A green coupling hydrogen production system and method

Abstract

The application provides a green coupling hydrogen production system and method, which comprises a green electricity system, a catalyst preparation and hydrogen production system, an aluminum recovery system and a catalytic hydrogenation system. Green electricity generated by renewable energy is used to form aluminum-based alloy through smelting, the aluminum-based alloy is crushed and dealloyed to form a high-efficiency porous catalyst, and high-purity hydrogen is generated. Finally, the generated hydrogen and catalyst are used for catalytic hydrogenation reaction to produce high-value-added chemicals. In addition, aluminum salt obtained from the aluminum-based alloy is precipitated and calcined to obtain alumina, the green electricity is passed into the alumina, and the alumina is electrolyzed to obtain aluminum, and the aluminum raw material enters the cycle again. In the application, the hydrogen produced by coupling has high purity, does not need to be separated, and has a fast hydrogen production rate, the porous catalyst produced by coupling has excellent performance and is widely used, the metal aluminum is recycled, the entire system uses green electricity, the entire process is green, and there is no carbon emission.

Description

Technical Field

[0001] This invention belongs to the field of new energy and new material preparation technology, and relates to a system and method for green coupling of hydrogen production and catalyst creation. Background Technology

[0002] Hydrogen energy is an important component of the future national energy system and a crucial vehicle for achieving a green and low-carbon transformation. Therefore, developing hydrogen production technology is particularly important for improving the hydrogen energy industry chain.

[0003] Currently, mature hydrogen production technologies include hydrogen production from fossil fuels, industrial by-product hydrogen, and water electrolysis. However, hydrogen produced from fossil fuels and industrial by-products is classified as gray or blue hydrogen, and its production process generates large amounts of carbon dioxide. Hydrogen produced by water electrolysis is classified as green hydrogen, and combined with renewable energy power generation, it can achieve the goal of almost zero carbon emissions in the hydrogen production process. However, the cost of hydrogen production is high, and the investment cost of electrolyzers is also high, which is not conducive to distributed hydrogen production. Therefore, it is crucial to develop new hydrogen production technologies suitable for distributed production.

[0004] Aluminum hydrolysis for hydrogen production has advantages such as low equipment investment and high hydrogen purity. For example, patents CN101525119A, CN101665239A, and CN101428758A disclose a variety of aluminum-based hydrogen production devices, which are characterized by simple equipment and portability. However, aluminum-based hydrogen production has problems such as slow hydrogen production rate and high cost. To increase the hydrogen production rate, patent CN108975269A discloses a high-energy ball milling method, which adds various organic substances and organic solvents to aluminum powder, increasing costs and making aluminum unrecoverable. Similarly, patents CN101428757A and CN101249939A disclose a formula for hydrogen production by hydrolysis of aluminum, adding inorganic salts such as AlCl3 and AlBr3 to aluminum powder, increasing hydrogen production costs and offering no aluminum recovery. Furthermore, patent CN105819399A discloses a method for controlling the rate of aluminum-based hydrogen production, adding solid catalysts and slow-release agents to the system, leading to increased hydrogen production costs and making aluminum unrecoverable.

[0005] Patent CN109795984A discloses a recyclable, integrated system and method for producing hydrogen from aluminum by electrolyzing aluminum using renewable energy. This system utilizes renewable energy to generate electricity for aluminum recovery. However, the hydrogen production rate is slow, and the addition of a slow-release agent affects the purity of the recovered aluminum. Furthermore, the high cost of hydrogen production remains a problem. Only by coupling aluminum production with hydrogen production to generate high-value-added products can the cost of hydrogen production be reduced.

[0006] Furthermore, the high cost of hydrogen storage and transportation makes it crucial to achieve on-demand hydrogen production, requiring hydrogen production technology to be distributed. Therefore, developing new green hydrogen production technologies that are suitable for distributed hydrogen production, low in cost, and can be coupled with integrated technologies for catalyst preparation and hydrogen utilization is of great significance. Summary of the Invention

[0007] The purpose of this invention is to overcome the above-mentioned problems in the prior art and provide a green coupled hydrogen production system and method, which includes a renewable energy power generation system, a catalyst preparation and hydrogen production system, an aluminum recovery system, and a catalytic hydrogenation system.

[0008] The technical solution of this invention is as follows:

[0009] A green coupled hydrogen production system and method are provided, comprising a green electricity system, a catalyst preparation and hydrogen production system, an aluminum recovery system, and a catalytic hydrogenation system. The catalyst preparation and hydrogen production system includes metals, aluminum-based alloys, water, porous catalysts, and hydrogen, while the aluminum recovery system includes aluminum and aluminum salts.

[0010] First, green electricity is generated by a green electricity system. This green electricity is then fed into a catalyst preparation and hydrogen production system, where it is used to smelt metals and aluminum to obtain aluminum-based alloys. These aluminum-based alloys are then coupled with hydrogen production to produce porous catalysts and hydrogen gas. Finally, the porous catalysts and hydrogen gas are fed into a catalytic hydrogenation system to react and produce high-value-added chemicals.

[0011] In addition, aluminum-based alloys react with water to obtain aluminum salts, which are then precipitated and calcined to obtain alumina. Green electricity is passed into the alumina, and the alumina is electrolyzed to obtain aluminum, which then enters the recycling process.

[0012] As a preferred option, green electricity systems generate electricity by combining one or more renewable energy sources, such as wind, solar, hydro, biomass, geothermal, and ocean energy.

[0013] As a preferred option, the precursor of the aluminum-based alloy includes one or more metallic elements such as nickel, copper, iron, cobalt, molybdenum, chromium, titanium, cerium, and manganese, with an atomic content between 5% and 20%.

[0014] As a preferred method, aluminum-based alloys are crushed to a mesh size of 80 or higher, and inorganic strong alkalis are added to dealloy the aluminum-based alloys. A porous metal catalyst and high-purity hydrogen are then produced through a coupled hydrogen production reaction, with the hydrogen purity reaching over 99.9%.

[0015] As a preferred option, the hydrogen production rate coupled with aluminum-based alloys is 0.05-0.6 kg H2 / h kg.

[0016] As a preferred option, the precipitant used for aluminum salt precipitation is one or a combination of dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, CO2, and electrolytic aluminum tail gas.

[0017] As a preferred embodiment, the catalytic hydrogenation reaction is one of the following: olefin hydrogenation, alkyne hydrogenation, aromatic hydrocarbon hydrogenation, nitro hydrogenation, cyano hydrogenation, carbonyl hydrogenation, hydrodeoxygenation, denitrification, and desulfurization.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] ① The entire process is green and environmentally friendly, producing no carbon emissions;

[0020] ② The prepared porous metal catalyst has high activity and a wide range of applications;

[0021] ③ The hydrogen produced has high purity, requires no separation, and the hydrogen production rate is adjustable;

[0022] ④ This achieves the recycling of aluminum resources, saving costs;

[0023] ⑤ The prepared hydrogen and catalyst are directly used for catalytic hydrogenation reaction, which reduces the storage and transportation of hydrogen and saves costs.

[0024] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0025] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0026] Figure 1 This is a schematic diagram of the hydrogen production system coupled according to the present invention.

[0027] Figure 2 This is an XRD diffraction pattern of part of the catalyst in this invention.

[0028] Figure 3 This is a partial pore size distribution diagram of the catalyst in this invention. Detailed Implementation

[0029] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] The present invention will be further described in detail below with reference to the accompanying drawings.

[0031] Example 1

[0032] The photovoltaic power generation system uses solar cell modules (photovoltaic arrays) to absorb light energy, generate direct current (DC) which is stored in the battery bank, and then converted into alternating current (AC) by an inverter for use in all subsequent power-consuming units.

[0033] Electricity is supplied to the smelting workshop, where a high-current heating electromagnetic coil is passed through a high-temperature induction melting furnace to melt pure nickel and pure aluminum. The mixture is then stirred mechanically to form a molten alloy, which is poured into a molding die and rapidly cooled to form an alloy block. The generated electricity is then fed into a crushing device, employing a combination of jaw crusher and disc mill to crush the alloy block to a mesh size of 80 or larger. Alloy materials that cannot pass through the 80-mesh sieve are repeatedly disc-milled until all the alloy raw materials pass through the sieve.

[0034] In the catalyst preparation room, the alloy is dealloyed using a reaction vessel. The dealloying reagent is NaOH solution, with the NaOH concentration adjusted (0.01M-6M) and the reaction temperature controlled (0-90°C). o C) To achieve the controllable synthesis of porous nickel-based catalysts and the regulation of hydrogen production rate until no gas is produced (monitored by a gas flow meter), porous nickel-based catalysts with different structural phases and hydrogen gas with a purity higher than 99.9% were finally obtained, and the hydrogen production rate was regulated (as shown in Table 1). Simultaneously, an alkaline solution of sodium aluminate was produced. The porous nickel catalyst was separated from the reactor for later use, and the hydrogen gas was dried by adsorption and then stored in a tank for later use.

[0035] In the catalytic hydrogenation operation room, green electricity provides the energy required for catalytic hydrogenation. The produced porous nickel-based catalyst and hydrogen are directly used in the batch-type hydrogenation reaction of 1,4-butynediol to 1,4-butanediol (1,4-butynediol (5 wt%), catalyst / 1,4-butynediol (10 wt%), reaction temperature 50 °C). o At C, reaction pressure 2 MPa, reaction time 1.5 h), it exhibits excellent catalytic performance, with a faster reaction rate and higher selectivity compared to industrial Raney nickel catalysts (1,4-butynediol conversion rate 88%, 1,4-butanediol selectivity 92%).

[0036] In the catalyst preparation room, electrolytic aluminum tail gas (mainly carbon dioxide) is passed into a sodium aluminate alkaline solution. The tail gas flow rate is adjusted to control the pH of the solution between 9 and 10. Aluminum hydroxide precipitate gradually forms. When the solution becomes weakly acidic, the precipitation is complete, and the aluminum hydroxide precipitate is recovered by filtration. The solution is then transferred to the aluminum recovery room, where the aluminum hydroxide is dried and calcined in a muffle furnace to obtain alumina raw material (600). oC) Backup. Green electricity is introduced into the electrolytic cell. In the electrolytic cell, alumina is used as the cathode and carbon as the anode. Alumina is electrolytically reduced to aluminum. After electrolysis, the molten aluminum is poured into a mold to form a shape. After cooling, the aluminum raw material needed for alloy smelting is obtained. The exhaust gas generated at the anode is connected to a sodium aluminate alkaline solution for purification and also as a precipitant. The entire system is as follows: Figure 1 As shown.

[0037] Table 1

[0038]

[0039] Example 2

[0040] The system uses a wind power generation system to generate electricity, which is converted from wind energy into electrical energy. The generated AC power is charged, rectified, and stored in a battery bank for use in all subsequent power-consuming units.

[0041] Electricity is supplied to the smelting workshop, where a high-current heating electromagnetic coil is passed through a high-temperature induction melting furnace to melt pure metal and pure aluminum. The mixture is then stirred mechanically to form a molten alloy, which is poured into a molding die and rapidly cooled to form an alloy block. The generated electricity is then introduced into a crushing device, employing a combination of jaw crusher and disc mill to crush the alloy block to a mesh size of 80 or larger. Alloy materials that cannot pass through an 80-mesh sieve are repeatedly disc-milled until all the alloy raw materials pass through the sieve.

[0042] In the catalyst preparation room, the alloy was dealloyed using a reaction vessel. The dealloying reagent was a 0.5 M NaOH solution, and the dealloying temperature was 30 °C. o C, until no more gas is produced (monitored by a gas flow meter), ultimately yielding a porous metal catalyst and hydrogen with a purity higher than 99.9%, with the hydrogen production rate varying accordingly (as shown in Table 2). Simultaneously, an alkaline solution of sodium aluminate is produced. The porous catalyst is separated from the reactor for later use, and the hydrogen, after adsorption drying, is stored in a tank for later use.

[0043] In the catalytic hydrogenation operation room, green electricity provides the energy required for catalytic hydrogenation, and the produced porous metal catalyst and hydrogen are directly used in the catalytic hydrogenation reaction (as shown in Table 3), which exhibits excellent catalytic performance.

[0044] In the catalyst preparation room, dilute hydrochloric acid was slowly added to the sodium aluminate alkaline solution, controlling the pH value of the solution between 9 and 10. Aluminum hydroxide precipitate gradually formed. When the solution became weakly acidic, the precipitation was complete, and the aluminum hydroxide precipitate was recovered by filtration. The solution was then transferred to the aluminum recovery room, where the aluminum hydroxide was dried and calcined in a muffle furnace to obtain alumina raw material (600). oC) Backup. Green electricity is introduced into the electrolytic cell device. In the electrolytic cell, alumina is used as the cathode and carbon is used as the anode. Alumina is electrolytically reduced to aluminum. After electrolysis is completed, the aluminum liquid is poured into a mold to form a shape. After cooling, the aluminum raw material required for smelting alloys can be obtained.

[0045] Table 2

[0046]

[0047] Table 3

[0048]

[0049] Figure 2 The XRD diffraction pattern of the catalyst obtained in this invention shows that the phase composition of the catalyst can be controlled, combined with... Figure 3 It can be seen that the prepared catalysts all have a porous structure and a high specific surface area.

[0050] Example 3

[0051] The system uses a wind power generation system to generate electricity, which is converted from wind energy into electrical energy. The generated AC power is charged, rectified, and stored in a battery bank for use in all subsequent power-consuming units.

[0052] Electricity is supplied to the smelting workshop, where a high-current heating electromagnetic coil is passed through a high-temperature induction melting furnace to melt pure cobalt and pure aluminum. The mixture is then stirred mechanically to form a molten alloy, which is poured into a molding die and rapidly cooled to form an alloy block. The generated electricity is then fed into a crushing device, employing a combination of jaw crusher and disc mill to crush the alloy block to a mesh size of 80 or larger. Alloy materials that cannot pass through an 80-mesh sieve are repeatedly disc-milled until all the alloy raw materials pass through the sieve.

[0053] In the catalyst preparation room, the alloy was dealloyed using a reaction vessel. The dealloying reagent was a 4M NaOH solution, and the dealloying temperature was 30°C. o C, until no more gas is produced (monitored by a gas flow meter), ultimately yielding the corresponding porous cobalt catalyst and hydrogen gas with a purity higher than 99.9%, while simultaneously producing an alkaline solution of sodium aluminate. The porous catalyst is separated from the reactor for later use, and the hydrogen gas is dried by adsorption and then stored in a tank for later use.

[0054] In the catalytic hydrogenation operation room, green electricity provides the energy required for catalytic hydrogenation, and the produced porous cobalt catalyst and hydrogen are directly used for the carbon dioxide hydrogenation reaction, exhibiting excellent catalytic performance.

[0055] In the catalyst preparation room, dilute acids of varying concentrations are slowly added to the sodium aluminate alkaline solution, or electrolytic aluminum tail gas (mainly carbon dioxide) is introduced to control the pH value of the solution between 9 and 10. Aluminum hydroxide precipitate gradually forms, and precipitation is complete when the solution becomes weakly acidic. The precipitate is then filtered and recovered. The solution is transferred to the aluminum recovery room, where the aluminum hydroxide is dried and calcined in a muffle furnace to obtain alumina raw material (600). o C) Backup. Green electricity is introduced into the electrolytic cell device. In the electrolytic cell, alumina is used as the cathode and carbon is used as the anode. Alumina is electrolytically reduced to aluminum. After electrolysis is completed, the aluminum liquid is poured into a mold to form a shape. After cooling, the aluminum raw material required for smelting the alloy can be obtained. The aluminum recovery rate is shown in Table 4.

[0056] Table 4

[0057]

[0058] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

[0059] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A green coupled hydrogen production method, comprising a green electricity system, a catalyst preparation and hydrogen production system, an aluminum recovery system, and a catalytic hydrogenation system, wherein the catalyst preparation and hydrogen production system comprises a metal, an aluminum-based alloy, water, a porous catalyst, and hydrogen; and the aluminum recovery system comprises aluminum and aluminum salts; characterized in that, The green electricity system generates green electricity, which is then fed into the catalyst preparation and hydrogen production system for smelting metals and aluminum to obtain an aluminum-based alloy. The aluminum-based alloy is coupled with hydrogen production to obtain a porous catalyst and hydrogen. The porous catalyst and hydrogen are then fed into a catalytic hydrogenation system to react and obtain high-value-added chemicals. Aluminum-based alloy coupled hydrogen production refers to the process of producing porous catalysts and hydrogen from aluminum-based alloys through crushing and dealloying. Inorganic strong bases were selected as reagents for dealloying the aluminum-based alloys. The dealloying reaction of the aluminum-based alloy also yields aluminate, which is then precipitated and calcined to obtain alumina. The green electricity is passed into the alumina, and the alumina is electrolyzed to obtain aluminum, which then enters the recycling process.

2. The method of claim 1, wherein, The green electricity system generates electricity from one or more renewable energy sources, including wind, solar, hydro, biomass, geothermal, and ocean energy.

3. The green coupled hydrogen production method according to claim 1, characterized in that, The precursor of the aluminum-based alloy includes one or more metallic elements such as nickel, copper, iron, cobalt, molybdenum, chromium, titanium, cerium, and manganese, with an atomic content between 5% and 20%.

4. The green coupled hydrogen production method according to claim 1, characterized in that, The aluminum-based alloy is crushed to a mesh size of 80 or higher.

5. The green coupled hydrogen production method according to claim 1, characterized in that, The porous catalyst is a porous metal catalyst, and the hydrogen has a purity of over 99%.

6. The green coupled hydrogen production method according to claim 1, characterized in that, The hydrogen production rate coupled by the aluminum-based alloy is 0.05-0.6 kg H2 / h·kg.

7. The green coupled hydrogen production method according to claim 1, characterized in that, The precipitant used for aluminum salt precipitation is one or a combination of dilute hydrochloric acid, dilute sulfuric acid, dilute nitric acid, CO2, and electrolytic aluminum tail gas.

8. The green coupled hydrogen production method according to claim 1, characterized in that, The catalytic hydrogenation reaction is one of the following: olefin hydrogenation, alkyne hydrogenation, aromatic hydrocarbon hydrogenation, nitro hydrogenation, cyano hydrogenation, carbonyl hydrogenation, hydrogenation deoxygenation, denitrification, and desulfurization.

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