A method and device for high-temperature steel slag swirl oscillation-enhanced hydrothermal hydrogen production

Abstract

The present invention discloses a method and device for hydrothermal hydrogen production by intensifying high-temperature steel slag swirl oscillation, which belongs to the field of hydrogen preparation technology and aims to solve the problem of how to fully utilize the thermal energy of high-temperature steel slag to improve the hydrogen production effect. The hydrogen production method provided by the present invention further forms a mechanism of heat exchange reaction in the particle pores on the basis of the heat exchange reaction on the surface of porous steel slag particles, effectively promoting the effect of hydrogen production by the reaction between porous steel slag particles and water vapor; by controlling the three-dimensional rotating turbulent flow field, so that there is at least a flow field section with alternating scale changes, not only the reaction interface is promoted to expand from the surface of the porous steel slag particles to the pores inside them, and it can ensure that the reaction products can be discharged from the pores in time, and water vapor can be replenished into the pores in time, and it can ensure that the water vapor entering the pores continues to oscillate to produce a heat exchange reaction, so that the porous steel slag particles and water vapor can react continuously to ensure the hydrogen production effect.

Description

Technical Field

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

[0002] The steel industry produces a large amount of steel slag every year (accounting for 8% to 15% of crude steel production). Traditionally, landfill is the main method of disposal, which leads to problems such as land occupation, heavy metal pollution, and resource waste. Steel slag is rich in FeO (20% to 30%) and other iron oxides, and has high-temperature melting properties (1300 to 1700°C), which can provide a thermal energy basis for chemical reactions. Directly utilizing uncooled liquid high-temperature steel slag to react with water vapor, and producing hydrogen while cooling the high-temperature steel slag, can avoid the energy consumption of secondary heating and solve the problem of waste slag disposal. The principle of the reaction between high-temperature steel slag and water vapor is as follows:

[0003]

[0004] For example, Chinese utility model patent publication number CN216638917U discloses a system for producing hydrogen from liquid steel slag. This system introduces water vapor into the liquid steel slag from the bottom, allowing the water vapor to react with the hot liquid slag to produce hydrogen. Furthermore, the system recovers some of the heat energy from the liquid slag through heat exchange with the heat energy of the escaping gas. Chinese invention patent publication number CN119503728A discloses a method for producing H2-CO energy gas from steel slag. The method proposes injecting a weakly oxidizing gas containing water vapor onto the surface of the hot liquid steel slag to oxidize the FeO in the slag, converting the iron oxide into an easily separable magnetic phase while producing hydrogen and carbon monoxide gases, thereby improving the comprehensive utilization rate of the steel slag.

[0005] However, when liquid slag reacts with water vapor, the reaction interface remains confined to the surface of the liquid slag. As the surface cools, it is covered by the reaction product, Fe₂O₃, which hinders heat and mass transfer between the water vapor and the liquid slag, resulting in wasted internal heat energy. Therefore, to improve hydrogen production, it is necessary to fully and rapidly utilize the internal heat energy of the liquid slag, essentially enhancing the heat transfer performance between the slag and the gas. Furthermore, it is necessary to increase contact between the gas and the slag, such as by providing more reaction interfaces. In recent years, the use of cyclone heat exchangers to promote two-phase heat transfer between gas and particles has shown promising potential in gas-solid heat transfer applications across various industries. The convective heat transfer equation (Equation 1) shows that the fundamental reason for this is that the rotation of the particles allows for full contact between the spirally flowing gas, promoting an increase in the convective heat transfer coefficient (k), thereby improving heat transfer efficiency. Similarly, numerous studies have shown that reducing particle size can increase the gas-solid contact area (A), thereby improving heat transfer performance.

[0006] (1)

[0007] In previous hydrogen production devices, the coupling characteristics of the particle structure and the swirl flow were often ignored. During the reaction, the liquid steel slag is affected by the surface temperature drop and the airflow, forming high-temperature porous particles. The porosity of porous steel slag can reach 12.05%, and the specific surface area of porous steel slag can reach 0.4 m 2 / g, and a rich pore structure (visible pores, macropores, micropores, mesopores, etc.) can provide more reaction interfaces. Improving the heat transfer between porous slag and water vapor, thereby promoting the reaction between water vapor and porous slag to produce abundant hydrogen, is one of the urgent issues in the field of hydrogen production. Summary of the Invention

[0008] The present invention provides a method and device for hydrothermal hydrogen production by intensified hydrothermal oscillation of high-temperature steel slag, aiming to solve the problem of how to fully utilize 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 the technical problem is: a high-temperature steel slag swirl oscillation intensified hydrothermal hydrogen production method, comprising the following steps:

[0010] S1. Molten steel slag and pressurized hydrogen production reaction gas are separately transported to a fluid-solid mixing zone, where the main component of the hydrogen production reaction gas is water vapor. The molten steel slag and the water vapor undergo a preliminary heat exchange and hydrogen production reaction. After the preliminary heat exchange, the molten steel slag cools down 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.

[0011] S2. The fluid-solid mixture is guided to perform a three-dimensional spiral motion to form a three-dimensional rotating turbulent flow field; the fluid-solid mixture revolves around the center line of the three-dimensional rotating turbulent flow field, and simultaneously, the high-temperature porous slag particles are affected by the flow velocity difference of the surrounding fluid in the three-dimensional rotating turbulent flow field and rotate, thereby causing the water vapor in the pores of the high-temperature porous slag particles to oscillate and exchange flash heat with the water vapor, further generating a hydrogen production reaction;

[0012] S3. Controlling the three-dimensional rotating turbulent flow field so that it has at least one flow field segment with alternating scale changes, so that the high-temperature porous slag particles are repeatedly subjected to the action of a 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, the diameter of the flow field segment gradually decreases and then gradually increases in a downward direction;

[0013] 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;

[0014] S5, using excess water vapor to react with carbon monoxide in the gaseous product to produce carbon dioxide and hydrogen;

[0015] S6. Purify the gaseous product to obtain hydrogen.

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

[0017] Furthermore, the minimum diameter of the flow field segment with alternating scales is 0.5 to 0.8 times the maximum inner diameter.

[0018] Furthermore, step S5 comprises: transporting a portion of the gaseous product as a circulating gas to the fluid-solid mixing zone, and transporting the remaining gaseous product into a water-gas shift device to further react the carbon monoxide with excess water vapor to produce 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 gaseous product;

[0019] Step S6 is as follows: after further reaction, the remaining gaseous product is conveyed into a condenser to condense the water vapor therein into liquid water, thereby obtaining a mixed gas whose main components are carbon dioxide and hydrogen; the liquid water is conveyed into a steam generator, re-evaporated into water vapor, and then conveyed to a 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 more than 99.999%.

[0020] The present invention also provides a high-temperature steel slag swirl oscillation intensified hydrothermal hydrogen production device, comprising a feeding module, a fluid-solid swirl 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 transport them to the fluid-solid mixing zone;

[0022] The fluid-solid swirl module includes a swirl generator body connected to the output end of the feeding module, and a swirl generating structure disposed within the swirl generator body for guiding the fluid-solid mixture to perform a three-dimensional spiral motion; the inner cavity of the swirl generator body located above the swirl generating structure is a fluid-solid mixing zone;

[0023] The oscillation excitation module includes at least one diameter-reducing cylinder section coaxially connected to the vortex generator body, wherein the inner diameter of the diameter-reducing cylinder section gradually decreases 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 to separate the solid phase product and the gas phase product;

[0025] The input end of the exhaust module is connected to the gas phase output end of the fluid-solid separation module for external exhaust phase products.

[0026] Furthermore, the feeding module includes two gas inlet pipes symmetrically arranged on the sides of the vortex generator body, and two high-temperature slag inlet pipes symmetrically arranged on the top of the vortex generator body.

[0027] Furthermore, the vortex generator body is a cylindrical structure with a closed upper end, and the vortex generating structure includes at least two vortex generating blades arranged in the vortex generator body and distributed in a ring array around the axis of the vortex generator body.

[0028] Furthermore, 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 reducing cylinder section max Equal to the inner diameter D of the vortex generator body, its minimum inner diameter D min The maximum inner diameter D max 0.5 to 0.8 times of.

[0030] Furthermore, the fluid-solid separation module includes an inverted cone cylinder connected to the lower end of the oscillation excitation module and maintained coaxially therewith, and the lower end of the inverted cone cylinder is provided with a particle discharge pipeline;

[0031] The exhaust module includes a gas exhaust pipe, which is coaxially arranged with the vortex maker body. The upper end of the gas exhaust pipe has a gas exhaust port higher than the vortex maker body, and the lower end of the gas exhaust pipe passes through the inner cavity of the vortex maker body and the inner cavity of the reducing cylinder section and extends into the inner cavity of the inverted cone cylinder.

[0032] Furthermore, the hydrogen production device also includes a water-gas shift device, a condenser, a water vapor generator and a pressure swing adsorption device;

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

[0034] The output end of the water-gas conversion 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 water vapor 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 water vapor 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 the fluid-solid mixing zone respectively, and the two are initially heat exchanged and hydrogen production reaction occurs, and then mixed to form a fluid-solid mixture, and the fluid-solid mixture is formed into a three-dimensional rotating turbulent flow field, which can make the porous steel slag particles rotate while performing orbital motion, thereby causing the water vapor in its pores to oscillate and flash heat exchange with the porous steel slag particles and further produce hydrogen 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 the gas and solid phases, and effectively promotes the effect of the porous steel slag particles and water vapor to produce hydrogen.

[0039] (2) By controlling the three-dimensional rotating turbulent flow field so that there is at least one flow field segment with alternating scale changes, not only can the reaction interface be expanded from the surface of the porous slag particles to the pores inside them, but also it can ensure that the reaction products can be discharged from the pores in time and water vapor can be replenished into the pores in time, and it can also ensure that the water vapor entering the pores continues to oscillate to produce a heat exchange reaction, so that the porous slag particles and water vapor can react continuously and ensure the hydrogen production effect.

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

[0041] The technical effects brought about or directly produced by other technical features of the present invention will be described in detail in the subsequent specific implementation methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 This is a flow chart of a method for producing hydrogen by hydrothermal intensification of high-temperature steel slag using swirl oscillation provided by the present invention;

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

[0044] Figure 3 This 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] Marked in the figure: 100-feeding module, 101-gas inlet pipe, 102-slag inlet pipe, 103-gas exhaust pipe, 110-fluid-solid swirling module, 111-swirling blades, 120-oscillation excitation module, 130-fluid-solid separation module, 131-particle discharge pipeline. DETAILED DESCRIPTION

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

[0047] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like to indicate orientations or positions, and dimensional relationships are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the 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 therefore should not be understood as limiting the present invention.

[0048] When the term "plurality" refers to a quantity, it generally refers to three or more. For example, "a plurality" generally refers to three or more. Terms like "about" and "approximately" used to describe a numerical range generally refer to a range within ±10%. For example, "approximately 100 mm" generally refers to 90-110 mm. The expression "consisting primarily of" should be interpreted as including components not mentioned in the sentence. Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0049] like Figure 1 As shown, a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production method comprises the following steps:

[0050] S1. Molten steel slag and pressurized hydrogen production reaction gas are transported to the fluid-solid mixing zone separately. The main component of the hydrogen production reaction gas is water vapor. The molten steel slag and the water vapor undergo initial heat exchange and hydrogen production reaction. 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. The temperature of the molten steel slag is usually above 1400°C. The hydrogen production reaction gas can be single-element water vapor or a weak oxidizing gas formed by water vapor mixed with carbon dioxide. The pressurized hydrogen production reaction gas is mainly obtained by mixing the hydrogen production reaction gas with pressurized gas, which is generally argon or nitrogen. 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 with the water vapor on its surface and reacts to produce a small amount of hydrogen (compared to the subsequent output).

[0051] S2. Guide the fluid-solid mixture to perform three-dimensional spiral motion to form a three-dimensional rotating turbulent flow field; the fluid-solid mixture revolves around the center line of the three-dimensional rotating turbulent flow field, and at the same time, the high-temperature porous steel slag particles are affected by the flow velocity difference of the surrounding fluid in the three-dimensional rotating turbulent flow field to rotate, thereby causing the water vapor in the pores of the high-temperature porous steel slag particles to oscillate and exchange flash heat with it to further produce hydrogen production reaction; generally, the fluid-solid mixture can be guided to perform three-dimensional spiral motion by using vortex-generating structures such as three-dimensional spiral grooves, vortex-generating impellers, vortex-generating blade groups, and circular cavity tangential inlet structures; the high-temperature porous steel slag particles are subjected to a rotating force couple in the three-dimensional rotating turbulent flow field due to the gradient change of the rotational linear velocity, thereby rotating;

[0052] S3. Control the three-dimensional rotating turbulent flow field so that it has at least one flow field segment with alternating scale changes, so that the high-temperature porous steel slag particles are repeatedly subjected to the action of a rotating force couple, thereby promoting the continuous hydrogen production reaction; the flow field segment with alternating scale changes is: along the downward direction of the center line of the three-dimensional rotating turbulent flow field, the diameter of the flow field segment first gradually decreases and then gradually increases; during the reaction process of this step, not only the reaction interface is promoted to expand from the surface of the porous steel slag particles to the pores inside them, and it can also ensure that the reaction products can be discharged in time and water vapor is replenished into the pores in time, but also the water vapor entering the pores can be ensured to continuously oscillate for heat exchange and concurrent hydrogen production reaction, so that the porous steel slag particles and water vapor can continuously react to ensure the hydrogen production effect;

[0053] 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. The two phases of the product can generally be separated by centrifugation or filtration. Preferably, a cyclone separator is used, and its centrifugal effect causes the solid-phase product to spiral downward along the conical wall of the cyclone separator and be discharged from the bottom outlet, while the gas-phase product forms an internal vortex flow field and spirals upward and is discharged from the top outlet;

[0054] S5, using excess water vapor to react with carbon monoxide in the gaseous product to produce carbon dioxide and hydrogen;

[0055] S6. Purify the gaseous product to obtain hydrogen.

[0056] Based on the heat transfer reaction on the surface of porous slag particles, this hydrogen production method further forms a mechanism of heat transfer reaction in the particle pores, that is, when the porous slag particles rotate, the water vapor in the pores will be affected by the vortex outside the pores and the movement of the particles themselves. The periodic alternating shedding of the vortex around the surface of the porous slag particles causes alternating fluctuations in the pressure outside the pores, and the self-revolution coupled centrifugal force generated by the self-revolution coupled motion of the particles causes the fluid in the pores to be subjected to periodic tension and compression transformations. Therefore, the water vapor continuously oscillates in the pores and participates in the convective heat transfer and hydrogen production reaction inside the pores, which increases the convection area and reaction area of the porous slag particles, that is, the surface of the porous slag particles (A surface ) and its inner surface of the pore (A pore ) are involved in the heat transfer reaction, see formula 2. At the same time, since the convective heat transfer coefficient (k) of the oscillating flow of water vapor in the pore is not only related to the basic Nusselt number (Nu), Prandtl number (Pr) and Reynolds number (Re), but also to the oscillation frequency (F pore ) (see Equation 3). The increased oscillation frequency caused by the alternating scales contributes to an increase in the convective heat transfer coefficient; thus, the porous slag particles can rapidly and fully exchange heat with water vapor, significantly enhancing hydrogen production. Furthermore, the alternating scale flow field segments allow the porous slag particles to repeatedly break away from the walls that constrain them, allowing them to move toward the axis, thus preventing their accumulation on the walls and further ensuring the smooth progress of the hydrogen production reaction.

[0057] (2)

[0058] (3)

[0059] In some embodiments, in order to ensure smooth flow of the fluid-solid mixture and reduce the wall-adherence time of the porous slag particles, the minimum diameter of the flow field segment with alternating scales is preferably 0.5 to 0.8 times its maximum inner diameter.

[0060] like Figure 1As shown, in some embodiments, step S5 is: a portion of the gaseous product is transported to the fluid-solid mixing zone as circulating gas, and the remaining gaseous product is transported into the water-gas shift device so that the carbon monoxide therein further reacts with excess water vapor to produce 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 gaseous product. In this way, on the one hand, the waste heat of the circulating gas can be used to increase the temperature of the water vapor at the feed to facilitate the reaction, while the residual water vapor in the circulating gas can continue to react, reducing the amount of water vapor introduced at the feed; on the other hand, controlling the circulating gas volume to above 20% and below 50% can reduce the energy consumption of circulating gas transportation, ensure sufficient gas volume is introduced into the gas post-processing process, and maintain a balance between circulation and hydrogen production. Among them, the water-gas shift device is a device for reacting carbon monoxide and water vapor to produce hydrogen and carbon dioxide, which is preferably arranged in a fixed bed structure.

[0061] For example Figure 1 As shown, in some embodiments, step S6 is: after the remaining gaseous 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, re-evaporated into water vapor, and then transported to a fluid-solid mixing zone; the mixed gas obtained by condensation and separation is subjected to pressure swing adsorption to obtain high-purity hydrogen with a purity of more than 99.999%.

[0062] like 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 swirl 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 them to the fluid-solid mixing zone;

[0064] The fluid-solid swirl module 110 includes a swirl generator body connected to the output end of the feeding module 100, and a swirl generating structure disposed within the swirl generator body for guiding the fluid-solid mixture to perform a three-dimensional spiral motion. The inner cavity of the swirl generator body located above the swirl generating structure serves as a fluid-solid mixing zone. The swirl generating structure can be a three-dimensional spiral groove, a swirl generating impeller, a swirl generating blade assembly, a circular cavity tangential inlet structure, or the like.

[0065] The oscillation excitation module 120 includes at least one variable diameter cylinder section coaxially connected to the vortex generator body, the inner diameter of which gradually decreases and then gradually increases along its own axis. The variable diameter cylinder section serves as an important structure for oscillation excitation and maintenance, and has an oscillation excitation unit consisting of a coaxially connected gradually converging flow channel and a gradually expanding flow channel, and the internal space is generally hourglass-shaped. Generally, one or more variable diameter cylinder sections can be selected according to the particle size of the porous steel slag particles. The inner diameters of the upper and lower ends of the cylinder section are generally equal.

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

[0067] The input end of the exhaust module is connected to the gas phase output end of the fluid-solid separation module 130 for external exhaust phase products.

[0068] For example Figure 2 As shown, in order to improve the uniformity of feeding, in some embodiments, the feeding module 100 includes two gas inlet pipes 101 symmetrically arranged on the sides of the vortex generator body, and two high-temperature slag inlet pipes 102 symmetrically arranged on the top of the vortex generator body.

[0069] For example Figure 2 As shown, in order to facilitate gas-solid mixing, based on the previous embodiment, it is preferred that the axis of the gas inlet pipe 101 and the axis of the vortex generator body are perpendicular to each other, and the axis of the high-temperature slag inlet pipe 102 and the axis of the vortex generator body are parallel to each other.

[0070] For example Figure 2 As shown, in some embodiments, the swirler body is a cylindrical structure with a closed upper end. The swirling structure includes at least two swirling blades 111 disposed within the swirler body and arranged in an annular array around the axis of the swirler body to guide the fluid-solid mixture into a three-dimensional spiral motion. Considering that the swirling motion of the fluid-solid mixture significantly influences the oscillation excitation of gas within the pores of the porous slag particles, 4 to 8 swirling blades 111 are preferably provided to ensure sufficient rotation of the fluid-solid mixture.

[0071] For example Figure 2 As shown, in some embodiments, the oscillation excitation module 120 includes at least two coaxially arranged variable diameter cylinder sections, and two adjacent variable diameter cylinder sections are connected by a transition cylinder section; in order to facilitate the connection and matching, the maximum inner diameter D of the variable diameter cylinder section is usually max Equal to the inner diameter D of the swirl maker body; in order to ensure that the porous slag particles can smoothly pass through the minimum inner diameter D of the variable diameter cylinder section min To avoid particle blockage, the minimum inner diameter D of the reducer section is usuallymin Not less than the maximum inner diameter D max 0.5 times; at the same time, in order to avoid the minimum inner diameter D of the reducer section min Too large, which causes the porous slag particles to stick to the inner wall for too long, usually making the minimum inner diameter D of the reducer section min Not greater than the maximum inner diameter D max In this way, it is ensured that the fluid-solid mixture flows smoothly through the interior of the oscillation excitation module 120 and that the porous slag particles and water vapor can fully exchange heat and react.

[0072] For example Figure 2 As shown, in some embodiments, the fluid-solid separation module 130 includes an inverted cone-shaped cylinder connected to the lower end of the oscillation excitation module 120 and maintained coaxially therewith. The lower end of the inverted cone-shaped cylinder is provided with a particle discharge pipeline 131. To achieve efficient separation of the fluid-solid mixture, the cone angle of the inverted cone-shaped cylinder is preferably half α, and 3°≤α≤45°.

[0073] For example Figure 2 As shown, in some embodiments, the exhaust module includes a gas exhaust pipe 103, which is coaxially arranged with the vortex generator body, and has a gas exhaust port at its upper end that is higher than the vortex generator body, and its lower end passes through the inner cavity of the vortex generator body and the inner cavity of the reducing cylinder section and extends into the inner cavity of the inverted cone body, so as to facilitate the smooth discharge of gaseous products. Since the gas exhaust pipe 103 passes through the inner cavity of the vortex generator body and the inner cavity of the reducing cylinder section and extends into the inner cavity of the inverted cone body, an annular space for the movement of the fluid-solid mixture is formed in the hydrogen production device, which is conducive to the rotational flow of the porous slag particles and the water vapor while ensuring the time for the two to fully contact and react in each area, thereby suppressing the generation of gas-phase short-circuit flow and resulting in insufficient gas-solid two-phase reaction time.

[0074] Combine Figure 1 and Figure 2 As shown, in some embodiments, the hydrogen production device also includes a water-gas conversion 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 conversion device and the input end of the feeding module 100; the output end of the water-gas conversion 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, 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 water vapor generator is connected to the input end of the feeding module 100.

[0075] Combine Figure 2 and Figure 3As shown, in the process of hydrogen production by using a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device provided by the present invention, the main principle of heat exchange and hydrogen production reaction is: the high-temperature porous steel slag particles are acted upon by the swirl blades 111 to perform self-rotation and revolution coupling motion in the swirl maker body, at this time, the surface airflow of the porous steel slag particles is simultaneously affected by the self-rotation motion of the particles, and the surface airflow continuously falls off at the tail vortex to form Karman vortex steps, so the surface airflow is in an oscillating state, causing the gas in the pores to be affected by the oscillation of the airflow outside the pores, thereby inducing gas inflow and outflow, and in addition, the centrifugal force generated by the revolution and self-rotation of the porous steel slag particles intensifies the gas in the pores. The tendency of the porous slag to move toward the surface of the particles causes the fluid in the pores to be subjected to periodic tension and compression transformations; and because the variable diameter cylinder section of the oscillation excitation module 120 has an oscillation excitation unit, the spin and revolution coupled motion of the porous slag particles in the hydrogen production device is maintained through the constraint effect of the gradually contracting and expanding flow channels, the wall movement of the porous slag particles is suppressed, and the time for water vapor to fully contact and react with the inner and outer surfaces of the porous slag particles is increased. In this process, the water vapor in the pores of the porous slag particles fully exchanges heat with them, the reaction products can be discharged from the pores in time, and the water vapor is replenished into the pores in time, thereby achieving the effect of continuous reaction and hydrogen production.

[0076] Example 1

[0077] Hydrogen is produced by using a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production method and device 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 0.02 kg / s; the hydrogen production reaction gas is water vapor, and argon is used as a carrier gas to pass water vapor into the hydrogen production device. The water vapor feed flow rate is 2 L / s, the average flow rate of the pressurized hydrogen production reaction gas is 10 m / s, and 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, it has two oscillation excitation units. Compared with the traditional method of spraying water vapor onto the surface of molten steel slag to produce hydrogen, the hydrogen production rate in this embodiment is increased by about 40%, reaching 5.5×10 -3 mmol / s.

[0078] Example 2

[0079] Hydrogen is produced by using a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production method and device 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 weak oxidizing gas formed by a mixture of carbon dioxide and water vapor (wherein the volume ratio of water vapor to carbon dioxide is 3:2), and nitrogen is used as a carrier gas to pass the hydrogen production reaction gas into the hydrogen production device. The hydrogen production reaction gas feed flow rate is 4 L / s, the average flow rate of the pressurized hydrogen production reaction gas is 27 m / s, and 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, it has two oscillation excitation units. This embodiment can achieve 4.92×10 -3 The hydrogen production rate is mmol / s, which is about 12% higher than that of the cyclone hydrogen production device without an oscillation excitation unit.

[0080] Example 3

[0081] Hydrogen is produced by using a high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production method and device 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, and argon is used as a carrier gas to pass water vapor into the hydrogen production device. The water vapor feed flow rate is 3 L / s, the average flow rate of the pressurized hydrogen production reaction gas is 16 m / s, and the temperature of the pressurized hydrogen production reaction gas is controlled at 120 ° C to prevent water vapor condensation. The change of 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 a peak value, and the maximum can reach 5.65×10 -3 The hydrogen production rate is mmol / s, which shows that the more oscillation excitation units, the better.

[0082]

[0083] The description of various embodiments of the present invention is presented herein for illustrative purposes only and is not intended to be exhaustive or limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terms used herein are selected to best explain the principles of the embodiments, practical applications, or technological advancements, or to enable others skilled in the art to understand the embodiments disclosed herein, as compared to commercially available technology.

[0084] In this article, various embodiments of the present invention may be presented in the form of ranges. It should be understood that the description in range form is merely for convenience and brevity and should not be construed as a hard limit to the scope of the invention. Therefore, the description of a range should be considered to specifically disclose all possible sub-ranges and individual values within the 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 individual values within the range, such as 1, 2, 3, 4, 5, 6, which has nothing to do with the width of the range.

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

[0086] All publications, patents, and patent applications mentioned herein are incorporated herein by reference in their entirety, to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated as being incorporated herein by reference. In addition, the citation or identification of any reference herein should not be construed as an admission that such reference is available as prior art to the present invention. To the extent that section headings are used, such headings should not be construed as necessarily limiting.

Claims

1. A high-temperature steel slag swirl oscillation intensified hydrothermal hydrogen production method, characterized in that: The following steps are involved: S1. Molten steel slag and pressurized hydrogen production reaction gas are separately transported to a fluid-solid mixing zone. The hydrogen production reaction gas is mainly composed of water vapor. The molten steel slag and the water vapor undergo a preliminary heat exchange and hydrogen production reaction. After the preliminary heat exchange, the molten steel slag cools down 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. The fluid-solid mixture is guided to perform a three-dimensional spiral motion to form a three-dimensional rotating turbulent flow field; the fluid-solid mixture revolves around the center line of the three-dimensional rotating turbulent flow field, and simultaneously, the high-temperature porous slag particles are affected by the flow velocity difference of the surrounding fluid in the three-dimensional rotating turbulent flow field and rotate, thereby causing the water vapor in the pores of the high-temperature porous slag particles to oscillate and exchange flash heat with the water vapor, further generating a hydrogen production reaction; S3. Controlling the three-dimensional rotating turbulent flow field so that it has at least one flow field segment with alternating scale changes, so that the high-temperature porous slag particles are repeatedly subjected to the action of a 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, the diameter of the flow field segment gradually decreases and then gradually increases in a downward direction; 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 gaseous product to produce carbon dioxide and hydrogen; S6. Purify the gaseous product to obtain hydrogen.

2. The method for producing hydrogen by hydrothermal intensification of high-temperature steel slag by swirl oscillation 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 producing hydrogen by hydrothermal intensification of high-temperature steel slag by swirl oscillation 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. The method for producing hydrogen by hydrothermal intensification of high-temperature steel slag by swirl oscillation according to any one of claims 1 to 3, characterized in that: Step S5 comprises: conveying a portion of the gaseous product as circulating gas to the fluid-solid mixing zone, and conveying the remaining gaseous product into the water-gas shift device to further react the carbon monoxide with excess water vapor to produce 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 gaseous product; Step S6 is as follows: after further reaction, the remaining gaseous product is conveyed into a condenser to condense the water vapor therein into liquid water, thereby obtaining a mixed gas whose main components are carbon dioxide and hydrogen; the liquid water is conveyed into a steam generator, re-evaporated into water vapor, and then conveyed to a 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 more than 99.999%.

5. A high-temperature steel slag swirl oscillation intensified hydrothermal hydrogen production device, characterized by: It includes 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 swirl generating module (110) comprises a swirl generating body connected to the output end of the feeding module (100), and a swirl generating structure arranged in the swirl generating body for guiding the fluid-solid mixture to perform three-dimensional spiral motion; the inner cavity space of the swirl generating body located on the upper side of the swirl generating structure is a fluid-solid mixing zone; The oscillation excitation module (120) comprises at least one diameter-reducing cylinder section coaxially connected to the vortex generator body, wherein the inner diameter of the diameter-reducing cylinder section gradually decreases and then gradually increases along its own axial direction; 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 to separate solid-phase products from gas-phase products; The input end of the exhaust module is in communication with the gas phase output end of the fluid-solid separation module (130) for external exhaust phase products.

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

7. The high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device according to claim 5, characterized in that: The vortex generator body is a cylindrical structure with a closed upper end, and the vortex generating structure comprises at least two vortex generating blades (111) arranged in the vortex generator body and distributed in a ring array around the axis of the vortex generator body.

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

9. The high-temperature steel slag swirl oscillation enhanced hydrothermal hydrogen production device according to claim 8, characterized in that: The fluid-solid separation module (130) comprises an inverted cone 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 cone cylinder; The exhaust module comprises a gas exhaust pipe (103), which is coaxially arranged with the vortex generator body, has a gas exhaust port at its upper end that is higher than the vortex generator body, and extends into the inner cavity of the inverted cone cylinder through the inner cavity of the vortex generator body and the inner cavity of the reducing cylinder section at its lower end.

10. The 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 conversion device and the input end of the feeding module (100); The output end of the water-gas conversion 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, 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 water vapor generator is connected to the input end of the feeding module (100).

Images