CN114604821A - 一种固态储氢颗粒 - Google Patents
一种固态储氢颗粒 Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- 239000007787 solid Substances 0.000 title claims abstract description 32
- 239000002245 particle Substances 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000008188 pellet Substances 0.000 claims abstract description 8
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- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 18
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
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- 239000004280 Sodium formate Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- FYPZKRVMRWWQBC-UHFFFAOYSA-N carbonic acid;formic acid Chemical compound OC=O.OC(O)=O FYPZKRVMRWWQBC-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0084—Solid storage mediums characterised by their shape, e.g. pellets, sintered shaped bodies, sheets, porous compacts, spongy metals, hollow particles, solids with cavities, layered solids
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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
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C11/00—Use of gas-solvents or gas-sorbents in vessels
- F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2221/00—Handled fluid, in particular type of fluid
- F17C2221/01—Pure fluids
- F17C2221/012—Hydrogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/01—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the phase
- F17C2223/0107—Single phase
- F17C2223/0138—Single phase solid
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
- F17C2223/00—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel
- F17C2223/03—Handled fluid before transfer, i.e. state of fluid when stored in the vessel or before transfer from the vessel characterised by the pressure level
- F17C2223/031—Not under pressure, i.e. containing liquids or solids only
Abstract
本发明涉及一种固态储氢颗粒。本发明属于氢气存储技术领域。一种固态储氢颗粒，其特征是：固态储氢颗粒由碳酸氢盐/甲酸盐，催化剂和水组成；碳酸氢盐/甲酸盐，催化剂和水混合成固体凝胶状；储氢颗粒表面包覆防水透气膜。本发明的储氢材料具有储氢量高，成本低，运输安全，吸放氢条件温和等优点，可广泛应用于氢气储存装置中。
Description
技术领域
本发明属于氢气存储技术领域，特别是涉及一种固态储氢颗粒。
背景技术
氢能是能量密度最高的能源之一,被视为21世纪最具发展潜力的清洁能源，尤其在能源日益短缺的今天，发展以氢能为代表的新能源已迫在眉睫。发展氢能的过程中，合理地解决氢能的存储和运输具有十分重要的意义。目前现有的储氢技术主要有：1)高压气态储氢，采用碳纤维缠绕的气瓶储存压力可高达 70MPa；2)低温液态储氢；3)固态材料储氢。固态材料储氢是通过物理吸附的方式吸附或者化学的(与金属元素)反应的方式实现储存氢气的目的。但总体而言，现有的储氢方式和材料均存在着这样或那样的问题，无法满足日益增长的氢储能应用场景对安全性，储氢量，使用条件，成本等提出的要求。由此，探索安全可靠、低成本、储氢容量高的储氢材料及储氢方式具有显著的现实意义。
利用碳酸氢盐-甲酸盐的可逆转化可实现储氢，如反应式(1)所示(M代表碱土金属)，即通过碳酸氢盐加氢生成甲酸盐，甲酸盐脱氢生成碳酸氢盐，以此实现氢气的储存和释放。
与现有的储氢技术相比，碳酸氢盐-甲酸盐可逆转化储氢在以下方面展现出显著的优势：1)较高的储氢容量，以HCO3Na为例，理论储氢量可达2.38wt％，比常用的固体金属储氢合金都要高(如AB5合金储氢量约为1.4wt％)；2)吸放氢条件温和；3)成本低，储氢成本约为AB5储氢合金的十分之一；4)甲酸盐和碳酸氢盐常温常压下性质稳定，安全性好且便于运输。但目前碳酸氢盐- 甲酸盐的可逆转化吸放氢需在水溶液中实现，由于受限于碳酸氢盐的溶解度和温度条件，因此实际获得的储氢量还比较低。
发明内容
本发明为解决公知技术中存在的技术问题而提供一种固态储氢颗粒。
本发明的目的是提供一种具有较高储氢量，成本低，运输安全，吸放氢条件温和等优点，可广泛应用于氢气储存装置中的固态储氢颗粒。
本发明固态储氢颗粒为解决公知技术中存在的技术问题所采取的技术方案是：
一种固态储氢颗粒，其特征是：固态储氢颗粒由碳酸氢盐/甲酸盐，催化剂和水组成；碳酸氢盐/甲酸盐，催化剂和水混合成固体凝胶状；储氢颗粒表面包覆防水透气膜。
本发明固态储氢颗粒还可以采取如下技术方案：
所述的固态储氢颗粒，其特征是：通过控制水添加量将碳酸氢盐/甲酸盐和催化剂调制成固体凝胶状。
所述的所述的固态储氢颗粒，其特征是：催化剂为贵金属基如Pd、Ru、Ir 及其络合物/复合物或无机过渡金属NixFe1-xX(X为N或P)氮化物或磷化物。
所述的所述的固态储氢颗粒，其特征是：储氢颗粒表面包覆防水透气膜，防水透气膜为聚乙烯或聚丙烯材料。
所述的固态储氢颗粒，其特征是：碳酸氢盐或甲酸盐和水的摩尔比为1:1～2。
本发明具有的优点和积极效果是：
由于采用了本发明全新的固态储氢颗粒技术方案，与现有溶液技术路线相比，可有效提升系统的体积和重量储氢效率；同时采用防水透气膜包覆碳酸氢盐/甲酸盐和催化剂调制成的固体凝胶，可在空气条件下保存和运输，简化运输条件和成本。
本发明的固态储氢颗粒具有储氢量高，成本低，运输安全，吸放氢条件温和等优点，可广泛应用于氢气储存装置中。
附图说明
图1是固态储氢颗粒示意图：1-防水透气膜；2-碳酸氢盐或甲酸盐凝胶；3-催化剂
具体实施方式
为能进一步了解本发明的技术内容、特点及功效，兹例举以下实施例，详细说明如下：
实施例1
称取10g碳酸氢钠，一定量的纳米级Pd/C复合催化剂，研磨混合后添加3ml 蒸馏水，继续研磨成凝胶状，最后用聚乙烯和聚丙烯复合膜包覆所获得的凝胶状混合物成球形。将该球形颗粒放置于密闭的高压反应釜中，该反应釜置于水浴锅中，在5MPa氢气压力，50℃水浴条件下反应4小时，通过吸氢量检测(定容积法)，换算成碳酸氢钠的转化率为79.6％。在0.1MPa氢气压力，25℃水浴条件下反应4小时，已转化甲酸钠转化成碳酸氢钠的转化率为92％。
实施例2
称取10g碳酸氢钠，一定量的纳米级NixFe1-xP催化剂，研磨混合后添加3.5 ml蒸馏水，继续研磨成凝胶状，最后用聚乙烯和聚丙烯复合膜包覆所获得的凝胶状混合物成球形。将该球形颗粒放置于密闭的高压反应釜中，该反应釜置于水浴锅中，在5MPa氢气压力，50℃水浴条件下反应4小时，通过吸氢量检测(定容积法)，换算成碳酸氢钠的转化率为72.7％。在0.1MPa氢气压力，25℃水浴条件下反应4小时，已转化甲酸钠转化成碳酸氢钠的转化率为87.5％。
实施例3
称取10g碳酸氢钠，一定量的纳米级NixFe1-xN催化剂，研磨混合后添加3ml 蒸馏水，继续研磨成凝胶状，最后用聚乙烯和聚丙烯复合膜包覆所获得的凝胶状混合物成球形。将该球形颗粒放置于密闭的高压反应釜中，该反应釜置于水浴锅中，在5MPa氢气压力，50℃水浴条件下反应4小时，通过吸氢量检测(定容积法)，换算成碳酸氢钠的转化率为77.6％。在0.1MPa氢气压力，25℃水浴条件下反应4小时，已转化甲酸钠转化成碳酸氢钠的转化率为91.3％。
以上实施例仅用于说明本发明，是本发明的一部分实施例，不是全部的实施例，并非对本发明的限制。有关技术领域的普通技术人员，在不脱离本发明的精神和范围的情况下，还可以做出各种变化和变型，因此所有等同的技术方案也属于本发明的范畴，本发明的专利保护范围应由权利要求限定。
Claims (5)
1.一种固态储氢颗粒，其特征是：固态储氢颗粒由碳酸氢盐/甲酸盐，催化剂和水组成；碳酸氢盐/甲酸盐，催化剂和水混合成固体凝胶状；储氢颗粒表面包覆防水透气膜。
2.按照权利要求1所述的固态储氢颗粒，其特征是：通过控制水添加量将碳酸氢盐/甲酸盐和催化剂调制成固体凝胶状。
3.按照权利要求1所述的固态储氢颗粒，其特征是：催化剂为贵金属基如Pd、Ru、Ir及其络合物/复合物或无机过渡金属NixFe1-xX(X为N或P)氮化物或磷化物。
4.按照权利要求1所述的固态储氢颗粒，其特征是：储氢颗粒表面包覆防水透气膜，防水透气膜为聚乙烯或聚丙烯材料。
5.按照权利要求1或2所述的固态储氢颗粒，其特征是：碳酸氢盐或甲酸盐和水的摩尔比为1:1～2。
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| US20180085738A1 (en) * | 2016-09-29 | 2018-03-29 | Korea Institute Of Science And Technology | Catalyst for dehydrogenation reaction of formate and hydrogenation reaction of bicarbonate and preparation method thereof |
| CN112390224A (zh) * | 2019-08-16 | 2021-02-23 | 中国科学院大连化学物理研究所 | 一种聚合物包覆储氢材料及其制备方法和应用 |
| CN111412380A (zh) * | 2020-03-27 | 2020-07-14 | 东南大学 | 一种氢气制、储、用及运输一体系统 |
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