WO2023216547A1

WO2023216547A1 - Biomass-based liquid organic hydrogen storage system and method

Info

Publication number: WO2023216547A1
Application number: PCT/CN2022/133353
Authority: WO
Inventors: 张会岩; 罗炳炳; 吴凯; 储晨阳
Original assignee: 东南大学
Priority date: 2022-05-10
Filing date: 2022-11-22
Publication date: 2023-11-16
Also published as: CN114874800A

Abstract

Disclosed in the present invention are a biomass-based liquid organic hydrogen storage system and method. The system comprises a catalytic pyrolysis device, a pyrolysis product separation and collection device, and a hydrogen storage and transportation device; the catalytic pyrolysis device is used for carrying out catalytic pyrolysis on a biomass raw material; the pyrolysis product separation and collection device is used for separating and collecting coke, a bed material, bio-oil, and a non-condensable gas in the pyrolysis products; the hydrogen storage and transportation device is used for storing and transporting hydrogen in biomass-based liquid organics obtained by the pyrolysis product separation and collection device. According to the system, liquid organics produced by catalytic pyrolysis of biomass are used as a hydrogen storage medium, and safe and efficient storage and transportation of hydrogen are implemented by means of catalytic hydrogenation and dehydrogenation reactions and by existing oil storage and transportation facilities. According to the present invention, effective use of renewable biomass energy is implemented, and dependence on conventional fossil energy is reduced; the production process is simple, and energy is saved; moreover, the present invention improves the flexibility of hydrogen storage and transportation mode, and the hydrogen transportation efficiency and safety.

Description

A biomass-based organic liquid hydrogen storage system and method

Technical field

The present invention relates to the technical field of organic liquid hydrogen storage, and specifically to a biomass-based organic liquid hydrogen storage system and method.

Background technique

In the context of the carbon economy era, the development of the global economy is based on a large amount of carbon-based fossil fuels, which we use as the main energy source for electricity, industry, transportation and heating. However, the increasingly serious global energy and environmental crisis has prompted the transformation of energy carriers from traditional fossil energy to clean and renewable energy, of which hydrogen energy has always been regarded as a potential solution. The hydrogen energy economic system mainly consists of three aspects: hydrogen production, storage, transportation and application. Among them, the production and application aspects are relatively mature. Hydrogen energy storage and transportation are the key issues restricting its widespread and efficient utilization and large-scale industrial development. Therefore, it is crucial to develop a safe and efficient hydrogen storage technology.

Existing hydrogen storage technologies mainly include physical methods such as compressed hydrogen, liquefied hydrogen, metal alloy hydrogen storage, metal organic frameworks, adsorption hydrogen storage, and chemical methods such as organic liquid hydrogen storage and ammonia hydrogen storage. Among them, the transportation cost of compressed hydrogen storage is high, and there are unsafe factors such as hydrogen leakage and container explosion; liquefied hydrogen storage consumes a lot of energy and is easy to leak, which has extremely high requirements for the thermal insulation performance of the tank; metal alloy hydrogen storage currently The technology is not yet mature, and there are still problems such as small hydrogen storage capacity, poor resistance to impurity gases, and easy pulverization of metals; NH ₃ is toxic, and trace amounts of NH ₃ easily remain in H ₂ ; organic liquid hydrogen storage technology uses liquid organic matter This technology realizes hydrogen storage and transportation through the reversible processes of hydrogenation and dehydrogenation without destroying the main structure of organic matter. It has the advantages of high hydrogen storage density, can form a closed carbon cycle, and can realize transoceanic transportation and long-term storage. The molecules of organic liquid hydrogen storage media after hydrogenation and hydrogen evolution are mostly liquid at room temperature. Existing oil storage and transportation facilities can be used. Compared with other hydrogen storage methods, it has obvious advantages in many situations and is the most potential low-carbon hydrogen storage medium. One of the price storage and transportation technologies.

At present, the more studied organic liquid hydrogen storage systems can be divided into two categories: aromatic hydrocarbons and N-doping. The aromatic hydrocarbons mainly include benzene, toluene, naphthalene and dibenzyltoluene, and the N-doping categories mainly include carbazole, Pyrrole, pyridine and indole compounds. However, in the industrial production process, these hydrogen storage media are prepared from non-renewable fossil energy through complex refining processes. For example, aromatics are produced by naphtha reforming and petroleum cracking, pyrrole is produced by reacting petroleum-derived furans with ammonia in the presence of a solid acid catalyst, and pyridine is produced by aldehydes, ketones, or α, β-unsaturated carbonyl groups. The compound is synthesized by condensation with ammonia or ammonia derivatives over a zeolite catalyst. Indole is produced from aniline and ethylene glycol. This not only increases the dependence of industrial production on fossil energy, but also has a certain impact on the ecological environment.

However, there are a large number of such hydrogen storage media in bio-oils prepared by catalytic pyrolysis of renewable, carbon-neutral and abundant biomass resources. For example, under the action of zeolite molecular sieve catalyst, when the pyrolysis reactants do not contain nitrogen donors, bio-oil mainly includes benzene, toluene, xylene, naphthalene and their homologues; when the pyrolysis reactants contain nitrogen donors In vivo, bio-oil mainly includes pyrrole, pyridine, indole, aniline and their homologues.

Contents of the invention

Technical problem: The technical problem to be solved by the present invention is to provide a biomass-based organic liquid hydrogen storage system and method, use renewable biomass catalytic pyrolysis to efficiently prepare organic hydrogen storage liquid, reduce dependence on traditional fossil energy, and achieve The effective use of biomass energy improves the carbon efficiency and economic prospects of the biorefinery industry.

Technical solution: In order to solve the above technical problems, in the first aspect, the present invention provides a biomass-based organic liquid hydrogen storage system: including a catalytic pyrolysis device, a pyrolysis product separation and collection device and a hydrogen storage and transportation device; the catalytic pyrolysis The device is used to catalyze pyrolysis of biomass raw materials; the pyrolysis product separation and collection device is used to separate and collect coke, bed material, bio-oil and non-condensable gas in the pyrolysis products; the hydrogen storage and transportation device is used to Biomass-based organic liquid stores and transports hydrogen; the catalytic pyrolysis device is provided with a pyrolysis product outlet; the pyrolysis product outlet is connected to the inlet of the pyrolysis product separation and collection device; the pyrolysis product separation and collection device The outlet is connected to the inlet of the hydrogen storage and transportation device.

As a preferred example, the catalytic pyrolysis device includes a biomass feeding device, a bed material feeding device and a fluidized bed pyrolyzer; the lower end of the fluidized bed pyrolyzer is provided with a high-temperature carrier gas inlet, and the upper end is provided with a thermal Decomposition product outlet; the biomass feeding device and the bed material feeding device are respectively connected with the fluidized bed pyrolyzer; the pyrolysis product separation and collection device includes a cyclone separator, a fractionation device, a gas storage tank, and a coke warehouse and oil storage tank; the inlet of the cyclone separator is connected to the pyrolysis product outlet; the upper end of the cyclone separator is provided with a high-temperature gas product outlet, and the high-temperature gas product outlet is connected to the inlet of the fractionation device; the cyclone The lower end of the separator is provided with a solid product outlet, and the solid product outlet is connected to the coke bin; the gas outlet of the fractionation device is connected to the gas storage tank, and the organic liquid outlet of the fractionation device is connected to the inlet of the oil storage tank; the hydrogen The storage and transportation device includes a high-pressure hydrogen inlet, a first organic liquid storage tank, a second organic liquid storage tank, an organic liquid hydrogenation device, a first hydrogen-rich organic liquid storage tank, a second hydrogen-rich organic liquid storage tank and a hydrogen outlet. Hydrogen-rich organic liquid dehydrogenation device; the inlet of the first organic liquid storage tank is connected to the outlet of the oil storage tank, the outlet of the first organic liquid storage tank is connected to the inlet of the organic liquid hydrogenation device, and the organic liquid The outlet of the hydrogenation device is connected to the inlet of the first hydrogen-rich organic liquid storage tank; the organic liquid hydrogenation device is provided with a high-pressure hydrogen inlet; the outlet of the first hydrogen-rich organic liquid storage tank is connected to the second hydrogen-rich organic liquid storage tank. The inlet of the liquid storage tank is connected, the outlet of the second hydrogen-rich organic liquid storage tank is connected with the inlet of the hydrogen-rich organic liquid dehydrogenation device, and the outlet of the hydrogen-rich organic liquid dehydrogenation device is connected with the inlet of the second organic liquid storage tank. Connection; the outlet of the second organic liquid storage tank is connected to the inlet of the first organic liquid storage tank.

As a preferred example, the first organic liquid storage tank and the second organic liquid storage tank contain a first hydrogen storage medium; the first hydrogen storage medium is an organic liquid in an oil storage tank; the first hydrogen-rich organic The liquid storage tank and the second hydrogen-rich organic liquid storage tank contain a second hydrogen storage medium; the second hydrogen storage medium is a product of catalytic hydrogenation of the organic liquid.

As a preferred example, the fractionation device includes a fractionator; the fractionator and the oil storage tank are arranged in one-to-one correspondence; the organic liquid outlet of the fractionator is connected to the inlet of the oil storage tank; when there are more than two fractionators, Among the two adjacent fractionators, the gas outlet of one fractionator is connected to the inlet of the other fractionator; the inlet of the most upstream fractionator is connected to the high-temperature gas product outlet of the cyclone separator, and the gas outlet of the most downstream fractionator is connected. The outlet is connected to the gas tank.

As a preferred example, the bed material in the fluidized bed pyrolyzer is a selected catalyst, and the carrier gas is a mixture of nitrogen and ammonia; both the organic liquid hydrogenation device and the hydrogen-rich organic liquid dehydrogenation device are reaction A device that continuously inputs raw materials and outputs reaction products continuously.

In a second aspect, embodiments of the present invention also provide a biomass-based organic liquid hydrogen storage method: the method includes the following steps:

Step 10) The biomass raw material and catalyst enter the fluidized bed pyrolyzer through the biomass feeding device and the bed material feeding device respectively, a catalytic pyrolysis reaction occurs, and the pyrolysis product enters the cyclone separator;

Step 20) The pyrolysis products are separated into gas and solid phases in the cyclone separator. The solid phase products enter the coke bin, and the gas phase products enter the fractionation device. After fractionation by the fractionation device, the condensed organic liquid enters the oil storage tank, while the non-condensable gas enters. gas tank;

Step 30) The organic liquid in the oil storage tank (10) is transported to the first organic liquid storage tank as a hydrogen storage medium. The organic liquid and the high-pressure hydrogen source enter the organic liquid hydrogenation device at the same time. After setting the reaction temperature, pressure and hydrogenation Under the action of a catalyst, a catalytic hydrogenation reaction is performed, and the obtained hydrogen-rich organic liquid is used as the second hydrogen storage medium and stored in the first hydrogen-rich organic liquid storage tank;

Step 40) The second hydrogen storage medium is transported to the second hydrogen-rich organic liquid storage tank through the first hydrogen-rich organic liquid storage tank, and then transported into the hydrogen-rich organic liquid dehydrogenation device through the second hydrogen-rich organic liquid storage tank. Under the action of reaction temperature, pressure and dehydrogenation catalyst, a catalytic dehydrogenation reaction is carried out, the released hydrogen is discharged through the hydrogen outlet, and the obtained dehydrogenated organic liquid is stored in the second organic liquid storage tank and transported into the first organic liquid storage tank. tank to realize the storage and transportation of hydrogen and the closed-loop use of hydrogen storage media.

As a preferred example, the catalyst in step S10) is at least one of ZSM-5, Hβ, USY, MCM-41, and Al ₂ O ₃ ; the catalytic pyrolysis reaction temperature range in step S10) is 400-700 ℃; in the step S30), the reaction temperature is 50-250°C, and the pressure is 0.1-20MPa; in the step S40), the reaction temperature is 150-350°C, and the pressure is 0.05-0.5MPa.

As a preferred example, in step S30), the hydrogenation catalyst includes an active component and a carrier, wherein the active component is one or more of Pd, Pt, Ru, Rh, Ni, Mo, and Cu, The carrier is selected from at least one of activated carbon, carbon-based composite materials, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , and gC ₃ N ₄ .

As a preferred example, in step S40), the dehydrogenation catalyst includes an active component and a carrier, wherein the active component is Pd, Pt, Ru, Rh, Au, Ni, Co, Mo, W, Cu, Sn One or more of them, the carrier is at least one of activated carbon, carbon-based composite materials, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , and gC ₃ N ₄ .

As a preferred example, in step S30), the oil storage tank goes to the first organic liquid storage tank, in step S40), the second organic liquid storage tank goes to the first organic liquid storage tank, and the first hydrogen-rich organic liquid storage tank goes to the second Hydrogen-rich organic liquid storage tanks are transported through existing oil product storage and transportation facilities, which include pipeline transportation, waterway transportation, railway transportation, and road transportation.

Beneficial effects: Compared with the existing technology, the technical solution of the present invention has the following beneficial effects: compared with the existing technology, the solution of the present invention utilizes renewable biomass catalytic pyrolysis to efficiently prepare organic hydrogen storage liquid by adjusting the catalyst and The reaction conditions further regulate the component structure of the organic liquid, achieving effective utilization of biomass energy and reducing dependence on traditional fossil energy; at the same time, the production process is simple and energy-saving. In addition, the present invention improves the flexibility of hydrogen storage and transportation methods while improving the efficiency and safety of hydrogen transportation.

Description of the drawings

Figure 1 is a schematic structural diagram of the present invention;

The figure shows: catalytic pyrolysis device 1, pyrolysis product separation and collection device 2, cyclone separator 3, fractionation device 4, gas storage tank 5, fluidized bed pyrolyzer 6, bed material feeding device 7, biomass feeding device Material device 8, coke bin 9, oil storage tank 10, hydrogen storage and transportation device 11, high-pressure hydrogen inlet 12, organic liquid hydrogenation device 13, first organic liquid storage tank 14, first hydrogen-rich organic liquid storage tank 15, Two organic liquid storage tanks 16 , a second hydrogen-rich organic liquid storage tank 17 , a hydrogen-rich organic liquid dehydrogenation device 18 , and a hydrogen outlet 19 .

Detailed ways

The technical solution of the present invention will be described in detail below with reference to the accompanying drawings.

As shown in Figure 1, a biomass-based organic liquid hydrogen storage system according to an embodiment of the present invention includes a catalytic pyrolysis device 1, a pyrolysis product separation and collection device 2 and a hydrogen storage and transportation device 11; the catalytic pyrolysis device 1 It is used for catalytic pyrolysis of biomass raw materials; the pyrolysis product separation and collection device 2 is used to separate and collect coke, bed material, bio-oil and non-condensable gas in the pyrolysis products; the hydrogen storage and transportation device 11 is used for Store and transport hydrogen in biomass-based organic liquid; the catalytic pyrolysis device 1 is provided with a pyrolysis product outlet; the pyrolysis product outlet is connected to the inlet of the pyrolysis product separation and collection device 2; the pyrolysis product separation The outlet of the collection device 2 is connected to the inlet of the hydrogen storage and transportation device 11 .

In a biomass-based organic liquid hydrogen storage system with the above structure, the organic hydrogen storage liquid is prepared by catalytic pyrolysis of renewable biomass. By regulating the structure of organic liquid components, the resource utilization and efficient utilization of biomass energy can be achieved and the dependence on traditional fossil energy can be reduced.

In the process of hydrogen storage, biomass and catalyst are first subjected to a catalytic pyrolysis reaction in the catalytic pyrolysis device 1. The catalytic pyrolysis product enters the pyrolysis product separation device 2, and is separated into gas and solid phases in the cyclone separator 3. Combined with the fractionation device 4, the organic hydrogen storage liquid is obtained. The organic hydrogen storage liquid is transported to the first organic liquid storage tank 14 in the hydrogen storage and transportation device 11 through the oil storage tank 10. The organic hydrogen storage liquid in the first organic liquid storage tank 14 and the high-pressure hydrogen source enter the organic liquid hydrogenation device together. 13. Perform a catalytic hydrogenation reaction to obtain a hydrogen-rich organic liquid, and store the hydrogen-rich organic liquid in the first hydrogen-rich organic liquid storage tank 15. Then, the hydrogen-rich organic liquid in the first hydrogen-rich organic liquid storage tank 15 is transported to the second hydrogen-rich organic liquid storage tank 17 , and the hydrogen-rich organic liquid in the second hydrogen-rich organic liquid storage tank 17 is sent into the hydrogen-rich organic liquid. The dehydrogenation device 18 performs a catalytic dehydrogenation reaction. The hydrogen released after the dehydrogenation reaction is discharged through the hydrogen outlet 19. At the same time, the dehydrogenated organic liquid is stored in the second organic liquid storage tank 16 and transported to the first organic liquid storage tank 14 through transportation, so that the hydrogen storage medium can be reused. . The overall device makes full use of renewable biomass energy, reduces the use of traditional fossil energy, and at the same time has higher hydrogen storage efficiency and better safety.

As a preferred example, the catalytic pyrolysis device 1 includes a biomass feeding device 8, a bed material feeding device 7 and a fluidized bed pyrolyzer 6; the lower end of the fluidized bed pyrolyzer 6 is provided with a high-temperature carrier gas inlet , the upper end is provided with a pyrolysis product outlet; the biomass feeding device 8 and the bed material feeding device 7 are respectively connected with the fluidized bed pyrolyzer 6; the pyrolysis product separation and collection device 2 includes a cyclone separator 3. Fractionation device 4, gas storage tank 5, coke bin 9 and oil storage tank 10; the inlet of the cyclone separator 3 is connected to the pyrolysis product outlet; the upper end of the cyclone separator 3 is provided with a high-temperature gas product outlet, and The high-temperature gas product outlet is connected to the inlet of the fractionation device 4; the lower end of the cyclone separator 3 is provided with a solid product outlet, and the solid product outlet is connected to the coke bin 9; the gas outlet of the fractionation device 4 is connected to the gas storage The tank 5 is connected, and the organic liquid outlet of the fractionation device 4 is connected with the inlet of the oil storage tank 10; the hydrogen storage and transportation device 11 includes a high-pressure hydrogen inlet 12, a first organic liquid storage tank 14, a second organic liquid storage tank 16, and an organic liquid storage tank 16. Liquid hydrogenation device 13, a first hydrogen-rich organic liquid storage tank 15, a second hydrogen-rich organic liquid storage tank 17 and a hydrogen-rich organic liquid dehydrogenation device 18 containing a hydrogen outlet 19; the first organic liquid storage tank 14 The inlet is connected to the outlet of the oil storage tank 10, the outlet of the first organic liquid storage tank 14 is connected to the inlet of the organic liquid hydrogenation device 13, and the outlet of the organic liquid hydrogenation device 13 is connected to the first hydrogen-rich organic liquid storage tank. The inlet of the tank 15 is connected; the organic liquid hydrogenation device 13 is provided with a high-pressure hydrogen inlet 12; the outlet of the first hydrogen-rich organic liquid storage tank 15 is connected with the inlet of the second hydrogen-rich organic liquid storage tank 17, so The outlet of the second hydrogen-rich organic liquid storage tank 17 is connected to the inlet of the hydrogen-rich organic liquid dehydrogenation device 18, and the outlet of the hydrogen-rich organic liquid dehydrogenation device 18 is connected to the inlet of the second organic liquid storage tank 16; The outlet of the second organic liquid storage tank 16 is connected with the inlet of the first organic liquid storage tank 14 . During the hydrogen storage process, the catalytic pyrolysis device 1, the pyrolysis product separation and collection device 2 and the hydrogen storage and transportation device 11 cooperate with each other to make the overall system more complete and complete the hydrogen storage work efficiently and safely. At the same time, the pyrolysis product separation and collection device 2 and the hydrogen storage and transportation device 11 can work independently without being restricted by geographical factors, making the overall hydrogen storage system more widely applicable.

As a preferred example, the first organic liquid storage tank 14 and the second organic liquid storage tank 16 contain a first hydrogen storage medium; the first hydrogen storage medium is the organic liquid in the oil storage tank 10; the first The hydrogen-rich organic liquid storage tank 15 and the second hydrogen-rich organic liquid storage tank 17 contain a second hydrogen storage medium; the second hydrogen storage medium is a product of catalytic hydrogenation of organic liquid. The first hydrogen storage medium undergoes a catalytic hydrogenation reaction in the on-machine liquid hydrogenation device 13 to obtain the second hydrogen storage medium; the second hydrogen storage medium obtains hydrogen and the first hydrogen storage medium after dehydrogenation reaction in the hydrogen-rich organic liquid dehydrogenation device 18 medium. The overall structure is complete, and the hydrogen storage medium can be reused, saving energy and improving dehydrogenation efficiency. The organic liquid hydrogenation device 13 and the hydrogen-rich organic liquid dehydrogenation device 18 are devices that continuously input reaction raw materials and continuously output reaction products, further improving the working efficiency of the hydrogen storage and transportation device 11, thereby improving the efficiency of the overall system. . The hydrogen storage medium can be transported between the first organic liquid storage tank 14 and the second organic liquid storage tank 16 and between the first hydrogen-rich organic liquid storage tank 15 and the second hydrogen-rich organic liquid storage tank 17, so that the entire The system is more flexible, not subject to geographical constraints, and has a wider range of applications.

As a preferred example, the fractionation device 4 includes one or more fractionators connected in series; the fractionator and the oil storage tank 10 are arranged in one-to-one correspondence, and the organic liquid outlet of the fractionator and the inlet of the oil storage tank 10 Connection; when there are more than two fractionators, among the two adjacent fractionators, the gas outlet of one fractionator is connected to the inlet of the other fractionator; the inlet of the most upstream fractionator and the high-temperature gas of cyclone separator 3 The product outlet is connected, and the gas outlet of the most downstream fractionator is connected to the gas storage tank 5 . The fractionation device 4 achieves preliminary separation of organic liquid components during the collection process by setting up a multi-stage fractionator, thereby realizing cascade utilization of organic liquids in different condensation temperature ranges, which is beneficial to improving hydrogen storage efficiency and the service life of the catalyst.

As a preferred example, the bed material in the fluidized bed pyrolyzer 6 is the selected catalyst, and the carrier gas is a mixture of nitrogen and ammonia; when the carrier gas in the catalytic pyrolysis reaction is pure nitrogen, use It is used to prepare aromatic hydrocarbon hydrogen storage liquid; when the gas is mixed with ammonia, it is used to prepare N-doped hydrogen storage liquid. Using a mixture of nitrogen and ammonia as the carrier gas in the fluidized bed pyrolyzer, the ratio between the gases can be adjusted according to actual needs to achieve the production of different target products.

Embodiments of the present invention also provide a biomass-based organic liquid hydrogen storage method, including:

Step 10) The biomass raw material and catalyst enter the fluidized bed pyrolyzer 6 through the biomass feeding device 8 and the bed material feeding device 7 respectively, a catalytic pyrolysis reaction occurs, and the pyrolysis product enters the cyclone separator 3;

Step 20) The pyrolysis product undergoes gas-solid phase separation in the cyclone separator 3, the solid phase product enters the coke bin 9, and the gas phase product enters the fractionation device 4. After fractionation by the fractionation device 4, the condensed organic liquid enters the oil storage tank 10, The non-condensable gas enters the gas storage tank 5;

Step 30) The organic liquid in the oil storage tank 10 is transported to the first organic liquid storage tank 14 as the first hydrogen storage medium. The organic liquid and the high-pressure hydrogen source enter the organic liquid hydrogenation device 13 at the same time. At the set reaction temperature and pressure Under the action of a hydrogenation catalyst, a catalytic hydrogenation reaction is performed, and the obtained hydrogen-rich organic liquid is used as the second hydrogen storage medium and stored in the first hydrogen-rich organic liquid storage tank 15;

Step 40) The second hydrogen storage medium is transported to the second hydrogen-rich organic liquid storage tank 17 through the first hydrogen-rich organic liquid storage tank 15, and then transported into the hydrogen-rich organic liquid dehydrogenation device 18 through the second hydrogen-rich organic liquid storage tank 17. , under the set reaction temperature, pressure and dehydrogenation catalyst, the catalytic dehydrogenation reaction is carried out, the released hydrogen is discharged through the hydrogen outlet 19, and the obtained dehydrogenated organic liquid is stored in the second organic liquid storage tank 16. It is transported into the first organic liquid storage tank 14 to realize the storage and transportation of hydrogen and the closed-loop use of hydrogen storage medium.

In a biomass-based organic liquid hydrogen storage method with the above structure, organic liquid prepared from biomass is used as a hydrogen storage medium, and through continuous catalytic hydrogenation and catalytic dehydrogenation reactions, in conjunction with existing oil product storage and transportation facilities, the hydrogen storage method is realized. It ensures the efficient and safe storage and transportation of hydrogen, while breaking the geographical restrictions, making the overall system more widely used. The distance from the oil storage tank 10 to the first organic liquid storage tank 14, the distance from the second organic liquid storage tank 16 to the first organic liquid storage tank 14, and the distance from the first hydrogen-rich organic liquid storage tank 15 to the second hydrogen-rich organic liquid storage tank 15. The distance between the hydrogen organic liquid storage tank 17 can be long distance, for example, greater than 50 kilometers respectively. These components can be connected through pipelines or directly transported by vehicle.

As a preferred example, the catalyst in step S10) is at least one of HZSM-5, Hβ, USY, MCM-41, and Al ₂ O ₃ ; using the above catalyst, a highly enriched organic hydrogen storage liquid can be prepared; so The catalytic pyrolysis reaction temperature range in the step S10) is 400-700°C; the reaction temperature in the step S30) is 50-250°C, and the pressure is 0.1-20MPa; the reaction temperature in the step S40) is 150-350°C , the pressure is 0.05-0.5MPa. Under these temperature and pressure conditions, the yield of organic hydrogen storage liquid can reach the optimal value, improving the efficiency of hydrogen storage.

As a preferred example, in step S30), the hydrogenation catalyst includes an active component and a carrier, wherein the active component is one or more of Pd, Pt, Ru, Rh, Ni, Mo, and Cu, The carrier is selected from at least one of activated carbon, carbon-based composite materials, Al2O3, _SiO2 , _TiO2 , _ZrO2 , _and _gC3N4 . When the above components and carriers are used for catalytic hydrogenation reaction, the conversion rate of raw materials and the selectivity of products can be improved.

As a preferred example, in step S40), the dehydrogenation catalyst includes an active component and a carrier, wherein the active component is Pd, Pt, Ru, Rh, Au, Ni, Co, Mo, W, Cu, Sn One or more of them, the carrier is at least one of activated carbon, carbon-based composite materials, Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , and gC ₃ N ₄ . When using the above components and carriers, the selectivity of the product and the stability of the dehydrogenation reaction can be improved.

As a preferred example, in step S30), the oil storage tank 10 to the first organic liquid storage tank 14, the second organic liquid storage tank 16 to the first organic liquid storage tank 14 and the first hydrogen-rich organic liquid storage tank in S40) The tank 15 to the second hydrogen-rich organic liquid storage tank 17 are transported through existing oil storage and transportation facilities, and the transportation of the existing oil storage and transportation facilities includes pipeline transportation, water transportation, railway transportation and road transportation. The overall system does not need to be set up in the same area. The devices of the overall system can be coordinated through transportation, breaking the geographical restrictions, making the overall system not restricted by regional factors and having a wider range of applications.

The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the above-mentioned specific embodiments. The above-mentioned specific embodiments and descriptions in the specification are only for further illustrating the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention The invention is subject to various changes and improvements, and these changes and improvements fall within the scope of the claimed invention. The scope of protection of the present invention is defined by the claims and their equivalents.

Claims

A biomass-based organic liquid hydrogen storage system, characterized by comprising a catalytic pyrolysis device (1), a pyrolysis product separation and collection device (2) and a hydrogen storage and transportation device (11); the catalytic pyrolysis device (1) ) is used to catalyze pyrolysis of biomass raw materials; the pyrolysis product separation and collection device (2) is used to separate and collect coke, bed material, bio-oil and non-condensable gas in the pyrolysis products; the hydrogen storage and transportation The device (11) is used to store and transport hydrogen in the biomass-based organic liquid produced by the pyrolysis product separation and collection device (2); the catalytic pyrolysis device (1) is provided with a pyrolysis product outlet; the pyrolysis The product outlet is connected with the inlet of the pyrolysis product separation and collection device (2).
A biomass-based organic liquid hydrogen storage system according to claim 1, characterized in that the catalytic pyrolysis device (1) includes a biomass feeding device (8), a bed material feeding device (7) and Fluidized bed pyrolyzer (6); the lower end of the fluidized bed pyrolyzer (6) is provided with a high-temperature carrier gas inlet, and the upper end is provided with a pyrolysis product outlet; the biomass feeding device (8) and bed material The feeding device (7) is connected to the fluidized bed pyrolyzer (6) respectively; the pyrolysis product separation and collection device (2) includes a cyclone separator (3), a fractionation device (4), and a gas storage tank ( 5), coke bin (9) and oil storage tank (10); the inlet of the cyclone separator (3) is connected to the pyrolysis product outlet; the upper end of the cyclone separator (3) is provided with a high-temperature gas product outlet, and The high-temperature gas product outlet is connected to the inlet of the fractionation device (4); the lower end of the cyclone separator (3) is provided with a solid product outlet, and the solid product outlet is connected to the coke bin (9); the fractionation device (4) The gas outlet of 4) is connected to the gas storage tank (5), and the organic liquid outlet of the fractionation device (4) is connected to the inlet of the oil storage tank (10); the hydrogen storage and transportation device (11) includes a high-pressure hydrogen inlet (12) , the first organic liquid storage tank (14), the second organic liquid storage tank (16), the organic liquid hydrogenation device (13), the first hydrogen-rich organic liquid storage tank (15), the second hydrogen-rich organic liquid storage tank (17) and a hydrogen-rich organic liquid dehydrogenation device (18) containing a hydrogen outlet (19); the inlet of the first organic liquid storage tank (14) is connected to the outlet of the oil storage tank (10), and the first The outlet of the organic liquid storage tank (14) is connected to the inlet of the organic liquid hydrogenation device (13), and the outlet of the organic liquid hydrogenation device (13) is connected to the inlet of the first hydrogen-rich organic liquid storage tank (15); The organic liquid hydrogenation device (13) is provided with a high-pressure hydrogen inlet (12); the outlet of the first hydrogen-rich organic liquid storage tank (15) is connected to the inlet of the second hydrogen-rich organic liquid storage tank (17) , the outlet of the second hydrogen-rich organic liquid storage tank (17) is connected to the inlet of the hydrogen-rich organic liquid dehydrogenation device (18), and the outlet of the hydrogen-rich organic liquid dehydrogenation device (18) is connected to the second organic liquid The inlet of the storage tank (16) is connected; the outlet of the second organic liquid storage tank (16) is connected with the inlet of the first organic liquid storage tank (14).
A biomass-based organic liquid hydrogen storage system according to claim 2, characterized in that the first organic liquid storage tank (14) and the second organic liquid storage tank (16) contain a first hydrogen storage medium ; The first hydrogen storage medium is the organic liquid in the oil storage tank (10); the first hydrogen-rich organic liquid storage tank (15) and the second hydrogen-rich organic liquid storage tank (17) contain a second storage tank. Hydrogen medium; the second hydrogen storage medium is a product of catalytic hydrogenation of organic liquid.
A biomass-based organic liquid hydrogen storage system according to claim 2, characterized in that the fractionation device (4) includes a fractionator; the fractionator and the oil storage tank (10) are arranged in one-to-one correspondence, so The organic liquid outlet of the fractionator is connected to the inlet of the oil storage tank (10); when there are more than two fractionators, among the two adjacent fractionators, the gas outlet of one fractionator is connected to the inlet of the other fractionator; The inlet of the most upstream fractionator is connected to the high-temperature gas product outlet of the cyclone separator (3), and the gas outlet of the most downstream fractionator is connected to the gas storage tank (5).
A biomass-based organic liquid hydrogen storage system according to claim 2, characterized in that the bed material in the fluidized bed pyrolyzer (6) is a selected catalyst, and the carrier gas is a mixture of nitrogen and ammonia. Mixed gas; the organic liquid hydrogenation device (13) and the hydrogen-rich organic liquid dehydrogenation device (18) are devices that continuously input reaction raw materials and continuously output reaction products.
A biomass-based organic liquid hydrogen storage method, characterized in that the method includes the following steps;

Step 10) The biomass raw material and catalyst enter the fluidized bed pyrolyzer (6) through the biomass feeding device (8) and the bed material feeding device (7) respectively, where a catalytic pyrolysis reaction occurs, and the pyrolysis product enters the cyclone for separation device(3);

Step 20) The pyrolysis product is separated into gas and solid phases in the cyclone separator (3), the solid phase product enters the coke bin (9), and the gas phase product enters the fractionation device (4); after fractionation by the fractionation device (4), the condensed The organic liquid enters the oil storage tank (10), and the non-condensable gas enters the gas storage tank (5);

Step 30) The organic liquid in the oil storage tank (10) is transported to the first organic liquid storage tank (14) as a hydrogen storage medium. The organic liquid and the high-pressure hydrogen source enter the organic liquid hydrogenation device (13) at the same time. Under the action of reaction temperature, pressure and hydrogenation catalyst, the catalytic hydrogenation reaction is carried out, and the obtained hydrogen-rich organic liquid is used as the second hydrogen storage medium and stored in the first hydrogen-rich organic liquid storage tank (15);

Step 40) The second hydrogen storage medium is transported to the second hydrogen-rich organic liquid storage tank (17) through the first hydrogen-rich organic liquid storage tank (15), and then transported into the hydrogen-rich medium through the second hydrogen-rich organic liquid storage tank (17). The organic liquid dehydrogenation device (18) performs a catalytic dehydrogenation reaction under the set reaction temperature, pressure and dehydrogenation catalyst. The released hydrogen is discharged through the hydrogen outlet (19), and the obtained dehydrogenated organic liquid is stored. From the second organic liquid storage tank (16), it is transported into the first organic liquid storage tank (14) to realize the storage and transportation of hydrogen and the closed-loop use of the hydrogen storage medium.
A biomass-based organic liquid hydrogen storage method according to claim 6, characterized in that the catalyst in step S10) is at least one of ZSM-5, Hβ, USY, MCM-41, and Al 2 O 3 species; the catalytic pyrolysis reaction temperature range in step S10) is 400-700°C; the reaction temperature in step S30) is 50-250°C, and the pressure is 0.1-20MPa; the reaction temperature in step S40) is 150 -350℃, pressure 0.05-0.5MPa.
A biomass-based organic liquid hydrogen storage method according to claim 6, characterized in that in step S30), the hydrogenation catalyst includes an active component and a carrier, wherein the active component is Pd, Pt , one or more of Ru, Rh, Ni, Mo, and Cu, and the carrier is selected from at least one of activated carbon, carbon-based composite materials, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , and gC 3 N 4 kind.
A biomass-based organic liquid hydrogen storage method according to claim 6, characterized in that in step S40), the dehydrogenation catalyst includes an active component and a carrier, wherein the active component is Pd, Pt , one or more of Ru, Rh, Au, Ni, Co, Mo, W, Cu, Sn, the carrier is activated carbon, carbon-based composite materials, Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , gC At least one of 3 N 4 .
A biomass-based organic liquid hydrogen storage method according to claim 6, characterized in that in the step S30), the first organic liquid storage tank (14) from the oil storage tank (10) to the first organic liquid storage tank (14), S40) The second organic liquid storage tank (16) to the first organic liquid storage tank (14) and the first hydrogen-rich organic liquid storage tank (15) to the second hydrogen-rich organic liquid storage tank (17) pass through the existing oil storage and transportation facilities Transportation, the transportation of existing oil storage and transportation facilities includes pipeline transportation, water transportation, railway transportation and road transportation.