，换热后天然气经加热后，进入天然气转化工段转化成富氢气体；富氢气体经变压吸附工段提浓后；进入增压单元进行增压和冷却降温后进入深冷单元进行冷却；深冷单元出口的氢气进入氢气深冷段与He/Ne混合物换热后，经节流阀节流后进入液氢储罐。
实施例1、
(1)增压后的LNG(7MPaG)与(H2+He)换热后，进入预冷单元与低温冷剂进行换热并升温至-20℃(物流2-4-5-6)。
(2)升温后的天然气经燃烧炉加热到820℃后进入天然气转化工段(物流6-7)。
(3)在天然气转化工段内，天然气经转化、变换和变压吸附提浓后，制备氢气浓度大于99.9％的富氢气体混合物(物流7-9-10-12-14)。
(4)富氢气体混合物经压缩工段增压3.0MPAG后，进入氢气冷却段冷却后，进行深冷单元与低温冷剂氮气换热至-155℃(物流14-16-17-19-20)。
(5)经深冷单元冷却后的氢气进入氢气液化工段与He/Ne混合物(Ne的浓度为40％)进行换热冷却，冷却温度-248℃(物流20-21)。
(6)经氢气液化工段冷却后的氢气经节流阀节流至0.1MPaG后，进行氢气储罐(物流17-22)。
实施例2、
(1)增压后的LNG(5MPaG)与(H2+He)换热后，进入预冷单元与低温混合冷剂进行换热并升温至-40℃(物流2-4-5-6)。
(2)升温后的天然气经燃烧炉加热到900℃后进入天然气转化工段(物流6-7)。
(3)在天然气转化工段内，天然气经转化、变换和变压吸附提浓后，制备氢气浓度大于99.9％的富氢气体混合物(物流7-8-10-14)。
(4)富氢气体混合物经压缩工段增压3.0MPAG后，进入氢气冷却段冷却后，进行深冷单元与低温冷剂混合冷剂(N2(50mol％)、C2H4(20mol％)、CH4(15mol％)和C3H8(15mol％))换热至-158℃(物流28-26-8-29-27)。
(5)经深冷单元冷却后的氢气进入氢气液化工段与He/Ne混合物(Ne的浓度为40)进行换热冷却，冷却温度-250℃(物流20-23)。
(6)经氢气液化工段冷却后的氢气经节流阀节流至0.08MPaG后制备液氢(物流21-22)。

Claims (3)

1.一种LNG制备液氢的方法，包括如下步骤：
1）增压后的LNG与He/Ne混合物换热后，进入预冷单元与氮气或混合冷剂进行换热并升温；
采用低温LNG增压泵将所述LNG增压至0.3~10MPaG；
所述LNG升温至-100~0℃；
2）升温后的天然气经加热后进入天然气转化工段；
将所述天然气加热至600℃~1000℃；
3）在所述天然气转化工段内，所述天然气经转化、变换和变压吸附提浓得到富氢气体；
所述富氢气体中氢气的浓度大于99.9%；
4）所述富氢气体经压缩工段增压后，进入氢气预冷段，与氮气或混合冷剂进行换热冷却；
5）经所述氢气预冷段冷却后的氢气进入氢气液化段与所述He/Ne混合物进行换热冷却，经节流阀节流后，制得液氢；
所述氢气液化段中，所述He/Ne混合物增压后与LNG换热后进行冷却，冷却后的He/Ne混合物节流至0.1~2MPaG后，与氢气换热，将氢气冷却至-254℃~-170℃；
所述He/Ne混合物中Ne的浓度范围为5%~30%；
所述混合冷剂为N2、C2H4和CH4的混合气，浓度分别为10%~90%、5%~50%和5%~40%。
2.根据权利要求1所述的方法，其特征在于：步骤1）中，所述氮气或所述混合冷剂增压至0.5~5MPAG后与所述LNG换热被冷却至-180~10℃，经冷却后的氮气或混合冷剂节流后与步骤4）中的氢气换热后继续增压而循环使用。
3.根据权利要求1或2所述的方法，其特征在于：步骤4）中，所述氢气预冷段采用N2或混合冷剂进行冷却。
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