A green hydrogen storage coupled catalytic reforming device and process

Abstract

This invention discloses a green hydrogen storage coupled catalytic reforming device and process, comprising a hydrogen storage device and a reforming device. The hydrogen storage device includes a hydrogen storage reactor and a first separator. The hydrogen storage reactor is filled with a self-made hydrogen storage catalyst, and its bottom outlet is connected to the side wall inlet of the first separator. The reforming device includes a heater, a reforming reactor, a second separator, and a distillation column. The outlet of the heater is connected to the top inlet of the reforming reactor, the bottom outlet of the reforming reactor is connected to the side wall inlet of the second separator, and the bottom outlet of the second separator is connected to the side wall inlet of the distillation column. Green hydrogen reacts with a hydrogen storage medium in the hydrogen storage reactor to generate a hydrogen storage liquid. The hydrogen storage liquid and the reforming feedstock enter the catalytic reforming device, where dehydrogenation is performed to generate a hydrogen storage medium and hydrogen gas. The hydrogen storage medium is returned to the hydrogen storage device for recycling, and the hydrogen gas is supplied to the refinery.

Description

Technical Field

[0001] The present invention relates to the field of chemical engineering, and in particular to a green hydrogen storage coupled catalytic reforming device and process. Background Art

[0002] In order to comply with the global trend of green and low-carbon development, my country formally proposed the goal of "carbon peak in 2030 and carbon neutrality in 2060" (i.e., the "dual carbon" goal) in September 2020. Under the "dual carbon" goal, accelerating the pace of energy structure transformation to clean and low-carbon, and vigorously developing green hydrogen energy based on renewable energy such as photovoltaic and wind power have become the main choices for refining and chemical companies.

[0003] According to statistics from the National Land Satellite Remote Sensing Application Center of the Ministry of Natural Resources of my country, China's wind energy, solar energy and other renewable resources are mainly distributed in the northwest, while China's hydrogen load center is in the southeast, resulting in a spatial misalignment between green electricity hydrogen production and hydrogen load centers. How to safely and efficiently store and transport hydrogen is the main problem in the practical application of hydrogen energy. In recent years, the economic issues of hydrogen preparation and the safety issues of hydrogen utilization have developed rapidly, while the storage and transportation issues and cost issues of hydrogen have become the biggest bottleneck restricting the use of hydrogen energy.

[0004] In recent years, many new hydrogen storage technologies have emerged, including hydrogen storage alloys, carbon materials, metal organic framework materials, complexes, minerals, and organic liquid hydride. Compared with other hydrogen storage technologies, organic liquid hydride hydrogen storage technology has the advantages of large hydrogen storage capacity, high hydrogen storage density, high hydrogen storage efficiency, safe and convenient storage, transportation, maintenance and maintenance of hydrogen carriers, simple hydrogen storage facilities, highly reversible hydrogenation and dehydrogenation reactions, and can be recycled many times.

[0005] Chinese patent document CN101575257B discloses a catalytic hydrogenation method using toluene as a hydrogen storage agent; this technology uses toluene as a hydrogen storage medium for chemical hydrogen storage. Toluene hydrogen storage has the characteristics of large hydrogen storage capacity, high energy density, simple hydrogen storage equipment, safe and convenient hydrogen storage, transportation, and maintenance. However, this method does not mention the dehydrogenation reaction with high energy consumption, and the economic benefits are poor.

[0006] Chinese patent document CN201811406303.8 discloses a liquid hydrogen storage material and its preparation method; this technology uses carbazoles such as N-ethylcarbazole as hydrogen storage media for chemical hydrogen storage, and adds low melting point thermal conductive additives to carbazole compounds, which can quickly make the hydrogen storage material as a whole reach the dehydrogenation temperature during the dehydrogenation process, thereby increasing the release rate of hydrogen. Although this method reduces the dehydrogenation cost, the hydrogen storage efficiency of carbazoles in organic liquids is low.

[0007] The present invention proposes a green hydrogen storage coupled catalytic reforming process technology, which realizes green hydrogen storage while utilizing the existing catalytic reforming device for dehydrogenation, thereby reducing the dehydrogenation cost and having the advantages of high hydrogen storage efficiency and good economic benefits. Summary of the invention

[0008] In order to address the deficiencies in the prior art, the object of the present invention is to provide a green hydrogen storage coupled catalytic reforming device and process. The present invention utilizes a homemade hydrogen storage catalyst to store hydrogen, and couples with an existing catalytic reforming device to regenerate green hydrogen, which not only saves the investment in dehydrogenation equipment and greatly reduces the overall cost of green hydrogen, but also has high hydrogen storage and dehydrogenation efficiency and good selectivity.

[0009] In order to achieve the above object, the present invention adopts the following technical solution:

[0010] A green hydrogen storage coupled catalytic reforming device comprises a hydrogen storage device 1 and a reforming device 2; the hydrogen storage device 1 comprises a hydrogen storage reactor 101 and a first separator 102, the hydrogen storage reactor 101 is filled with a self-made hydrogen storage catalyst, and the bottom outlet of the hydrogen storage reactor 101 is connected to the side wall inlet of the first separator 102; the reforming device 2 comprises a heating furnace 201, a reforming reactor 202, a second separator 203 and a distillation tower 204, the outlet of the heating furnace 201 is connected to the top inlet of the reforming reactor 202, the bottom outlet of the reforming reactor 202 is connected to the side wall inlet of the second separator 203, and the bottom outlet of the second separator 203 is connected to the side wall inlet of the distillation tower 204.

[0011] Preferably, the hydrogen storage device 1 also includes a first raw material pump 103, the top inlet of the hydrogen storage reactor 101 is connected to the hydrogen pipeline 111, and the hydrogen storage medium is fed into the hydrogen pipeline 111 through the first raw material pump 103; the first separator 102 is provided with a first gas phase outlet 121 at the top and a first liquid phase outlet 122 at the bottom, and the first gas phase outlet 121 is connected to the hydrogen pipeline 111 through a residual hydrogen pipeline 123; the first gas phase outlet 121 outputs the residual hydrogen in the hydrogen storage product, and the first liquid phase outlet 122 outputs the hydrogen storage liquid, and the hydrogen storage liquid is input into the reforming device 2 through a pipeline or a transportation tool; the hydrogen storage medium is one or more of benzene, toluene or xylene.

[0012] Preferably, the reforming device 2 also includes a second raw material pump 205, the inlet of the heating furnace 201 is connected to the raw material pipeline 211, and the reforming raw material is delivered to the raw material pipeline 211 through the second raw material pump 205; the reforming reactor 202 is filled with a reforming catalyst; the second separator 203 is provided with a second gas phase outlet 231 at the top, and a second liquid phase outlet 232 at the bottom, the second gas phase outlet 231 is connected to the product hydrogen pipeline through the circulating hydrogen pipeline 233, and the second liquid phase outlet 232 is connected to the side wall inlet of the distillation tower 204; the distillation tower 204 is provided with a light hydrocarbon outlet and a gasoline outlet at the top, a BTX outlet 241 at the middle, and a C9 aromatics outlet and a heavy aromatics outlet at the bottom.

[0013] Preferably, in parts by weight, the preparation method of the homemade hydrogen storage catalyst is:

[0014] (A) dispersing 150 to 350 parts of pseudo-boehmite in a 1 to 5 wt% dilute nitric acid solution, then placing the dispersion in a kneader and kneading for 30 to 60 minutes, and then extruding the resulting product into strips, drying the product at 80 to 120° C. for 4 to 6 hours, and then calcining the product at 300 to 500° C. for 6 to 12 hours to obtain an Al2O3 carrier;

[0015] (B) dissolving 200 to 400 parts of Ni(NO3)2·6H2O and 1 to 5 parts of PtCl4 in deionized water to prepare a solution, and then adding the Al2O3 carrier obtained in step (A) to the solution and mixing well to obtain a mixed solution;

[0016] (C) The mixed solution obtained in step (B) is subjected to rotary evaporation at 80-120° C. to remove water, and then dried and calcined to obtain the self-made hydrogen storage catalyst Ni-Pt / Al2O3.

[0017] Preferably, in step (C), the drying temperature is 80-150° C., and the drying time is 4-6 hours; the roasting temperature is 300-500° C., and the roasting time is 4-6 hours.

[0018] The present invention also claims a process for green hydrogen storage coupled catalytic reforming using the green hydrogen storage coupled catalytic reforming device, the specific steps of which are as follows: hydrogen and hydrogen storage medium are fed from the top of the hydrogen storage reactor 101, and react in the hydrogen storage reactor 101 to obtain hydrogen storage products; the hydrogen storage products enter from the side wall inlet of the first separator 102, and undergo gas-liquid separation in the first separator 102 to obtain hydrogen storage liquid and residual hydrogen;

[0019] The heating furnace 201 heats the hydrogen storage liquid, reforming raw materials and hydrogen and then transports them to the top of the reforming reactor 202, where they react to obtain reforming products. The reforming products enter the second separator 203 from the side wall inlet of the second separator 203 and then undergo gas-liquid separation; the gaseous products in the reforming products are output from the second gas phase outlet 231; the liquid products in the reforming products are output from the second liquid phase outlet 232, enter the distillation tower 204 from the side wall inlet, and BTX is output from the middle of the distillation tower 204 after the reaction; the BTX is circulated and used as a hydrogen storage medium.

[0020] Preferably, the reaction temperature in the hydrogen storage reactor 101 is 100-300° C., and the reaction pressure is 0.5-6 MPa.

[0021] Preferably, the molar ratio of hydrogen to hydrogen storage medium in the hydrogen storage reactor 101 is 4 to 15:1, and the volume space velocity is 0.1 to 3 h -1 .

[0022] Preferably, the reaction temperature in the reforming reactor 202 is 500-530° C., and the reaction pressure is 0.3-1 MPa.

[0023] Preferably, the volume ratio of hydrogen to the mixed material in the reforming reactor 202 is 200-800:1, wherein the mixed material is composed of hydrogen storage liquid and reforming raw material, the volume ratio of hydrogen storage liquid to reforming raw material is 5-15:95-85, and the volume space velocity is 1-3h -1 .

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1) The present invention provides a self-made Ni-Pt series hydrogen storage catalyst, which significantly improves the hydrogen storage efficiency of BTX, and the hydrogen storage efficiency can reach 7.1wt%; the dehydrogenation efficiency exceeds 98% by using a catalytic reforming device, and by controlling the volume proportion of hydrogen storage liquid in the reforming raw material to 5% to 15%, it will not have a negative impact on the catalytic reforming reaction of the refinery.

[0026] 2) The present invention proposes a green hydrogen storage coupled catalytic reforming process, which uses green electricity to electrolyze water to prepare green hydrogen, and uses organic liquids such as benzene, toluene, and xylene as hydrogen storage media; at the same time, it is coupled with an existing catalytic reforming device, eliminating the high investment in dehydrogenation equipment, reducing the energy consumption of the dehydrogenation equipment, and reducing the cost of green hydrogen storage and transportation; compared with the existing technology, it has the advantages of high hydrogen storage efficiency, low energy consumption, low investment, and good environmental protection and economy.

[0027] 3) When constructing green electricity in the main green electricity supply areas in my country, such as seawater wind power, the "Three Norths" and the southwest region, on-site hydrogenation equipment should be built to produce green hydrogen by electrolyzing water with green electricity. Through the low-temperature moderate hydrogenation process, the green hydrogen is converted into liquid at room temperature and pressure, which is convenient to transport. It can effectively solve the problem of transporting green hydrogen to refineries. At the same time, the hydrogen storage liquid product is stored in the refinery tank area and then used in the dehydrogenation process of the catalytic reforming unit. There is no need to build a new liquid hydrogen storage and dehydrogenation device, which not only ensures stability and continuity during use, but also saves investment and energy consumption, thereby saving energy and reducing emissions.

[0028] 4) Utilizing green hydrogen and green electricity to coordinately reconstruct the refining and chemical process flow that is mainly based on fossil energy, and creating an integrated "green electricity-green hydrogen-refining and chemical" process, it not only promotes deep carbon reduction in the petrochemical industry, but also promotes the high-quality development of the petrochemical industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show schematic diagrams of certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0030] Figure 1 This is a schematic diagram of the green hydrogen storage coupled catalytic reforming process provided by the present invention.

[0031] In the figure: 1. hydrogen storage device; 101. hydrogen storage reactor; 102. first separator; 103. first raw material pump; 111. hydrogen pipeline; 121. first gas phase outlet; 122. first liquid phase outlet; 123. residual hydrogen pipeline; 2. reforming device; 201. heating furnace; 202. reforming reactor; 203. second separator; 204. distillation tower; 205. second raw material pump; 211. raw material pipeline; 231. second gas phase outlet; 232. second liquid phase outlet; 233. circulating hydrogen pipeline; 241. BTX outlet. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. Of course, the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0033] like Figure 1As shown, the present invention discloses a green hydrogen storage coupled catalytic reforming device, comprising a hydrogen storage device 1 and a reforming device 2; the hydrogen storage device 1 comprises a hydrogen storage reactor 101 and a first separator 102, and the bottom outlet of the hydrogen storage reactor 101 is connected to the side wall inlet of the first separator 102; the reforming device 2 comprises a heating furnace 201, a reforming reactor 202, a second separator 203 and a distillation tower 204, the outlet of the heating furnace 201 is connected to the top inlet of the reforming reactor 202, the bottom outlet of the reforming reactor 202 is connected to the side wall inlet of the second separator 203, and the bottom outlet of the second separator 203 is connected to the side wall inlet of the distillation tower 204.

[0034] The specific process flow of the present invention is as follows: hydrogen and hydrogen storage medium are fed from the top of the hydrogen storage reactor 101, and react in the hydrogen storage reactor 101 to obtain hydrogen storage products; the hydrogen storage products enter from the side wall inlet of the first separator 102, and undergo gas-liquid separation in the first separator 102 to obtain hydrogen storage liquid and residual hydrogen; the heating furnace 201 heats the hydrogen storage liquid, reforming raw materials, and hydrogen and transports them to the top of the reforming reactor 202, and reacts in the reforming reactor 202 to obtain reforming products, and the reforming products enter the second separator 203 from the side wall inlet of the second separator 203, and then undergo gas-liquid separation; the gas phase product in the reforming product is output from the top outlet of the second separator 203; the liquid phase product in the reforming product is output from the bottom outlet of the second separator 203, enters the distillation tower 204 from the side wall inlet, and after the reaction, BTX is output from the BTX outlet 241 in the middle of the distillation tower; the reforming raw material is naphtha; and the BTX is circulated as a hydrogen storage medium.

[0035] Specifically, the hydrogen storage device 1 also includes a first raw material pump 103, the top inlet of the hydrogen storage reactor 101 is connected to the hydrogen pipeline 111, and the hydrogen storage medium is fed into the hydrogen pipeline 111 through the first raw material pump 103; the hydrogen storage reactor 101 is filled with a hydrogen storage catalyst; the first separator 102 is provided with a first gas phase outlet 121 at the top and a first liquid phase outlet 122 at the bottom, and the first gas phase outlet 121 is connected to the hydrogen pipeline 111 through a residual hydrogen pipeline 123; the first gas phase outlet 121 outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen is connected to the hydrogen pipeline 111 through the residual hydrogen pipeline 123, and can continue to be used as a hydrogen storage raw material; the first liquid phase outlet 122 outputs a hydrogen storage liquid, and the hydrogen storage liquid is input into the reforming device 2 through a pipeline or a transportation tool; the hydrogen storage medium is one or more of benzene, toluene or xylene.

[0036] Specifically, the reforming device 2 further includes a second raw material pump 205, the inlet of the heating furnace 201 is connected to a raw material pipeline 211, and the reforming raw material is fed into the raw material pipeline 211 through the second raw material pump 205; the reforming reactor 202 is filled with a reforming catalyst; the second separator 203 is provided with a second gas phase outlet 231 at the top and a second liquid phase outlet 232 at the bottom; hydrogen is output through the second gas phase outlet 231, and can be used for processes such as hydrofining and hydrocracking; the liquid phase product in the reforming product is output through the second liquid phase outlet 232, enters the distillation tower 204 from the side wall inlet of the distillation tower 204, and BTX is obtained after reaction in the distillation tower 204, and BTX is output from the BTX outlet 241 in the middle of the distillation tower;

[0037] The preparation method of the self-made hydrogen storage catalyst described in Examples 1 to 10 is as follows:

[0038] (A) 200 g of pseudo-boehmite was dispersed in a 2.5 wt% dilute nitric acid solution, and the dispersion was placed in a kneader and kneaded for 30 min before extrusion. The obtained product was dried at 120° C. for 4 h and then calcined at 400° C. for 8 h to obtain an Al2O3 carrier;

[0039] (B) 148 g of Ni(NO3)2·6H2O and 0.86 g of PtCl4 were dissolved in 100 mL of deionized water to prepare a solution, and then 100 g of the Al2O3 carrier obtained in step (A) was added to the solution and mixed uniformly to obtain a mixed solution;

[0040] (C) The mixed solution obtained in step (B) is subjected to rotary evaporation at 80° C. to remove moisture, the obtained product is dried at 120° C. for 4 hours, and then calcined at 400° C. for 4 hours to obtain the self-made hydrogen storage catalyst Ni-Pt / Al2O3.

[0041] More specifically, the reaction temperature in the hydrogen storage reactor 101 is 100-300°C, the reaction pressure is 0.5-6MPa; the molar ratio of hydrogen to hydrogen storage medium in the hydrogen storage reactor 101 is 4-15:1, and the volume space velocity is 0.1-3h -1 ; The reaction temperature in the reforming reactor 202 is 500-530°C, and the reaction pressure is 0.3-1MPa; The volume ratio of hydrogen to the mixed material in the reforming reactor 202 is 200-800:1, wherein the mixed material is composed of hydrogen storage liquid and reforming raw material, the volume ratio of hydrogen storage liquid to reforming raw material is 5-15:95-85, and the volume space velocity is 1-3h -1 The proportion of hydrogen storage liquid in the mixture can be determined according to the actual situation. The hydrogen storage liquid can be 0 to 100 v% of the mixture. To ensure that the reforming reaction is not affected, it is preferably 5 to 15 v%.

[0042] In the embodiments, the hydrogen storage effect of the hydrogen storage medium is defined by the hydrogen storage density, that is, the ratio of the mass of the stored hydrogen to the mass of the hydrogen storage medium. Taking toluene as an example, toluene generates methylcyclohexane after hydrogen storage. Each unit of substance in methylcyclohexane can store 3 units of substance in hydrogen, which can be calculated by the amount of methylcyclohexane. The calculation formula is as follows:

[0043]

[0044] Among them, X 甲基环己烷 is the content of methylcyclohexane in the hydrogen storage liquid;

[0045] M 氢气 is the molar mass of hydrogen (g / mol);

[0046] M 甲苯 is the molar mass of toluene (g / mol).

[0047] In the embodiments, the dehydrogenation effect of the hydrogen storage liquid is defined by the dehydrogenation rate. Taking methylcyclohexane as an example, methylcyclohexane generates toluene after dehydrogenation, which can be calculated by the amount of methylcyclohexane remaining after dehydrogenation. The calculation formula is as follows:

[0048] ξ=(1-Y 甲基环己烷 )×100%

[0049] Among them, Y 甲基环己烷 is the content of methylcyclohexane in the liquid after dehydrogenation.

[0050] It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention were purchased through commercial channels.

[0051] The reforming catalyst used in the present invention was purchased from Liaoning Haitai Technology Development Co., Ltd., with a specific surface area of ​​180-220m 2 / g, particle size 1.4~2.0mm, pore volume 0.7mL / g.

[0052] The nickel-based catalyst used in Comparative Example 1 was purchased from Dalian General Chemical Co., Ltd., and the active ingredients were Ni and Al, with a bulk density of 1.5 g / cm 3 .

[0053] Example 1

[0054] Hydrogen and hydrogen storage medium benzene were fed from the top of the hydrogen storage reactor. The hydrogen storage reactor was filled with 100 mL of self-made hydrogen storage catalyst. The feed rate of hydrogen storage medium benzene was 50 mL / h, the feed rate of hydrogen was 125 L / h, the temperature in the hydrogen storage reactor was 200 °C, the reaction pressure was 2 MPa, the molar ratio of hydrogen to benzene was 10:1, and the volume space velocity was 0.5 h -1, react in the hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains hydrogen storage liquid cyclohexane and residual hydrogen; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, and the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid cyclohexane, and the cyclohexane is input into the reforming device through the pipeline.

[0055] The heating furnace heats the hydrogen storage liquid cyclohexane, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the cyclohexane feed rate is 10mL / h, the naphtha feed rate is 90mL / h, the hydrogen feed rate is 70L / h, the temperature in the reforming reactor is 520℃, the reaction pressure is 0.3MPa, and the volume space velocity is 1.0h -1 , react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, benzene is output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; benzene is cyclically used as a hydrogen storage medium.

[0056] Under this condition, the hydrogen storage density is 7.1wt% and the dehydrogenation efficiency is 99.9%.

[0057] Example 2

[0058] Hydrogen and hydrogen storage medium benzene were fed from the top of the hydrogen storage reactor. The hydrogen storage reactor was filled with 100 mL of self-made hydrogen storage catalyst. The feed rate of hydrogen storage medium benzene was 100 mL / h, the feed rate of hydrogen was 177 L / h, the temperature in the hydrogen storage reactor was 140 °C, the reaction pressure was 1.5 MPa, the molar ratio of hydrogen to benzene was 7:1, and the volume space velocity was 1.0 h -1 , react in the hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains hydrogen storage liquid cyclohexane and residual hydrogen; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, and the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid cyclohexane, and the cyclohexane is input into the reforming device through the pipeline.

[0059] The heating furnace heats the hydrogen storage liquid cyclohexane, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the cyclohexane feed rate is 20mL / h, the naphtha feed rate is 180mL / h, the hydrogen feed rate is 60L / h, the temperature in the reforming reactor is 530℃, the reaction pressure is 0.4MPa, and the volume space velocity is 2.0h -1 , react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, benzene is output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; benzene is cyclically used as a hydrogen storage medium.

[0060] Under this condition, the hydrogen storage density is 5.8wt% and the dehydrogenation efficiency is 99.6%.

[0061] Example 3

[0062] Hydrogen and hydrogen storage medium toluene were fed from the top of the hydrogen storage reactor. The hydrogen storage reactor was filled with 100 mL of self-made hydrogen storage catalyst. The feed rate of hydrogen storage medium toluene was 80 mL / h, the feed rate of hydrogen was 203 L / h, the temperature in the hydrogen storage reactor was 220 °C, the reaction pressure was 3 MPa, the molar ratio of hydrogen to toluene was 12:1, and the volume space velocity was 0.8 h -1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains hydrogen storage liquid methylcyclohexane and residual hydrogen; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, and the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid methylcyclohexane, and the methylcyclohexane is input into the reforming device through the pipeline.

[0063] The heating furnace heats the hydrogen storage liquid methylcyclohexane, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the methylcyclohexane feed rate is 25mL / h, the naphtha feed rate is 225mL / h, the hydrogen feed rate is 175L / h, the temperature in the reforming reactor is 525℃, the reaction pressure is 0.8MPa, and the volume space velocity is 2.5h -1, react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, toluene is output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; toluene is recycled as a hydrogen storage medium.

[0064] Under this condition, the hydrogen storage density is 5.9wt% and the dehydrogenation efficiency is 99.8%.

[0065] Example 4

[0066] Hydrogen and hydrogen storage medium toluene were fed from the top of the hydrogen storage reactor. The hydrogen storage reactor was filled with 100 mL of self-made hydrogen storage catalyst. The feed rate of hydrogen storage medium toluene was 150 mL / h, the feed rate of hydrogen was 191 L / h, the temperature in the hydrogen storage reactor was 160 °C, the reaction pressure was 1 MPa, the molar ratio of hydrogen to toluene was 6:1, and the volume space velocity was 1.5 h -1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains hydrogen storage liquid methylcyclohexane and residual hydrogen; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, and the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid methylcyclohexane, and the methylcyclohexane is input into the reforming device through the pipeline.

[0067] The heating furnace heats the hydrogen storage liquid methylcyclohexane, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the methylcyclohexane feed rate is 30mL / h, the naphtha feed rate is 270mL / h, the hydrogen feed rate is 90L / h, the temperature in the reforming reactor is 500℃, the reaction pressure is 1MPa, and the volume space velocity is 3.0h -1 , react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, toluene is output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; toluene is recycled as a hydrogen storage medium.

[0068] Under this condition, the hydrogen storage density is 5.0wt% and the dehydrogenation efficiency is 99.8%.

[0069] Example 5

[0070] Hydrogen and hydrogen storage medium xylene were fed from the top of the hydrogen storage reactor. The hydrogen storage reactor was filled with 100 mL of self-made hydrogen storage catalyst. The feed rate of hydrogen storage medium xylene was 20 mL / h, the feed rate of hydrogen was 36 L / h, the temperature in the hydrogen storage reactor was 250 °C, the reaction pressure was 4 MPa, the molar ratio of hydrogen to xylene was 15:1, and the volume space velocity was 0.2 h -1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains hydrogen storage liquid dimethylcyclohexane and residual hydrogen; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, and the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid dimethylcyclohexane, and the dimethylcyclohexane is input into the reforming device through the pipeline.

[0071] The heating furnace heats the hydrogen storage liquid dimethylcyclohexane, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the dimethylcyclohexane feed rate is 20mL / h, the naphtha feed rate is 180mL / h, the hydrogen feed rate is 40L / h, the temperature in the reforming reactor is 510℃, the reaction pressure is 0.4MPa, and the volume space velocity is 2.0h -1 , react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, xylene is output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; xylene is cyclically used as a hydrogen storage medium.

[0072] Under this condition, the hydrogen storage density is 5.5wt% and the dehydrogenation efficiency is 98.1%.

[0073] Example 6

[0074] Hydrogen and hydrogen storage medium xylene were fed from the top of the hydrogen storage reactor. The hydrogen storage reactor was filled with 100 mL of self-made hydrogen storage catalyst. The feed rate of hydrogen storage medium xylene was 200 mL / h, the feed rate of hydrogen was 291 L / h, the temperature in the hydrogen storage reactor was 100 °C, the reaction pressure was 2 MPa, the molar ratio of hydrogen to xylene was 8:1, and the volume space velocity was 2.0 h-1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains hydrogen storage liquid dimethylcyclohexane and residual hydrogen; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, and the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid dimethylcyclohexane, and the dimethylcyclohexane is input into the reforming device through the pipeline.

[0075] The heating furnace heats the hydrogen storage liquid dimethylcyclohexane, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the dimethylcyclohexane feed rate is 10mL / h, the naphtha feed rate is 90mL / h, the hydrogen feed rate is 50L / h, the temperature in the reforming reactor is 510℃, the reaction pressure is 0.6MPa, and the volume space velocity is 1.0h -1 , react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, xylene is output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; xylene is cyclically used as a hydrogen storage medium.

[0076] Under this condition, the hydrogen storage density is 5.4wt% and the dehydrogenation rate is 99.5%.

[0077] Example 7

[0078] Hydrogen and hydrogen storage medium were fed from the top of the hydrogen storage reactor. The hydrogen storage medium was a mixture of benzene and toluene in a molar ratio of 1:1. The hydrogen storage reactor was filled with 100 mL of a homemade hydrogen storage catalyst. The hydrogen storage medium feed rate was 50 mL / h, the hydrogen feed rate was 109 L / h, the temperature in the hydrogen storage reactor was 220 °C, the reaction pressure was 1.5 MPa, the molar ratio of hydrogen to hydrogen storage medium was 12:1, and the volume space velocity was 0.5 h -1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains a hydrogen storage liquid and residual hydrogen, wherein the hydrogen storage liquid is a mixture of cyclohexane and methylcyclohexane; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline, and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid, and the hydrogen storage liquid is input into the reforming device through the pipeline.

[0079] The heating furnace heats the hydrogen storage liquid, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the hydrogen storage liquid feed rate is 10mL / h, the naphtha feed rate is 90mL / h, and the hydrogen feed rate is 80L / h. The temperature in the reforming reactor is 515℃ and the reaction pressure is 0.4MPa. The reforming product is reacted in the reforming reactor, and the reforming product enters the second separator from the side wall inlet of the second separator, and then the gas-liquid separation is carried out. The gaseous product among the reforming products is output from the second gaseous phase outlet, wherein a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product among the reforming products is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, benzene and toluene are output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; benzene and toluene are recycled as hydrogen storage media.

[0080] Under this condition, the hydrogen storage density is 6.6wt% and the dehydrogenation rate is 99.7%.

[0081] Example 8

[0082] Hydrogen and hydrogen storage medium were fed from the top of the hydrogen storage reactor. The hydrogen storage medium was a mixture of benzene and xylene in a molar ratio of 1:1. 100 mL of self-made hydrogen storage catalyst was filled in the hydrogen storage reactor. The hydrogen storage medium feed rate was 70 mL / h, the hydrogen feed rate was 133 L / h, the temperature in the hydrogen storage reactor was 260 °C, the reaction pressure was 5 MPa, the molar ratio of hydrogen to hydrogen storage medium was 9:1, and the volume space velocity was 0.7 h -1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains a hydrogen storage liquid and residual hydrogen, wherein the hydrogen storage liquid is a mixture of cyclohexane and dimethylcyclohexane; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline, and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid, and the hydrogen storage liquid is input into the reforming device through the pipeline.

[0083] The heating furnace heats the hydrogen storage liquid, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the hydrogen storage liquid feed rate is 15mL / h, the naphtha feed rate is 135mL / h, the hydrogen feed rate is 90L / h, the temperature in the reforming reactor is 520℃, the reaction pressure is 0.6MPa, and the volume space velocity is 1.5h -1, react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, benzene and xylene are output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; benzene and xylene are used as hydrogen storage media for recycling.

[0084] Under this condition, the hydrogen storage density is 6.2wt% and the dehydrogenation rate is 99.5%.

[0085] Example 9

[0086] Hydrogen and hydrogen storage medium were fed from the top of the hydrogen storage reactor. The hydrogen storage medium was a mixture of toluene and xylene in a molar ratio of 1:1. The hydrogen storage reactor was filled with 100 mL of a homemade hydrogen storage catalyst. The hydrogen storage medium feed rate was 40 mL / h, the hydrogen feed rate was 88 L / h, the temperature in the hydrogen storage reactor was 210 °C, the reaction pressure was 1.8 MPa, the molar ratio of hydrogen to hydrogen storage medium was 11:1, and the volume space velocity was 0.4 h -1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains a hydrogen storage liquid and residual hydrogen, wherein the hydrogen storage liquid is a mixture of methylcyclohexane and dimethylcyclohexane; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline, and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid, and the hydrogen storage liquid is input into the reforming device through the pipeline.

[0087] The heating furnace heats the hydrogen storage liquid, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the hydrogen storage liquid feed rate is 10mL / h, the naphtha feed rate is 90mL / h, the hydrogen feed rate is 60L / h, the temperature in the reforming reactor is 520℃, the reaction pressure is 0.5MPa, and the volume space velocity is 1.0h -1, react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, toluene and xylene are output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; toluene and xylene are cyclically used as hydrogen storage media.

[0088] Under this condition, the hydrogen storage density is 5.6wt% and the dehydrogenation rate is 99.6%.

[0089] Example 10

[0090] Hydrogen and hydrogen storage medium were fed from the top of the hydrogen storage reactor. The hydrogen storage medium was a mixture of benzene, toluene and xylene in a molar ratio of 1:1:1. 100 mL of self-made hydrogen storage catalyst was loaded into the hydrogen storage reactor. The feed rate of hydrogen storage medium was 50 mL / h, the feed rate of hydrogen was 106 L / h, the temperature in the hydrogen storage reactor was 200 °C, the reaction pressure was 2 MPa, the molar ratio of hydrogen to hydrogen storage medium was 10:1, and the volume space velocity was 0.5 h -1 , react in a hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains a hydrogen storage liquid and residual hydrogen, wherein the hydrogen storage liquid is a mixture of cyclohexane, methylcyclohexane and dimethylcyclohexane; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline, and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid, and the hydrogen storage liquid is input into the reforming device through the pipeline.

[0091] The heating furnace heats the hydrogen storage liquid, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the hydrogen storage liquid feed rate is 10mL / h, the naphtha feed rate is 90mL / h, the hydrogen feed rate is 70L / h, the temperature in the reforming reactor is 520℃, the reaction pressure is 0.3MPa, and the volume space velocity is 1.0h -1, react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, benzene, toluene and xylene are output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; benzene, toluene and xylene are used as hydrogen storage media for recycling.

[0092] Under this condition, the hydrogen storage density is 5.9wt% and the dehydrogenation rate is 99.6%.

[0093] Comparative Example 1

[0094] Hydrogen and hydrogen storage medium benzene are fed from the top of the hydrogen storage reactor. The hydrogen storage reactor is filled with 100 mL of nickel-based catalyst. The feed rate of hydrogen storage medium benzene is 50 mL / h, the feed rate of hydrogen is 125 L / h, the temperature in the hydrogen storage reactor is 200 ° C, the reaction pressure is 2 MPa, the molar ratio of hydrogen to benzene is 10:1, and the volume space velocity is 0.5 h -1 , react in the hydrogen storage reactor to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator, undergoes gas-liquid separation in the first separator, and obtains hydrogen storage liquid cyclohexane and residual hydrogen; the first gas phase outlet outputs the residual hydrogen in the hydrogen storage product, and the residual hydrogen is connected to the hydrogen pipeline through the residual hydrogen pipeline and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid cyclohexane, and the cyclohexane is input into the reforming device through the pipeline.

[0095] The heating furnace heats the hydrogen storage liquid cyclohexane, reforming raw material naphtha and hydrogen and then transports them to the top of the reforming reactor. The reforming reactor is filled with 100mL of reforming catalyst, the cyclohexane feed rate is 10mL / h, the naphtha feed rate is 90mL / h, the hydrogen feed rate is 70L / h, the temperature in the reforming reactor is 520℃, the reaction pressure is 0.3MPa, and the volume space velocity is 1.0h -1 , react in the reforming reactor to obtain a reforming product, the reforming product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gaseous product in the reforming product is output from the second gas phase outlet, a part of the hydrogen is used as a product for hydrotreating, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for reforming reaction recycling; the liquid product in the reforming product is output from the second liquid phase outlet, enters the distillation tower from the side wall inlet, and after the reaction, benzene is output from the BTX outlet in the middle of the distillation tower, light hydrocarbons and gasoline are output from the upper part of the distillation tower, and C9 aromatics and heavy aromatics are output from the lower part of the distillation tower; benzene is cyclically used as a hydrogen storage medium.

[0096] Under this condition, the hydrogen storage density is 4.5wt% and the dehydrogenation efficiency is 99.5%.

[0097] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A green hydrogen storage coupled catalytic reforming process, characterized in that: The specific steps are as follows: hydrogen and hydrogen storage medium are fed from the top of the hydrogen storage reactor (101), and react in the hydrogen storage reactor (101) to obtain hydrogen storage products; the hydrogen storage products enter from the side wall inlet of the first separator (102), and undergo gas-liquid separation in the first separator (102) to obtain hydrogen storage liquid and residual hydrogen; The heating furnace (201) heats the hydrogen storage liquid, the reforming raw material and the hydrogen and then transports them to the top of the reforming reactor (202). The reforming products are reacted in the reforming reactor (202) to obtain reforming products. The reforming products enter the second separator (203) from the side wall inlet of the second separator (203) and then undergo gas-liquid separation. The gas phase products in the reforming products are output from the second gas phase outlet (231). The liquid phase products in the reforming products are output from the second liquid phase outlet (232) and enter the distillation tower (204) from the side wall inlet. After the reaction, BTX is output from the middle of the distillation tower (204). The BTX is cyclically used as a hydrogen storage medium; The hydrogen storage reactor (101) is filled with a self-made hydrogen storage catalyst; In parts by weight, the preparation method of the homemade hydrogen storage catalyst is: (A) dispersing 150 to 350 parts of pseudo-boehmite in a 1 to 5 wt% dilute nitric acid solution, then placing the dispersion in a kneader and kneading for 30 to 60 minutes, and then extruding the resulting product into strips, drying the product at 80 to 120° C. for 4 to 6 hours, and then calcining the product at 300 to 500° C. for 6 to 12 hours to obtain an Al2O3 carrier; (B) dissolving 200 to 400 parts of Ni(NO3)2·6H2O and 1 to 5 parts of PtCl4 in deionized water to prepare a solution, and then adding the Al2O3 carrier obtained in step (A) to the solution and mixing well to obtain a mixed solution; (C) The mixed solution obtained in step (B) is subjected to rotary evaporation at 80-120° C. to remove water, and then dried and calcined to obtain the self-made hydrogen storage catalyst Ni-Pt / Al2O3.

2. The green hydrogen storage coupled catalytic reforming process according to claim 1, characterized in that: In step (C), the drying temperature is 80-150° C., and the drying time is 4-6 hours; the roasting temperature is 300-500° C., and the roasting time is 4-6 hours.

3. The green hydrogen storage coupled catalytic reforming process according to claim 1, characterized in that: The reaction temperature in the hydrogen storage reactor (101) is 100 to 300°C, and the reaction pressure is 0.5 to 6 MPa.

4. The green hydrogen storage coupled catalytic reforming process according to claim 1, characterized in that: The molar ratio of hydrogen to hydrogen storage medium in the hydrogen storage reactor (101) is 4 to 15:1, and the volume space velocity is 0.1 to 3 h -1 .

5. The green hydrogen storage coupled catalytic reforming process according to claim 1, characterized in that: The reaction temperature in the reforming reactor (202) is 500-530°C, and the reaction pressure is 0.3-1 MPa.

6. The green hydrogen storage coupled catalytic reforming process according to claim 1, characterized in that: The volume ratio of hydrogen to the mixed material in the reforming reactor (202) is 200-800:1, wherein the mixed material is composed of hydrogen storage liquid and reforming raw material, the volume ratio of hydrogen storage liquid to reforming raw material is 5-15:95-85, and the volume space velocity is 1-3h -1 .

7. A green hydrogen storage coupled catalytic reforming device using the green hydrogen storage coupled catalytic reforming process according to any one of claims 1 to 6, characterized in that: The invention comprises a hydrogen storage device (1) and a reforming device (2); the hydrogen storage device (1) comprises a hydrogen storage reactor (101) and a first separator (102); the hydrogen storage reactor (101) is filled with a self-made hydrogen storage catalyst; the bottom outlet of the hydrogen storage reactor (101) is connected to the side wall inlet of the first separator (102); the reforming device (2) comprises a heating furnace (201), a reforming reactor (202), a second separator (203) and a distillation tower (204); the outlet of the heating furnace (201) is connected to the top inlet of the reforming reactor (202); the bottom outlet of the reforming reactor (202) is connected to the side wall inlet of the second separator (203); the bottom outlet of the second separator (203) is connected to the side wall inlet of the distillation tower (204).

8. The green hydrogen storage coupled catalytic reforming device according to claim 7, characterized in that: The hydrogen storage device (1) further comprises a first raw material pump (103); the top inlet of the hydrogen storage reactor (101) is connected to a hydrogen pipeline (111); the hydrogen storage medium is fed into the hydrogen pipeline (111) through the first raw material pump (103); the top of the first separator (102) is provided with a first gas phase outlet (121), and the bottom is provided with a first liquid phase outlet (122); the first gas phase outlet (121) is connected to the hydrogen pipeline (111) through a residual hydrogen pipeline (123); the first gas phase outlet (121) outputs residual hydrogen in the hydrogen storage product, and the first liquid phase outlet (122) outputs hydrogen storage liquid, and the hydrogen storage liquid is fed into the reforming device (2) through a transportation tool; the hydrogen storage medium is BTX.

9. The green hydrogen storage coupled catalytic reforming device according to claim 7, characterized in that: The reforming device (2) further comprises a second raw material pump (205), the inlet of the heating furnace (201) is connected to a raw material pipeline (211), and the reforming raw material is fed into the raw material pipeline (211) through the second raw material pump (205); the reforming reactor (202) is filled with a reforming catalyst; the second separator (203) is provided with a second gas phase outlet (231) at the top and a second liquid phase outlet (232) at the bottom, the second gas phase outlet (231) is connected to a product hydrogen pipeline through a circulating hydrogen pipeline (233), and the second liquid phase outlet (232) is connected to a side wall inlet of a distillation tower (204); the distillation tower (204) is provided with a light hydrocarbon outlet and a gasoline outlet at the top, a BTX outlet (241) at the middle, and a C9 aromatics outlet and a heavy aromatics outlet at the bottom.

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