WO2016110215A1 - 液态储氢体系 - Google Patents

液态储氢体系 Download PDF

Info

Publication number
WO2016110215A1
WO2016110215A1 PCT/CN2015/099863 CN2015099863W WO2016110215A1 WO 2016110215 A1 WO2016110215 A1 WO 2016110215A1 CN 2015099863 W CN2015099863 W CN 2015099863W WO 2016110215 A1 WO2016110215 A1 WO 2016110215A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen storage
storage system
liquid hydrogen
melting point
hydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2015/099863
Other languages
English (en)
French (fr)
Inventor
程寒松
吴金平
董媛
杨明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Qingyang Energy Co Ltd
Original Assignee
Jiangsu Qingyang Energy Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Qingyang Energy Co Ltd filed Critical Jiangsu Qingyang Energy Co Ltd
Priority to JP2017554630A priority Critical patent/JP6692374B2/ja
Priority to EP15876715.2A priority patent/EP3243795B1/en
Priority to US15/541,801 priority patent/US20180065849A1/en
Publication of WO2016110215A1 publication Critical patent/WO2016110215A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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; Reversible storage of hydrogen
    • C01B3/0005—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes
    • C01B3/001—Reversible storage of hydrogen, e.g. by hydrogen getters or electrodes characterised by the uptaking media; Treatment thereof
    • C01B3/0015—Organic compounds, e.g. liquid organic hydrogen carriers [LOHC] or metalorganic compounds; Solutions thereof
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/22—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1064—Platinum group metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1252—Cyclic or aromatic hydrocarbons
    • 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

Definitions

  • the invention relates to the field of hydrogen storage technology, in particular to a liquid hydrogen storage system.
  • the existing hydrogen storage methods can be roughly divided into two types, namely, physical methods and chemical methods.
  • Typical methods in physical methods include low temperature liquid hydrogen storage and high pressure gaseous hydrogen storage.
  • the low-temperature liquid hydrogen storage method has a high volumetric energy density, since the critical temperature of hydrogen is low, hydrogen liquefaction consumes a large amount of cooling energy, and evaporation loss is inevitable in storage, and the storage cost is high.
  • the high-pressure gas storage hydrogen storage method is convenient to use, but the energy density is low, and there is a safety hazard.
  • the existing hydrogen storage system based on the chemical reaction method generally has the following defects: the hydrogen storage system has a too high freezing point (melting point) and exhibits a solid state at room temperature. This makes the hydrogen storage system which is liquid after hydrogenation in the process of dehydrogenation, and the hydrogen storage system recovered after preferential dehydrogenation easily condenses into a solid. These coagulations easily cover the surface of the dehydrogenation catalyst, causing the dehydrogenation reaction to be interrupted.
  • the present invention aims to provide a liquid hydrogen storage system to solve the problem of difficulty in dehydrogenation caused by excessive melting point of the hydrogen storage system in the prior art.
  • a liquid hydrogen storage system comprising at least two different hydrogen storage components, the hydrogen storage component being an unsaturated aromatic hydrocarbon or a heterocyclic unsaturated compound, and
  • the at least one hydrogen storage component is a low melting point compound having a melting point of less than 80 °C.
  • the hydrogen storage component is selected from the group consisting of heterocyclic unsaturated compounds, and the hetero atom in the heterocyclic unsaturated compound is one or more of N, S, O and P.
  • the total number of the heterocyclic ring and the aromatic ring in the heterocyclic unsaturated compound is from 1 to 20, and the total number of the hetero atoms is from 1 to 20.
  • the mass fraction of the low melting point compound is 5 to 95% with respect to the total mass of the liquid hydrogen storage system.
  • liquid hydrogen storage system further includes a hydrogenation additive, and the hydrogenation additive is a polar solvent and/or a non-polar solvent.
  • the hydrogenation additive is added in an amount of 0.1 to 10 ml per gram of the hydrogen storage component.
  • the different hydrogen storage components are respectively selected from the group consisting of benzene, toluene, ethylbenzene, o-xylene, p-xylene, styrene, phenylacetylene, anthracene, naphthalene, anthracene, aniline, carbazole, N-methylcarbazole , N-ethylcarbazole, N-n-propyl carbazole, N-isopropylcarbazole, N-n-butylcarbazole, anthracene, N-methylhydrazine, N-ethylhydrazine, N a group consisting of propyl hydrazine, quinoline, isoquinoline, pyridine, pyrrole, furan, benzofuran, thiophene, pyrimidine and imidazole.
  • the polar solvent is selected from the group consisting of ethanol, methanol, diethyl ether, methyl ether, acetonitrile, ethyl acetate, formamide, isopropanol, n-butanol, dioxane, n-butyl ether, diisopropyl ether, dichloromethane One or more of chloroform and dichloroethane.
  • non-polar solvent is selected from one or more of n-hexane, n-pentane, cyclohexane, mesitylene, carbon disulfide, petroleum ether, and carbon tetrachloride.
  • the hydrogen storage system further comprises a dehydrogenation additive selected from one or more of decalin, mesitylene, petroleum ether and phenyl ether.
  • the dehydrogenation additive is added in an amount of 0.1 to 10 ml per gram of the hydrogen storage component.
  • the invention provides a liquid hydrogen storage system, which is actually a multi-mixed liquid unsaturated aromatic hydrocarbon and/or heterocyclic aromatic hydrocarbon hydrogen storage system.
  • the liquid hydrogen storage system comprises at least two different hydrogen storage components selected from the group consisting of unsaturated aromatic hydrocarbons or heterocyclic unsaturated compounds, wherein at least one hydrogen storage component has a melting point of less than 80 °C.
  • Different unsaturated aromatic hydrocarbon or heterocyclic unsaturated compounds have different melting points, and after mixing two or more kinds of fused heterocyclic unsaturated compounds, the mixed system formed has a lower melting point than at least one of the melting points of one of the components. Co-melting point.
  • the use of at least one low melting point compound having a melting point of less than 80 ° C in two or more kinds of unsaturated aromatic hydrocarbon or heterocyclic unsaturated compound can lower the eutectic point of the entire hydrogen storage system to near room temperature. This makes it possible to obtain a hydrogen storage system which exhibits a liquid state at room temperature. After the hydrogen storage system provided by the present invention is hydrogenated, the hydrogen storage system recovered in contact with the dehydrogenation catalyst and preferentially dehydrogenation reaction in the dehydrogenation process still exhibits a liquid state. This is beneficial to prevent the solid condensate from covering the dehydrogenation catalyst and to improve the difficulty of dehydrogenation caused by the solid hydrogen storage system.
  • Example 1 is a graph showing changes in hydrogen storage content of a hydrogen storage system under different additives in accordance with Example 34 of the present invention
  • Example 35 of the present invention is a graph showing changes in hydrogen storage content of a hydrogen storage system with time according to different additive amounts in Example 35 of the present invention
  • Example 3 is a graph showing changes in hydrogen storage content of a hydrogen storage system under different additives in accordance with Example 36 of the present invention.
  • Example 37 is a graph showing changes in hydrogen storage content of a hydrogen storage system with time under different additive types and different additive amounts in Example 37 of the present invention
  • Figure 5 is a graph showing the change in the amount of dehydrogenation of a fully hydrogenated hydrogen storage system with time for different types of additives and different amounts of additives in Examples 38 to 41 of the present invention.
  • the existing hydrogen storage system has a problem that dehydrogenation is difficult due to an excessively high melting point.
  • the inventors of the present invention provide a liquid hydrogen storage system comprising at least two different hydrogen storage components, the hydrogen storage component being an unsaturated aromatic hydrocarbon or a fused heterocyclic unsaturated compound, and at least One hydrogen storage component is a low melting point compound having a melting point of less than 80 °C.
  • Different unsaturated aromatic hydrocarbon or heterocyclic unsaturated compounds have different melting points, and after mixing two or more kinds of unsaturated aromatic hydrocarbons and/or heterocyclic unsaturated compounds, the mixed system formed has at least one lower than one of them.
  • a low eutectic point of melting point of a component The use of at least one low melting point compound having a melting point of less than 80 ° C in two or more kinds of unsaturated aromatic hydrocarbons and/or heterocyclic unsaturated compounds can lower the eutectic point of the entire hydrogen storage system to near room temperature. This makes it possible to obtain a hydrogen storage system which exhibits a liquid state at room temperature.
  • the hydrogen storage system recovered from the dehydrogenation catalyst and preferably dehydrogenation reaction is still in a liquid state during the dehydrogenation process. This is beneficial to prevent the solid condensate from covering the dehydrogenation catalyst and to improve the difficulty of dehydrogenation caused by the solid hydrogen storage system.
  • the liquid hydrogen storage system provided by the present invention has a melting point of -50 ° C to 60 ° C.
  • the hydrogen storage component is selected from a heterocyclic unsaturated compound, and the hetero atom in the heterocyclic unsaturated compound is one or more of N, S, O, and P.
  • Heterocyclic unsaturated compounds containing one or more heteroatoms which have better reversible hydrogenation/dehydrogenation properties.
  • the two different heterocyclic unsaturated compounds are mixed, and the resulting hydrogen storage system has both a lower eutectic point and a higher reversible hydrogenation/dehydrogenation performance.
  • the total number of the heterocyclic unsaturated compound heterocyclic ring and aromatic ring is from 1 to 20, and the total number of hetero atoms is from 1 to 20.
  • the total number of heterocyclic rings and aromatic rings in the heterocyclic unsaturated compound is controlled in the range of 1 to 20, and the hydrogen storage component in the hydrogen storage system has a relatively low melting point, and the hydrogen storage system formed has a correspondingly lower Co-melting point. This allows the hydrogen storage system to remain liquid in a lower temperature environment, facilitating hydrogen storage, transportation and dehydrogenation operations in different regions and seasons.
  • the ratio of each hydrogen storage component in the liquid hydrogen storage system can select the ratio of each hydrogen storage component in the liquid hydrogen storage system.
  • the mass fraction of the low melting point compound in the above liquid hydrogen storage system is 5 to 95% with respect to the total mass of the liquid hydrogen storage system. Controlling the ratio of the low melting point compound to the above range is advantageous for further lowering the melting point of the hydrogen storage system.
  • the above liquid hydrogen storage system provided by the present invention can effectively reduce the melting point of the hydrogen storage system by including at least two hydrogen storage components in the above range, so that it can maintain a liquid state at room temperature and prevent recovery in a late dehydrogenation process.
  • the hydrogen storage system condenses into a solid state to hinder the normal progress of dehydrogenation.
  • the liquid hydrogen storage system further includes a hydrogenation additive, and the hydrogenation additive is a polar solvent and/or a non-polar solvent.
  • the hydrogen storage component selected from the group consisting of an unsaturated compound or a heterocyclic unsaturated compound has a high intermolecular force.
  • excessive intermolecular forces may weaken the effective contact of the hydrogen storage component with the surface of the hydrogenation catalyst. This will reduce the rate of hydrogenation of the hydrogen storage system.
  • the molecular spacing between the hydrogen storage components is reduced by the force, which may hinder the entry of hydrogen atoms from the decomposition of the catalyst surface, thereby slowing down the hydrogenation rate of the hydrogen storage system.
  • the introduction of a polar solvent and/or a non-polar solvent as a hydrogenation additive in the above liquid hydrogen storage system can reduce the force between the hydrogen storage components, thereby improving the hydrogenation rate of the liquid hydrogen storage system.
  • the above liquid hydrogen storage system can reduce the intermolecular force of the hydrogen storage component to a certain extent and increase the hydrogen storage rate and the hydrogenation rate as long as the hydrogenation additive is added.
  • the hydrogenation additive is added in an amount of from 0.1 to 10 ml per gram of the hydrogen storage component. Controlling the proportion of the hydrogenation additive in the above range can weaken the intermolecular force of the hydrogen storage component, increase the hydrogenation rate of the hydrogen storage system, and also promote the effective dispersion of the hydrogen storage component in the overall liquid system. Thereby, the hydrogen storage component can be more sufficiently contacted with the surface of the hydrogenation catalyst, thereby further increasing the hydrogenation rate and the amount of hydrogenation of the hydrogen storage system.
  • the different hydrogen storage components are respectively selected from the group consisting of benzene, toluene, ethylbenzene, o-xylene, p-xylene, styrene, phenylacetylene, anthracene, naphthalene, anthracene, aniline, carbazole.
  • benzene, toluene, ethylbenzene, o-xylene, p-xylene, styrene, phenylacetylene, anthracene, naphthalene and anthracene are unsaturated aromatic hydrocarbons, aniline, carbazole, N-methylcarbazole, N-ethylhydrazine.
  • the hydrogen storage component any two or more of these unsaturated aromatic hydrocarbons and heterocyclic unsaturated compounds are used. These compounds are relatively easy to obtain and have low cost. At the same time, these compounds all have a lower melting point. At least two of them are selected as the hydrogen storage component, and the obtained hydrogen storage system has a lower eutectic point and also has better reversible hydrogenation/dehydrogenation performance.
  • unsaturated aromatic hydrocarbons such as benzene, toluene, ethylbenzene, o-xylene, p-xylene, styrene, phenylacetylene and anthracene having a melting point of less than 50 ° C
  • aniline N-n-propyl carbazole, N-methyl hydrazine, N-ethyl hydrazine, N-propyl hydrazine, quinoline, isoquinoline, pyridine, pyrrole, furan, benzofuran, thiophene Heterocyclic unsaturated compounds such as pyrimidines.
  • the hydrogen storage system provided by the present invention more preferably, the low melting point compound is selected from the group consisting of compounds having a melting point of less than 50 °C.
  • the hydrogenation additive used may be any polar solvent or non-polar solvent.
  • the above polar solvent includes, but is not limited to, ethanol, methanol, diethyl ether, methyl ether, acetonitrile, ethyl acetate, formamide, isopropanol, n-butanol, dioxane, n-butyl
  • ether, diisopropyl ether, dichloromethane, chloroform and dichloroethane is ether, diisopropyl ether, dichloromethane, chloroform and dichloroethane.
  • non-polar solvents include, but are not limited to, one or more of n-hexane, n-pentane, cyclohexane, mesitylene, carbon disulfide, petroleum ether, and carbon tetrachloride. These polar solvents and non-polar solvents have good compatibility with the above hydrogen storage components. The use of these polar solvents and non-polar solvents as hydrogenation additives for hydrogen storage systems can more effectively reduce the intermolecular forces of hydrogen storage components and increase the hydrogenation rate of hydrogen storage systems.
  • the liquid hydrogen storage system provided by the present invention can be dehydrogenated by hydrogenating it and then directly contacting the dehydrogenation catalyst during dehydrogenation and reacting.
  • the liquid hydrogen storage system further includes a dehydrogenation additive selected from one or more of petroleum ether, decalin, mesitylene, and phenyl ether.
  • a dehydrogenation additive selected from one or more of petroleum ether, decalin, mesitylene, and phenyl ether.
  • the above dehydrogenation additive is introduced into the system to increase the dehydrogenation rate of the system.
  • the dehydrogenation additive is added in an amount of from 0.1 to 10 ml per gram of the hydrogen storage component.
  • N-n-propyl carbazole (melting point of 48 ° C) and N-ethylcarbazole (melting point of 70 ° C) were used as hydrogen storage components to form a hydrogen storage system.
  • the ratio of the two components in each of the examples and the eutectic of the hydrogen storage system are as follows:
  • Example 1 N-n-propyl carbazole (wt%) N-ethylcarbazole (wt%) Hydrogen storage system eutectic (°C) Example 1 40 60 twenty four Example 2 50 50 15 Example 3 60 40 13 Example 4 70 30 29
  • N-n-propyl carbazole (melting point: 48 ° C) and N-methyl hydrazine (melting point -29.6 ° C) were used as hydrogen storage components to form a hydrogen storage system.
  • the ratio of the two components in each of the examples and the eutectic of the hydrogen storage system are as follows:
  • N-n-propyl carbazole (melting point 48 ° C), N-ethyl carbazole (melting point 70 ° C) and N-methyl hydrazine (melting point -29.6 ° C) as hydrogen storage components, mixed to form a reservoir Hydrogen system.
  • the ratio of the three components in each of the examples and the eutectic of the hydrogen storage system are as follows:
  • Example 9 6 4 90 -4.1
  • Example 10 12 8 80 -4.3
  • Example 11 18 12 70 -4.1
  • Example 12 twenty four 16 60 -4.1
  • N-n-propyl carbazole (melting point: 48 ° C), carbazole (melting point: 246.3 ° C) and N-ethyl carbazole (melting point of 70 ° C) were used as hydrogen storage components, and mixed to form a hydrogen storage system.
  • the ratio of the three components in each of the examples and the eutectic of the hydrogen storage system are as follows:
  • Example 13 N-n-propyl carbazole (wt%) N-ethylcarbazole (wt%) Carbazole (wt%) Hydrogen storage system eutectic (°C) Example 13 54 36 10 60.3 Example 14 48 32 20 62.4 Example 15 42 28 30 64.5 Example 16 36 twenty four 40 65.1
  • hydrogen storage amount of hydrogen storage system in the present invention means a weight percentage with respect to the total mass of the original hydrogen storage system.
  • the hydrogenation additives used in the hydrogen storage system are the amounts of cyclohexane (Examples 29, 30, 31), n-hexane (Examples 32, 33), and the contents of the products of different hydrogenation levels after different treatment times are as follows:
  • the obtained hydrogenated product is subjected to dehydrogenation under the following conditions: dehydrogenation treatment of 3 g of the fully hydrogenated product, dehydrogenation temperature of 170 ° C, pressure It was 1.01 ⁇ 10 5 Pa, the stirring speed was 200 rpm, and 0.6 g of a dehydrogenation catalyst Pd-Al 2 O 3 and an optional dehydrogenation additive were used.
  • dehydrogenation additives employed in the different examples are as follows:
  • Dehydrogenation additive Dehydrogenation additive dosage Example 38 -- 0
  • Petroleum ether 10ml
  • Example 40 Decalin 10ml
  • Example 41 Mesitylene 10ml
  • dehydrogenation amount in the present invention is a weight percentage relative to the total mass of the original hydrogen storage system.
  • the hydrogen storage system provided by the present invention has a lower melting point and can remain liquid in the vicinity of room temperature. From the data of the above Examples 17 to 41, it is known that the hydrodehydrogenation test is carried out using the liquid hydrogen storage system provided by the present invention, which has a high hydrodehydrogenation rate and a reversible hydrogenation/dehydrogenation property. In addition, the hydrogenation and dehydrogenation operations are relatively simple, which is beneficial to further reduce the cost of hydrogen storage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Fuel Cell (AREA)

Abstract

提供一种液态储氢体系，包括至少两种不同的储氢组分，该组分为不饱和芳香烃或杂环不饱和化合物，且至少一种组分为熔点低于80℃的低熔点化合物。该体系为多元混合液态稠杂环芳烃，并具有至少低于其中某一组分熔点的低共熔点，这使得储氢体系的共熔点下降至室温附近，从而在室温下呈现液态。

Description

液态储氢体系 技术领域
本发明涉及储氢技术领域，具体而言，涉及一种液态储氢体系。
背景技术
氢能作为一种储量丰富、来源广泛、能量密度高的绿色能源，在燃料电池以及代替化石燃料等方面展现了很好的应用前景。在实际应用过程中，其储存和运输是关键。寻找高效低成本且能够规模化利用的储氢方法更是关键。
现有的储氢方法大致可以分为两种，即物理法和化学法。物理法中典型的有低温液态储氢法、高压气态储氢法等。其中低温液态储氢法虽然具有较高的体积能量密度，但由于氢气的临界温度较低，氢气液化要消耗很大的冷却能量，储存中还不可避免地存在蒸发损失，储存成本较高。高压气态储氢法使用方便，但能量密度较低，且存在安全隐患。
近年来，基于化学反应法的储氢技术以其储氢量大，能量密度高，运输方便等优点引起了很多研究者的关注。理想的储氢体系应该具有较好的可逆加氢/脱氢性能。然而，现有的基于化学反应法的储氢体系普遍以下存在缺陷：储氢体系的自身凝固点(熔点)过高，在室温下呈现固态。这使得加氢后呈液态的储氢体系在脱氢过程中，经优先脱氢后所恢复的储氢体系容易凝结为固体。这些凝结物容易覆盖在脱氢催化剂表面，从而导致脱氢反应中断。
基于上述原因，有必要提供一种在室温下呈现液态的储氢体系，以解决固态储氢体系易导致的脱氢困难的问题。
发明内容
本发明旨在提供一种液态储氢体系，以解决现有技术中储氢体系熔点过高导致的脱氢困难的问题。
为了实现上述目的，根据本发明的一个方面，提供了一种液态储氢体系，其包括至少两种不同的储氢组分，储氢组分为不饱和芳香烃或杂环不饱和化合物，且至少一种储氢组分为熔点低于80℃的低熔点化合物。
进一步地，储氢组分选自杂环不饱和化合物，杂环不饱和化合物中的杂原子为N、S、O及P中的一种或多种。
进一步地，杂环不饱和化合物中杂环和芳环的总数为1～20，杂原子的总数为1～20。
进一步地，相对于液态储氢体系的总质量而言，低熔点化合物的质量分数为5～95％。
进一步地，液态储氢体系还包括加氢添加剂，加氢添加剂为极性溶剂和/或非极性溶剂。
进一步地，相对于每克储氢组分而言，加氢添加剂的加入量为0.1～10ml。
进一步地，不同的储氢组分分别选自苯、甲苯、乙苯、邻二甲苯、对二甲苯、苯乙烯、苯乙炔、蒽、萘、芴、苯胺、咔唑、N-甲基咔唑、N-乙基咔唑、N-正丙基咔唑、N-异丙基咔唑、N-正丁基咔唑、吲哚、N-甲基吲哚、N-乙基吲哚、N-丙基吲哚、喹啉、异喹啉、吡啶、吡咯、呋喃、苯并呋喃、噻吩、嘧啶及咪唑所组成的组。
进一步地，极性溶剂选自乙醇、甲醇、乙醚、甲醚、乙腈、乙酸乙酯、甲酰胺、异丙醇、正丁醇、二氧六环、正丁醚、异丙醚、二氯甲烷、氯仿及二氯乙烷中的一种或多种。
进一步地，非极性溶剂选自正己烷、正戊烷、环己烷、均三甲苯、二硫化碳、石油醚及四氯化碳中的一种或多种。
进一步地，储氢体系还包括脱氢添加剂，脱氢添加剂选自十氢化萘、均三甲苯、石油醚及苯醚中的一种或多种。
进一步地，相对于每克储氢组分而言，脱氢添加剂的加入量为0.1～10ml。
本发明提供了一种液态储氢体系，其实为多元混合液态不饱和芳烃和/或杂环芳烃类储氢体系。该液态储氢体系包括至少两种不同的储氢组分，储氢组分选自不饱和芳香烃或杂环不饱和化合物，其中至少一种储氢组分的熔点小于80℃。不同的不饱和芳香烃或杂环不饱和化合物具有不同的熔点，将两种或两种以上的稠杂环不饱和化合物混合后，形成的混合体系具有至少低于其中某一组分熔点的低共熔点。而在两种或两种以上的不饱和芳香烃或杂环不饱和化合物中选用至少一种自身熔点小于80℃的低熔点化合物，能够使整个储氢体系的低共熔点下降至室温附近。这就能够获得在室温下呈现液态的储氢体系。本发明所提供的这种储氢体系经加氢后，在脱氢过程中，接触脱氢催化剂而优先发生脱氢反应所恢复的储氢体系依然呈现液态。这就有利于防止固态凝结物覆盖脱氢催化剂，改善固态储氢体系易造成的脱氢困难的问题。
附图说明
构成本申请的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1示出了本发明实施例34中不同添加剂下储氢体系的储氢量含量随时间的变化图；
图2示出了本发明实施例35中不同添加剂用量下储氢体系的储氢量含量随时间的变化图；
图3示出了本发明实施例36中不同添加剂下储氢体系的储氢量含量随时间的变化图；
图4示出了本发明实施例37中不同添加剂种类和不同添加剂用量下储氢体系的储氢量含量随时间的变化图；以及
图5示出了本发明实施例38至41中不同添加剂种类和不同添加剂用量下全氢化储氢体系的脱氢量随时间的变化图。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
正如背景技术部分所介绍的，现有的储氢体系因熔点过高而存在脱氢困难的问题。为了解决这一问题，本发明发明人提供了一种液态储氢体系，其包括至少两种不同的储氢组分，储氢组分为不饱和芳香烃或稠杂环不饱和化合物，且至少一种储氢组分为熔点低于80℃的低熔点化合物。
不同的不饱和芳香烃或杂环不饱和化合物具有不同的熔点，将两种或两种以上的不饱和芳香烃和/或杂环不饱和化合物混合后，形成的混合体系具有至少低于其中某一组分熔点的低共熔点。而在两种或两种以上的不饱和芳香烃和/或杂环不饱和化合物中选用至少一种自身熔点小于80℃的低熔点化合物，能够使整个储氢体系的共熔点下降至室温附近。这就能够获得在室温下呈现液态的储氢体系。本发明所提供的这种储氢体系经加氢后，在脱氢过程中，接触脱氢催化剂而优选发生脱氢反应所恢复的储氢体系依然呈现液态。这就有利于防止固态凝结物覆盖脱氢催化剂，改善固态储氢体系易造成的脱氢困难的问题。本发明所提供的这种液态储氢体系的熔点可以达到-50℃～60℃。
根据本发明上述的教导，本领域技术人员可以选择具体的储氢体系中的组分。在一种优选的实施方式中，上述储氢组分选自杂环不饱和化合物，杂环不饱和化合物中的杂原子为N、S、O及P中的一种或多种。含有一种或多种杂原子的杂环不饱和化合物，其具有较好的可逆加氢/脱氢性能。将两种不同的杂环不饱和化合物混合，所形成的储氢体系兼具较低的共熔点和较高的可逆加氢/脱氢性能。更优选地，上述杂环不饱和化合物杂环和芳环的总数为1～20，杂原子的总数为1～20。将杂环不饱和化合物中杂环和芳环的总数控制在1～20的范围内，储氢体系中各储氢组分的熔点相对较低，所形成的储氢体系也相应具有更低的共熔点。这就使得储氢体系能够在更低的温度环境中保持液态，方便在不同地域、不同季节下进行储氢、运输及脱氢操作。
根据本发明上述的教导，本领域技术人员可以选择液态储氢体系中各储氢组分的比例。在一种优选的实施方式中，上述液态储氢体系中相对于液态储氢体系的总质量而言，低熔点化合物的质量分数为5～95％。将低熔点化合物的比例控制在上述范围，有利于进一步降低储氢体系的熔点。
本发明所提供的上述液态储氢体系，只要包括上述范围的至少两种储氢组分，就能够有效降低储氢体系的熔点，使其能够在室温下保持液态，防止后期脱氢过程中恢复的储氢体系凝结成固态阻碍脱氢的正常进行。在一种优选的实施方式中，上述液态储氢体系还包括加氢添加剂，加氢添加剂为极性溶剂和/或非极性溶剂。
选自不饱和化合物或杂环不饱和化合物的储氢组分之间具有较高的分子间作用力。在对储氢体系进行加氢的阶段，过高的分子间作用力可能会使储氢组分与加氢催化剂表面的有效接触减弱。这会降低储氢体系的加氢速率。另一方面，储氢组分之间的分子间距会因作用力减小，这可能会阻碍催化剂表面分解得到的氢原子的进入，从而减缓储氢体系的加氢速率。在上述液态储氢体系中引入极性溶剂和/或非极性溶剂作为加氢添加剂，能够降低储氢组分之间的作用力，从而能够改善液态储氢体系的加氢速率。
本发明所提供的上述液态储氢体系，只要加入加氢添加剂，就能够在一定程度上降低储氢组分的分子间作用力，提高液态储氢体系的及加氢速率。在一种优选的实施方式中，相对于每克储氢组分而言，加氢添加剂的加入量为0.1～10ml。将加氢添加剂的用量比例控制在上述范围内，能够在减弱储氢组分分子间作用力，提高储氢体系加氢速率的同时，还能够促使储氢组分在整体液体体系中有效地分散，从而使储氢组分能够与加氢催化剂表面更充分地接触，从而进一步提高储氢体系的加氢速率和加氢量。
根据本发明上述的教导，本领域技术人员可以选择各储氢组分的具体类型。在一种优选的实施方式中，上述不同的储氢组分分别选自苯、甲苯、乙苯、邻二甲苯、对二甲苯、苯乙烯、苯乙炔、蒽、萘、芴、苯胺、咔唑、N-甲基咔唑、N-乙基咔唑、N-正丙基咔唑、N-异丙基咔唑、N-正丁基咔唑、吲哚、N-甲基吲哚、N-乙基吲哚、N-丙基吲哚、喹啉、异喹啉、吡啶、吡咯、呋喃、苯并呋喃、噻吩、嘧啶及咪唑所组成的组。其中苯、甲苯、乙苯、邻二甲苯、对二甲苯、苯乙烯、苯乙炔、蒽、萘和芴属于不饱和芳香烃，苯胺、咔唑、N-甲基咔唑、N-乙基咔唑、N-正丙基咔唑、N-异丙基咔唑、N-正丁基咔唑、吲哚、N-甲基吲哚、N-乙基吲哚、N-丙基吲哚、喹啉、异喹啉、吡啶、吡咯、呋喃、苯并呋喃、噻吩、嘧啶及咪唑属于杂环不饱和化合物。以这些不饱和芳香烃和杂环不饱和化合物中的任意两种及以上的组分作为储氢组分。这些化合物均较为易得，成本较低。同时，这些化合物均具有较低的熔点。选用其中的至少两种作为储氢组分，得到的储氢体系具有较低的共熔点，同时，还具有较好的可逆加氢/脱氢性能。
根据本发明给出的上述几种化合物，上述化合物中，熔点低于50℃的有苯、甲苯、乙苯、邻二甲苯、对二甲苯、苯乙烯、苯乙炔、蒽等不饱和芳香烃，以及苯胺、N-正丙基咔唑、N-甲基吲哚、N-乙基吲哚、N-丙基吲哚、喹啉、异喹啉、吡啶、吡咯、呋喃、苯并呋喃、噻吩和嘧啶等杂环不饱和化合物。本发明所提供的储氢体系，更优选低熔点化合物选自这些熔点低于50℃的化合物。
本发明所提供的上述液态储氢体系中，采用的加氢添加剂可以是任意的极性溶剂或非极性溶剂。在一种优选的实施方式中，上述极性溶剂包括但不限于乙醇、甲醇、乙醚、甲醚、乙腈、乙酸乙酯、甲酰胺、异丙醇、正丁醇、二氧六环、正丁醚、异丙醚、二氯甲烷、氯仿及二氯乙烷中的一种或多种。上述非极性溶剂包括但不限于正己烷、正戊烷、环己烷、均三甲苯、二硫化碳、石油醚及四氯化碳中的一种或多种。这些极性溶剂和非极性溶剂与上述储氢组分具有较好的相容性。采用这些极性溶剂和非极性溶剂作为储氢体系的加氢添加剂，能够更有效地降低储氢组分的分子间作用力，提高储氢体系的加氢速率。
本发明所提供的上述液态储氢体系，将其进行加氢后，在脱氢时直接与脱氢催化剂进行接触并反应，就能够进行脱氢。在一种优选的实施方式中，上述液态储氢体系还包括脱氢添加剂，脱氢添加剂选自石油醚、十氢化萘、均三甲苯及苯醚中的一种或多种。在对加氢后的储氢体系进行脱氢处理时，向体系中引入上述脱氢添加剂，能够提高体系的脱氢速率。在一种优选的实施方式中，相对于每克储氢组分而言，脱氢添加剂的加入量为0.1～10ml。
以下结合具体实施例对本发明作进一步详细描述，这些实施例不能理解为限制本发明所要求保护的范围。
实施例1至16中制备得到了不同的储氢体系，并测量了每一个储氢体系的共熔点
实施例1至4
以N-正丙基咔唑(熔点为48℃)和N-乙基咔唑(熔点为70℃)作为储氢组分，混合形成储氢体系。各实施例中两种组分的比例及储氢体系的共熔点如下：
  N-正丙基咔唑(wt％) N-乙基咔唑(wt％) 储氢体系共熔点(℃)
实施例1 40 60 24
实施例2 50 50 15
实施例3 60 40 13
实施例4 70 30 29
实施例5至8
以N-正丙基咔唑(熔点为48℃)和N-甲基吲哚(熔点为-29.6℃)作为储氢组分，混合形成储氢体系。各实施例中两种组分的比例及储氢体系的共熔点如下：
  N-正丙基咔唑(wt％) N-甲基吲哚(wt％) 储氢体系共熔点(℃)
实施例5 10 90 -5.2
实施例6 30 70 -4.6
实施例7 50 50 -4.3
实施例8 70 30 -4.2
实施例9至12
以N-正丙基咔唑(熔点为48℃)、N-乙基咔唑(熔点为70℃)和N-甲基吲哚(熔点为-29.6℃)作为储氢组分，混和形成储氢体系。各实施例中三种组分的比例及储氢体系的共熔点如下：
  N-正丙基咔唑(wt％) N-乙基咔唑(wt％) N-甲基吲哚(wt％) 储氢体系共熔点(℃)
实施例9 6 4 90 -4.1
实施例10 12 8 80 -4.3
实施例11 18 12 70 -4.1
实施例12 24 16 60 -4.1
实施例13至16
以N-正丙基咔唑(熔点为48℃)、咔唑(熔点为246.3℃)和N-乙基咔唑(熔点为70℃)作为储氢组分，混和形成储氢体系。各实施例中三种组分的比例及储氢体系的共熔点如下：
  N-正丙基咔唑(wt％) N-乙基咔唑(wt％) 咔唑(wt％) 储氢体系共熔点(℃)
实施例13 54 36 10 60.3
实施例14 48 32 20 62.4
实施例15 42 28 30 64.5
实施例16 36 24 40 65.1
实施例17至33中采用储氢体系进行了加氢试验
实施例17至22
以12gN-正丙基咔唑(熔点为48℃)和8gN-乙基咔唑(熔点为70℃)作为储氢组分，以环己烷作为加氢添加剂，混合形成储氢体系。在压力为8Mpa、搅拌速率为600rpm及2g加氢催化剂Ru-Al2O3的催化作用下进行加氢处理。加氢添加剂的用量、加氢温度及不同加氢时间下全氢化产物的含量如下：
Figure PCTCN2015099863-appb-000001
本发明中“储氢体系的储氢量”的含义是相对于原储氢体系的总质量的重量百分比。
实施例23
以12gN-正丙基咔唑(熔点为48℃)和8gN-乙基咔唑(熔点为70℃)作为储氢组分，以20ml乙醇作为加氢添加剂，混合形成储氢体系。在温度150℃、压力为8Mpa、搅拌速率为600rpm及2g加氢催化剂Ru-Al2O3的催化作用下进行加氢处理。不同加氢时间下储氢量变化如下：
  4h(wt％) 6h(wt％)
实施例23 3.91 5.57
实施例24至26
以2.5gN-正丙基咔唑(熔点为48℃)和2.5gN-甲基吲哚(熔点为-29.6℃)作为储氢组分，可选地与加氢添加剂混合形成储氢体系。在温度140℃、压力为7Mpa及0.5g加氢催化剂Ru-Al2O3的催化作用下进行加氢处理，处理时间为5h。储氢体系中采用的加氢添加剂的种类和用量、5h后不同氢化程度的产物的含量如下：
Figure PCTCN2015099863-appb-000002
实施例27和实施例28
以3gN-正丙基咔唑(熔点为48℃)、2gN-乙基咔唑(熔点为70℃)和5g N-甲基吲哚(熔点为-29.6℃)作为储氢组分，可选地与加氢添加剂正己烷混合形成储氢体系。在温度140℃、压力为6Mpa及1g加氢催化剂Ru-Al2O3的催化作用下进行加氢处理。储氢体系中采用的加氢添加剂正己烷的用量、不同处理时间后储氢量如下：
Figure PCTCN2015099863-appb-000003
Figure PCTCN2015099863-appb-000004
实施例29至33
以6g N-正丙基咔唑(熔点为48℃)、4g N-乙基咔唑(熔点为70℃)和10g咔唑(熔点为246.3℃)作为储氢组分，可选地与加氢添加剂环己烷混合形成储氢体系。在温度150℃、压力为7Mpa及2g加氢催化剂Ru-Al2O3的催化作用下进行加氢处理。储氢体系中采用的加氢添加剂为环己烷(实施例29、30、31)、正己烷(实施例32、33)的用量、不同处理时间后不同氢化程度的产物的含量如下：
Figure PCTCN2015099863-appb-000005
实施例34
该实施例中分别在N-正丙基咔唑—N-乙基咔唑(质量比为6:4，共计20g)二元体系中添加了20ml不同的加氢添加剂，在150℃、8MPa及Ru-Al2O3的催化作用下进行加氢处理。不同添加剂下储氢体系的储氢量含量随时间的变化如图1所示。
实施例35
该实施例中分别在N-正丙基咔唑—N-乙基咔唑(质量比为6:4，共计20g)二元体系中添加了不同用量的加氢添加剂环己烷，在150℃、8MPa及Ru-Al2O3的催化作用下进行加氢处理。不同添加剂用量下储氢体系的储氢量含量随时间的变化如图2所示。
实施例36
该实施例中分别在N-正丙基咔唑—甲基吲哚(质量比为5:5)共计5g)二元体系中添加了30ml的加氢添加剂，在140℃、7MPa及Ru-Al2O3的催化作用下进行加氢处理。不同添加剂下储氢体系的储氢量含量随时间的变化如图3所示。
实施例37
该实施例中分别在N-正丙基咔唑—N-乙基咔唑—咔唑(质量比为3:2:5:共计20g)三元体系中添加了不同用量、不同种类的加氢添加剂，在150℃、7MPa及Ru-Al2O3的催化作用下进行加氢处理。不同添加剂种类和不同添加剂用量下储氢体系的储氢量含量随时间的变化如图4所示。
实施例38至41中对不同储氢体系的全氢化产物进行了脱氢试验
实施例38至41
对实施例19中所提供的储氢体系进行加氢处理后，对得到的全氢化产物进行脱氢，脱氢条件如下：对3g全氢化产物进行脱氢处理，脱氢温度为170℃，压力为1.01×105Pa，搅拌速度为200rpm，采用0.6g脱氢催化剂Pd-Al2O3和可选的脱氢添加剂。不同实施例中采用的脱氢添加剂的种类和用量如下：
  脱氢添加剂 脱氢添加剂用量
实施例38 -- 0
实施例39 石油醚 10ml
实施例40 十氢化萘 10ml
实施例41 均三甲苯 10ml
对实施例38至41中全氢化产物的脱氢效果进行表征，表征方法为：GC-MS检测。(型号：Agilent GC-MSD 7890/5795)对加氢/脱氢反应的各级中间产物进行在线分析。
仪器使用时采用的相关参数如下表所示：
Figure PCTCN2015099863-appb-000006
Figure PCTCN2015099863-appb-000007
检测时柱箱升温程序设置：
Figure PCTCN2015099863-appb-000008
Figure PCTCN2015099863-appb-000009
本发明中“脱氢量”的含义是相对于原储氢体系的总质量的重量百分比。
上述实施例38至41中不同添加剂种类和不同添加剂用量下全氢化储氢体系的脱氢量随时间的变化如图5所示。
从以上的数据中，可以看出，本发明上述的实施例实现了如下技术效果：
由本发明实施例1至16的实验数据可知，本发明所提供的储氢体系具有较低的熔点，在室温附近仍然能够保持液态。由上述实施例17至41的数据可知，采用本发明所提供的液态储氢体系进行加氢脱氢试验，其具有较高的加氢脱氢速率和可逆加氢/脱氢性能。此外，加氢和脱氢操作均较为简单，这有利于进一步降低储氢成本。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (11)

  1. 一种液态储氢体系，其特征在于，所述液态储氢体系包括至少两种不同的储氢组分，所述储氢组分为不饱和芳香烃或杂环不饱和化合物，且至少一种所述储氢组分为熔点低于80℃的低熔点化合物。
  2. 根据权利要求1所述的液态储氢体系，其特征在于，所述储氢组分选自所述杂环不饱和化合物，所述杂环不饱和化合物中的杂原子为N、S、O及P中的一种或多种。
  3. 根据权利要求2所述的液态储氢体系，其特征在于，所述杂环不饱和化合物中杂环和芳环的总数为1～20，所述杂原子的总数为1～20。
  4. 根据权利要求1至3中任一项所述的液态储氢体系，其特征在于，相对于所述液态储氢体系的总质量而言，所述低熔点化合物的质量分数为5～95％。
  5. 根据权利要求1至3中任一项所述的液态储氢体系，其特征在于，所述液态储氢体系还包括加氢添加剂，所述加氢添加剂为极性溶剂和/或非极性溶剂。
  6. 根据权利要求5所述的液态储氢体系，其特征在于，相对于每克所述储氢组分而言，所述加氢添加剂的加入量为0.1～10ml。
  7. 根据权利要求1所述的液态储氢体系，其特征在于，不同的所述储氢组分分别选自苯、甲苯、乙苯、邻二甲苯、对二甲苯、苯乙烯、苯乙炔、蒽、萘、芴、苯胺、咔唑、N-甲基咔唑、N-乙基咔唑、N-正丙基咔唑、N-异丙基咔唑、N-正丁基咔唑、吲哚、N-甲基吲哚、N-乙基吲哚、N-丙基吲哚、喹啉、异喹啉、吡啶、吡咯、呋喃、苯并呋喃、噻吩、嘧啶及咪唑所组成的组。
  8. 根据权利要求5所述的液态储氢体系，其特征在于，所述极性溶剂选自乙醇、甲醇、乙醚、甲醚、乙腈、乙酸乙酯、甲酰胺、异丙醇、正丁醇、二氧六环、正丁醚、异丙醚、二氯甲烷、氯仿及二氯乙烷中的一种或多种。
  9. 根据权利要求5所述的液态储氢体系，其特征在于，所述非极性溶剂选自正己烷、正戊烷、环己烷、均三甲苯、二硫化碳、石油醚及四氯化碳中的一种或多种。
  10. 根据权利要求1至9中任一项所述的液态储氢体系，其特征在于，所述储氢体系还包括脱氢添加剂，所述脱氢添加剂选自十氢化萘、均三甲苯、石油醚及苯醚中的一种或多种。
  11. 根据权利要求10所述的液态储氢体系，其特征在于，相对于每克所述储氢组分而言，所述脱氢添加剂的加入量为0.1～10ml。
PCT/CN2015/099863 2015-01-06 2015-12-30 液态储氢体系 Ceased WO2016110215A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2017554630A JP6692374B2 (ja) 2015-01-06 2015-12-30 液体状態水素の貯蔵組成物
EP15876715.2A EP3243795B1 (en) 2015-01-06 2015-12-30 Liquid hydrogen storage system
US15/541,801 US20180065849A1 (en) 2015-01-06 2015-12-30 Liquid hydrogen storage system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510005811.5A CN104555914B (zh) 2015-01-06 2015-01-06 液态储氢体系
CN201510005811.5 2015-01-06

Publications (1)

Publication Number Publication Date
WO2016110215A1 true WO2016110215A1 (zh) 2016-07-14

Family

ID=53073127

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/099863 Ceased WO2016110215A1 (zh) 2015-01-06 2015-12-30 液态储氢体系

Country Status (5)

Country Link
US (1) US20180065849A1 (zh)
EP (1) EP3243795B1 (zh)
JP (1) JP6692374B2 (zh)
CN (1) CN104555914B (zh)
WO (1) WO2016110215A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190059462A (ko) * 2017-11-23 2019-05-31 서울여자대학교 산학협력단 액상의 수소 저장 물질
CN114180516A (zh) * 2021-11-24 2022-03-15 株洲铂陆新能源科技有限公司 一种储氢材料及其制备方法
CN116332124A (zh) * 2021-12-22 2023-06-27 中国石油天然气股份有限公司 基于石油组分的液态有机储氢材料及其制备和应用

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104555914B (zh) * 2015-01-06 2017-06-13 江苏氢阳能源有限公司 液态储氢体系
CN106882765A (zh) * 2015-12-14 2017-06-23 江苏氢阳能源有限公司 液态氢源材料脱氢自加热系统及进行脱氢的方法
CN106299421B (zh) * 2016-08-27 2019-03-08 温州集智科技有限公司 一种生物质能和氢能联合发电装置
CN106252686A (zh) * 2016-08-27 2016-12-21 温州集智科技有限公司 一种可制氢储氢的氢能发电系统
CN106208910A (zh) * 2016-08-27 2016-12-07 温州集智科技有限公司 一种基于海洋能、太阳能和氢能的互补发电系统
CN106185805B (zh) * 2016-08-27 2018-04-20 温州集智科技有限公司 一种太阳能生物质能氢能联合发电装置
CN106252691A (zh) * 2016-08-27 2016-12-21 温州集智科技有限公司 一种液态有机物作为储氢材料的储氢发电系统
KR101862012B1 (ko) * 2016-09-09 2018-05-30 한국화학연구원 피리딘계 수소저장 물질을 활용한 수소 저장 및 방출 시스템
CN106926724A (zh) * 2017-03-20 2017-07-07 浙江农业商贸职业学院 基于可再生能源的电动汽车充电站及电动汽车充电方法
CN109704275B (zh) * 2017-10-26 2021-08-03 中国石油化工股份有限公司 有机液体储氢体系及储氢方法
CN109704274B (zh) * 2017-10-26 2021-08-03 中国石油化工股份有限公司 有机液体储氢的原料体系
CN109353987A (zh) * 2018-11-23 2019-02-19 汽解放汽车有限公司 一种液态储氢材料及其制备方法
CN110078021B (zh) * 2019-04-29 2021-03-05 株洲铂陆新能源科技有限公司 一种液态有机储氢材料及制备方法
CN110504043A (zh) * 2019-08-16 2019-11-26 宁夏中色新材料有限公司 一种环保型氧化锌压敏电阻用电极银浆及其制备方法
CN112194098A (zh) * 2020-09-11 2021-01-08 武汉长海电力推进和化学电源有限公司 一种储氢有机液体载体及其制备方法
CN113184804A (zh) * 2021-04-02 2021-07-30 上海簇睿低碳能源技术有限公司 一种液态有机材料及其制备方法和应用
KR102579532B1 (ko) * 2021-08-23 2023-09-19 에이치앤파워 주식회사 액상유기수소운반체 기반 수소화 반응기 운전방법
CN116768147A (zh) * 2022-03-07 2023-09-19 中国石油化工股份有限公司 有机氢载体脱氢的方法
CN114735643B (zh) * 2022-05-07 2023-10-27 瀚锐氢能科技集团有限公司 一种有机液态储氢材料及其性能调控方法和应用
CN118561233A (zh) * 2023-02-28 2024-08-30 武汉氢阳能源有限公司 一种液态储氢组合物及其制备方法
CN117105169B (zh) * 2023-05-11 2026-04-03 中国地质大学（武汉） 一种低熔点混合液态储氢材料的制备方法及其应用
CN117164070B (zh) * 2023-11-03 2024-02-23 浙江百能科技有限公司 芳环含盐废水处置耦合储氢的装置、系统与方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102800877A (zh) * 2011-05-27 2012-11-28 中国地质大学（武汉） 一种基于液态储氢材料的并列式直接燃料电池储能供能系统
EP2648314A1 (en) * 2010-12-03 2013-10-09 Hitachi, Ltd. Natural energy storage system
CN104555914A (zh) * 2015-01-06 2015-04-29 江苏氢阳能源有限公司 液态储氢体系

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6284088A (ja) * 1985-10-09 1987-04-17 Mitsubishi Chem Ind Ltd コタルニンの製造方法
JP2003095603A (ja) * 2001-09-26 2003-04-03 Sekisui Chem Co Ltd 水素貯蔵・供給システム
JP4107566B2 (ja) * 2002-04-12 2008-06-25 勝 市川 水素分離精製装置
JP2004083385A (ja) * 2002-06-04 2004-03-18 Sekisui Chem Co Ltd 水素供給媒体およびそれを利用した水素貯蔵・供給システム
JP2004026759A (ja) * 2002-06-27 2004-01-29 Sekisui Chem Co Ltd 水素供給体の製造方法
EP2960204B1 (en) * 2003-05-06 2018-06-13 Air Products And Chemicals, Inc. Hydrogen storage by reversible hydrogenation of pi-conjugated substrates
EP2470503B1 (en) * 2009-08-24 2014-03-12 Keki Hormusji Gharda Method for synthesis of n-alkyl carbazole and derivatives thereof
CN102442644B (zh) * 2010-10-15 2013-07-31 上海工程技术大学 一种有机物载体储氢系统及其制备方法
EP2717372A4 (en) * 2011-05-27 2014-07-09 Univ China Geosciences Wuhan HYDROGEN STORAGE DIRECT FUEL CELL FROM LIQUID ORGANIC MATERIAL AND ENERGY STORAGE AND ENERGY SUPPLY SYSTEM THEREWITH

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2648314A1 (en) * 2010-12-03 2013-10-09 Hitachi, Ltd. Natural energy storage system
CN102800877A (zh) * 2011-05-27 2012-11-28 中国地质大学（武汉） 一种基于液态储氢材料的并列式直接燃料电池储能供能系统
CN104555914A (zh) * 2015-01-06 2015-04-29 江苏氢阳能源有限公司 液态储氢体系

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANG, ZHAO ET AL.: "Current situation and prospect for hydrogen storage technology with new organic liquid", CHEMICAL INDUSTRY AND ENGINEERING PROGRESS, vol. 31, 31 December 2012 (2012-12-31), pages 315 - 322, XP029066299 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190059462A (ko) * 2017-11-23 2019-05-31 서울여자대학교 산학협력단 액상의 수소 저장 물질
KR101987553B1 (ko) 2017-11-23 2019-06-10 서울여자대학교 산학협력단 액상의 수소 저장 물질
US10934164B2 (en) 2017-11-23 2021-03-02 Korea University Research And Business Foundation Liquid hydrogen storage material
CN114180516A (zh) * 2021-11-24 2022-03-15 株洲铂陆新能源科技有限公司 一种储氢材料及其制备方法
CN116332124A (zh) * 2021-12-22 2023-06-27 中国石油天然气股份有限公司 基于石油组分的液态有机储氢材料及其制备和应用

Also Published As

Publication number Publication date
CN104555914A (zh) 2015-04-29
EP3243795B1 (en) 2020-11-11
EP3243795A4 (en) 2018-02-14
CN104555914B (zh) 2017-06-13
EP3243795A1 (en) 2017-11-15
JP2018504364A (ja) 2018-02-15
JP6692374B2 (ja) 2020-05-13
US20180065849A1 (en) 2018-03-08

Similar Documents

Publication Publication Date Title
JP6692374B2 (ja) 液体状態水素の貯蔵組成物
Kan et al. Production of gasoline and diesel from coal tar via its catalytic hydrogenation in serial fixed beds
CN105131299B (zh) 一种长链烷基改性苯基含氢硅油的制备方法
CN102430409B (zh) 一种催化愈创木酚加氢脱氧反应的催化剂及制备方法
CN104059697B (zh) 具有高热沉的碳氢燃料组合物
CN102887809A (zh) 以负载型磷化镍催化剂正构烷烃加氢异构化的方法
CN102517071B (zh) 一种洗油和煤直接液化油混合加工方法
CN102992931B (zh) 一种由低碳数含氧化合物混合原料合成轻质芳烃及液化石油气的方法
CN103285876A (zh) 乙烯基乙炔加氢催化剂及其制备方法和用途
CN104164225B (zh) 一种降粘组合物和稠油降粘的方法
CN103980938A (zh) 一种含氯塑料油生产清洁燃料的方法
CN101370914A (zh) 一种褐煤直接液化循环溶剂的加氢方法
CN103396818A (zh) 一种生物沥青及其制备方法
CN104178212B (zh) 一种煤焦油加氢提质方法
CN106807439A (zh) 一种钴基催化剂及其制备方法
WO2015165402A1 (zh) 一种卤化镁溶液及其制备方法和应用
CN106975502A (zh) 稀土改性的Ni3P催化剂及其应用
CN109999921A (zh) 一种用于费托合成的改性Fe基催化剂及其制备方法与应用
CN105597771A (zh) 一种氢解用催化剂以及2,5-二甲基呋喃的制备方法
CN104069863B (zh) 浆态床合成气制取戊烷的铜锌铝催化剂及制备和应用方法
CN110157459A (zh) 中间相沥青小球的制备方法
CN117414840A (zh) 采用介质阻挡放电等离子体制备担载型Ni-MoOx催化剂的方法及其应用
CN103611529A (zh) 一种正戊烷异构化催化剂及其制备方法
CN104789261B (zh) 一种脱酚酚油制茚满和清洁燃料的方法
CN103665348B (zh) 噻吩共聚物及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15876715

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017554630

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2015876715

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15541801

Country of ref document: US