Solid hydrogen storage and chemical hydrogen utilization combined system and operation method thereof

Abstract

The invention relates to the technical field of hydrogen storage, and discloses a solid hydrogen storage and chemical hydrogen utilization combined system and an operation method thereof. The system comprises a solid hydrogen storage unit, a hydrodesulfurization unit and a hydrogen purification unit, the hydrodesulfurization unit is communicated with the solid hydrogen storage unit and is used for carrying out hydrodesulfurization reaction on hydrogen from the solid hydrogen storage unit and a hydrocarbon oil raw material to obtain hydrogen / hydrocarbon mixed waste gas; the hydrogen purification unit is communicated with the hydrodesulfurization unit and is used for recovering the hydrogen / hydrocarbon mixed waste gas to obtain purified hydrogen and hydrocarbon products; the hydrogen purification unit is communicated with the hydrodesulfurization unit and is used for providing at least part of purified hydrogen for the hydrodesulfurization unit; wherein the hydrodesulfurization unit is used for providing heat for hydrogen desorption of the solid hydrogen storage unit and the hydrogen purification unit. According to the system, waste heat of the hydrodesulfurization device is fully utilized, the energy utilization efficiency of the system is effectively improved, the economical efficiency of solid hydrogen storage is improved, and meanwhile recycling of hydrogen / hydrocarbon mixed waste gas is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of hydrogen storage technology, in particular to a solid-state hydrogen storage and hydrogen combined system for chemical industry and a running method thereof. BACKGROUND

[0002] As a secondary energy, hydrogen energy has the characteristics of wide sources, clean and carbon-free, flexible and efficient, and wide application scenarios, and can be widely used in energy, transportation, industry, construction and other fields. It is an ideal interconnection medium to promote the clean and efficient use of traditional fossil energy and support the large-scale development of renewable energy, and will gradually become an important direction of global energy technology development.

[0003] Hydrogen can be stored and transported, but due to its low density and low volume energy density, it has become one of the key factors restricting the development of hydrogen energy. Improving hydrogen storage and transportation efficiency and reducing hydrogen storage and transportation cost are the development priorities of hydrogen storage and transportation technology. Common hydrogen storage methods include high-pressure gaseous hydrogen storage, liquid hydrogen, organic liquid hydrogen storage and solid-state hydrogen storage. For high-pressure gaseous hydrogen storage, the volume hydrogen storage density is low, the hydrogen storage pressure is high (35-70 MPa), and there is a high safety risk; liquid hydrogen needs to be stored below 20K, the energy consumption of the liquefaction process is high, and there is evaporation loss during use, which is a problem that needs to be solved urgently; organic liquid has low hydrogen purity and poor cycle performance, and further research is still needed. Solid-state hydrogen storage provides a feasible hydrogen storage solution, which has high volume hydrogen storage density, low working pressure and good reversibility, and has wide application prospects in transportation, microgrid, hydrogen compression, heat storage and other fields.

[0004] Under normal circumstances, solid-state hydrogen storage materials need to absorb a large amount of heat during hydrogen release to maintain sufficient hydrogen release rate and hydrogen release capacity, resulting in the need for additional energy supply, which increases the energy consumption and cost of the hydrogen release process, and reduces the economic efficiency of solid-state hydrogen storage. At the same time, waste heat is generated during the operation of hydrogen plants for chemical industry such as gasoline hydrodesulfurization, but the mixed waste gas of hydrogen / hydrogen-containing compounds is difficult to recover and utilize, and is usually discharged outside the system with waste heat. Therefore, how to successfully couple solid-state hydrogen storage and hydrogen plants for chemical industry is a technical problem to be solved. SUMMARY

[0005] The purpose of the present application is to overcome the problems existing in the prior art, and to provide a solid-state hydrogen storage and hydrogen combined system for chemical industry and a running method thereof. By constructing the solid-state hydrogen storage and hydrogen combined system for chemical industry, the waste heat of the hydrodesulfurization device is fully utilized, which can effectively improve the energy utilization efficiency of the system, improve the economic efficiency of solid-state hydrogen storage, and realize the recovery and utilization of hydrogen / hydrocarbon mixed waste gas.

[0006] In order to achieve the above object, the present application provides a solid-state hydrogen storage and hydrogen combined system for chemical industry in one aspect, which comprises a solid-state hydrogen storage unit, a hydrodesulfurization unit and a hydrogen purification unit.

[0007] The gas inlet of the hydrodesulfurization unit is communicated with the gas outlet of the solid-state hydrogen storage unit, and is used for carrying out hydrodesulfurization reaction of hydrogen from the solid-state hydrogen storage unit and hydrocarbon oil raw materials to obtain hydrogen / hydrocarbon mixed waste gas.

[0008] The gas inlet of the hydrogen purification unit is communicated with the first gas outlet of the hydrodesulfurization unit, and is used for recycling the hydrogen / hydrocarbon mixed waste gas to obtain purified hydrogen and hydrocarbon products; the first gas outlet of the hydrogen purification unit is communicated with the gas inlet of the hydrodesulfurization unit, and is used for providing at least part of the purified hydrogen for the hydrodesulfurization unit.

[0009] The hydrodesulfurization unit is used for providing heat for hydrogen release of the solid-state hydrogen storage unit and the hydrogen purification unit.

[0010] The second aspect of the present application provides a running method of the solid-state hydrogen storage and hydrogen combined system for chemical industry in the first aspect, which comprises:

[0011] (1) The solid-state hydrogen storage unit releases hydrogen, and the hydrogen is introduced into the hydrodesulfurization unit to carry out hydrodesulfurization reaction with hydrocarbon oil raw materials to obtain hydrogen / hydrocarbon mixed waste gas;

[0012] (2) The hydrogen / hydrocarbon mixed waste gas is sent into the hydrogen purification unit for recycling to obtain purified hydrogen and hydrocarbon products;

[0013] (3) The hydrogen purification unit releases purified hydrogen, and the purified hydrogen is recycled to step (1);

[0014] The hydrodesulfurization unit provides heat for hydrogen release process of the solid-state hydrogen storage unit and hydrogen release process of the hydrogen purification unit.

[0015] In the prior art, solid-state hydrogen storage has a wide application prospect in the fields of transportation, micro-grid, hydrogen compression, heat storage and the like due to its high volumetric hydrogen storage density, low working pressure and good reversibility. However, in general, the solid-state hydrogen storage material needs to absorb a large amount of heat during the hydrogen release process to maintain sufficient hydrogen release rate and hydrogen release capacity, which leads to the need for additional energy supply, increases the energy consumption and cost of the hydrogen release process, and reduces the economic efficiency of the solid-state hydrogen storage application. At the same time, the inventors of the present application found that waste heat is generated during the operation of a hydrogen device for gasoline hydrodesulfurization and the like, but there is a problem that the mixed waste gas of hydrogen / hydrogen-containing compounds generated is difficult to recycle. The inventors of the present application further found in the research process that by constructing the solid-state hydrogen storage and hydrogen device for chemical industry combined system described in the present application, the low-grade waste heat of the hydrodesulfurization unit is fully utilized, the energy utilization efficiency is effectively improved, and the economic efficiency of the solid-state hydrogen storage technology is improved; at the same time, the hydrogen and hydrogen-containing compounds (hydrocarbon products) can be recycled.

[0016] The system described in the present application provides a way for the solid-state hydrogen storage unit to supply hydrogen for the hydrodesulfurization unit, which has the advantages of large volumetric hydrogen storage density, high safety, small occupied area and the like compared with the gas tank hydrogen supply. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 is a schematic diagram of the solid-state hydrogen storage and hydrogen device for chemical industry combined system described in the present application;

[0018] Figure 2 is a schematic diagram of the hydrogen purification unit described in embodiment 1 of the present application.

[0019] BRIEF DESCRIPTION OF DRAWINGS

[0020] In Figures 1-2 , the present application provides a solid-state hydrogen storage and hydrogen device for chemical industry combined system.

[0021] 1, solid-state hydrogen storage unit; 2, hydrodesulfurization unit; 3, first flow controller;

[0022] 4, hydrogen purification unit; 5, second flow controller; 6, first pressure reducing valve;

[0023] 7, second pressure reducing valve; 8, buffer tank; 9, liquid storage tank;

[0024] 10, liquid mixer; 11, solid-state hydrogen storage and purification reactor; 12, heat circulation unit;

[0025] 13, pressure sensor. DETAILED DESCRIPTION

[0026] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the invention. Any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed

[0027] In the present invention, the "first" and "second" do not represent the order of precedence, nor do they represent the limitation of each material or step, but are only used to distinguish the same material or step.

[0028] In one aspect of the present invention, a hydrogen storage and hydrogen use system is provided, which comprises a hydrogen storage unit, a hydrodesulfurization unit and a hydrogen purification unit.

[0029] The gas inlet of the hydrodesulfurization unit is in communication with the gas outlet of the hydrogen storage unit, and is used for carrying out a hydrodesulfurization reaction on hydrogen from the hydrogen storage unit and a hydrocarbon oil raw material, to obtain a hydrogen / hydrocarbon mixed waste gas.

[0030] The gas inlet of the hydrogen purification unit is in communication with the first gas outlet of the hydrodesulfurization unit, and is used for recovering the hydrogen / hydrocarbon mixed waste gas, to obtain purified hydrogen and a hydrocarbon product; the first gas outlet of the hydrogen purification unit is in communication with the gas inlet of the hydrodesulfurization unit, and is used for providing at least part of the purified hydrogen to the hydrodesulfurization unit.

[0031] The hydrodesulfurization unit is used to provide heat for hydrogen release of the hydrogen storage unit and the hydrogen purification unit.

[0032] In the system of the present invention, in addition to the hydrodesulfurization unit, a carbon dioxide hydrogenation to methane unit, a catalytic cracking unit and other hydrogen units for chemical industry can also be used in combination with the hydrogen storage unit.

[0033] According to a preferred embodiment of the present invention, the hydrogen storage unit is connected to an external hydrogenation device through a first control valve, and is used to provide hydrogen to the hydrogen storage unit.

[0034] In the present invention, when the hydrogen storage unit stores hydrogen, the first control valve is opened; when the hydrogen storage unit releases hydrogen, the first control valve is closed.

[0035] The present invention has a wide range of choices for the type of hydrogen storage material filled in the hydrogen storage unit, which can be various hydrogen storage materials commonly used in the art, such as at least one selected from titanium-based hydrogen storage materials, rare earth-based hydrogen storage materials and vanadium-based hydrogen storage materials. The present invention preferably uses titanium-based hydrogen storage materials. The use of this preferred embodiment better controls the hydrogen release pressure.

[0036] The specific selection range of the above-mentioned titanium-based hydrogen storage material, rare earth-based hydrogen storage material and vanadium-based hydrogen storage material is wide, which can be the conventional selection in the field, and will not be described in detail herein.

[0037] In the present application, the hydrogen / hydrocarbon mixed waste gas refers to the mixed waste gas of hydrogen and hydrocarbon.

[0038] In the hydrogen desulfurization unit of the present application, not only the hydrogen desulfurization device is included, but also the downstream processing device, so that the hydrogen / hydrocarbon mixed waste gas can be obtained, and the specific setting mode is the conventional selection in the field, which will not be described in detail herein.

[0039] According to a preferred embodiment of the present application, the system further comprises a buffer tank arranged between the solid-state hydrogen storage unit and the hydrogen desulfurization unit, for buffering hydrogen from the solid-state hydrogen storage unit.

[0040] According to a preferred embodiment of the present application, the first inlet of the buffer tank is in communication with the gas outlet of the solid-state hydrogen storage unit.

[0041] According to a preferred embodiment of the present application, the second inlet of the buffer tank is in communication with the first gas outlet of the hydrogen purification unit. The use of this preferred embodiment is conducive to the reuse of purified hydrogen recovered by the hydrogen purification unit.

[0042] According to a preferred embodiment of the present application, the outlet of the buffer tank is in communication with the gas inlet of the hydrogen desulfurization unit.

[0043] According to a preferred embodiment of the present application, the system further comprises a first flow controller arranged between the solid-state hydrogen storage unit and the buffer tank, for maintaining stable hydrogen pressure and flow.

[0044] According to a preferred embodiment of the present application, the system further comprises a pressure sensor arranged above the buffer tank, for monitoring the pressure of the solid-state hydrogen storage unit.

[0045] According to a preferred embodiment of the present application, the system further comprises a second control valve arranged between the solid-state hydrogen storage unit and the first flow controller, for switching the hydrogen storage / release mode of the solid-state hydrogen storage unit.

[0046] In the present application, when the solid-state hydrogen storage unit stores hydrogen, the second control valve is closed; when the solid-state hydrogen storage unit releases hydrogen, the second control valve is opened.

[0047] According to a preferred embodiment of the present application, the system further comprises a first pressure reducing valve arranged between the second control valve and the first flow controller, for ensuring stable solid-state hydrogen outlet pressure to meet the demand of the hydrogen unit.

[0048] According to a preferred embodiment of the present application, the system further comprises a second flow controller arranged between the buffer tank and the hydrodesulfurization unit for maintaining the hydrogen pressure and flow stable.

[0049] According to a preferred embodiment of the present application, the system further comprises a second pressure reducing valve arranged between the buffer tank and the second flow controller for ensuring the hydrogen pressure stable to meet the pressure requirement of the chemical hydrogen unit.

[0050] According to a preferred embodiment of the present application, the hydrogen purification unit comprises a solid-state hydrogen storage purification reactor.

[0051] The solid-state hydrogen storage purification reactor of the present application has a wide range of selection for the hydrogen storage material filled therein, which can be any hydrogen storage material commonly used in the art, such as at least one selected from titanium-based hydrogen storage material, rare earth-based hydrogen storage material and vanadium-based hydrogen storage material. The present application preferably uses titanium-based hydrogen storage material. The use of this preferred embodiment can better control the hydrogen release pressure.

[0052] The titanium-based hydrogen storage material, the rare earth-based hydrogen storage material and the vanadium-based hydrogen storage material of the present application have a wide range of selection, which can be the conventional selection in the art, and will not be described in detail herein.

[0053] According to a preferred embodiment of the present application, the gas inlet of the solid-state hydrogen storage purification reactor is in communication with the first gas outlet of the hydrodesulfurization unit.

[0054] According to a preferred embodiment of the present application, the first gas outlet of the solid-state hydrogen storage purification reactor is in communication with the second inlet of the buffer tank.

[0055] According to a preferred embodiment of the present application, the second gas outlet of the solid-state hydrogen storage purification reactor is in communication with a downstream hydrocarbon product recovery unit for recovering hydrocarbon products.

[0056] In the present application, the purified hydrogen is stored in the solid-state hydrogen storage purification reactor.

[0057] The solid-state hydrogen storage purification reactor of the present application is not particularly limited in the selection of the type thereof, and any conventional selection in the art can be used as long as the function thereof can be achieved.

[0058] According to a preferred embodiment of the present application, third and fourth control valves are arranged between the solid-state hydrogen storage purification reactor and the hydrodesulfurization unit and between the solid-state hydrogen storage purification reactor and the buffer tank, respectively, for hydrogen and hydrocarbon purification and recovery.

[0059] When the purified hydrogen is reused, the third control valve is opened, and when the hydrocarbon is recovered, the third control valve is closed.

[0060] When the hydrocarbon is recovered, the fourth control valve is opened, and when the purified hydrogen is reused, the fourth control valve is closed.

[0061] The number of the solid-state hydrogen storage and purification reactors is not particularly limited in the present application, and can be one, two or more, which is determined according to the actual hydrogen / hydrocarbon mixed waste gas output.

[0062] When the solid-state hydrogen storage and purification reactors are two or more, they are generally connected in parallel. According to a preferred embodiment of the present application, the hydrogen purification unit comprises at least two solid-state hydrogen storage and purification reactors connected in parallel.

[0063] According to a preferred embodiment of the present application, each solid-state hydrogen storage and purification reactor is in communication with the buffer tank, the hydrodesulfurization unit and the downstream hydrocarbon product recovery unit.

[0064] The way of realizing the above communication is not particularly limited in the present application, and can be realized by using conventional technical means in the art. In the example of the present application, fluid pipes and valve groups (three-way valves and control valves) are provided to make all the solid-state hydrogen storage and purification reactors in communication with the buffer tank, the hydrodesulfurization unit and the downstream hydrocarbon product recovery unit.

[0065] When two solid-state hydrogen storage and purification reactors (for example, solid-state hydrogen storage and purification reactor A and solid-state hydrogen storage and purification reactor B) are provided, the following can be referred to Figure 2 According to a preferred embodiment of the present application, the solid-state hydrogen storage and purification reactor A is first made in communication with the hydrodesulfurization unit by adjusting the control valve, and the hydrogen / hydrocarbon mixed waste gas is sent into the solid-state hydrogen storage and purification reactor A; when the solid-state hydrogen storage and purification reactor A is saturated with hydrogen, the solid-state hydrogen storage and purification reactor B is made in communication with the hydrodesulfurization unit by adjusting the control valve, and the hydrogen / hydrocarbon mixed waste gas is continuously sent in to absorb hydrogen; the solid-state hydrogen storage and purification reactor A is made in communication with the downstream hydrocarbon product recovery unit by adjusting the control valve, and the hydrocarbon product is recovered; when the hydrocarbon product recovery is completed, the solid-state hydrogen storage and purification reactor A is made in communication with the buffer tank by adjusting the control valve, and the purified hydrogen is released from the solid-state hydrogen storage and purification reactor A into the buffer tank to supply purified hydrogen to the hydrodesulfurization unit. In the above process, the high-temperature heat-conducting fluid is sent into the solid-state hydrogen storage and purification reactor A to provide heat for hydrogen release of the solid-state hydrogen storage and purification reactor A. The solid-state hydrogen storage and purification reactor B also has the same process.

[0066] According to a preferred embodiment of the present application, the system further comprises a heat recycling unit in communication with the solid-state hydrogen storage unit, the hydrodesulfurization unit and the hydrogen purification unit, for heat recycling.

[0067] According to a preferred embodiment of the present application, the heat recycling unit comprises a liquid storage tank, and the first liquid outlet of the liquid storage tank is connected with the liquid inlet of the hydrodesulfurization unit for absorbing the heat generated by the hydrodesulfurization unit. In the above process, the low-temperature heat-conducting fluid from the liquid storage tank absorbs the heat generated by the hydrodesulfurization unit to obtain high-temperature steam.

[0068] According to a preferred embodiment of the present application, the heat recycling unit comprises a liquid mixer, and the second gas outlet of the hydrodesulfurization unit is connected with the first inlet of the liquid mixer for obtaining high-temperature heat-conducting fluid. In the above process, the high-temperature steam from the hydrodesulfurization unit exchanges heat with the low-temperature heat-conducting fluid in the liquid mixer to obtain high-temperature heat-conducting fluid.

[0069] According to a preferred embodiment of the present application, the liquid outlet of the liquid mixer is connected with the liquid inlet of the solid-state hydrogen storage unit and the liquid inlet of the hydrogen purification unit respectively for providing heat for the hydrogen release process of the solid-state hydrogen storage unit and the hydrogen release process of the hydrogen purification unit.

[0070] According to a preferred embodiment of the present application, the liquid outlet of the solid-state hydrogen storage unit is connected with the first liquid inlet of the liquid storage tank for recycling the low-temperature heat-conducting fluid from the solid-state hydrogen storage unit.

[0071] According to a preferred embodiment of the present application, the liquid outlet of the hydrogen purification unit is connected with the second liquid inlet of the liquid storage tank for recycling the low-temperature heat-conducting fluid from the hydrogen purification unit.

[0072] According to a preferred embodiment of the present application, the second liquid outlet of the liquid storage tank is connected with the second inlet of the liquid mixer for providing low-temperature heat-conducting fluid for the liquid mixer.

[0073] It should be noted that part of the low-temperature heat-conducting fluid in the liquid storage tank is introduced into the hydrodesulfurization unit to absorb heat and generate high-temperature steam, and part of the low-temperature heat-conducting fluid is introduced into the liquid mixer to form a cycle.

[0074] According to a specific embodiment of the present application, it can be referred to Figure 1 , opening the first control valve and closing the second control valve, the solid-state hydrogen storage unit 1 is connected with the external hydrogenation equipment, and the solid-state hydrogen storage unit 1 stores hydrogen;

[0075] The system is started, the second control valve is opened, the first control valve is closed, the first pressure reducing valve 6 and the first flow controller 3 are adjusted, so that the solid-state hydrogen storage unit 1 releases hydrogen; the hydrogen from the solid-state hydrogen storage unit 1 enters the hydrodesulfurization unit 2 through the buffer tank 8 (the pressure sensor 13 at the top measures the pressure), the second pressure reducing valve 7 and the second flow controller 5, and reacts with the hydrocarbon oil raw material to produce part of the heat, and at the same time, the hydrogen / hydrocarbon mixed waste gas is obtained; the low-temperature heat-conducting fluid in the liquid storage tank 9 in the heat circulation unit 12 absorbs the heat generated by the hydrodesulfurization unit 2 to obtain high-temperature steam; the high-temperature steam from the hydrodesulfurization unit 2 is sent into the liquid mixer 10 to exchange heat with the low-temperature heat-conducting fluid therein to obtain high-temperature heat-conducting fluid;

[0076] The hydrogen / hydrocarbon mixed waste gas is sent into the solid-state hydrogen storage purification reactor 11 of the hydrogen purification unit 4 for recovery to obtain purified hydrogen and hydrocarbon products; the hydrocarbon products are sent into a downstream hydrocarbon product recovery unit for recovery, and the purified hydrogen is stored in the solid-state hydrogen storage purification reactor 11;

[0077] The solid-state hydrogen storage purification reactor 11 releases hydrogen and is sent into the buffer tank 8 to provide at least part of the purified hydrogen for the hydrodesulfurization unit 2;

[0078] The high-temperature heat-conducting fluid provides heat for the hydrogen release process of the solid-state hydrogen storage unit 1 and the hydrogen release process of the solid-state hydrogen storage purification reactor 11; the low-temperature heat-conducting fluid obtained after the heat exchange of the solid-state hydrogen storage unit 1 and the solid-state hydrogen storage purification reactor 11 is sent into the liquid storage tank 9; part of the low-temperature heat-conducting fluid in the liquid storage tank 9 absorbs the heat generated by the hydrodesulfurization unit 2, and the remaining part is sent into the liquid mixer 10 of the heat circulation unit 12 to realize circulation.

[0079] The second aspect of the present application provides a method for operating the solid-state hydrogen storage and hydrodesulfurization combined system of the first aspect, and the method comprises the following steps:

[0080] (1) The solid-state hydrogen storage unit releases hydrogen, and the hydrogen is introduced into the hydrodesulfurization unit to react with the hydrocarbon oil raw material to obtain hydrogen / hydrocarbon mixed waste gas;

[0081] (2) The hydrogen / hydrocarbon mixed waste gas is sent into the hydrogen purification unit for recovery to obtain purified hydrogen and hydrocarbon products;

[0082] (3) The hydrogen purification unit releases purified hydrogen, and the purified hydrogen is circulated to step (1);

[0083] The hydrodesulfurization unit provides heat for the hydrogen release process of the solid-state hydrogen storage unit and the hydrogen release process of the hydrogen purification unit.

[0084] The application does not have special limitations on the hydrogen release conditions of the solid-state hydrogen storage unit and the hydrogen purification unit, and can be performed according to conventional methods in the art. According to a preferred embodiment of the application, the conditions of the hydrogen release reaction during the hydrogen release process of the solid-state hydrogen storage unit and the hydrogen purification unit independently include a pressure of 1-4 MPa and a temperature of 60-80°C.

[0085] It should be noted that in the art, the high-temperature heat-conducting fluid temperature is generally considered as the hydrogen release temperature.

[0086] The application does not have special limitations on the hydrogen release rate of the solid-state hydrogen storage unit and the hydrogen purification unit, and can be appropriately selected according to the actual needs of the hydrodesulfurization reaction in the hydrodesulfurization unit, and can be performed according to conventional methods in the art.

[0087] The application does not have special limitations on the specific conditions of the hydrodesulfurization reaction, and can be performed according to conventional methods in the art, which will not be described in detail herein.

[0088] According to a preferred embodiment of the application, in step (1), the first heat-conducting fluid from the heat recycling unit absorbs the heat generated by the hydrodesulfurization reaction to obtain high-temperature steam.

[0089] According to a preferred embodiment of the application, the second heat-conducting fluid from the heat recycling unit is heat-exchanged with the high-temperature steam to obtain a high-temperature heat-conducting fluid.

[0090] According to a preferred embodiment of the application, the high-temperature heat-conducting fluid provides heat for the hydrogen release process of the solid-state hydrogen storage unit and the hydrogen release process of the hydrogen purification unit.

[0091] According to a preferred embodiment of the application, the temperature of the high-temperature steam is 100-150°C.

[0092] The application does not have special limitations on the temperature of the high-temperature heat-conducting fluid, as long as it can achieve hydrogen release. According to a preferred embodiment of the application, the temperature of the high-temperature heat-conducting fluid is 60-80°C.

[0093] The application does not have special limitations on the types of the first heat-conducting fluid and the second heat-conducting fluid, which can be conventional choices in the art. According to a preferred embodiment of the application, the first heat-conducting fluid and the second heat-conducting fluid are water.

[0094] The application has a wide range of choices for the type of hydrocarbon oil feedstock. According to a preferred embodiment of the application, the hydrocarbon oil feedstock is gasoline.

[0095] According to a preferred embodiment of the application, the hydrocarbon product includes at least one of methane, ethane, and ethylene.

[0096] The application will be described in detail below by way of examples.

[0097] Example 1

[0098] The system used in the application is shown in Figure 1 .

[0099] The first control valve is opened, the second control valve is closed, the solid-state hydrogen storage unit 1 is connected with the external hydrogenation equipment, and the solid-state hydrogen storage unit 1 stores hydrogen;

[0100] The system is started, the second control valve is opened, the first control valve is closed, the first pressure reducing valve 6 is controlled, and the pressure is adjusted to 1 MPa, so that the solid-state hydrogen storage unit 1 (filled with TiMn-based hydrogen storage material, purchased from Xiamen Xiawang New Energy Materials Co., Ltd.) releases hydrogen; the hydrogen gas enters the hydrogenation desulfurization unit 2 after passing through the first flow controller 3, the buffer tank 8, the second pressure reducing valve 7 and the second flow controller 5, and reacts with gasoline to obtain hydrogen / hydrocarbon mixed waste gas (hydrocarbons including methane and ethane), and at the same time, part of the heat is generated; the low-temperature heat-conducting fluid from the liquid storage tank 9 in the heat circulation unit 12 absorbs the heat of the hydrogenation desulfurization unit 2 to obtain high-temperature steam at 120℃; the high-temperature steam from the hydrogenation desulfurization unit is sent into the liquid mixer 10 to exchange heat with the low-temperature heat-conducting fluid therein to obtain high-temperature heat-conducting fluid at 70℃;

[0101] The hydrogen / hydrocarbon mixed waste gas is sent into the solid-state hydrogen storage purification reactor 11 (filled with TiMn-based hydrogen storage material, purchased from Xiamen Xiawang New Energy Materials Co., Ltd.) of the hydrogen purification unit 4 for recovery to obtain purified hydrogen and hydrocarbon products, the hydrocarbon products are sent into the downstream hydrocarbon product recovery unit for recovery, and the purified hydrogen is stored in the solid-state hydrogen storage purification reactor 11;

[0102] The solid-state hydrogen storage purification reactor 11 releases hydrogen and is sent into the buffer tank 8 to provide at least part of the purified hydrogen for the hydrogenation desulfurization unit 2;

[0103] The high-temperature heat-conducting fluid at 70℃ provides heat for the hydrogen release process of the solid-state hydrogen storage unit 1 and the hydrogen release process of the solid-state hydrogen storage purification reactor 11; the low-temperature heat-conducting fluid obtained after the heat exchange of the solid-state hydrogen storage unit 1 and the solid-state hydrogen storage purification reactor 11 is sent into the liquid storage tank 9; part of the low-temperature heat-conducting fluid in the liquid storage tank 9 absorbs the heat of the hydrogenation desulfurization unit 2, and the remaining part is sent into the liquid mixer 10 of the heat circulation unit 12 to realize circulation.

[0104] As can be seen from the above examples, the solid-state hydrogen storage and hydrogen combined system for chemical industry used in the application can make full use of the low-grade waste heat of the hydrogenation desulfurization unit, effectively improve the energy utilization efficiency, and improve the economy of the solid-state hydrogen storage technology; at the same time, the hydrogen and hydrogen-containing compounds (hydrocarbon products) can be recycled.

[0105] The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A solid-state hydrogen storage and chemical hydrogen combination system, characterized in that, The system comprises a solid-state hydrogen storage unit, a hydrodesulfurization unit and a hydrogen purification unit; The gas inlet of the hydrodesulfurization unit is in communication with the gas outlet of the solid-state hydrogen storage unit, for hydrogen desulfurization reaction of hydrogen from the solid-state hydrogen storage unit and hydrocarbon oil raw material, to obtain hydrogen / hydrocarbon mixed waste gas; The gas inlet of the hydrogen purification unit is in communication with the first gas outlet of the hydrodesulfurization unit, for recycling the hydrogen / hydrocarbon mixed waste gas, to obtain purified hydrogen and hydrocarbon product; the first gas outlet of the hydrogen purification unit is in communication with the gas inlet of the hydrodesulfurization unit, for providing at least part of the purified hydrogen for the hydrodesulfurization unit; The hydrodesulfurization unit is used to provide heat for hydrogen release of the solid-state hydrogen storage unit and the hydrogen purification unit.

2. The system according to claim 1, wherein The solid-state hydrogen storage unit is filled with hydrogen storage material, which is preferably selected from at least one of titanium-based hydrogen storage material, rare earth-based hydrogen storage material and vanadium-based hydrogen storage material.

3. The system according to claim 1, wherein The system further comprises a buffer tank arranged between the solid-state hydrogen storage unit and the hydrodesulfurization unit, for buffering hydrogen from the solid-state hydrogen storage unit; Preferably, the first inlet of the buffer tank is in communication with the gas outlet of the solid-state hydrogen storage unit; Preferably, the second inlet of the buffer tank is in communication with the first gas outlet of the hydrogen purification unit; Preferably, the outlet of the buffer tank is in communication with the gas inlet of the hydrodesulfurization unit.

4. The system according to claim 3, wherein The hydrogen purification unit comprises a solid-state hydrogen storage purification reactor; Preferably, the hydrogen storage material filled in the solid-state hydrogen storage purification reactor is selected from at least one of titanium-based hydrogen storage material, rare earth-based hydrogen storage material and vanadium-based hydrogen storage material; Preferably, the gas inlet of the solid-state hydrogen storage purification reactor is in communication with the first gas outlet of the hydrodesulfurization unit; Preferably, the first gas outlet of the solid-state hydrogen storage purification reactor is in communication with the second inlet of the buffer tank; Preferably, the second gas outlet of the solid-state hydrogen storage purification reactor is in communication with a downstream hydrocarbon product recycling unit, for recycling hydrocarbon product.

5. The system according to any one of claims 1-4, wherein The system further comprises a heat recycling unit, which is in communication with the solid-state hydrogen storage unit, the hydrodesulfurization unit and the hydrogen purification unit, for heat recycling; Preferably, the heat recycling unit comprises a liquid storage tank, the first liquid outlet of the liquid storage tank is in communication with the liquid inlet of the hydrodesulfurization unit, for absorbing heat generated by the hydrodesulfurization unit; Preferably, the heat recycling unit comprises a liquid mixer, the second gas outlet of the hydrodesulfurization unit is in communication with the first inlet of the liquid mixer, for obtaining high-temperature heat-conducting fluid; Preferably, the liquid outlet of the liquid mixer is respectively connected with the liquid inlet of the solid-state hydrogen storage unit and the liquid inlet of the hydrogen purification unit, for providing heat for hydrogen release process of the solid-state hydrogen storage unit and hydrogen release process of the hydrogen purification unit.

6. The system according to claim 5, wherein The liquid outlet of the solid-state hydrogen storage unit is in communication with the first liquid inlet of the liquid storage tank for recycling the low-temperature heat-conducting fluid from the solid-state hydrogen storage unit; Preferably, the liquid outlet of the hydrogen purification unit is in communication with the second liquid inlet of the liquid storage tank for recycling the low-temperature heat-conducting fluid from the hydrogen purification unit; Preferably, the second liquid outlet of the liquid storage tank is in communication with the second inlet of the liquid mixer for providing the low-temperature heat-conducting fluid to the liquid mixer.

7. A method for operating the solid-state hydrogen storage and chemical hydrogen combined system according to any one of claims 1-6, the method comprising: (1) the solid-state hydrogen storage unit releases hydrogen gas, which is introduced into the hydrodesulfurization unit to perform a hydrodesulfurization reaction with a hydrocarbon oil raw material to obtain a hydrogen / hydrocarbon mixed waste gas; (2) the hydrogen / hydrocarbon mixed waste gas is sent to the hydrogen purification unit for recycling to obtain purified hydrogen gas and a hydrocarbon product; (3) the hydrogen purification unit releases purified hydrogen gas, which is recycled to step (1); wherein the hydrodesulfurization unit provides heat for the hydrogen release process of the solid-state hydrogen storage unit and the hydrogen release process of the hydrogen purification unit.

8. The method according to claim 7, wherein, in the hydrogen release process of the solid-state hydrogen storage unit and the hydrogen purification unit, the conditions of the hydrogen release reaction are each independently: the pressure is 1-4 MPa, and the temperature is 60-80℃.

9. The method according to claim 7, wherein, in step (1), the first heat-conducting fluid from the heat recycling unit absorbs heat generated by the hydrodesulfurization reaction to obtain high-temperature steam; Preferably, the second heat-conducting fluid from the heat recycling unit is heat-exchanged with the high-temperature steam to obtain high-temperature heat-conducting fluid; Preferably, the high-temperature heat-conducting fluid provides heat for the hydrogen release process of the solid-state hydrogen storage unit and the hydrogen release process of the hydrogen purification unit; Preferably, the temperature of the high-temperature steam is 100-150℃; Preferably, the temperature of the high-temperature heat-conducting fluid is 60-80℃.

10. The method according to any one of claims 7-9, wherein, the hydrocarbon oil raw material is gasoline; Preferably, the hydrocarbon product comprises at least one of methane, ethane and ethylene.

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