Organic liquid component of hydrogen carrier and preparation method thereof

Abstract

The invention discloses an organic liquid component of a hydrogen carrier and a preparation method of the organic liquid component. The organic liquid component comprises 72-88% by mass of a high-melting-point hydrogen storage component and 28-12% by mass of a low-melting-point solvent component, the high-melting-point hydrogen storage component is naphthalene or indole or a mixture of the naphthalene and the indole; and the low-melting-point solvent component is at least one of trans-decahydronaphthalene, methyl cyclohexane and perhydrogenated indole. The hydrogen storage organic liquid carrier has the advantage that the melting point of the hydrogen storage carrier can be reduced to-32 DEG C or below. The melting point is lower, and the material can be stored and transported at lower temperature, so that the energy consumption and the cost are reduced. Low-temperature storage: because the melting point of the low-melting-point organic liquid is relatively low, the low-melting-point organic liquid can be stored and transported at relatively low temperature, so that the energy consumption and the cost are reduced. The organic liquid has high hydrogen storage capacity, more hydrogen can be stored under the same volume, and the hydrogen storage efficiency is improved. And the organic liquid has good cycle life and can be recycled for multiple times, so that the waste and the cost are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogen storage organic liquid, in particular to an organic liquid component of a hydrogen carrier and a preparation method thereof. Background Art

[0002] As a clean, environmentally friendly, efficient and sustainable new energy, hydrogen energy has the characteristics of abundant sources, convenient and efficient conversion with electricity, diverse storage and transportation methods, and good environmental compatibility. It has a wide range of applications in the fields of power energy, transportation, chemical industry, electronics industry, metallurgy, light industry, etc. It is regarded as the clean energy with the most development potential in the 21st century. Major countries in the world such as the United States, Germany, France, Japan and China are vigorously developing hydrogen energy development and utilization technologies and actively building hydrogen energy infrastructure.

[0003] At present, global hydrogen storage and transportation are mainly carried out in the following four ways: high-pressure gaseous hydrogen storage, low-temperature liquid hydrogen storage, solid hydrogen storage and organic liquid hydrogen storage. Among them, organic liquid uses liquid condensed heterocyclic organic molecular materials containing unsaturated carbon bonds as hydrogen storage carriers, which undergo reversible chemical reactions with hydrogen to achieve a cyclic hydrogenation-dehydrogenation process. It has high quality and high volume hydrogen storage density, fast dehydrogenation response speed and high hydrogen purity. The dehydrogenation products are hydrogen and liquid, which are easy to separate and store. Existing pipeline equipment can be used for long-term storage and long-distance transportation, which meets the development needs of hydrogen source technology for future normal underwater submersibles.

[0004] At present, Japan has developed hydrogen storage technology based on traditional organic liquid carriers such as toluene, and has built an international hydrogen storage and transportation chain between Brunei and Japan, but the dehydrogenation temperature is relatively high, and other impurity gases are easily produced during the dehydrogenation process. Germany has developed hydrogen storage technology based on dibenzyltoluene organic liquid carriers, but its dehydrogenation rate is relatively low, and it is difficult to meet the requirements of mobile hydrogen supply. The United States has developed a new type of nitrogen heterocyclic hydrogen storage organic liquid, a typical representative of which is N-ethylcarbazole, which has the advantages of low dehydrogenation temperature and high dehydrogenation rate, and is suitable for mobile hydrogen supply occasions. However, the melting point of N-ethylcarbazole is 68°C. It is solid at room temperature and easily blocks the pipeline of the dehydrogenation device at low temperatures, which cannot meet the needs of low-temperature use. Summary of the invention

[0005] 1. Technical issues to be resolved

[0006] In view of the deficiencies in the prior art, the present invention provides an organic liquid component of a hydrogen carrier and a preparation method thereof, which has the advantages of low hydrogen storage melting point, low-temperature storage, high hydrogen storage capacity, and good cycle life, thereby solving the problems existing in the above-mentioned prior art.

[0007] (II) Technical solution

[0008] To achieve the above object, the present invention provides the following technical solution: an organic liquid component of a hydrogen carrier, characterized in that it comprises 72% to 88% by mass of a high melting point hydrogen storage component and 28% to 12% by mass of a low melting point solvent component;

[0009] The high melting point hydrogen storage component is naphthalene or indole or a mixture of the two; the low melting point solvent component is at least one of trans-decalin, methylcyclohexane and perhydroindole.

[0010] Preferably, the organic liquid of the hydrogen carrier is composed of 88% indole and 12% trans-decalin and has a melting point of -1°C.

[0011] Preferably, the organic liquid of the hydrogen carrier is composed of 80% naphthalene and 20% methylcyclohexane, and has a melting point of -12°C.

[0012] Preferably, the organic liquid of the hydrogen carrier is composed of 60% naphthalene, 20% indole and 20% perhydroindole, and has a melting point of -15°C.

[0013] Preferably, the organic liquid of the hydrogen carrier is composed of 50% naphthalene, 32% indole, 10% perhydroindole, and 8% methylcyclohexane, and has a melting point of -19°C.

[0014] Preferably, the organic liquid of the hydrogen carrier is composed of 36% naphthalene, 36% indole, 10% perhydroindole, 10% methylcyclohexane and 8% trans-decalin, and has a melting point of -32°C.

[0015] The hydrogen storage organic liquid carrier of the present invention can reduce the melting point of the hydrogen storage carrier to below -32°C. Due to the low melting point, it can be stored and transported at a lower temperature, thereby reducing energy consumption and costs. Low temperature storage: Since the low melting point organic liquid has a low melting point, it can be stored and transported at a lower temperature, thereby reducing energy consumption and costs. High hydrogen storage capacity: The organic liquid has a high hydrogen storage capacity and can store more hydrogen in the same volume, thereby improving hydrogen storage efficiency. Good cycle life: The organic liquid has a good cycle life and can be recycled many times, reducing waste and costs.

[0016] A method for preparing an organic liquid as a hydrogen carrier comprises the following steps:

[0017] 1) heating the mixture of naphthalene, indole and perhydroindole to a temperature of 130-135° C. so that naphthalene, indole and perhydroindole can be fully dissolved;

[0018] 2) Add a catalyst, such as palladium or platinum, to the mixed solution under stirring to catalyze the hydrogenation reaction, introduce hydrogen into the reactor, and maintain the pressure at 8.0-9.0 MPa. During the hydrogenation reaction, the hydrogen reacts with the naphthalene, indole, and perhydroindole in the mixed solution to generate a hydrogen carrier organic liquid, which lasts for 40-50 minutes;

[0019] 3) After the hydrogenation reaction is completed, the hydrogen carrier organic liquid is cooled to room temperature and filtered to remove the catalyst and other impurities therein.

[0020] 4) By distillation, the water and other volatile components in the hydrogen carrier organic liquid are separated to obtain a high-purity hydrogen carrier organic liquid.

[0021] A method for preparing a hydrogen carrier organic liquid comprises the following steps:

[0022] 1) Mixing naphthalene, indole, trans-decalin, methylcyclohexane and perhydroindole;

[0023] 2) Heat the mixed solution to 120-130° C. to allow naphthalene, indole, trans-decalin, methylcyclohexane, and perhydroindole to fully dissolve. This step can promote the mixing and dissolution of the raw materials and prepare for subsequent reactions;

[0024] 3) Adding a catalyst, such as palladium or platinum, to the mixed solution under stirring to catalyze the hydrogenation reaction, introducing hydrogen into the reactor, maintaining the pressure at 8.5-9.0 MPa, promoting the reaction of hydrogen with naphthalene, indole, trans-decalin, methylcyclohexane, and perhydroindole in the mixed solution to generate a low melting point hydrogen carrier organic liquid;

[0025] 4) During the hydrogenation reaction, the reaction temperature needs to be controlled at 120-130°C and the pressure needs to be controlled at 8.5-9.0MPa to maintain appropriate reaction conditions. At the same time, the reaction progress needs to be monitored to ensure that the reaction is complete;

[0026] 5) After the hydrogenation reaction is completed, the low-melting-point hydrogen carrier organic liquid is cooled to room temperature and filtered to remove the catalyst and other impurities therein. This step can ensure the purity and quality of the low-melting-point hydrogen carrier organic liquid;

[0027] 6) Separate the water and other volatile components in the low-melting-point hydrogen carrier organic liquid by distillation or other methods to obtain a high-purity low-melting-point hydrogen carrier organic liquid. This step can further purify the low-melting-point hydrogen carrier organic liquid to improve its purity and quality.

[0028] The present invention mixes high melting point substances such as naphthalene and indole, then adds low melting point substances such as trans-decalin, perhydroindole and methylcyclohexane, adjusts the components and their ratios, reduces the melting points of the naphthalene and indole hydrogen carrier organic liquid carriers, and uses the above-mentioned organic liquid preparation method to obtain a high-purity low melting point hydrogen carrier organic liquid, thereby forming a hydrogen carrier organic liquid carrier suitable for low temperature environments.

[0029] Compared with the prior art, the hydrogen carrier organic liquid carrier of the present invention can reduce the melting point of the hydrogen storage carrier to below -32°C.

[0030] (III) Beneficial effects

[0031] Compared with the prior art, the present invention provides an organic liquid component of a hydrogen carrier and a preparation method thereof, which has the following beneficial effects:

[0032] The core of the hydrogen carrier organic liquid component and the preparation method thereof is the carrier component of the hydrogen carrier organic liquid and the detailed preparation method of the organic liquid. By mixing high melting point substances such as naphthalene and indole, and then adding low melting point substances such as trans-decalin, perhydroindole, and methylcyclohexane, the melting points of the naphthalene and indole hydrogen carrier organic liquid carriers are reduced by adjusting the components and their proportions, and the organic liquid preparation method is used to obtain a relatively high purity low melting point hydrogen carrier organic liquid, thereby forming a hydrogen carrier organic liquid carrier suitable for low temperature environments.

[0033] Compared with the prior art, the hydrogen carrier organic liquid carrier of the present invention can reduce the melting point of the hydrogen storage carrier to below -32°C. The low melting point allows storage and transportation at lower temperatures, thereby reducing energy consumption and costs. Low temperature storage: Since the low melting point organic liquid has a low melting point, it can be stored and transported at lower temperatures, thereby reducing energy consumption and costs. High hydrogen storage capacity: This organic liquid has a high hydrogen storage capacity and can store more hydrogen in the same volume, thereby improving hydrogen storage efficiency. Good cycle life: This organic liquid has a good cycle life and can be recycled many times, reducing waste and costs. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a flow chart of a first method for preparing an organic liquid hydrogen carrier proposed by the present invention;

[0035] Figure 2 This is a flow chart of a second method for preparing an organic liquid hydrogen carrier proposed by the present invention;

[0036] Figure 3 This is a melting point diagram of various formulas of organic liquids for a hydrogen carrier proposed in the present invention. DETAILED DESCRIPTION

[0037] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] See also Figure 1-3 , an organic liquid component of a hydrogen carrier, characterized in that it includes 72% to 88% by mass of a high melting point hydrogen storage component and 28% to 12% by mass of a low melting point solvent component;

[0039] The high melting point hydrogen storage component is naphthalene or indole or a mixture of the two; the low melting point solvent component is at least one of trans-decalin, methylcyclohexane and perhydroindole.

[0040] Example 1: An organic liquid of hydrogen carrier, composed of 88% indole and 12% trans-decalin, with a melting point of -1°C.

[0041] Example 2: An organic liquid hydrogen carrier is composed of 80% naphthalene and 20% methylcyclohexane, and has a melting point of -12°C.

[0042] Example 3: An organic liquid of hydrogen carrier, consisting of 60% naphthalene, 20% indole and 20% perhydroindole, has a melting point of -15°C.

[0043] Example 4: An organic liquid of hydrogen carrier, consisting of 50% naphthalene, 32% indole, 10% perhydroindole, and 8% methylcyclohexane, has a melting point of -19°C.

[0044] Example 5: An organic liquid of hydrogen carrier, consisting of 36% naphthalene, 36% indole, 10% perhydroindole, 10% methylcyclohexane and 8% trans-decalin, has a melting point of -32°C.

[0045] Embodiment 6: A method for preparing a hydrogen carrier organic liquid, comprising the following steps:

[0046] 1) heating the mixture of naphthalene, indole and perhydroindole to a temperature of 130-135° C. so that naphthalene, indole and perhydroindole can be fully dissolved;

[0047] 2) Add a catalyst, such as palladium or platinum, to the mixed solution under stirring to catalyze the hydrogenation reaction, introduce hydrogen into the reactor, and maintain the pressure at 8.0-9.0 MPa. During the hydrogenation reaction, the hydrogen reacts with the naphthalene, indole, and perhydroindole in the mixed solution to generate a hydrogen carrier organic liquid, which lasts for 40-50 minutes;

[0048] 3) After the hydrogenation reaction is completed, the hydrogen carrier organic liquid is cooled to room temperature and filtered to remove the catalyst and other impurities therein.

[0049] 4) By distillation, the water and other volatile components in the hydrogen carrier organic liquid are separated to obtain a high-purity hydrogen carrier organic liquid.

[0050] Embodiment 7: A method for preparing a hydrogen carrier organic liquid, comprising the following steps:

[0051] 1) Mixing naphthalene, indole, trans-decalin, methylcyclohexane and perhydroindole;

[0052] 2) Heat the mixed solution to 120-130° C. to allow naphthalene, indole, trans-decalin, methylcyclohexane, and perhydroindole to fully dissolve. This step can promote the mixing and dissolution of the raw materials and prepare for subsequent reactions;

[0053] 3) Adding a catalyst, such as palladium or platinum, to the mixed solution under stirring to catalyze the hydrogenation reaction, introducing hydrogen into the reactor, maintaining the pressure at 8.5-9.0 MPa, promoting the reaction of hydrogen with naphthalene, indole, trans-decalin, methylcyclohexane, and perhydroindole in the mixed solution to generate a low melting point hydrogen carrier organic liquid;

[0054] 4) During the hydrogenation reaction, the reaction temperature needs to be controlled at 120-130°C and the pressure needs to be controlled at 8.5-9.0MPa to maintain appropriate reaction conditions. At the same time, the reaction progress needs to be monitored to ensure that the reaction is complete;

[0055] 5) After the hydrogenation reaction is completed, the low-melting-point hydrogen carrier organic liquid is cooled to room temperature and filtered to remove the catalyst and other impurities therein. This step can ensure the purity and quality of the low-melting-point hydrogen carrier organic liquid;

[0056] 6) Separate the water and other volatile components in the low-melting-point hydrogen carrier organic liquid by distillation or other methods to obtain a high-purity low-melting-point hydrogen carrier organic liquid. This step can further purify the low-melting-point hydrogen carrier organic liquid to improve its purity and quality.

[0057] In summary, the organic liquid component of the hydrogen carrier and the preparation method thereof, the organic liquid component of the hydrogen carrier and the preparation method thereof, the core of which is the carrier component of the hydrogen carrier organic liquid and the detailed preparation method of the organic liquid, by mixing naphthalene and indole high melting point substances, and then adding trans-decalin, perhydroindole, methylcyclohexane and other low melting point substances, by adjusting the components and their ratios, reducing the melting point of the naphthalene and indole hydrogen carrier organic liquid carrier, and using the above-mentioned organic liquid preparation method, a high purity low melting point hydrogen carrier organic liquid can be obtained. A hydrogen carrier organic liquid carrier suitable for low temperature environment is formed.

[0058] Compared with the prior art, the hydrogen carrier organic liquid carrier of the present invention can reduce the melting point of the hydrogen storage carrier to below -32°C. The low melting point allows storage and transportation at lower temperatures, thereby reducing energy consumption and costs. Low temperature storage: Since the low melting point organic liquid has a low melting point, it can be stored and transported at lower temperatures, thereby reducing energy consumption and costs. High hydrogen storage capacity: This organic liquid has a high hydrogen storage capacity and can store more hydrogen in the same volume, thereby improving hydrogen storage efficiency. Good cycle life: This organic liquid has a good cycle life and can be recycled many times, reducing waste and costs.

[0059] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the statement "comprise one" do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0060] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An organic liquid component of a hydrogen carrier, characterized in that: It includes 72% to 88% by mass of a high melting point hydrogen storage component and 28% to 12% by mass of a low melting point solvent component; The high melting point hydrogen storage component is naphthalene or indole or a mixture of the two; the low melting point solvent component is at least one of trans-decalin, methylcyclohexane and perhydroindole.

2. The organic liquid component of a hydrogen carrier according to claim 1, characterized in that: It is composed of 88% indole and 12% trans-decalin, with a melting point of -1°C.

3. The organic liquid component of a hydrogen carrier according to claim 1, characterized in that: It is composed of 80% naphthalene and 20% methylcyclohexane, with a melting point of -12°C.

4. The organic liquid component of a hydrogen carrier according to claim 1, characterized in that: It is composed of 60% naphthalene, 20% indole and 20% perhydroindole, with a melting point of -15°C.

5. The organic liquid component of a hydrogen carrier according to claim 1, characterized in that: It is composed of 50% naphthalene, 32% indole, 10% perhydroindole and 8% methylcyclohexane, with a melting point of -19°C.

6. The organic liquid component of a hydrogen carrier according to claim 1, characterized in that: It is composed of 36% naphthalene, 36% indole, 10% perhydroindole, 10% methylcyclohexane and 8% trans-decalin, with a melting point of -32°C.

7. A method for preparing the organic liquid component of the hydrogen carrier as claimed in claim 1, characterized in that: The following steps are involved: 1) heating the mixture of naphthalene, indole and perhydroindole to a temperature of 130-135° C. so that naphthalene, indole and perhydroindole can be fully dissolved; 2) Under stirring conditions, a catalyst such as palladium or platinum is added to the mixed solution to catalyze a hydrogenation reaction, and hydrogen is introduced into the reactor to maintain a pressure of 8.0-9.0 MPa. During the hydrogenation reaction, the hydrogen reacts with naphthalene, indole, and perhydroindole in the mixed solution to generate a hydrogen storage organic liquid, which lasts for 40-50 minutes; 3) After the hydrogenation reaction is completed, the hydrogen storage organic liquid is cooled to room temperature and filtered to remove the catalyst and other impurities therein; 4) By distillation, the water and other volatile components in the hydrogen storage organic liquid are separated to obtain a high-purity hydrogen storage organic liquid.

8. A method for preparing the organic liquid component of the hydrogen carrier as claimed in claim 1, characterized in that: The following steps are involved: 1) Mixing naphthalene, indole, trans-decalin, methylcyclohexane and perhydroindole; 2) Heat the mixed solution to 120-130° C. to allow naphthalene, indole, trans-decalin, methylcyclohexane, and perhydroindole to fully dissolve. This step can promote the mixing and dissolution of the raw materials and prepare for subsequent reactions; 3) Under stirring conditions, adding a catalyst, such as palladium or platinum, to the mixed solution to catalyze a hydrogenation reaction, introducing hydrogen into the reactor, maintaining the pressure at 8.5-9.0 MPa, promoting the reaction of hydrogen with naphthalene, indole, trans-decalin, methylcyclohexane, and perhydroindole in the mixed solution to generate a low melting point hydrogen storage organic liquid; 4) During the hydrogenation reaction, the reaction temperature needs to be controlled at 120-130°C and the pressure needs to be controlled at 8.5-9.0MPa to maintain appropriate reaction conditions. At the same time, the reaction progress needs to be monitored to ensure that the reaction is complete; 5) After the hydrogenation reaction is completed, the low melting point hydrogen storage organic liquid is cooled to room temperature and filtered to remove the catalyst and other impurities therein. This step can ensure the purity and quality of the low melting point hydrogen storage organic liquid; 6) Separate the water and other volatile components in the low-melting-point hydrogen storage organic liquid by distillation or other methods to obtain a high-purity low-melting-point hydrogen storage organic liquid. This step can further purify the low-melting-point hydrogen storage organic liquid to improve its purity and quality.

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