CN1133489C - Paste-like hydrogen storage material - Google Patents

Paste-like hydrogen storage material Download PDF

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Publication number
CN1133489C
CN1133489C CNB021112223A CN02111222A CN1133489C CN 1133489 C CN1133489 C CN 1133489C CN B021112223 A CNB021112223 A CN B021112223A CN 02111222 A CN02111222 A CN 02111222A CN 1133489 C CN1133489 C CN 1133489C
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hydrogen
hydrogen storage
slurry
storing materials
storage material
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CN1380136A (en
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陈长聘
陈立新
蔡官明
安越
徐国华
王启东
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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  • Hydrogen, Water And Hydrids (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

The present invention relates to slurry hydrogen storing materials, which is characterized in that one kind or several kinds of solid inorganic hydrogen storing materials and one kind or several kinds of liquid organic hydrogen storing materials are put into a reactive container together to be composed into slurry which is under certain temperature and hydrogen pressure, wherein the solid inorganic hydrogen storing materials firstly suck hydrogen and immediately catalyze the liquid organic hydrogen storing materials, and hydrogenation is carried out. The whole slurry generates hydrogenization reaction and forms a hydride, and the hydrogen is stored in the slurry hydrogen storing materials. Compared with the prior art, the weight and the hydrogen storing density of the slurry hydrogen storing materials are as high as 6.5%, and the present invention has the advantages of high hydrogenization speed and hydrogenation conversion rates, simple flow paths, low cost and good safety and is particularly suitable for being used as a mobile hydrogen source or a portable hydrogen source, for example, the present invention is used as hydrogen fuel cases of environment protecting vehicles using hydrogen fuel batteries or hydrogen combusting internal combustion engines as power.

Description

Slurry hydrogen storage material
Technical Field
The invention relates to a hydrogen storage and transportation technology.
Background
Hydrogen is an important industrial feedstock and is also an ideal clean fuel. Hydrogen energy has become widely accepted as an important secondary energy source in the future. Particularly, the fuel cell using hydrogen as fuel is gradually pushed away in the application fields such as automobiles, mopeds, motorcycles, mobile phones, communication, computers, cameras, electric tools, military equipment and the like, and how to solve the problem of supplying safe and efficient onboard (or portable) hydrogen sources becomes the key of large-scale popularization and application of the fuel cell.
The utilization process of hydrogen, no matter being used as raw material or fuel, mostly relates to the storage and transportation links of the hydrogen, and the technical requirements of the link firstly ensure safety, and secondly the used device has high hydrogen storage density, namely the device is required to be small and light. There are three main methods for storing and transporting hydrogen gas in practical use in industry, namely, high-pressure vessel (steel cylinder), liquid hydrogen storage tank (low-temperature dewar) and metal hydride hydrogen storage device. Wherein, the weight hydrogen storage density of the steel high-pressure vessel is generally 1.0% (weight percentage, the same below); the hydrogen storage density of the normal temperature type metal hydride is 1.4-2.0% (not containing the weight of the container for containing the metal hydride); and the liquid hydrogen storage density is above 5.0%. Although the gravimetric hydrogen storage density of liquid hydrogen is much higher, it is difficult to realize commercial application due to problems such as volatilization loss, high manufacturing cost, and poor safety performance.
The hydrogen storage and transportation by the metal hydride method has the biggest advantages of good safety performance and high hydrogen storage density in unit volume, and has the defects of low hydrogen storage density by weight, and lack of competitiveness due to heavy weight when being used as a vehicle-mounted or mobile hydrogen storage carrier, and in addition, the problems of heat transfer and mass transfer performance of a metal hydride powder bed can be solved by utilizing the metal hydride to store and transport hydrogen firstly: firstly, the hydrogen storage alloy has a thermal effect in the hydrogen absorption and desorption process, the value of the thermal effect is 25-75/kilojoule/mol hydrogen, which means that the heat needs to be output from the system or input into the system to maintain the smooth hydrogen absorption or hydride desorption of the alloy, but the heat conductivity of the metal hydride powder is poor (equivalent to that of glass and sand stone), and the heat is difficult to output or input in time; secondly, once the alloy absorbs hydrogen, phase change occurs, the volume expansion is 15-25%, the alloy is pulverized into fine powder, and the fine powder is accumulated and burst in a container under the driving of hydrogen flow, so that the technical problems needing to be solved preferentially in the application of metal hydride engineering technology are solved by improving heat transfer and preventing the container from being damaged. For this reason, the national laboratory of brueck haiwen has proposed a technical problem that is to be solved preferentially. For this reason, the national laboratory of bruke hei in the united states proposed a technique of injecting an organic solvent such as n-undecane, n-octane or silicone oil into a container containing a hydrogen storage alloy to form a suspension with alloy particles, and the hydrogen storage alloy can perform a hydrogen absorption and desorption reaction in these solvents, and can effectively improve the heat transfer performance and prevent the container from being swollen. As a large amount of inert solvent which can not absorb and release hydrogen is added to the hydrogen storage alloy, the weight and volume hydrogen storage density of the whole system are greatly reduced.
In addition to the above-described high-pressure vessel, liquid hydrogen and metal hydride hydrogen storage and transportation method, aromatic hydrocarbons, such as benzene (C)6H6) Toluene (C)7H8) And naphthalene (C)10H8) And the like are substances capable of reversibly absorbing and desorbing hydrogen. Benzene, toluene and naphthalene react with hydrogen to generate cyclohexane, methylcyclohexane and decalin organic hydrides respectively, and the organic hydrides have high hydrogen storage density, are all organic liquids and do not have the defects of a metal hydride powder bed. However, liquid organic hydrocarbon hydrogen storage technology also has its fatal weaknesses, including: (1) the hydrogenation and dehydrogenation reactions of the organic hydrocarbon are carried out in a gaseous state, and the reaction conditions are harsh, namely the hydrogenation temperature is 300-350 ℃, the hydrogen pressure is 1-10 MPa, the dehydrogenation temperature is 350-500 ℃, and noble metal Pt or Pd is also used as a catalyst; (2) side reactions are easy to occur to generate some useless products, and the conversion rate of the target product is low; (3) process streamThe process and the equipment are complicated, and if two storage tanks, two liquid pumps, a catalytic reactor, a heat exchanger and the like are required to be arranged; (4) the catalyst is easy to coke and lose effectiveness, and the service life is short.
Disclosure of Invention
The invention aims to provide a safe, efficient and cheap hydrogen storage material, and the hydrogen storage material for storing and transporting hydrogen has the advantages of high hydrogen storage density, good heat transfer performance in a hydrogen storage system, no expansion and damage to a container during hydrogen absorption and the like, is suitable for hydrogen storage application in fixed occasions, is also suitable for mobile (such as vehicle-mounted and random) or portable hydrogen storage and transportation, and particularly has wide market on hydrogen fuel tanks of hydrogen fuel batteries and hydrogen-burning internal combustion engine vehicles.
A pulpy hydrogen storage material is characterized in that one or more solid hydrogen storage materials which can reversibly absorb and release hydrogen and can catalyze liquid hydrogen storage materials to hydrogenate and one or more aromatic hydrocarbon liquid hydrogen storage materials which can reversibly absorb and release hydrogen are placed in a reaction container and stirred together to form the pulpy material, namely slurry for short, the slurry is contacted with the hydrogen at certain temperature and pressure, wherein the solid hydrogen storage materials begin to absorb the hydrogen to form metal hydride, the metal hydride is used as a catalyst to immediately catalyze the liquid hydrogen storage materials to hydrogenate to form liquid hydride until the solid hydrogen storage materials and the liquid hydrogen storage materials are completely converted into hydride (namely the hydrogenation reaction is finished), and the hydrogen is stored in the pulpy hydrogen storage materials. When hydrogen is needed, the slurry hydride is allowed to desorb hydrogen (i.e., dehydrogenate), which in turn is restored to a slurry of solid hydrogen storage material mixed with liquid hydrogen storage material. The hydrogen can be stored and transported by the material repeatedly and reversibly.
In the slurry hydrogen storage material, the solid hydrogen storage material forming the slurry is hydrogen storage metal or alloy which can reversibly absorb and release hydrogen and can catalyze the hydrogenation of the liquid hydrogen storage material, and the solid hydrogen storage material is rare earth hydrogen storage alloy, or titanium binary and multi-element hydrogen storage alloy, or zirconium hydrogen storage alloy, or alkaline earth metals such as Mg, Ca and the like and hydrogen storage alloy mainly comprising the alkaline earth metals or the multi-element hydrogen storage alloy, or metal hydride, namely metal hydride formed by pre-absorbing hydrogen by selecting one or more of the hydrogen storage alloys.
In the slurry hydrogen storage material of the present invention, the liquid hydrogen storage material constituting the slurry is an aromatic hydrocarbon which reversibly adsorbs and desorbs hydrogen, and the liquid hydrogen storage material is benzene, or toluene, or naphthalene, or a mixture thereof. When the solid hydrogen storage material in the slurry begins to absorb hydrogen to form metal hydride (or the solid material is directly selected from the metal hydride), the metal hydride existing in the slurry will immediately catalyze benzene, toluene or naphthalene, and the hydrogen is added to form cyclohexane, methylcyclohexane or decalin, andthe hydrogenation reaction formula of the hydrocarbons in the slurry can be represented by the following equation:
wherein P is 2.5-4.5 MPa; t is 150-200 DEG C
Wherein P is 2.5-4.5 MPa; t is 150-200 DEG C
Wherein P is 2.5-4.5 MPa; t is 150-200 DEG C
One or more of the solid hydrogen storage materials and one or more of the liquid hydrogen storage materials are selected, the solid hydrogen storage materials and the liquid hydrogen storage materials are randomly matched and weighed according to the weight ratio of 1: 9-9: 1, and then the solid hydrogen storage materials and the liquid hydrogen storage materials are placed into a reactor and stirred together to form a slurry hydrogen storage material system. Once the system is heated and hydrogen is introduced, the slurry undergoes hydrogenation reaction to form slurry hydride, and the hydrogen is stored in the slurry.
The saturated hydrogen storage densities of cyclohexane, methylcyclohexane and decalin liquid hydrides were 7.19%, 6.16% and 7.29%, respectively. The metallic hydrogen storage material has a hydrogen storage density of about 1.4% by weight of rare earth, 1.6 to 2.0% by weight of titanium, and 3.6 to 7.6% by weight of magnesium (pure magnesium). The hydrogen storage density of the slurry-like hydrogen storage material differs depending on the kind of the hydrogen storage metal or alloy and the organic hydrocarbon compound constituting the slurry-like hydrogen storage material and the weight ratio of the two, and the slurry-like hydrogen storage material composed of the hydrogen storage metal or alloy of the slurry-like hydrogen storage material and the liquid hydrocarbon compound of high hydrogen storage density can obtain a high hydrogen storage density. The proportion of the high hydrogen storage density material in the slurry is increased, and the hydrogen storage density of the slurry hydrogen storage material can be improved. The higher the catalytic activity of the metal hydride in the slurry, the faster the rate at which liquid hydrocarbons in the slurry form liquid hydrides, the higher the conversion rate, and the greater the hydrogen storage density.
Compared with the prior art, the invention has the following outstanding advantages:
1. compared with a 15MPa high-pressure container hydrogen storage method, the slurry hydrogen storage material has the hydrogen storage pressure not more than 4.5MPa and the weight hydrogen storage density increased by 3-5 times.
2. Compared with the liquid hydrogen storage method, the slurry hydrogen storage material of the invention has no volatilization loss of hydrogen and the associated safety problem, and the hydrogen does not need to be purified in advance and liquefied at low temperature, and a Dewar container is not needed, thus having the advantages of higher efficiency, more energy consumption saving and lower cost.
3. Compared with the metal hydride hydrogen storage method, the invention is a slurry hydrogen storage material instead of a powder hydrogen storage material of the metal hydride, and has no various defects caused by poor heat transfer and mass transfer performance of metal hydride powder. The slurry hydride has a higher hydrogen storage density due to the incorporation of an organic hydride having a higher hydrogen storage density than the metal hydride.
4. Compared with the suspension hydrogen storage method which is provided by the national key laboratory of Bruk Hai province and consists of hydrogen storage alloy and inert solvent which does not absorb hydrogen, the slurry hydrogen storage material of the invention is a solid inorganic hydrogen storage material and a liquid organic hydrogen storage material which simultaneously store hydrogen, and the liquid solvent in the suspension method has no hydrogen absorption function, so the hydrogen storage density of the hydrogen storage material per unit weight is 5-10 times higher than that of the hydrogen storage material per unit weight.
5. Compared with the hydrogen storage method of aromatic hydrocarbon, the hydrogenation of the organic hydrocarbon in the slurry is carried out in a liquid phase state, so that the operation temperature is lower, the reaction speed is higher, the conversion rate is higher, the flow and the equipment are simpler, and the cost is lower.
Detailed Description
Example 1:
selecting rare earth system MINi5(MI: lanthanum-rich misch metal) alloy as solid hydrogen storage and absorption material, and industrial pure organic benzene (C)6H6) Is a liquid hydrogen storage material. MINi5The chemical formula of MI and Ni are mixed and melted in a vacuum induction furnace, ingot is crushed into particles with the particle size of less than 200 meshes and then put into a reaction vessel for activation in advance, and then the reaction vessel is added with the MINi5Equal weight of benzene (the weight ratio of the solid material to the liquid material is 1: 1) is mixed into slurryCharging, introducing hydrogen gas with purity of 99.9% and pressure of 4.0MPa into the container, and then MINi5Quickly absorbing hydrogen to saturate and converting into metal hydride, then heating the slurry to 180 deg.C, making the metal hydride in the slurry implement catalytic benzene hydrogenation reaction to produce cyclohexane liquid hydride, after 20 min, the whole slurry hydrogenation process is completed, and the hydrogen is stored in the slurry hydride. The weight hydrogen storage density of the slurry hydrogen storage material was found to be 4.15%.
Example 2:
selecting magnesium alloy Mg2Ni as solid hydrogen storage material and industrial pure benzene (C)6H6) And toluene (C)7H8) 50% of each mixed liquid is a liquid hydrogen storage material. Mg (magnesium)2Ni is prepared by melting metal Mg and Ni in a vacuum induction furnace or an electric heating crucible according to the chemical formula, the ingot is crushed into 200-mesh particles and then is put into a container, and then 4 times of Mg is added into the container2Mixing Ni with benzene and toluene at a weight ratio of solid material to liquid material of 1: 4, stirring with the solid material, introducing hydrogen gas with purity of 99.9% and pressure of 4.0MPa into the container, heating the slurry to 200 deg.C, and maintaining the temperature while adding Mg2Ni and C6H6、C7H8And absorbing hydrogen successively, wherein the whole slurry hydrogenation process tends to be completed after 15-20 minutes, and the hydrogen is stored in the slurry hydride. Due to Mg2The weight hydrogen storage density of Ni is 3.6%, and the proportion in the slurry is only 20%; the toluene accounts for 6.16 percent, and accounts for 40 percent in the slurry; benzene content 7.19% inThe slurry accounted for 40% of the total slurry hydrogen storage density, which was higher than that of example 1, and was found to be 5.6% by weight.
Example 3:
selecting rare earth-magnesium alloy La2Mg16Ni as solid hydrogen storage material and industrial pure benzene (C)6H6) Isa liquid hydrogen storage material. La2Mg16The Ni is prepared by melting metal raw materials of La, Mg and Ni in a vacuum induction furnace or an electric heating crucible furnace according to the formula proportion, after ingot casting is crushed into 200-mesh particles, surface modification treatment is carried out in advance, then the particles are put into a container for activation, and then 4 times of La is added into the container2Mg16Benzene solution with Ni weight, i.e. the weight ratio of solid material to liquid material is 1: 4, after mixing, introducing hydrogen with purity of 99.9% and pressure of 4.0MPa into a container, then heating the slurry to 180 deg.C, and keeping the temperature at this moment, La2Mg16Ni and C6H6The hydrogen is absorbed successively, and the whole slurry hydrogenation process tends to be completed in 4 minutes, and the hydrogen is stored in the slurry hydride. In the slurry system, La2Mg16Ni weight hydrogen storage density of 5.2%, C6H6The hydrogen storage density by weight of (1) is 7.19%; the solid material accounts for 20 percent, the liquid material accounts for 80 percent, so the weight hydrogen storage density of the slurry hydrogen storage material is higher than that of the example 1 and the example 2, and the measured result shows that the weight hydrogen storage density is 6.5 percent.

Claims (3)

1. A slurry hydrogen storage material, characterized by: the hydrogen storage material is slurry formed by mixing one or more solid hydrogen storage materials which can reversibly absorb and release hydrogen and can catalyze the hydrogenation of a liquid hydrogen storage material and one or more aromatic hydrocarbon liquid hydrogen storage materials which can reversibly absorb and release hydrogen, and theweight ratio of the solid hydrogen storage materials to the liquid hydrogen storage materials in the slurry is 1: 9-9: 1.
2. The slurried hydrogen storage material as recited in claim 1, wherein: the solid hydrogen storage material constituting the slurry is a rare earth-based hydrogen storage alloy, or a titanium-based hydrogen storage alloy, or a zirconium-based hydrogen storage alloy, or an alkaline earth metal of Mg or Ca and a hydrogen storage alloy thereof, or a hydride of the above metal or alloy.
3. The slurried hydrogen storage material as recited in claim 1, wherein: the liquid hydrogen storage material is benzene, or toluene, or naphthalene, or a mixture of the above liquid hydrogen storage materials.
CNB021112223A 2002-03-24 2002-03-24 Paste-like hydrogen storage material Expired - Fee Related CN1133489C (en)

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Publication number Priority date Publication date Assignee Title
CN101961631A (en) * 2010-09-14 2011-02-02 浙江大学 Device and method using aromatic compound to continuously absorb and discharge hydrogen
CN104650997A (en) * 2015-02-05 2015-05-27 淮安金鑫新能源科技有限公司 Fuel oil and preparation method thereof
CN110078021B (en) * 2019-04-29 2021-03-05 株洲铂陆新能源科技有限公司 Liquid organic hydrogen storage material and preparation method thereof
CN111020302A (en) * 2019-12-30 2020-04-17 有研工程技术研究院有限公司 High-temperature hydrogen release metal composite material and preparation method thereof
CN113200515A (en) * 2021-04-19 2021-08-03 有研工程技术研究院有限公司 Hydrogen slurry material for storing and transporting hydrogen at normal temperature and normal pressure and hydrogen storage method
CN114804020A (en) * 2022-05-24 2022-07-29 苏州清德氢能源科技有限公司 Slurry hydrogen storage material and preparation method thereof

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