High-temperature steel slag rotational flow oscillation enhanced hydrothermal hydrogen production method and device

Abstract

The invention discloses a high-temperature steel slag rotational flow oscillation enhanced hydrothermal hydrogen production method and device, belongs to the technical field of hydrogen preparation, and aims to solve the problem of how to fully utilize heat energy of high-temperature steel slag to improve the hydrogen production effect. According to the hydrogen production method provided by the invention, on the basis of the surface heat exchange reaction of the porous steel slag particles, a particle pore channel heat exchange reaction mechanism is further formed, and the hydrogen production effect of the reaction of the porous steel slag particles and water vapor is effectively promoted; by controlling a three-dimensional rotating turbulent flow field, the three-dimensional rotating turbulent flow field at least has a flow field section with the size changing alternately, a reaction interface is promoted to expand from the surfaces of porous steel slag particles to internal pore channels, it can be guaranteed that reaction products can be discharged out of the pore channels in time, and water vapor can be supplemented into the pore channels in time; and the water vapor entering the pore channel can be ensured to continuously oscillate to generate a heat exchange reaction, so that the porous steel slag particles and the water vapor can continuously react, and the hydrogen production effect is ensured.

Description

Technical Field

[0001] The present invention belongs to the technical field of hydrogen production, and particularly relates to a method and device for enhancing hydrothermal hydrogen production by swirling oscillation of high-temperature steel slag. Background Art

[0002] The iron and steel industry produces a large amount of steel slag every year (accounting for 8% - 15% of the crude steel output). The traditional treatment method mainly focuses on landfill, which has problems such as land occupation, heavy metal pollution, and resource waste. Steel slag is rich in FeO (20% - 30%) and other iron oxides, and has high-temperature melting characteristics (1300 - 1700°C), which can provide a thermal energy basis for chemical reactions. By directly reacting uncooled liquid high-temperature steel slag with water vapor, hydrogen can be produced while cooling the high-temperature steel slag, which can avoid the energy consumption of secondary heating and solve the problem of waste residue disposal at the same time. The reaction principle of high-temperature steel slag and water vapor is as follows:

[0003]

[0004] For example, the Chinese utility model patent with the publication number CN216638917U discloses a hydrogen production system from liquid steel slag, which adopts the method of introducing water vapor into the liquid steel slag from the bottom, so that the water vapor undergoes a chemical reaction to produce hydrogen after contacting the high-temperature liquid steel slag; at the same time, the heat energy of the overflowing gas is recovered through heat exchange, and part of the heat energy in the liquid steel slag is recovered. The Chinese invention patent application with the publication number CN119503728A discloses a method for preparing H2-CO energy gas using steel slag, and proposes to spray a weakly oxidizing gas containing water vapor onto the surface of the high-temperature liquid steel slag to oxidize FeO in the steel slag, so that hydrogen and carbon monoxide gases are generated while the iron oxide is transformed into an easily separable magnetic phase, improving the comprehensive utilization rate of steel slag.

[0005] However, when the liquid steel slag reacts with water vapor, the reaction interface only stays on the surface of the liquid steel slag; when the surface of the liquid steel slag cools, it is covered by the reaction product Fe2O3, which hinders the heat and mass transfer process between the water vapor and the liquid steel slag, resulting in waste of the internal heat energy of the steel slag. Therefore, to improve the hydrogen production effect, on the one hand, it is necessary to fully and quickly utilize the internal heat energy of the liquid steel slag, which essentially is to improve the heat transfer performance between the steel slag and the gas; on the other hand, it is necessary to increase the contact between the gas and the steel slag, such as providing more reaction interfaces. In recent years, in the gas-solid heat exchange requirements of different industries, the method of applying a swirl heat exchanger to promote heat transfer between gas and particle two-phase has certain potential. It can be seen from the convective heat transfer formula (Formula 1) that the essential reason is that the rotation of the particles can make the gas flowing in a spiral fully contact, promoting the improvement of the convective heat transfer coefficient (k), and thus improving the heat transfer efficiency. Similarly, many studies have shown that the heat transfer performance can be improved by reducing the particle size to increase the gas-solid contact area (A).

[0006] (1)

[0007] In previous hydrogen production devices, the coupling characteristics between the structural characteristics of particles and swirling flow were often overlooked. When molten steel slag reacts, high-temperature porous particles are formed under the influence of decreasing surface temperature and gas flow. The porosity of the porous steel slag can reach 12.05%, and the specific surface area of the porous steel slag can reach 0.4 m 2 / g. The rich pore structure (visible pores, macropores, micropores, mesopores, etc.) can provide more reaction interfaces. How to improve the heat transfer effect between the porous steel slag and water vapor, thereby promoting the reaction between water vapor and porous steel slag to produce abundant hydrogen, is one of the problems that urgently need to be solved in the field of hydrogen production. Summary of the Invention

[0008] The present invention provides a method and device for enhancing hydrothermal hydrogen production by swirling oscillation of high-temperature steel slag, aiming to solve the problem of how to make full use of the thermal energy of high-temperature steel slag to improve the hydrogen production effect.

[0009] The technical solution adopted by the present invention to solve its technical problems is: a method for enhancing hydrothermal hydrogen production by swirling oscillation of high-temperature steel slag, including the following steps:

[0010] S1. Transport the molten steel slag and the pressurized hydrogen production reaction gas to the fluid-solid mixing zone respectively. The main component of the hydrogen production reaction gas is water vapor. The molten steel slag and water vapor exchange heat preliminarily and produce a hydrogen production reaction; after preliminary heat exchange, the molten steel slag cools down to form high-temperature porous steel slag particles, and is mixed with the gas phase in the fluid-solid mixing zone to form a fluid-solid mixture;

[0011] S2. Guide the fluid-solid mixture to perform a three-dimensional spiral motion to form a three-dimensional rotating turbulent flow field; the fluid-solid mixture performs a revolution around the center line of the three-dimensional rotating turbulent flow field. At the same time, the high-temperature porous steel slag particles rotate under the influence of the fluid velocity difference in the three-dimensional rotating turbulent flow field, so that the water vapor in the pores of the high-temperature porous steel slag particles oscillates and exchanges heat with it flashly and further produces a hydrogen production reaction;

[0012] S3. Control the three-dimensional rotating turbulent flow field so that it has at least one flow field section with alternating scales, so that the high-temperature porous steel slag particles are repeatedly affected by the rotating couple, thereby promoting the continuous progress of the hydrogen production reaction; the flow field section with alternating scales is: along the downward direction of the center line of the three-dimensional rotating turbulent flow field, the diameter of this flow field section first gradually becomes smaller and then gradually becomes larger;

[0013] S4. After sufficient reaction, perform gas-solid separation on the fluid-solid mixture to obtain a solid-phase product and a gas-phase product; the solid-phase product is low-temperature porous steel slag particles, and the main components of the gas-phase product are hydrogen, water vapor, carbon dioxide and carbon monoxide;

[0014] S5. React the excessive steam with carbon monoxide in the gas-phase product to generate carbon dioxide and hydrogen;

[0015] S6. Purify the gas-phase product to obtain hydrogen.

[0016] Furthermore, the feed flow rate of the pressurized hydrogen production reaction gas is 5 - 40 m / s, and the temperature is above 100 °C.

[0017] Furthermore, for the flow field section with alternating scales, its minimum diameter is 0.5 - 0.8 times the maximum inner diameter.

[0018] Furthermore, step S5 is as follows: Deliver a part of the gas-phase product as recycle gas to the fluid-solid mixing zone, and deliver the remaining part of the gas-phase product into the water-gas shift device to further react the carbon monoxide with excessive steam to generate carbon dioxide and hydrogen; the volume flow rate of the recycle gas accounts for 20% - 50% of the total volume flow rate of the gas-phase product;

[0019] Step S6 is as follows: After the remaining part of the gas-phase product further reacts, deliver it into a condenser to condense the steam into liquid water, and obtain a mixed gas mainly composed of carbon dioxide and hydrogen; deliver the liquid water into a steam generator, re-evaporate it into steam and then deliver it to the fluid-solid mixing zone; the mixed gas obtained by condensation and separation is subjected to pressure swing adsorption to obtain hydrogen with a purity of over 99.999%.

[0020] The present invention also provides a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device, including a feeding module, a fluid-solid swirling module, an oscillation excitation module, a fluid-solid separation module, and an exhaust module;

[0021] The feeding module is used to receive molten steel slag and pressurized hydrogen production reaction gas, and deliver the two to the fluid-solid mixing zone;

[0022] The fluid-solid swirling module includes a swirling device main body connected to the output end of the feeding module, and a swirling structure arranged in the swirling device main body for guiding the fluid-solid mixture to perform three-dimensional spiral motion; the inner cavity space of the swirling device main body above the swirling structure is the fluid-solid mixing zone;

[0023] The oscillation excitation module includes at least one variable-diameter cylinder section coaxially connected to the swirling device main body, and the inner diameter of the variable-diameter cylinder section gradually decreases first and then gradually increases along its own axis;

[0024] The input end of the fluid-solid separation module is connected to the output end of the oscillation excitation module, and is used to separate the solid-phase product and the gas-phase product;

[0025] The input end of the exhaust module is communicated with the gas-phase output end of the fluid-solid separation module, and is used to exhaust the gas-phase product externally.

[0026] Further, the feeding module includes two gas inlet pipes symmetrically arranged on the side of the swirler main body, and two high-temperature steel slag inlet pipes symmetrically arranged on the top of the swirler main body.

[0027] Further, the swirler main body is a cylindrical structure with a closed upper end, and the swirling structure includes at least two swirling vanes arranged in the swirler main body and distributed in an annular array around the axis of the swirler main body.

[0028] Further, the oscillation excitation module includes at least two coaxially arranged variable-diameter cylinder sections, and two adjacent variable-diameter cylinder sections are connected by a transition cylinder section;

[0029] The maximum inner diameter D of the variable-diameter cylinder section max is equal to the inner diameter D of the swirler main body, and its minimum inner diameter D min is 0.5 to 0.8 times the maximum inner diameter D max .

[0030] Further, the fluid-solid separation module includes an inverted cone cylinder connected to the lower end of the oscillation excitation module and coaxial with it, and a particle discharge pipeline is provided at the lower end of the inverted cone cylinder;

[0031] The exhaust module includes a gas discharge pipe, the gas discharge pipe is coaxially arranged with the swirler main body, its upper end has a gas discharge port higher than the swirler main body, and its lower end passes through the inner cavity of the swirler main body and the inner cavity of the variable-diameter cylinder section and extends into the inner cavity of the inverted cone cylinder.

[0032] Further, the hydrogen production device further includes a water-gas shift device, a condenser, a steam generator and a pressure swing adsorption device;

[0033] The output end of the exhaust module is respectively connected to the input end of the water-gas shift device and the input end of the feeding module;

[0034] The output end of the water-gas shift device is connected to the input end of the condenser;

[0035] The liquid-phase output end of the condenser is connected to the input end of the steam generator, and the gas-phase output end of the condenser is connected to the input end of the pressure swing adsorption device;

[0036] The output end of the steam generator is connected to the input end of the feeding module.

[0037] The beneficial effects of the present invention are as follows:

[0038] (1) The hydrogen production method provided by the present invention transports molten steel slag and pressurized hydrogen production reaction gas to a fluid-solid mixing zone respectively. After they are preliminarily heat-exchanged and a hydrogen production reaction occurs, they are mixed to form a fluid-solid mixture, and the fluid-solid mixture forms a three-dimensional rotating turbulent flow field, which enables the porous steel slag particles to rotate around their axes while making a revolution, thereby causing the water vapor in their pores to oscillate, flash heat-exchange with the porous steel slag particles, and further produce a hydrogen production reaction. On the basis of the heat-exchange reaction on the surface of the porous steel slag particles, a mechanism of heat-exchange reaction in the particle pores is further formed, which not only increases the heat-exchange area between the porous steel slag particles and water vapor, but also significantly improves the convective heat-transfer coefficient, strengthens the heat-transfer performance between gas-solid two phases, and effectively promotes the effect of hydrogen production by the reaction of porous steel slag particles and water vapor.

[0039] (2) By controlling the three-dimensional rotating turbulent flow field to have at least one flow field section with alternating scales, it not only promotes the reaction interface to expand from the surface of the porous steel slag particles to the pores inside them, ensures that the reaction products can be discharged from the pores in time, and water vapor can be replenished into the pores in time, but also ensures that the water vapor entering the pores continuously oscillates to undergo a heat-exchange reaction, so that the porous steel slag particles and water vapor can continuously react and ensure the hydrogen production effect.

[0040] (3) The hydrogen production device provided by the present invention mainly consists of a feeding module, a fluid-solid swirling module, an oscillation excitation module, a fluid-solid separation module, and an exhaust module. It can not only implement the above hydrogen production method, but also has a simple and compact structure, high hydrogen production efficiency, and low construction and maintenance costs of the equipment.

[0041] Other technical features of the present invention bring or directly produce technical effects, which will be described in detail in the subsequent specific implementation part. Description of the Drawings

[0042] Figure 1 is a flow block diagram of a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production method provided by the present invention;

[0043] Figure 2 is an implementation structure schematic diagram of a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device provided by the present invention;

[0044] Figure 3 is a hydrogen production principle diagram of a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device provided by the present invention;

[0045] The marks in the figure are: 100 - feeding module, 101 - gas inlet pipeline, 102 - steel slag inlet pipeline, 103 - gas discharge pipeline, 110 - fluid-solid swirling module, 111 - swirling blade, 120 - oscillation excitation module, 130 - fluid-solid separation module, 131 - particle discharge pipeline. Specific Implementation Modes

[0046] The present invention will be further described below in conjunction with the accompanying drawings and embodiments. The same reference numerals in the drawings denote components with the same or similar functions. Although various aspects of the embodiments are shown in the drawings, the drawings do not have to be drawn to scale unless otherwise specified.

[0047] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate the orientation or positional and dimensional relationships based on the orientation or positional relationships shown in the drawings. These are only for convenience of description and do not indicate or imply that the device or component referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation to the present invention.

[0048] When the term "plurality" represents a quantity, it generally refers to a quantity of three or more. For example, "a plurality" generally refers to three or more. The terms "about", "approximately", etc. when used to describe a numerical range generally refer to an error within ±10%. For example, about 100 mm generally refers to 90 - 110 mm. The expression of the term "mainly composed of... or constituted by..." is interpreted as also being able to contain structural components not mentioned in this sentence. In addition, the terms "first" and "second" are only for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0049] As Figure 1 shown, a method for enhancing hydrothermal hydrogen production by high-temperature steel slag swirl oscillation includes the following steps:

[0050] S1. Feed the molten steel slag and the pressurized hydrogen production reaction gas into the fluid-solid mixing zone respectively. The main component of the hydrogen production reaction gas is water vapor. The molten steel slag exchanges heat with the water vapor initially and undergoes a hydrogen production reaction. After the initial heat exchange, the molten steel slag cools down to form high-temperature porous steel slag particles, and is mixed with the gas phase in the fluid-solid mixing zone to form a fluid-solid mixture. The temperature of the molten steel slag is usually above 1400 °C. The hydrogen production reaction gas can be pure water vapor or a weakly oxidizing gas formed by mixing water vapor with carbon dioxide. The pressurized hydrogen production reaction gas is mainly obtained by mixing the hydrogen production reaction gas with a pressurizing gas. The pressurizing gas is generally argon or nitrogen, and the hydrogen production reaction gas is brought into the fluid-solid mixing zone by argon or nitrogen. The feed flow rate of the pressurized hydrogen production reaction gas is usually 5 - 40 m / s, and the temperature is above 100 °C. After the molten steel slag enters the fluid-solid mixing zone, it mainly exchanges heat and reacts with the water vapor on its surface, generating a small amount (compared with the subsequent production) of hydrogen.

[0051] S2. Guide the fluid-solid mixture to perform three-dimensional helical motion to form a three-dimensional rotating turbulent flow field. The fluid-solid mixture makes a revolution around the center line of the three-dimensional rotating turbulent flow field. At the same time, the high-temperature porous steel slag particles rotate under the influence of the fluid velocity difference around them in the three-dimensional rotating turbulent flow field, so that the water vapor in the pores of the high-temperature porous steel slag particles oscillates and exchanges heat with them flashly and further produces a hydrogen production reaction. Generally, a swirl structure such as a three-dimensional spiral groove, a swirl impeller, a swirl vane group, and a circular cavity tangential inlet structure can be used to guide the fluid-solid mixture to perform three-dimensional spiral motion. The high-temperature porous steel slag particles are applied with a rotating couple due to the gradient change of the rotating linear velocity in the three-dimensional rotating turbulent flow field, so as to rotate.

[0052] S3. Control the three-dimensional rotating turbulent flow field so that there is at least one flow field section with alternating scales, so that the high-temperature porous steel slag particles are repeatedly affected by the rotating couple, thereby promoting the continuous progress of the hydrogen production reaction. The flow field section with alternating scales is as follows: along the direction downward along the center line of the three-dimensional rotating turbulent flow field, the diameter of this flow field section first gradually decreases and then gradually increases. During the reaction process of this step, it not only promotes the reaction interface to expand from the surface of the porous steel slag particles to the pores inside them, and can ensure that the reaction products can be discharged in time and the water vapor can be replenished into the pores in time, but also can ensure that the water vapor entering the pores continuously oscillates to exchange heat and produce a hydrogen production reaction, so that the porous steel slag particles and the water vapor can continuously react to ensure the hydrogen production effect.

[0053] S4. After sufficient reaction, perform gas-solid separation on the fluid-solid mixture to obtain a solid-phase product and a gas-phase product. The solid-phase product is low-temperature porous steel slag particles, and the main components of the gas-phase product are hydrogen, water vapor, carbon dioxide, and carbon monoxide. Generally, the two-phase products can be separated by centrifugation or filtration. It is preferably to use a cyclone separator, and use its centrifugal action to make the solid-phase product spiral down along the wall in the conical section of the cyclone separator and discharge from the bottom outlet, and make the gas-phase product form an internal eddy flow field and spiral up and discharge from the top outlet.

[0054] S5. React the excessive water vapor with carbon monoxide in the gas-phase product to generate carbon dioxide and hydrogen.

[0055] S6. Purify the gas-phase product to obtain hydrogen.

[0056] Based on the heat exchange reaction on the surface of porous steel slag particles, a mechanism of heat exchange reaction in particle pore channels is further formed. That is, when the porous steel slag particles rotate, the water vapor in their pore channels will be affected by the eddy current outside the pore channels and the movement of the particles themselves. The periodic alternating shedding of the flow-around vortices on the surface of the porous steel slag particles causes periodic alternating fluctuations in the external pressure of the pore channels, and the self-rotation coupling centrifugal force generated by the self-rotation and revolution coupling movement of the particles causes periodic tensile and compressive transformations of the fluid in the pore channels. Therefore, the water vapor oscillates continuously in the pore channels and participates in the convective heat transfer and hydrogen production reaction inside the pore channels, increasing the convective area and reaction area of the porous steel slag particles, that is, the surface of the porous steel slag particles (A surface ), and the inner surface of its pore channels (A pore ) both participate in the heat exchange reaction, as shown in Equation 2. At the same time, since the convective heat transfer coefficient (k) of the oscillating flow of water vapor in the pore channels is not only related to the basic Nusselt number (Nu), Prandtl number (Pr), and Reynolds number (Re), but also related to the oscillation frequency (F pore ) (see Equation 3), the increased oscillation frequency caused by the alternating change of scale is beneficial to the increase of the convective heat transfer coefficient. Therefore, the porous steel slag particles can quickly and fully exchange heat with water vapor, greatly improving the hydrogen production effect. In addition, the flow field section with alternating scale can also enable the porous steel slag particles to repeatedly break away from the wall that restricts them, causing them to move towards the axis, thus avoiding the stacking of porous steel slag particles at the wall surface and further ensuring the smooth progress of the hydrogen production reaction.

[0057] (2)

[0058] (3)

[0059] In some embodiments, in order to ensure the smooth flow of the fluid-solid mixture and reduce the wall adhesion time of the porous steel slag particles, it is preferred that the minimum diameter of the flow field section with alternating scale is 0.5 to 0.8 times its maximum inner diameter.

[0060] Such as Figure 1As shown, in some embodiments, step S5 is as follows: A part of the gas-phase product is transported as recycle gas to the fluid-solid mixing zone, and the remaining part of the gas-phase product is transported into a water-gas shift device to further react carbon monoxide with excessive steam to generate carbon dioxide and hydrogen; the volume flow rate of the recycle gas accounts for 20% to 50% of the total volume flow rate of the gas-phase product. In this way, on the one hand, the waste heat of the recycle gas can be utilized to increase the temperature of the steam at the feed inlet to facilitate the reaction, and at the same time, the residual steam in the recycle gas can continue to react, reducing the amount of steam introduced at the feed inlet; on the other hand, controlling the recycle gas volume above 20% and below 50% can reduce the energy consumption of recycle gas transportation, ensure sufficient gas volume is introduced into the gas post-treatment process, and maintain the balance between recycling and hydrogen production. Among them, the water-gas shift device is a device for reacting carbon monoxide and steam to generate hydrogen and carbon dioxide, and it is preferably configured as a fixed-bed structure.

[0061] For another example Figure 1 As shown, in some embodiments, step S6 is as follows: After the remaining part of the gas-phase product further reacts, it is transported into a condenser to condense the steam into liquid water, and a gas mixture mainly composed of carbon dioxide and hydrogen is obtained; the liquid water is transported into a steam generator, re-evaporated into steam, and then transported to the fluid-solid mixing zone; the gas mixture obtained by condensation and separation is subjected to pressure swing adsorption to obtain high-purity hydrogen with a purity of over 99.999%.

[0062] Such as Figure 2 As shown, the present invention also provides a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device, including a feeding module 100, a fluid-solid swirling module 110, an oscillation excitation module 120, a fluid-solid separation module 130, and an exhaust module;

[0063] The feeding module 100 is used to receive molten steel slag and pressurized hydrogen production reaction gas, and transport the two to the fluid-solid mixing zone;

[0064] The fluid-solid swirling module 110 includes a swirling main body connected to the output end of the feeding module 100, and a swirling structure arranged inside the swirling main body for guiding the fluid-solid mixture to perform three-dimensional spiral motion; the inner cavity space of the swirling main body above the swirling structure is the fluid-solid mixing zone; the swirling structure can be various types such as a three-dimensional spiral groove, a swirling impeller, a swirling blade group, a circular cavity tangential inflow structure, etc.

[0065] The oscillation excitation module 120 includes at least one variable-diameter cylinder section coaxially connected to the swirl generator main body, and the inner diameter of the variable-diameter cylinder section gradually decreases and then gradually increases along its own axial direction; the variable-diameter cylinder section is an important structure for oscillation excitation and maintenance, and it has an oscillation excitation unit composed of a gradually shrinking flow channel and a gradually expanding flow channel connected coaxially, and the internal space is usually in the shape of an hourglass; generally, one or several variable-diameter cylinder sections can be selected according to the particle size of the porous steel slag particles; the inner diameters at the upper and lower ends of the variable-diameter cylinder section are usually equal;

[0066] The input end of the fluid-solid separation module 130 is connected to the output end of the oscillation excitation module 120, and is used for separating solid-phase products and gas-phase products; the fluid-solid separation module 130 can be a cyclone separator, a filter separator, etc.;

[0067] The input end of the exhaust module is communicated with the gas-phase output end of the fluid-solid separation module 130, and is used for exhausting gas-phase products externally.

[0068] Again, Figure 2 As shown, in some embodiments, the feeding module 100 includes two gas inlet pipes 101 symmetrically arranged on the side of the swirl generator main body, and two high-temperature steel slag inlet pipes 102 symmetrically arranged on the top of the swirl generator main body.

[0069] Again, Figure 2 As shown, in order to facilitate gas-solid mixing, on the basis of the previous embodiment, it is preferably that the axis line of the gas inlet pipe 101 is perpendicular to the axis line of the swirl generator main body, and the axis line of the high-temperature steel slag inlet pipe 102 is parallel to the axis line of the swirl generator main body.

[0070] Again, Figure 2 As shown, in some embodiments, the swirl generator main body is a cylindrical structure with a closed upper end, and the swirl structure includes at least two swirl vanes 111 arranged in an annular array around the axis line of the swirl generator main body to guide the fluid-solid mixture to perform a three-dimensional spiral motion. Considering that the swirl motion of the fluid-solid mixture has an important influence on the oscillation excitation of the gas in the pores of the porous steel slag particles, in order to ensure that the fluid-solid mixture can rotate sufficiently, it is preferably to set 4 to 8 swirl vanes 111.

[0071] Again, Figure 2 As shown, in some embodiments, the oscillation excitation module 120 includes at least two coaxially arranged variable-diameter cylinder sections, and adjacent two variable-diameter cylinder sections are connected by a transition cylinder section; for the convenience of connection and cooperation, usually make the maximum inner diameter D of the variable-diameter cylinder section max equal to the inner diameter D of the swirl generator main body; in order to ensure that the porous steel slag particles can smoothly pass through the minimum inner diameter D of the variable-diameter cylinder section min to avoid particle blockage problems, usually make the minimum inner diameter D of the variable-diameter cylinder sectionmin not less than 0.5 times the maximum inner diameter D max ; meanwhile, in order to avoid the minimum inner diameter D of the reduced-diameter cylinder section min from being too large, resulting in too long a fitting time between the porous steel slag particles and its inner wall surface, the minimum inner diameter D of the reduced-diameter cylinder section is usually made min not greater than 0.8 times the maximum inner diameter D max . In this way, it can be ensured that the fluid-solid mixture flows smoothly through the inside of the oscillation excitation module 120, and it can be ensured that the porous steel slag particles and water vapor can fully exchange heat and react.

[0072] For another example Figure 2 as shown, in some embodiments, the fluid-solid separation module 130 includes an inverted conical cylinder connected to the lower end of the oscillation excitation module 120 and coaxial therewith, and a particle discharge pipeline 131 is provided at the lower end of the inverted conical cylinder. In order to enable efficient separation of the fluid-solid mixture, it is preferred that half of the cone angle of the inverted conical cylinder is α, and 3° ≤ α ≤ 45°.

[0073] For another example Figure 2 as shown, in some embodiments, the exhaust module includes a gas discharge pipe 103, the gas discharge pipe 103 is coaxially arranged with the swirler main body, its upper end has a gas discharge port higher than the swirler main body, and its lower end passes through the inner cavity of the swirler main body and the inner cavity of the reduced-diameter cylinder section and extends into the inner cavity of the inverted conical cylinder, so as to facilitate the smooth discharge of the gas-phase product. Since the gas discharge pipe 103 penetrates through the inner cavity of the swirler main body and the inner cavity of the reduced-diameter cylinder section and extends into the inner cavity of the inverted conical cylinder, an annular space for the movement of the fluid-solid mixture is formed in the hydrogen production device, which is beneficial to the rotational flow of the porous steel slag particles and water vapor while ensuring sufficient contact and reaction time between the two in each region, thereby suppressing the drawback of insufficient gas-solid two-phase reaction time caused by the generation of gas-phase short-circuit flow.

[0074] Combined with Figure 1 and Figure 2 as shown, in some embodiments, the hydrogen production device further includes a water-gas shift device, a condenser, a water vapor generator and a pressure swing adsorption device; the output end of the exhaust module is respectively connected to the input end of the water-gas shift device and the input end of the feeding module 100; the output end of the water-gas shift device is connected to the input end of the condenser; the liquid-phase output end of the condenser is connected to the input end of the water vapor generator, the gas-phase output end of the condenser is connected to the input end of the pressure swing adsorption device; the output end of the water vapor generator is connected to the input end of the feeding module 100.

[0075] Combined with Figure 2 and Figure 3As shown in the figure, during the hydrogen production process using a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device provided by the present invention, the main principles of heat exchange and hydrogen production reactions are as follows: The high-temperature porous steel slag particles are subjected to the action of the swirl blades 111 and perform a coupled motion of self-rotation and revolution within the swirl device main body. At this time, the gas flow on the surface of the porous steel slag particles is simultaneously affected by the self-rotation motion of the particles, and the surface gas flow continuously detaches at the wake to form a Karman vortex street. Therefore, the surface gas flow is in an oscillating state, causing the gas in the pore channels to be oscillated by the gas flow outside the pore channels, thereby triggering the inflow and outflow of the gas. In addition, the centrifugal force formed by the revolution and self-rotation of the porous steel slag particles intensifies the tendency of the gas in the pore channels to move towards the particle surface, resulting in a periodic tensile and compressive transformation of the fluid in the pore channels. Also, since the variable-diameter cylinder section of the oscillation excitation module 120 has oscillation excitation units, through the constraint of the gradually shrinking and expanding flow channels, the coupled motion of self-rotation and revolution of the porous steel slag particles in the hydrogen production device is maintained, the wall-attached motion of the porous steel slag particles is inhibited, and the time for sufficient contact and reaction between the water vapor and the inner and outer surfaces of the porous steel slag particles is increased. During this process, the water vapor in the pore channels of the porous steel slag particles undergoes sufficient heat exchange reaction with it, and the reaction products can be discharged from the pore channels in a timely manner, and the water vapor is replenished into the pore channels in a timely manner, achieving the effect of continuous reaction hydrogen production.

[0076] Example 1

[0077] Hydrogen production is carried out using a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production method and device provided by the present invention. In this example, the temperature of the molten steel slag is 1600 °C, and the feed mass flow rate is 0.02 kg / s; the hydrogen production reaction gas is water vapor, and the water vapor is introduced into the hydrogen production device using argon as the carrier gas. The water vapor feed flow rate is 2 L / s, and the average flow rate of the pressurized hydrogen production reaction gas is 10 m / s. The temperature of the pressurized hydrogen production reaction gas is controlled at 120 °C to prevent water vapor condensation. The oscillation excitation module 120 of this hydrogen production device has two variable-diameter cylinder sections, that is, two oscillation excitation units. Compared with the traditional method of blowing water vapor onto the surface of molten steel slag for hydrogen production, the hydrogen production rate in this example is increased by about 40% and can reach 5.5×10 -3 mmol / s.

[0078] Example 2

[0079] Hydrogen production is carried out by using a method and device for enhancing hydrothermal hydrogen production by swirling oscillation of high-temperature steel slag provided by the present invention. In this embodiment, the temperature of the molten steel slag is 1500 °C, and the feed mass flow rate is 0.02 kg / s; the hydrogen production reaction gas is a weakly oxidizing gas formed by mixing carbon dioxide and water vapor (where the volume ratio of water vapor to carbon dioxide is 3:2). Nitrogen is used as the carrier gas to introduce the hydrogen production reaction gas into the hydrogen production device. The feed flow rate of the hydrogen production reaction gas is 4 L / s, and the average flow velocity of the pressurized hydrogen production reaction gas is 27 m / s. The temperature of the pressurized hydrogen production reaction gas is controlled at 120 °C to prevent water vapor condensation. The oscillation excitation module 120 of the hydrogen production device has two variable-diameter cylinder sections, that is, two oscillation excitation units. This embodiment can achieve a hydrogen production rate of 4.92×10 -3 mmol / s, which is about 12% higher than that of a swirling hydrogen production device without an oscillation excitation unit.

[0080] Example 3

[0081] Hydrogen production is carried out by using a method and device for enhancing hydrothermal hydrogen production by swirling oscillation of high-temperature steel slag provided by the present invention. In this embodiment, the temperature of the molten steel slag is 1600 °C, and the feed mass flow rate is 0.03 kg / s; the hydrogen production reaction gas is water vapor. Argon is used as the carrier gas to introduce water vapor into the hydrogen production device. The feed flow rate of water vapor is 3 L / s, and the average flow velocity of the pressurized hydrogen production reaction gas is 16 m / s. The temperature of the pressurized hydrogen production reaction gas is controlled at 120 °C to prevent water vapor condensation. The variation of the hydrogen production rate with the number of oscillation excitation units in this embodiment is shown in the following table. When there are more than 3 oscillation excitation units in the hydrogen production device, the hydrogen rate reaches the peak value, and the highest hydrogen production rate that can be achieved is 5.65×10 -3 mmol / s. It can be seen that the more oscillation excitation units are not necessarily better.

[0082]

[0083] This article only presents the description of various embodiments of the present invention for the purpose of illustration, and is not intended to be exhaustive or limited to the disclosed embodiments. Without departing from the scope and spirit of the described embodiments, many modifications and variations will be obvious to those skilled in the art. Compared with the technologies found in the market, the terms used in this article are selected to best explain the principles, practical applications, or technological advancements of the embodiments, or to enable other technicians in the field to understand the embodiments disclosed in this article.

[0084] In this document, various embodiments of the present invention may be presented in range form. It should be understood that the description in range form is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the present invention. Thus, the description of a range should be considered to specifically disclose all possible sub-ranges as well as the individual values within that range. For example, a description of a range such as from 1 to 6 should be considered to specifically disclose sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as the individual values within that range, such as 1, 2, 3, 4, 5, 6, regardless of the width of the range.

[0085] It should be understood that, for clarity, certain features of the present invention described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, for brevity, the various features of the present invention described in the context of a single embodiment may also be provided separately or in any suitable sub-combination, or, where appropriate, in any other described embodiment of the present invention. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments unless the embodiment cannot function without those features.

[0086] All publications, patents, and patent applications mentioned herein are hereby incorporated by reference in their entirety as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference. Additionally, the citation or identification of any reference in this document should not be construed as an admission that such reference is available as prior art to the present invention. With respect to the use of section headings, the section headings should not be construed as necessarily limiting.

Claims

1. A method for enhancing hydrothermal hydrogen production by swirling oscillation of high-temperature steel slag, characterized in that The following steps are involved: S1. The molten steel slag and the pressurized hydrogen production reaction gas are transported to the fluid-solid mixing zone respectively. The main component of the hydrogen production reaction gas is water vapor. The molten steel slag and the water vapor are initially heat exchanged and hydrogen production reaction occurs. After the initial heat exchange, the molten steel slag is cooled to form high-temperature porous steel slag particles, which are mixed with the gas phase in the fluid-solid mixing zone to form a fluid-solid mixture. S2, guiding the fluid-solid mixture to perform three-dimensional spiral motion to form a three-dimensional rotating turbulent flow field; the fluid-solid mixture performs revolution motion around the center line of the three-dimensional rotating turbulent flow field, and at the same time, the high-temperature porous slag particles rotate in the three-dimensional rotating turbulent flow field under the influence of the flow velocity difference of the surrounding fluid, thereby causing the water vapor in the pores of the high-temperature porous slag particles to oscillate and exchange flash heat with them and further produce hydrogen reaction; S3, controlling the three-dimensional rotating turbulent flow field so that there is at least one flow field segment with alternating scale changes, so that the porous steel slag particles in the high temperature state are repeatedly subjected to the action of the rotating force couple, thereby promoting the continuous hydrogen production reaction; the flow field segment with alternating scale changes is: along the center line of the three-dimensional rotating turbulent flow field downward, the diameter of the flow field segment first gradually decreases and then gradually increases; S4. After sufficient reaction, the fluid-solid mixture is subjected to gas-solid separation to obtain a solid phase product and a gas phase product; the solid phase product is porous steel slag particles in a low temperature state, and the main components of the gas phase product are hydrogen, water vapor, carbon dioxide and carbon monoxide; S5, using excess water vapor to react with carbon monoxide in the gas phase product to generate carbon dioxide and hydrogen; S6. Purify the gaseous product to obtain hydrogen.

2. The hydrothermal hydrogen production method by swirling oscillation enhancement of high-temperature steel slag according to claim 1, characterized in that: The feed flow rate of the pressurized hydrogen production reaction gas is 5 to 40 m / s, and the temperature is above 100 °C.

3. The method for hydrothermal hydrogen production with enhanced swirl oscillation of high-temperature steel slag according to claim 1, characterized in that: The minimum diameter of the flow field segment with alternating scales is 0.5 to 0.8 times the maximum inner diameter.

4. A high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production method according to any one of claims 1 to 3, characterized in that: Step S5 is: transporting a portion of the gas phase product as circulating gas to the fluid-solid mixing zone, and transporting the remaining portion of the gas phase product to the water-gas shift device so that the carbon monoxide therein further reacts with excess water vapor to generate carbon dioxide and hydrogen; the volume flow rate of the circulating gas accounts for 20% to 50% of the total volume flow rate of the gas phase product; Step S6 is: after the remaining gas phase product is further reacted, it is transported into a condenser to condense the water vapor therein into liquid water, and a mixed gas whose main components are carbon dioxide and hydrogen is obtained; the liquid water is transported into a steam generator, evaporated into water vapor again, and then transported to a fluid-solid mixing area; the mixed gas obtained by condensation and separation is subjected to pressure swing adsorption to obtain hydrogen with a purity of more than 99.999%.

5. A high-temperature steel slag hydrothermal hydrogen production device with enhanced swirl oscillation, characterized in that: It comprises a feeding module (100), a fluid-solid swirl generating module (110), an oscillation excitation module (120), a fluid-solid separation module (130) and an exhaust module; The feeding module (100) is used to receive molten steel slag and pressurized hydrogen production reaction gas, and transport the two to the fluid-solid mixing zone; The fluid-solid swirling module (110) includes a swirling device body connected to the output end of the feeding module (100), and a swirling structure arranged inside the swirling device body for guiding the fluid-solid mixture to perform three-dimensional spiral motion; the inner cavity space of the swirling device body above the swirling structure is a fluid-solid mixing area; The oscillation excitation module (120) includes at least one variable-diameter cylinder section coaxially connected to the swirling device body, and the inner diameter of the variable-diameter cylinder section gradually decreases first and then gradually increases along its own axis; The input end of the fluid-solid separation module (130) is connected to the output end of the oscillation excitation module (120) for separating solid-phase products and gas-phase products; The input end of the exhaust module is communicated with the gas-phase output end of the fluid-solid separation module (130) for exhausting gas-phase products externally.

6. The hydrothermal hydrogen production device with enhanced swirling oscillation of high-temperature steel slag according to claim 5, characterized in that: The feeding module (100) includes two gas inlet pipes (101) symmetrically arranged on the side of the swirling device body, and two high-temperature steel slag inlet pipes (102) symmetrically arranged on the top of the swirling device body.

7. The hydrothermal hydrogen production device with enhanced swirl oscillation of high-temperature steel slag according to claim 5, wherein: The swirling device body is a cylindrical structure with a closed upper end, and the swirling structure includes at least two swirling vanes (111) arranged inside the swirling device body and distributed in an annular array around the axis of the swirling device body.

8. The hydrothermal hydrogen production device with enhanced swirling oscillation of high-temperature steel slag according to claim 7, characterized in that: The oscillation excitation module (120) includes at least two coaxially arranged variable-diameter cylinder sections, and adjacent two variable-diameter cylinder sections are connected by a transition cylinder section; The maximum inner diameter D of the variable-diameter cylinder section max is equal to the inner diameter D of the swirler body, and its minimum inner diameter D min is 0.5 to 0.8 times of the maximum inner diameter D max .

9. The hydrothermal hydrogen production device with enhanced swirling oscillation of high-temperature steel slag according to claim 8, characterized in that: The fluid-solid separation module (130) includes an inverted cone cylinder connected to the lower end of the oscillation excitation module (120) and coaxial with it, and a particle discharge pipeline (131) is provided at the lower end of the inverted cone cylinder; The exhaust module includes a gas discharge pipe (103), the gas discharge pipe (103) is coaxially arranged with the swirling device body, its upper end has a gas discharge port higher than the swirling device body, and its lower end passes through the inner cavity of the swirling device body and the inner cavity of the variable-diameter cylinder section and extends into the inner cavity of the inverted cone cylinder.

10. A high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device according to any one of claims 5 to 9, characterized in that: It also includes a water-gas shift device, a condenser, a steam generator and a pressure swing adsorption device; The output end of the exhaust module is respectively connected to the input end of the water-gas shift device and the input end of the feeding module (100); The output end of the water-gas shift device is connected to the input end of the condenser; The liquid-phase output end of the condenser is connected to the input end of the steam generator, and the gas-phase output end of the condenser is connected to the input end of the pressure swing adsorption device; The output end of the steam generator is connected to the input end of the feeding module (100).

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