CN115893311A - Green hydrogen storage coupling catalytic reforming device and process - Google Patents

Abstract

The invention discloses a green hydrogen storage coupling catalytic reforming device and a process, which comprises a hydrogen storage device and a reforming device; the hydrogen storage device comprises a hydrogen storage reactor and a first separator, wherein a self-made hydrogen storage catalyst is filled in the hydrogen storage reactor, and the bottom outlet of the hydrogen storage reactor is communicated with the side wall inlet of the first separator; the reforming device comprises a heating furnace, a reforming reactor, a second separator and a rectifying tower, wherein an outlet of the heating furnace is communicated with a top inlet of the reforming reactor, a bottom outlet of the reforming reactor is communicated with a side wall inlet of the second separator, and a bottom outlet of the second separator is communicated with a side wall inlet of the rectifying tower. Reacting green hydrogen with a hydrogen storage medium in a hydrogen storage reactor to generate hydrogen storage liquid, feeding the hydrogen storage liquid and a reforming raw material into a catalytic reforming device, dehydrogenating in the reforming device to generate the hydrogen storage medium and hydrogen, returning the hydrogen storage medium to the hydrogen storage device for recycling, and using the hydrogen for a refinery.

Description

A green hydrogen storage coupled catalytic reforming device and process

technical field

The invention relates to the field of chemical engineering, in particular to a green hydrogen storage coupled catalytic reforming device and process.

Background technique

According to the statistics of the Land Satellite Remote Sensing Application Center of the Ministry of Natural Resources of my country, the distribution of China's wind energy, solar energy and other renewable resources is mainly concentrated in the northwest region, while China's hydrogen load center is in the southeast, resulting in the existence of green electricity hydrogen production and hydrogen load centers. dislocation. How to store and transport hydrogen safely and efficiently is the main problem in the practical application of hydrogen energy. In recent years, the economics of hydrogen production and the safety of hydrogen utilization have developed rapidly, while the storage, transportation and cost of hydrogen have become the biggest bottlenecks restricting the utilization of hydrogen energy.

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 hydrides. Compared with other hydrogen storage technologies, organic liquid hydride hydrogen storage technology has the advantages of large hydrogen storage capacity and high hydrogen storage density; high hydrogen storage efficiency; safe and convenient hydrogen carrier storage, transportation, maintenance, and convenient hydrogen storage facilities; hydrogenation The dehydrogenation reaction is highly reversible and can be recycled many times.

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 benefit is poor.

Chinese patent document CN201811406303.8 discloses a liquid hydrogen storage material and its preparation method; this technology uses carbazoles such as N-ethylcarbazole as the hydrogen storage medium for chemical hydrogen storage, and adds low melting point The thermal conductivity additive can make the whole hydrogen storage material reach the dehydrogenation temperature rapidly during the dehydrogenation process, and increase the release rate of hydrogen. Although this method reduces the cost of dehydrogenation, the hydrogen storage efficiency of carbazoles is low in organic liquids.

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, reduces dehydrogenation cost, has high hydrogen storage efficiency, and good economic benefits, etc. Advantage.

Contents of the invention

In order to solve the shortcomings of the existing technology, the purpose of the present invention is to provide a green hydrogen storage coupling catalytic reforming device and process. The present invention uses a self-made hydrogen storage catalyst to store hydrogen, and couples the existing catalytic reforming device to regenerate green hydrogen. It not only saves the investment in dehydrogenation equipment, greatly reduces the overall cost of green hydrogen, but also has high hydrogen storage and dehydrogenation efficiency and good selectivity.

In order to achieve the above object, the present invention adopts the following technical solutions:

A green hydrogen storage coupling catalytic reforming device, comprising two parts of a hydrogen storage device 1 and a reforming device 2; the hydrogen storage device 1 includes a hydrogen storage reactor 101 and a first separator 102, the hydrogen storage reactor 101 It is filled with a self-made hydrogen storage catalyst, and the bottom outlet of the hydrogen storage reactor 101 communicates with the side wall inlet of the first separator 102; the reformer 2 includes a heating furnace 201, a reforming reactor 202, a second Two separators 203 and a rectifying tower 204, the outlet of the heating furnace 201 communicates with the top inlet of the reforming reactor 202, and the bottom outlet of the reforming reactor 202 communicates with the side of the second separator 203 The wall inlet is connected, and the bottom outlet of the second separator 203 is connected with the side wall inlet of the rectification column 204 .

Preferably, the hydrogen storage device 1 further includes a first raw material pump 103, the top inlet of the hydrogen storage reactor 101 is connected with a hydrogen pipeline 111, and the hydrogen storage medium is sent 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, and the first gas phase outlet 121 communicates with the hydrogen pipeline 111 through a residual hydrogen pipeline 123; the first gas phase outlet 121 Output the remaining hydrogen in the hydrogen storage product, the first liquid phase outlet 122 outputs the hydrogen storage liquid, and the hydrogen storage liquid is input into the reformer 2 through pipelines or transport means; the hydrogen storage medium is benzene, toluene or xylene one or more of.

Preferably, the reformer 2 further includes a second raw material pump 205, the inlet of the heating furnace 201 is communicated with a raw material pipeline 211, and the reformed raw material is sent into the raw material pipeline 211 through the second raw material pump 205; The reactor 202 is filled with a reforming catalyst; the top of the second separator 203 is provided with a second gas phase outlet 231, and the bottom is provided with a second liquid phase outlet 232, and the second gas phase outlet 231 passes through a circulating hydrogen pipeline 233 and a product hydrogen pipeline. 234 is communicated, and the second liquid phase outlet 232 is communicated with rectification tower 204 side wall inlets; The top of described rectification tower 204 is provided with light hydrocarbon outlet and gasoline outlet, and middle part is provided with BTX outlet 241, and the bottom is provided with C9 aromatics outlet and Export of heavy aromatics.

Preferably, in parts by weight, the preparation method of the self-made hydrogen storage catalyst is:

(A) Disperse 150-350 parts of pseudo-boehmite in 1-5wt% dilute nitric acid solution, then place the dispersion in a kneader for 30-60 minutes and then extrude it into strips. Drying for 4-6 hours, followed by calcination at 300-500°C for 6-12 hours to prepare the Al ₂ O ₃ carrier;

(B) 200-400 parts of Ni(NO ₃ ) ₂ ·6H ₂ O and 1-5 parts of PtCl ₄ were dissolved in deionized water to prepare a solution, and then the Al ₂ O ₃ carrier obtained in step (A) was added to Mix evenly in the solution to obtain a mixed solution;

(C) The mixed liquid obtained in the step (B) is rotary-evaporated at 80-120° C. to remove moisture, then dried and roasted to obtain the self-made hydrogen storage catalyst Ni-Pt/Al ₂ O ₃ .

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

The present invention also claims to protect a green hydrogen storage coupled catalytic reforming process using the green hydrogen storage coupled catalytic reforming device. The specific steps are as follows: hydrogen gas and hydrogen storage medium are fed from the top of the hydrogen storage reactor 101, React in the hydrogen reactor 101 to obtain a hydrogen storage product; the hydrogen storage product enters from the side wall inlet of the first separator 102, and performs gas-liquid separation in the first separator 102 to obtain a hydrogen storage liquid and residual hydrogen;

The heating furnace 201 heats the hydrogen storage liquid, the reforming raw material, and the hydrogen gas, and then transports them to the top of the reforming reactor 202, and reacts in the reforming reactor 202 to obtain a reformed product, and the reformed product passes through the side wall of the second separator 203 The inlet enters the second separator 203, and then performs gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet 231; the liquid phase product in the reformed product is output from the second liquid phase outlet 232, and enters the refined product from the side wall inlet. Distillation tower 204, output BTX from the middle part of rectification tower 204 after reaction; The BTX is recycled as a hydrogen storage medium.

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

Preferably, 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 0.1-3 h ^-1 .

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

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

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

1) The present invention provides a self-made Ni-Pt hydrogen storage catalyst, which significantly improves the hydrogen storage efficiency of BTX, and the hydrogen storage efficiency can reach 7.1wt%. The catalytic reforming device is used for dehydrogenation, and the dehydrogenation efficiency exceeds 98%. Controlling the volume ratio of the hydrogen storage liquid in the reforming raw material to 5% to 15% will not have a negative impact on the catalytic reforming reaction in the refinery.

2) The present invention proposes a green hydrogen storage coupling catalytic reforming process, using green electricity to electrolyze water to prepare green hydrogen, using organic liquids such as benzene, toluene, xylene as the hydrogen storage medium; and coupling the existing catalytic reforming device at the same time , eliminating the need for expensive dehydrogenation device investment, reducing the energy consumption of the dehydrogenation device, and reducing the cost of green hydrogen storage and transportation; compared with the existing technology, it has high hydrogen storage efficiency, low energy consumption, less investment, and good environmental protection and economy and other advantages.

3) In seawater wind power, "Three Norths" and Southwest my country's main green power supply areas, such as China's main green power supply places, build supporting on-site hydrogenation devices, use green power to electrolyze water to produce green hydrogen, and use low temperature to ease the hydrogenation process. The conversion of green hydrogen into liquid at normal temperature and pressure is convenient for transportation, which can effectively solve the transportation problem of green hydrogen to the refinery; at the same time, the hydrogen storage liquid product is stored in the tank farm of the refinery, and then used in the dehydrogenation process of the catalytic reforming unit , no need to build a new liquid hydrogen storage and dehydrogenation device, which not only ensures the stability and continuity of use, but also saves investment and energy consumption, energy saving and emission reduction.

4) Utilize green hydrogen and green electricity to coordinate and reconstruct the refining and chemical process mainly based on fossil energy, and create an integrated process of "green electricity-green hydrogen-refining", which not only promotes the deep carbon reduction of the petrochemical industry, but also promotes The petrochemical industry achieved high-quality development.

Description of drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings that are used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show schematic diagrams of some embodiments of the present invention, so It should not be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings according to these drawings without creative work.

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

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 unit; 201, heating furnace; 202, reforming reactor; 203, second separator; 204, rectifying 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 ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the examples. Of course, the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

As shown in Figure 1, the present invention discloses a green hydrogen storage coupling catalytic reforming device, which includes two parts: a hydrogen storage device 1 and a reforming device 2; the hydrogen storage device 1 includes a hydrogen storage reactor 101 and a first separation device 102, the bottom outlet of the hydrogen storage reactor 101 communicates with the side wall inlet of the first separator 102; the reformer 2 includes a heating furnace 201, a reforming reactor 202, a second separator 203 and A rectification tower 204, the outlet of the heating furnace 201 communicates with the top inlet of the reforming reactor 202, and the bottom outlet of the reforming reactor 202 communicates with the side wall inlet of the second separator 203, so The bottom outlet of the second separator 203 communicates with the side wall inlet of the rectification column 204 .

The specific process flow of the present invention is as follows: hydrogen and hydrogen storage medium are fed from the top of hydrogen storage reactor 101, and react in hydrogen storage reactor 101 to obtain hydrogen storage product; hydrogen storage product enters from the side wall inlet of first separator 102 , gas-liquid separation is carried out in the first separator 102 to obtain hydrogen storage liquid and residual hydrogen; the heating furnace 201 heats the hydrogen storage liquid, reforming raw material, and hydrogen and transports them to the top of the reforming reactor 202. React in 202 to obtain the reformed product, the reformed product enters the second separator 203 from the side wall inlet of the second separator 203, and then undergoes gas-liquid separation; the gas phase product in the reformed product exits from the top of the second separator 203 output; the liquid phase product in the reformed product is exported from the bottom outlet of the second separator 203, enters the rectifying tower 204 from the side wall inlet, and outputs BTX from the BTX outlet 241 in the middle of the rectifying tower after the reaction; the reforming raw material is stone Naphtha; the BTX is recycled as a hydrogen storage medium.

Specifically, the hydrogen storage device 1 further includes a first raw material pump 103, the top inlet of the hydrogen storage reactor 101 is connected with a hydrogen pipeline 111, and the hydrogen storage medium is sent 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 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, and the first gas phase outlet 121 passes through the remaining The hydrogen pipeline 123 communicates with the hydrogen pipeline 111; the first gas phase outlet 121 outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen communicates with the hydrogen pipeline 111 through the remaining hydrogen pipeline 123 and can continue to be used as a raw material for hydrogen storage; The first liquid phase outlet 122 outputs the hydrogen storage liquid, and the hydrogen storage liquid is input into the reformer 2 through pipelines or means of transportation; the hydrogen storage medium is one or more of benzene, toluene or xylene.

Specifically, the reformer 2 also includes a second raw material pump 205, the inlet of the heating furnace 201 is communicated with a raw material pipeline 211, and the reformed raw material is sent into the raw material pipeline 211 through the second raw material pump 205; The inside of the reactor 202 is filled with a reforming catalyst; the top of the second separator 203 is provided with a second gas phase outlet 231, and the bottom is provided with a second liquid phase outlet 232; hydrogen is output through the second gas phase outlet 231, which can be supplied to Used in processes such as hydrogen refining and hydrocracking; the liquid phase product in the reformed product is output through the second liquid phase outlet 232, enters the rectification tower 204 from the side wall inlet of the rectification tower 204, and reacts in the rectification tower 204 to obtain BTX , BTX is exported from BTX outlet 241 in the middle of the rectifying tower;

Wherein, the preparation method of the self-made hydrogen storage catalyst described in Examples 1 to 10 is as follows:

(A) Disperse 200g of pseudo-boehmite in 2.5wt% dilute nitric acid solution, then place the dispersion in a kneader for 30 minutes and then extrude it into strips. The resulting product is dried at 120°C for 4 hours, and then dried at 400°C Calcined for 8h to prepare the Al ₂ O ₃ carrier;

(B) Prepare a solution by dissolving 148gNi(NO ₃ ) ₂ 6H ₂ O and 0.86g PtCl ₄ in 100mL deionized water, then add 100g of the Al ₂ O ₃ carrier obtained in step (A) into the solution and mix well , to obtain a mixture;

(C) The mixed solution obtained in step (B) was rotary evaporated at 80°C to remove moisture, and the obtained product was dried at 120°C for 4 hours, and then roasted at 400°C for 4 hours to obtain the self-made hydrogen storage catalyst Ni-Pt/ Al ₂ O ₃ .

More specifically, the reaction temperature in the hydrogen storage reactor 101 is 100-300°C, the reaction pressure is 0.5-6 MPa; the molar ratio of hydrogen to the hydrogen storage medium in the hydrogen storage reactor 101 is 4-15:1, and the volume space velocity 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:mixture in the reforming reactor 202 is 200-800: ¹ , where The mixture is composed of hydrogen storage liquid and reforming raw material, the volume ratio of hydrogen storage liquid and reforming raw material is 5-15:95-85, the volume space velocity is 1-3h ^-1 ; the doping ratio of hydrogen storage liquid in the mixture can be Depending on the actual situation, the hydrogen storage liquid may be 0-100v% of the mixture, preferably 5-15v% in order to ensure that the reforming reaction is not affected.

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 stored hydrogen to the mass of the hydrogen storage medium. Taking toluene as an example, toluene generates methylcyclohexane after storing hydrogen. Methylcyclohexane can store 3 units of hydrogen per unit of substance, which can be calculated by the amount of methylcyclohexane. The calculation formula as follows:

Wherein, X _{methylcyclohexane} is the content of methylcyclohexane in the hydrogen storage liquid;

M _hydrogen is the molar mass (g/mol) of hydrogen;

_Mtoluene is the molar mass (g/mol) of toluene.

In the examples, 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 remaining methylcyclohexane after dehydrogenation, and the calculation formula is as follows:

ξ=(1-Y _{methylcyclohexane} )×100%

Wherein, Y _{methylcyclohexane} is the content of methylcyclohexane in the liquid after dehydrogenation.

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

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

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

Example 1

Hydrogen and hydrogen storage medium benzene are fed from the top of the hydrogen storage reactor, and 100mL of self-made hydrogen storage catalyst is filled in the hydrogen storage reactor. The temperature in the reactor is 200°C, the reaction pressure is 2MPa, the molar ratio of hydrogen to benzene is 10:1, and the volume space velocity is 0.5h ^-1 , and the hydrogen storage product is obtained by reaction in the hydrogen storage reactor; the hydrogen storage product is obtained from the first separator The side wall inlet enters, and the gas-liquid separation is carried out in the first separator to obtain the hydrogen storage liquid cyclohexane and the remaining hydrogen; the first gas phase outlet outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen passes through the remaining hydrogen pipeline and the hydrogen pipeline connected, and continue to be used as a raw material for hydrogen storage; the first liquid phase outlet outputs hydrogen storage liquid cyclohexane, and cyclohexane is input into a reforming device through a pipeline.

The heating furnace heats the hydrogen storage liquid cyclohexane, reforming raw material naphtha, and hydrogen to the top of the reforming reactor. The reforming reactor is filled with 100 mL of reforming catalyst, and the feed rate of cyclohexane is 10 mL/h. The feed rate of naphtha is 90mL/h, the feed rate of hydrogen gas is 70L/h, the temperature inside the reforming reactor is 520°C, the reaction pressure is 0.3MPa, and the volume space velocity is 1.0h ^-1 . The reformed product is obtained by the reaction, and the reformed product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, and part of the hydrogen is supplied as a product for addition. Hydrogen refining, hydrocracking and other processes are used, and another part of the hydrogen is input into the heating furnace for the recycling of the reforming reaction; the liquid phase product in the reforming product is output from the second liquid phase outlet, and enters the rectification tower from the side wall inlet, and after the reaction Benzene is output from the BTX outlet in the middle of the rectification tower, light hydrocarbons and gasoline are output from the upper part of the rectification tower, and C9 aromatics and heavy aromatics are output from the lower part of the rectification tower; benzene is recycled as a hydrogen storage medium.

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

Example 2

Hydrogen and hydrogen storage medium benzene are fed from the top of the hydrogen storage reactor, and 100mL of self-made hydrogen storage catalyst is filled in the hydrogen storage reactor. The temperature in the reactor is 140°C, the reaction pressure is 1.5MPa, the molar ratio of hydrogen to benzene is 7:1, and the volume space velocity is 1.0h ^-1 , and the hydrogen storage product is reacted in the hydrogen storage reactor; the hydrogen storage product is separated from the first The side wall inlet of the device enters, and the gas-liquid separation is carried out in the first separator to obtain the hydrogen storage liquid cyclohexane and the remaining hydrogen; the first gas phase outlet outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen passes through the remaining hydrogen pipeline and hydrogen The pipeline is connected 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.

The heating furnace heats the hydrogen storage liquid cyclohexane, reforming raw material naphtha, and hydrogen to the top of the reforming reactor. The reforming reactor is filled with 100 mL of reforming catalyst, and the feed rate of cyclohexane is 20 mL/h. The feed rate of naphtha is 180mL/h, the feed rate of hydrogen gas is 60L/h, the temperature inside the reforming reactor is 530°C, the reaction pressure is 0.4MPa, and the volume space velocity is 2.0h ^-1 . The reformed product is obtained by the reaction, and the reformed product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, and part of the hydrogen is supplied as a product for addition. Hydrogen refining, hydrocracking and other processes are used, and another part of the hydrogen is input into the heating furnace for the recycling of the reforming reaction; the liquid phase product in the reforming product is output from the second liquid phase outlet, and enters the rectification tower from the side wall inlet, and after the reaction Benzene is output from the BTX outlet in the middle of the rectification tower, light hydrocarbons and gasoline are output from the upper part of the rectification tower, and C9 aromatics and heavy aromatics are output from the lower part of the rectification tower; benzene is recycled as a hydrogen storage medium.

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

Example 3

Hydrogen and hydrogen storage medium toluene are fed from the top of the hydrogen storage reactor, and the hydrogen storage reactor is filled with 100mL self-made hydrogen storage catalyst. The temperature in the reactor is 220°C, the reaction pressure is 3MPa, the molar ratio of hydrogen to toluene is 12:1, and the volume space velocity is 0.8h ^-1 , and the hydrogen storage product is obtained from the reaction in the hydrogen storage reactor; the hydrogen storage product is obtained from the first separator The side wall inlet enters, and gas-liquid separation is carried out in the first separator to obtain 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 passes through the residual hydrogen pipeline and The hydrogen pipeline is connected 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.

The heating furnace heats the hydrogen storage liquid methylcyclohexane, reforming raw material naphtha, and hydrogen to the top of the reforming reactor. The reforming reactor is filled with 100 mL of reforming catalyst, and the feeding amount of methylcyclohexane is 25mL/h, the naphtha feed rate is 225mL/h, the hydrogen feed rate is 175L/h, the temperature inside the reforming reactor is 525°C, the reaction pressure is 0.8MPa, and the volume space velocity is 2.5h ^-1 . The reaction in the reactor is carried out to obtain the reformed product, which enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, and a part of the hydrogen is As a product, it is used in hydrofining, hydrocracking and other processes, and another part of hydrogen is input into the heating furnace for reforming reaction recycling; the liquid phase product in the reforming product is output from the second liquid phase outlet, and enters rectification from the side wall inlet After the reaction, toluene is output from the BTX outlet in the middle of the rectification tower, light hydrocarbons and gasoline are output from the upper part of the rectification tower, and C9 aromatics and heavy aromatics are output from the lower part of the rectification tower; toluene is recycled as a hydrogen storage medium.

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

Example 4

Hydrogen and hydrogen storage medium toluene are fed from the top of the hydrogen storage reactor, and 100 mL of self-made hydrogen storage catalyst is filled in the hydrogen storage reactor. The temperature in the reactor is 160°C, the reaction pressure is 1MPa, the molar ratio of hydrogen to toluene is 6:1, and the volume space velocity is 1.5h ^-1 , and the hydrogen storage product is obtained from the reaction in the hydrogen storage reactor; the hydrogen storage product is obtained from the first separator The side wall inlet enters, and gas-liquid separation is carried out in the first separator to obtain 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 passes through the residual hydrogen pipeline and The hydrogen pipeline is connected 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.

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

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

Example 5

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

The heating furnace heats the hydrogen storage liquid dimethylcyclohexane, reforming raw naphtha, and hydrogen to the top of the reforming reactor. The reforming reactor is filled with 100mL reforming catalyst, and the dimethylcyclohexane is fed 20mL/h, naphtha feed rate 180mL/h, hydrogen feed rate 40L/h, reforming reactor temperature 510°C, reaction pressure 0.4MPa, volume space velocity 2.0h ^-1 , in The reaction in the reforming reactor is carried out to obtain a reformed product, and the reformed product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, wherein A part of the hydrogen is used as a product for hydrorefining, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for the recycling of the reforming reaction; the liquid phase product in the reforming product is output from the second liquid phase outlet and enters from the side wall inlet Rectification tower, after the reaction, xylene is output from the BTX outlet in the middle of the rectification tower, light hydrocarbons and gasoline are output from the upper part of the rectification tower, and C9 aromatics and heavy aromatics are output from the lower part of the rectification tower; xylene is recycled as a hydrogen storage medium.

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

Example 6

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

The heating furnace heats the hydrogen storage liquid dimethylcyclohexane, reforming raw naphtha, and hydrogen to the top of the reforming reactor. The reforming reactor is filled with 100mL reforming catalyst, and the dimethylcyclohexane is fed 10mL/h, naphtha feed rate 90mL/h, hydrogen feed rate 50L/h, reforming reactor internal temperature 510°C, reaction pressure 0.6MPa, volume space velocity 1.0h ^-1 , in The reaction in the reforming reactor is carried out to obtain a reformed product, and the reformed product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, wherein A part of the hydrogen is used as a product for hydrorefining, hydrocracking and other processes, and the other part of the hydrogen is input into the heating furnace for the recycling of the reforming reaction; the liquid phase product in the reforming product is output from the second liquid phase outlet and enters from the side wall inlet Rectification tower, after the reaction, xylene is output from the BTX outlet in the middle of the rectification tower, light hydrocarbons and gasoline are output from the upper part of the rectification tower, and C9 aromatics and heavy aromatics are output from the lower part of the rectification tower; xylene is recycled as a hydrogen storage medium.

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

Example 7

Hydrogen and hydrogen storage medium are fed from the top of the hydrogen storage reactor. The hydrogen storage medium is a mixture of benzene and toluene with a molar ratio of 1:1. The hydrogen storage reactor is filled with 100mL of self-made hydrogen storage catalyst, and the feed rate of hydrogen storage medium is 50mL/h , the hydrogen feed rate is 109L/h, the temperature in the hydrogen storage reactor is 220°C, the reaction pressure is 1.5MPa, the molar ratio of hydrogen to hydrogen storage medium is 12:1, and the volume space velocity is 0.5h ^-1 , in the hydrogen storage reactor The hydrogen storage product is obtained by reacting in the medium; the hydrogen storage product enters from the side wall inlet of the first separator, and the gas-liquid separation is carried out in the first separator to obtain the hydrogen storage liquid and the remaining hydrogen. The hydrogen storage liquid is cyclohexane and methyl Cyclohexane mixture; the first gas phase outlet outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen is connected to the hydrogen pipeline through the remaining 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 passes through The pipeline enters the reformer.

The heating furnace heats the hydrogen storage liquid, reforming raw material naphtha, and hydrogen and transports them to the top of the reforming reactor. The reforming reactor is filled with 100 mL of reforming catalyst, and the feed rate of the hydrogen storage liquid is 10 mL/h. The feed rate is 90mL/h, the hydrogen feed rate is 80L/h, the temperature inside the reforming reactor is 515°C, and the reaction pressure is 0.4MPa. The side wall inlet of the separator enters the second separator, and then performs gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, and part of the hydrogen is used as a product for hydrofining, hydrocracking and other processes, and the other part The hydrogen is input into the heating furnace for the reforming reaction cycle; the liquid phase product in the reformed product is output from the second liquid phase outlet, enters the rectification tower from the side wall inlet, and outputs benzene and toluene from the BTX outlet in the middle of the rectification tower after reaction. Output light hydrocarbons and gasoline from the upper part of the rectification tower, output C9 aromatics and heavy aromatics from the lower part of the rectification tower; benzene and toluene are recycled as hydrogen storage media.

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

Example 8

Hydrogen gas and hydrogen storage medium are fed from the top of the hydrogen storage reactor. The hydrogen storage medium is a mixture of benzene and xylene with a molar ratio of 1:1. The hydrogen storage reactor is filled with 100mL of self-made hydrogen storage catalyst, and the feed volume of hydrogen storage medium is 70mL/ h, the hydrogen feed rate is 133L/h, the temperature inside the hydrogen storage reactor is 260°C, the reaction pressure is 5MPa, the molar ratio of hydrogen to hydrogen storage medium is 9:1, and the volume space velocity is 0.7h ^-1 , in the hydrogen storage reactor The hydrogen storage product is obtained by the reaction in the medium; the hydrogen storage product enters from the side wall inlet of the first separator, and the gas-liquid separation is carried out in the first separator to obtain the hydrogen storage liquid and the remaining hydrogen. The hydrogen storage liquid is cyclohexane and dimethyl base cyclohexane mixture; the first gas phase outlet outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen is connected with the hydrogen pipeline through the remaining hydrogen pipeline, and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid, the hydrogen storage liquid Enter the reformer through the pipeline.

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

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

Example 9

Hydrogen gas and hydrogen storage medium are fed from the top of the hydrogen storage reactor. The hydrogen storage medium is a mixture of toluene and xylene with a molar ratio of 1:1. The hydrogen storage reactor is filled with 100mL of self-made hydrogen storage catalyst, and the feed volume of hydrogen storage medium is 40mL/ h, the hydrogen feed rate is 88L/h, the temperature in the hydrogen storage reactor is 210°C, the reaction pressure is 1.8MPa, the molar ratio of hydrogen to the hydrogen storage medium is 11:1, and the volume space velocity is 0.4h ^-1 . The hydrogen storage product is obtained by reaction in the container; the hydrogen storage product enters from the side wall inlet of the first separator, and the gas-liquid separation is carried out in the first separator to obtain the hydrogen storage liquid and the remaining hydrogen gas, and the hydrogen storage liquid is methylcyclohexane and dimethylcyclohexane mixture; the first gas phase outlet outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen is connected with the hydrogen pipeline through the remaining hydrogen pipeline, and continues to be used as a hydrogen storage raw material; the first liquid phase outlet outputs the hydrogen storage liquid, The hydrogen storage liquid is fed into the reformer through the pipeline.

The heating furnace heats the hydrogen storage liquid, reforming raw material naphtha, and hydrogen and transports them to the top of the reforming reactor. The reforming reactor is filled with 100 mL of reforming catalyst, and the feed rate of the hydrogen storage liquid is 10 mL/h. The feed rate is 90mL/h, the hydrogen feed rate is 60L/h, the temperature in the reforming reactor is 520°C, the reaction pressure is 0.5MPa, and the volume space velocity is 1.0h ^-1 , and the reaction is carried out in the reforming reactor to obtain the heavy The whole product, the reformed product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, and a part of the hydrogen is used as a product for hydrofining, It is used in hydrocracking and other processes, and another part of hydrogen is input into the heating furnace for the recycling of reforming reaction; the liquid phase product in the reforming product is output from the second liquid phase outlet, and enters the rectification tower from the side wall inlet. Toluene and xylene are output from the BTX outlet in the middle of the tower, light hydrocarbons and gasoline are output from the upper part of the rectification tower, and C9 aromatics and heavy aromatics are output from the lower part of the rectification tower; toluene and xylene are recycled as hydrogen storage media.

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

Example 10

Hydrogen gas and hydrogen storage medium are fed from the top of the hydrogen storage reactor. The hydrogen storage medium is a mixture of benzene, toluene and xylene in a molar ratio of 1:1:1. The hydrogen storage reactor is filled with 100mL self-made hydrogen storage catalyst, and the hydrogen storage medium is fed The volume is 50mL/h, the hydrogen feed rate is 106L/h, the temperature inside the hydrogen storage reactor is 200°C, the reaction pressure is 2MPa, the molar ratio of hydrogen to hydrogen storage medium is 10:1, and the volume space velocity is 0.5h ^-1 . The hydrogen storage product is reacted in the hydrogen storage reactor; the hydrogen storage product enters from the side wall inlet of the first separator, and the gas-liquid separation is carried out in the first separator to obtain the hydrogen storage liquid and the remaining hydrogen gas, and the hydrogen storage liquid is cyclohexane A mixture of alkane, methylcyclohexane and dimethylcyclohexane; the first gas phase outlet outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen is connected with the hydrogen pipeline through the remaining hydrogen pipeline, and continues to be used as a raw material for hydrogen storage; the first liquid The hydrogen storage liquid is output from the phase outlet, and the hydrogen storage liquid is input into the reforming device through the pipeline.

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

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

Comparative example 1

Hydrogen and hydrogen storage medium benzene are fed from the top of the hydrogen storage reactor, and the hydrogen storage reactor is filled with 100mL of nickel-based catalyst. The temperature inside the vessel is 200°C, the reaction pressure is 2MPa, the molar ratio of hydrogen to benzene is 10:1, and the volumetric space velocity is 0.5h ^-1 , the reaction in the hydrogen storage reactor is to obtain the hydrogen storage product; the hydrogen storage product is obtained from the first separator The side wall inlet enters, and the gas-liquid separation is carried out in the first separator to obtain the hydrogen storage liquid cyclohexane and the remaining hydrogen; the first gas phase outlet outputs the remaining hydrogen in the hydrogen storage product, and the remaining hydrogen communicates with the hydrogen pipeline through the remaining hydrogen pipeline , and continue to be used as a raw material for hydrogen storage; the first liquid phase outlet outputs hydrogen storage liquid cyclohexane, and cyclohexane is input into the reforming device through a pipeline.

The heating furnace heats the hydrogen storage liquid cyclohexane, reforming raw material naphtha, and hydrogen to the top of the reforming reactor. The reforming reactor is filled with 100 mL of reforming catalyst, and the feed rate of cyclohexane is 10 mL/h. The feed rate of naphtha is 90mL/h, the feed rate of hydrogen gas is 70L/h, the temperature inside the reforming reactor is 520°C, the reaction pressure is 0.3MPa, and the volume space velocity is 1.0h ^-1 . The reformed product is obtained by the reaction, and the reformed product enters the second separator from the side wall inlet of the second separator, and then undergoes gas-liquid separation; the gas phase product in the reformed product is output from the second gas phase outlet, and part of the hydrogen is supplied as a product for addition. Hydrogen refining, hydrocracking and other processes are used, and another part of the hydrogen is input into the heating furnace for the recycling of the reforming reaction; the liquid phase product in the reforming product is output from the second liquid phase outlet, and enters the rectification tower from the side wall inlet, and after the reaction Benzene is output from the BTX outlet in the middle of the rectification tower, light hydrocarbons and gasoline are output from the upper part of the rectification tower, and C9 aromatics and heavy aromatics are output from the lower part of the rectification tower; benzene is recycled as a hydrogen storage medium.

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

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.

Claims (10)

1. A green hydrogen storage coupling catalytic reforming device is characterized by 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), a self-made hydrogen storage catalyst is filled in the hydrogen storage reactor (101), and the bottom outlet of the hydrogen storage reactor (101) is communicated with 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 rectifying tower (204), wherein an outlet of the heating furnace (201) is communicated with a top inlet of the reforming reactor (202), a bottom outlet of the reforming reactor (202) is communicated with a side wall inlet of the second separator (203), and a bottom outlet of the second separator (203) is communicated with a side wall inlet of the rectifying tower (204).

2. A storage-coupled catalytic reforming device for hydrogen green according to claim 1, wherein the hydrogen storage device (1) further comprises a first raw material pump (103), a hydrogen pipeline (111) is connected to the top inlet of the hydrogen storage reactor (101), and 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), the bottom of the first separator is provided with a first liquid phase outlet (122), and the first gas phase outlet (121) is communicated with 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, the first liquid phase outlet (122) outputs a hydrogen storage liquid, which is fed to the reformer (2) via a pipeline or a vehicle; the hydrogen storage medium is one or more of benzene, toluene or xylene.

3. A hcd-coupled catalytic reformer in accordance with claim 1, wherein said reformer (2) further comprises a second feedstock pump (205), said heater (201) has a feedstock line (211) connected to an inlet, and the reformed feedstock is fed into the feedstock line (211) by said second feedstock pump (205); the reforming reactor (202) is internally filled with a reforming catalyst; the top of the second separator (203) is provided with a second gas phase outlet (231), the bottom of the second separator is provided with a second liquid phase outlet (232), the second gas phase outlet (231) is communicated with a product hydrogen pipeline (234) through a circulating hydrogen pipeline (233), and the second liquid phase outlet (232) is communicated with a side wall inlet of the rectifying tower (204); the upper portion of rectifying column (204) is equipped with light hydrocarbon export and gasoline export, and the middle part is equipped with BTX export (241), and the lower part is equipped with C9 arene export and heavy aromatics export.

4. The green hydrogen storage coupling catalytic reforming device according to claim 1, wherein the preparation method of the self-made hydrogen storage catalyst comprises the following steps:

(A) Dispersing 150-350 parts of pseudo-boehmite in 1-5 wt% dilute nitric acid solution, then placing the dispersion solution into a kneading machine for kneading for 30-60 min, extruding and molding, drying the obtained product at 80-120 ℃ for 4-6 h, and then roasting at 300-500 ℃ for 6-12 h to obtain Al ₂ O ₃ A carrier;

(B) 200-400 parts of Ni (NO) ₃ ) ₂ ·6H ₂ O, 1-5 parts of PtCl ₄ Dissolving the Al in deionized water to prepare a solution, and then adding the Al obtained in the step (A) ₂ O ₃ Adding the carrier into the solution, and uniformly mixing to obtain a mixed solution;

(C) The mixed solution obtained in the step (B) is subjected to rotary evaporation at the temperature of 80-120 ℃ to remove moisture, and then drying and roasting are carried out to obtain the self-made hydrogen storage catalyst Ni-Pt/Al ₂ O ₃ 。

5. The coupled catalytic reforming unit for storing green hydrogen as claimed in claim 4, wherein in the step (C), the drying temperature is 80-150 ℃ and the drying time is 4-6 h; the roasting temperature is 300-500 ℃, and the roasting time is 4-6 h.

6. A green hydrogen storage coupling catalytic reforming process, which utilizes the green hydrogen storage coupling catalytic reforming device as claimed in any one of claims 1 to 5, and is characterized by comprising the following specific steps: feeding hydrogen and a hydrogen storage medium from the top of the hydrogen storage reactor (101), and reacting in the hydrogen storage reactor (101) to obtain a hydrogen storage product; the hydrogen storage product enters from the inlet on the side wall of the first separator (102), and gas-liquid separation is carried out 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 conveys the heated hydrogen to the top of the reforming reactor (202), the heated hydrogen is reacted in the reforming reactor (202) to obtain a reforming product, the reforming product enters the second separator (203) from the inlet of the side wall of the second separator (203), and then gas-liquid separation is carried out; the gas phase product in the reformed product is output from a second gas phase outlet (231); the liquid phase product in the reformed product is output from a second liquid phase outlet (232), enters the rectifying tower (204) from a side wall inlet, and is output BTX from the middle part of the rectifying tower (204) after reaction; the BTX is recycled as a hydrogen storage medium.

7. The green-hydrogen storage coupled catalytic reforming process according to claim 6, wherein the reaction temperature in the hydrogen storage reactor (101) is 100-300 ℃ and the reaction pressure is 0.5-6 MPa.

8. The green-hydrogen storage coupled catalytic reforming process according to claim 6, wherein the molar ratio of hydrogen to hydrogen storage medium in the hydrogen storage reactor (101) is 4-15: 1, the volume space velocity is 0.1 to 3 hours ^-1 。

9. The storage-coupled catalytic reforming process of claim 6, wherein the reaction temperature in the reforming reactor (202) is 500-530 ℃ and the reaction pressure is 0.3-1 MPa.

10. The green-hydrogen storage coupled catalytic reforming process of claim 6, wherein the hydrogen gas: the volume ratio of the mixture is 200-800:1, wherein the mixture consists of hydrogen storage liquid and reforming raw materials, and the volume ratio of the hydrogen storage liquid to the reforming raw materials is not 5-15: 95 to 85 percent, and the volume space velocity is 1 to 3 hours ^-1 。

Images