Continuous hydrolysis hydrogen production device and continuous hydrolysis hydrogen production method based on multi-section helical ribbon reactor

Abstract

The invention provides a continuous hydrolysis hydrogen production device based on a multi-section helical ribbon reactor and a continuous hydrolysis hydrogen production method. The continuous hydrolysis hydrogen production device based on the multi-section helical ribbon reactor comprises a water circulation system, a reaction system, a hydrogen purification system and a control system. According to the continuous hydrolysis hydrogen production device based on the multi-section helical ribbon reactor, the reaction area is separated from the raw material storage area and the product storage area, and the purpose of large-scale in-situ hydrogen production can be achieved through a simple system composition in a continuous production mode. In the continuous hydrolysis hydrogen production process, the reaction system is maintained in a narrow interval between the set temperature and the water boiling point by balancing the heat exchange amount of each section of reaction tube, enhancing the heat transfer process inside and outside each section of reaction tube, absorbing heat by utilizing the vaporization process of excessive reaction water and the like, and the stability of the hydrogen production rate of the solid hydrogen storage material is maintained.

Description

Technical Field

[0001] The present invention relates to a hydrolysis hydrogen production technology, and in particular to a continuous hydrolysis hydrogen production device and a continuous hydrolysis hydrogen production method based on a multi-stage ribbon reactor. Background Art

[0002] With the gradual promotion and implementation of national carbon reduction initiatives, replacing traditional energy with clean energy has become a consensus across all sectors and the most important direction of change. Hydrogen, as the most promising zero-carbon energy source, is being actively used in production processes across various industries to achieve green transformation. However, difficulties in hydrogen storage and transportation have hindered its further utilization. To address this issue, in-situ hydrogen production technology, based on chemical reactions between active metals, hydrides, and water, offers an effective solution.

[0003] Hydrogen production devices using this in-situ hydrogen production technology often encounter complex systems, difficulty extracting heat, and unstable hydrogen release rates when scaled up. For example, when using the container storing the hydrogen production material as a reactor, the size of the individual container must be limited to meet heat and mass transfer requirements, resulting in the hydrogen production system being split into multiple small units and increasing the number of devices. For example, during the mixing process of the hydrogen production material and the reaction water, uncontrolled temperature conditions can cause large fluctuations in the reaction rate. Summary of the Invention

[0004] The purpose of the present invention is to address the problems of complex system, difficult heat extraction and unstable hydrogen release rate in existing in-situ hydrogen production devices, and to propose a continuous hydrolysis hydrogen production device based on a multi-stage spiral ribbon reactor. The device has sufficient and balanced heat extraction, stable reaction conditions and simple system composition, and can achieve safe and stable hydrogen production in scenarios with large-scale hydrogen production needs.

[0005] It should be noted that, in the present invention, unless otherwise specified, the specific meaning of "including" in relation to composition limitations and descriptions includes both open-ended "including", "comprising", etc. and similar meanings, as well as closed-ended "composed of", "composed of", etc. and similar meanings.

[0006] To achieve the above object, the technical solution adopted by the present invention is: a continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor, comprising a water circulation system, a reaction system, a hydrogen purification system and a control system;

[0007] The water circulation system includes an electric heating water tank, a circulation pump, a constant temperature water tank, an electric three-way valve, a radiator and a temperature sensor. The outlet of the electric heating water tank is connected to the inlet of the constant temperature water tank through the circulation pump. The outlet of the constant temperature water tank is connected to the inlet of the electric heating water tank and the heat medium inlet of the radiator through the electric three-way valve respectively. The heat medium outlet of the radiator is connected to the inlet of the electric heating water tank. Temperature sensors are provided in both the electric heating water tank and the constant temperature water tank.

[0008] The reaction system includes a motor, a reducer, a gear set, a silo, a feed regulating device, a reaction tube, a spiral ribbon stirring shaft, a water inlet pump, a water intake pipe, a water injection pipe and a product storage bin; there are multiple reaction tubes, and the multiple reaction tubes are arranged side by side from top to bottom, and the discharge port of the upper reaction tube is connected to the feed port of the lower reaction tube; the silo is connected to the feed port of the uppermost reaction tube through the feed regulating device, and the discharge port of the lowermost reaction tube is connected to the product storage bin; the inlet of the water intake pipe is located in a constant temperature water tank, the outlet of the water intake pipe is connected to the inlet of the water injection pipe through the outlet of the water inlet pump, and the outlet of the water injection pipe is connected to the reaction tube; the motor, reducer, gear set and spiral ribbon stirring shaft are connected in sequence, and the spiral ribbon stirring shaft is arranged in the reaction tube, and the rotation speed of the spiral ribbon stirring shaft in different reaction tubes can be the same or different, and the rotation speed of the spiral ribbon stirring shaft in different reaction tubes is adjusted by the gear set;

[0009] The hydrogen purification system includes a condenser and a dryer, the reaction tube (upper part) and the product storage bin (upper part) are respectively connected to the condenser, the top outlet of the condenser is connected to the dryer, and the dryer outlet is connected to a hydrogen-using device and / or a hydrogen storage device;

[0010] The electric heating water tank, the circulation pump, the electric three-way valve, the motor, the feed regulating device, the water feed pump and the temperature sensor are all communicatively connected with the control system.

[0011] Furthermore, the feed regulating device is a spiral feed structure or an adjustable valve.

[0012] Furthermore, a filter layer is provided at one end of the reaction tube close to the condenser. More specifically, the filter layer is provided in the reaction tube between the feed port and the condenser.

[0013] Furthermore, the outlet of the water injection pipe is located near the feed port and the discharge port of the reaction tube; preferably, the outlet of the water injection pipe is located near the feed port and the discharge port of the upper reaction tube; more preferably, the outlet of the water injection pipe is located near the feed port and the discharge port of the topmost reaction tube (first-stage reaction tube), and is also located near the feed port of the second reaction tube (second-stage reaction tube) from top to bottom.

[0014] Furthermore, a flap is provided on the spiral ribbon stirring shaft between adjacent spirals, and the provision of the flap can increase the intensity of stirring.

[0015] Furthermore, the angle between the adjacent extended surfaces of the flaps is 60-120°, preferably 90°.

[0016] Furthermore, the flap is a rectangular plate, the width of the flap is 1 / 2 to 2 / 3 of the screw pitch, and the height is flush with the screw belt.

[0017] Another object of the present invention is to disclose a method for producing hydrogen by continuous hydrolysis, comprising the following steps:

[0018] The water circulation system ensures that the reaction system (reaction system in the reaction tube) is maintained within the set temperature range through preheating and heat extraction processes;

[0019] Solid hydrogen production material enters the reaction tube from the feed port through the feed regulating device from the feed silo;

[0020] The water in the constant temperature water tank is injected into the reaction tube through the water intake pipe, water inlet pump and water injection pipe;

[0021] The spiral ribbon stirring shaft in the reaction tube rotates under the drive of the motor, stirring the solid hydrogen-producing material and water, and at the same time, pushing the mixture toward the discharge port. During the process of the mixture moving toward the discharge port, a chemical reaction occurs to generate hydrogen and release a large amount of heat;

[0022] A large amount of heat causes water to vaporize into water vapor. The vaporization process of water can take away a large amount of reaction heat, which is beneficial to maintaining the temperature of the reaction system. The water vapor and hydrogen flow through the filter layer, condenser and dryer in sequence and are sent to the subsequent process. The condenser realizes the condensation and separation of water vapor, and the dryer is used to absorb the residual water in the hydrogen.

[0023] The control unit can realize the automatic operation of the continuous hydrolysis hydrogen production device.

[0024] Furthermore, the preheating and heat extraction of the water circulation system includes the following steps:

[0025] 1) During the reaction preparation phase, the water in the electric heating water tank is heated to a set temperature of 70°C-90°C; then, a circulating pump injects high-temperature water into the constant-temperature water tank to preheat the reaction tubes;

[0026] 2) At the initial stage of the reaction, the water in the constant temperature water tank acts as one of the reactants, raising the overall temperature of the reactants;

[0027] 3) During the reaction, heat is exchanged between the constant temperature water tank and the reaction tube to quickly remove the heat released by the reaction and regulate the temperature of the reaction system;

[0028] When the temperature sensor detects that the temperature in the constant temperature water tank is lower than the set value (85-95℃, preferably 90℃), the circulating water directly flows back to the electric heating water tank; when it is higher than the set value (85-95℃, 90℃), the circulating water flows through the radiator to cool down and then flows back to the electric heating water tank, and the electric three-way valve controls the alternation of the reflux path;

[0029] The operating flow rate of the circulating pump is 50-70% of the maximum flow rate, preferably 60%. When the temperature in the constant temperature water tank continues to be higher than the set upper limit, the flow rate of the circulating pump is gradually increased to enhance the heat dissipation effect by increasing the amount of water flowing through the radiator until the temperature returns to the set range.

[0030] Furthermore, the solid hydrogen-producing material is magnesium hydride.

[0031] Furthermore, the feed rate of the solid hydrogen production material is determined by the target hydrogen release rate and the reaction properties of the solid hydrogen production material. Specifically, the feed rate q of the solid hydrogen production material is:

[0032] q=(V / 22.4*2) / K (Equation 1)

[0033] Where: q is the feed rate of solid hydrogen production material, g / min;

[0034] V——target hydrogen release rate, L / min;

[0035] k——the amount of hydrogen released per unit mass of solid hydrogen-generating material, g(H2) / g;

[0036] l——The distance the ribbon agitator shaft advances per revolution, m / r.

[0037] Furthermore, the amount of water injected into the reaction tube is 2-4 times the theoretical amount of water required for the solid hydrogen storage material contained therein to undergo a hydrogen production reaction.

[0038] Furthermore, the pitch and rotational speed of the ribbon stirring shaft and the length of the reaction tube determine the residence time of the mixture in the reaction tube, and the ratio of the number of teeth of the gear set is used to adjust the difference in the residence time of the mixture in different reaction tubes. Specifically, the residence time T of the mixture of the solid hydrogen-producing material and water in the reaction tube is:

[0039] T = L / (r × l) (Equation 2)

[0040] Where: T - residence time in the reaction tube, min;

[0041] L——reaction tube length, m;

[0042] r——Speed ​​of the ribbon stirring shaft, r / min;

[0043] l——The distance the ribbon agitator shaft advances per revolution, m / r.

[0044] Furthermore, to ensure the same amount of hydrogen released in each reaction tube, the residence time of the mixture in the reaction tubes is different, and the specific residence time is allocated according to the characteristics of the reaction process. For example, when three reaction tubes are used to carry out the hydrogen production reaction by hydrolysis of magnesium hydride, the residence time ratio of the mixture in the first reaction tube, the second reaction tube, and the third reaction tube is 30:15:30.

[0045] Furthermore, due to the characteristics of the hydrolysis hydrogen production reaction process: the conversion of the last 5% of magnesium hydride takes a long time and releases relatively little heat. Therefore, the conversion of the remaining 5% of magnesium hydride is completed in the product storage bin.

[0046] Furthermore, the reaction tube is connected to the feed regulating device, the water injection pipe, the spiral stirring shaft, the condenser and the product storage bin, and the residence time in each reaction tube is determined by the hydrogen release characteristics of the solid hydrogen-producing material. When the total amount of hydrogen released per unit mass of the solid hydrogen-producing material is N liters, the reaction tubes are divided into n tubes, and the amount of hydrogen released by magnesium hydride in each reaction tube remains consistent. The hydrogen release accumulation curve is divided into n parts, and the hydrogen release amount corresponding to each part is N / n liters. The corresponding time length on the hydrogen release accumulation curve is the residence time of the solid hydrogen-producing material in the reaction tube. For example, if the total hydrogen release amount is 9L, three reaction tubes are used. The total residence time of the reaction tube is the time spent on three 3L hydrogen releases. Since the reaction rates at different times are different, the corresponding time spent on each reaction tube is different. Each reaction tube has the same length, but different residence times, which requires different rotation speeds, and the corresponding material layer heights will be different, that is, the filling amount is different. The filling amount of the solid hydrogen-producing material in the reaction tube is 40%-70%;

[0047] 70% ≥ (q × T / ρ) / (L × A) ≥ 40% (Formula 3)

[0048] A=A1-A2 (Formula 4)

[0049] Where: ρ——bulk density of solid hydrogen production material, g / m 3 ;

[0050] A——available cross-sectional area of ​​reaction tube, m2;

[0051] A1——The cross-sectional area of ​​the reaction tube calculated based on the inner diameter, m2;

[0052] A2——Cross-sectional area of ​​the ribbon agitator shaft, m2.

[0053] The advantages of maintaining the same amount of hydrogen released from magnesium hydride in each reaction tube of the present invention are as follows: (1) by making the gas flow rate in each reaction tube similar, it is possible to avoid excessive concentration of hydrogen release, which would result in excessively high gas flow rate in a certain reaction tube, thereby preventing interference with the flow state of the slurry reactants, such as the reactants being carried out of the reaction tube too quickly by the high-speed gas flow; and (2) the same amount of hydrogen released means that the amount of magnesium hydride participating in the reaction is the same, and the corresponding heat release is the same, which can ensure that the heat load of each reaction tube is similar, which is beneficial to heat transfer and maintaining stable reaction conditions.

[0054] Another object of the present invention is to disclose a use of a continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor in the field of hydrolysis hydrogen production.

[0055] The present invention is based on a continuous hydrolysis hydrogen production device with a multi-stage ribbon reactor. It effectively solves the problems faced by large-scale in-situ hydrogen production devices with a compact structural design and accurate condition control. Specifically, compared with the existing technology, it has the following advantages:

[0056] 1) Sufficient heat extraction from the system: The reaction tube is located in a constant-temperature water tank, providing a large heat extraction area. The reaction tube contains a spiral rotating stirring structure to ensure sufficient heat exchange between the reactants and the wall. The reaction system temperature is maintained near the boiling point of water, and excess reaction heat can be dissipated by the latent heat of water vaporization. Therefore, the reaction system temperature is controlled through good heat exchange within the reaction tube, heat exchange between the reaction tube and the water in the constant-temperature water tank, and the vaporization process of the reactant water.

[0057] 2) System heat balance: In the multi-stage design of the reactor, the residence time of the hydrogen storage material in each reaction area is adjusted by changing the speed of the spiral ribbon according to the reaction properties of the solid hydrogen production material to ensure that the heat release of the reaction process in each reactor section is similar.

[0058] 3) Stable reaction conditions: The reaction tube is placed in a constant-temperature water tank, and the external temperature conditions are stable. The water involved in the reaction comes from the constant-temperature water tank. Due to the high heat capacity of water, the overall temperature of the reactants is stable. The conditions for sufficient heat extraction ensure that the temperature of the reaction system is maintained in a narrow temperature range close to the boiling point of water. The above measures ensure the stability of the reaction conditions and, accordingly, achieve a stable hydrogen release rate.

[0059] 4) Simple system composition: The reactor design achieves the separation of the reaction area from the raw material storage area and the product storage area, which is suitable for large-scale hydrogen production scenarios and avoids the problem of increasing the number of equipment caused by the use of multiple small units combined for hydrogen production.

[0060] In summary, the present invention is based on a continuous hydrolysis hydrogen production device with a multi-stage ribbon reactor, in which the reaction zone is separated from the raw material storage zone and the product storage zone. This device can achieve the purpose of large-scale in-situ hydrogen production through continuous production with a simple system configuration. During the continuous hydrolysis hydrogen production process, the present invention maintains the reaction system within a narrow range between the set temperature and the boiling point of water by balancing the heat exchange of each section of the reaction tube, enhancing the heat transfer process inside and outside each section of the reaction tube, and utilizing the heat absorption process of the vaporization process of excess reaction water, thereby maintaining the stability of the hydrogen production rate of the solid hydrogen storage material. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 It is a structural schematic diagram of a continuous hydrolysis hydrogen production device with a multi-stage ribbon reactor;

[0062] Figure 2 is the particle size distribution diagram of magnesium hydride;

[0063] Figure 3 The schematic diagram of the three-stage reactor design based on the unit mass magnesium hydride hydrolysis reaction curve;

[0064] Figure 4 Schematic diagram of the cross-sectional dimensions of the reaction tube;

[0065] Figure 5 Schematic diagram of the structure of the ribbon stirring shaft 1;

[0066] Figure 6 Schematic diagram of the structure of the second spiral ribbon stirring shaft.

[0067] Among them, 1-electric heating water tank, 2-circulation pump, 3-constant temperature water tank, 4-electric three-way valve, 5-radiator, 6-motor, 7-reducer, 8-gear set, 9-silo, 10-feed adjustment device, 11-reaction tube, 12-ribbon stirring shaft, 13-water inlet pump, 14-water intake pipe, 15-water injection pipe, 16-filter layer, 17-product storage bin, 18-condenser, 19-dryer, 20-temperature sensor, 21-control system. DETAILED DESCRIPTION

[0068] The multi-stage ribbon reactor continuous hydrolysis hydrogen production device of the present invention is divided into four parts: a water circulation system, a reaction system, a control system and a hydrogen purification system, including an electric heating water tank, a circulation pump, a constant temperature water tank, an electric three-way valve, a radiator, a motor, a reducer, a gear set, a silo, a feed adjustment device, a reaction tube, a ribbon stirring shaft, a water inlet pump, a water intake pipe, a water injection pipe, a filter layer, a product storage bin, a condenser, a radiator, a temperature sensor, a control system and other equipment or components.

[0069] (1) Water circulation system

[0070] The water circulation system consists of an electric heating water tank, a circulation pump, a constant-temperature water tank, an electric three-way valve, a radiator, and a temperature sensor. These three components are connected in sequence. The electric three-way valve is connected to the electric heating water tank directly via a pipeline or via a radiator. Temperature sensors are installed on the electric heating water tank and the constant-temperature water tank to monitor their temperatures.

[0071] The water circulation system ensures that the reaction system is maintained within the set temperature range through preheating and heat extraction processes.

[0072] ① During the reaction preparation stage, the water in the electric heating water tank is heated to the set temperature, which is between 70°C and 90°C. Subsequently, the circulating pump injects high-temperature water into the constant temperature water tank to preheat the reaction tube.

[0073] ② At the initial stage of the reaction, the water in the constant temperature water tank, as one of the reactants, increases the overall temperature of the reactants.

[0074] ③ During the reaction stage, heat is exchanged between the constant temperature water tank and the reaction tube to quickly take away the heat released by the reaction and adjust the temperature of the reaction system.

[0075] When the temperature sensor detects that the temperature inside the constant temperature water tank is lower than the set value, the circulating water flows directly back to the electric heating water tank; when it is higher than the set value, the circulating water flows through the radiator and back to the electric heating water tank. The alternation of the return path is controlled by an electric three-way valve.

[0076] The working flow of the circulating pump is 60% of the maximum flow. When the temperature in the thermostatic water tank is higher than the set upper limit or lower than the set lower limit, the flow is gradually increased to the maximum value.

[0077] (2) Reaction system

[0078] The reaction system consists of a motor, a reducer, a gear set, a silo, a feed adjustment device, a reaction tube, a spiral stirring shaft, a water inlet pump, a water intake pipe, a water injection pipe, a filter layer, a product storage bin and other parts.

[0079] The silo is connected to a feed regulating device, which can be a screw feed mechanism or an adjustable valve. The feed regulating device is connected to the front end of the reaction tube and feeds the solid hydrogen-generating material from the silo into the reaction tube. The feed rate of the solid hydrogen-generating material is determined by the target hydrogen release rate and the reactivity of the solid hydrogen-generating material.

[0080] q = (V / 22.4*2) / k (Equation 1)

[0081] Where: q is the feed rate of solid hydrogen production material, g / min;

[0082] V——target hydrogen release rate, L / min;

[0083] k——the amount of hydrogen released per unit mass of solid hydrogen-generating material, g(H2) / g;

[0084] l——The distance the ribbon agitator shaft advances per revolution, m / r.

[0085] The front and rear ends of the water inlet pump are connected to the water intake pipe and the water injection pipe. The end of the water intake pipe is located in the constant temperature water tank, and the end of the water injection pipe is located near the feed inlet and the discharge port, injecting the reactant water into the reaction tube. The water intake volume is 2-4 times the theoretical amount of water required for the solid hydrogen storage material to produce hydrogen.

[0086] The motor, reducer, gear train, and ribbon stirring shaft are connected in sequence and fixed in the reaction tube. The ribbon stirring shaft stirs the solid hydrogen-generating material and water, while also pushing the mixture backward. During this backward movement, the mixture undergoes a chemical reaction to produce hydrogen and release a large amount of heat.

[0087] A large amount of reaction heat will cause water to vaporize, and the water vapor and hydrogen flow through the filter layer into the condenser. The vaporization process of water vapor will take away a large amount of reaction heat, which is beneficial to maintaining the temperature of the reaction system.

[0088] The pitch and rotation speed of the ribbon stirring shaft and the length of the reaction tube determine the residence time of the mixture in the reaction tube, and the ratio of the number of teeth of the gear set is used to adjust the difference in the residence time of the mixture in different reaction tubes.

[0089] T = L / (r × l) (Equation 2)

[0090] Where: T - residence time in the reaction tube, min;

[0091] L——reaction tube length, m;

[0092] r——Speed ​​of the ribbon stirring shaft, r / min;

[0093] l——The distance the ribbon agitator shaft advances per revolution, m / r.

[0094] The reaction tube is connected to a feed regulator, water inlet pipe, ribbon agitator, condenser, and product storage bin. The residence time within each section of the reaction tube is determined by the hydrogen release characteristics of the solid hydrogen-generating material. If the total amount of hydrogen released per unit mass of solid hydrogen-generating material is N liters, and the reaction tube is divided into n sections, the residence time of each N / n liter on the time axis of the hydrogen release accumulation curve is the reaction tube residence time. The material filling level within the reaction tube should be between 40% and 70%.

[0095] 70% ≥ (q × T / ρ) / (L × A) ≥ 40% (Formula 3)

[0096] A=A1-A2 (Formula 4)

[0097] Where: ρ——bulk density of solid hydrogen production material, g / m 3 ;

[0098] A——available cross-sectional area of ​​reaction tube, m2;

[0099] A1——The cross-sectional area of ​​the reaction tube calculated based on the inner diameter, m2;

[0100] A2——Cross-sectional area of ​​the ribbon agitator shaft, m2.

[0101] The product storage box is connected to the discharge port of the last section of the reaction tube and the condenser and is used to store the reaction products.

[0102] (3) Control system

[0103] The control system consists of a control unit and communication lines. The control unit is connected to the electric heating water tank, circulation pump, electric three-way valve, feed adjustment device, water inlet pump, and temperature sensor through the communication lines. The control unit is used to realize the automatic operation of the continuous hydrolysis hydrogen production device.

[0104] (4) Purification system

[0105] The purification system consists of a condenser and a dryer. The condenser inlet is connected to the reaction tube, and the dryer inlet is connected to the condenser outlet. The condenser condenses and separates water vapor, while the dryer absorbs residual moisture in the hydrogen.

[0106] The present invention will be further described below with reference to the following examples. The following description of the technical features is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:

[0107] Unless otherwise stated, the units used in this specification are international standard units, and the numerical values ​​and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0108] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0109] In this specification, the numerical range expressed using "above" or "below" means a numerical range including the number.

[0110] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0111] In this specification, the use of "optional" or "optional" indicates that certain substances, components, execution steps, application conditions and other factors are used or not used.

[0112] In this specification, when "normal temperature" or "room temperature" is used, the temperature may be 15-25°C.

[0113] In this manual, the reagents or instruments used without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.

[0114] Example 1

[0115] This embodiment discloses a continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor. Figure 1 As shown, it includes a water circulation system, a reaction system, a hydrogen purification system and a control system;

[0116] The water circulation system includes an electric heating water tank 1, a circulation pump 2, a constant temperature water tank 3, an electric three-way valve 4, a radiator 5 and a temperature sensor 20. The outlet of the electric heating water tank 1 is connected to the inlet of the constant temperature water tank 3 through the circulation pump 2, and the outlet of the constant temperature water tank 3 is connected to the inlet of the electric heating water tank 1 and the heat medium inlet of the radiator 5 through the electric three-way valve 4 respectively. The heat medium outlet of the radiator 5 is connected to the inlet of the electric heating water tank 1; the electric heating water tank 1 and the constant temperature water tank 3 are both provided with a temperature sensor 20;

[0117] The reaction system includes a motor 6, a reducer 7, a gear set 8, a silo 9, a feed regulating device 10, a reaction tube 11, a spiral stirring shaft 12, a water inlet pump 13, a water intake pipe 14, a water injection pipe 15 and a product storage bin 17; there are three reaction tubes 11, and the three reaction tubes 11 are arranged side by side from top to bottom, the feed opening of the first reaction tube is connected to the feed opening of the second reaction tube, and the feed opening of the second reaction tube is connected to the feed opening of the third reaction tube; the silo 9 is connected to the feed opening of the first (topmost) reaction tube 11 through the feed regulating device 10, and the feed opening of the third (bottommost) reaction tube is connected to the product storage bin 17; the feed regulating device 10 is an adjustable valve. The inlet of the water intake pipe 14 is located in the constant temperature water tank 3, and the outlet of the water intake pipe 14 is connected to the inlet of the water injection pipe 15 through the outlet of the water inlet pump 13. The outlet of the water injection pipe 15 is located near the feed inlet and the discharge port of the reaction tube 11. Specifically, the water injection positions of the water injection pipe 15 are respectively located near the feed inlet of the first stage of the reaction tube 11, the top of the discharge position from the first stage to the second stage of the reaction tube 11, and the top of the discharge position from the second stage to the third stage of the reaction tube 11; the motor 6, the reducer 7, the gear set 8 and the spiral stirring shaft 12 are connected in sequence, and the spiral stirring shaft 12 is arranged in the reaction tube 11;

[0118] The spiral ribbon stirring shaft can be Figure 5 In order to improve the stirring intensity, the conventional structure can also be used. Figure 6The illustrated spiral ribbon agitator shaft with flaps is positioned on the agitator shaft, midway between adjacent spirals, with the angle between adjacent extended flaps being 90°. The flaps are rectangular, with a width equal to half the pitch of the spiral and a height flush with the spiral ribbon.

[0119] The hydrogen purification system includes a condenser 18 and a dryer 19. The reaction tube 11 and the product storage tank 17 are respectively connected to the condenser 18. A filter layer 16 is provided at one end of the reaction tube 11 near the condenser 18. The top outlet of the condenser 18 is connected to the dryer 19.

[0120] The electric heating water tank 1 , the circulation pump 2 , the electric three-way valve 4 , the motor 6 , the feed regulating device 10 , the water inlet pump 13 and the temperature sensor 20 are all communicatively connected to the control system 21 .

[0121] A continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor is used. The method for continuous hydrolysis hydrogen production is as follows:

[0122] Design goal: Hydrogen production system with a hydrogen supply rate of 100L / min.

[0123] Large-particle magnesium hydride is used as solid hydrogen production material, with a mass hydrogen storage density of 6.88%, a bulk density of 650g / L, and a particle size distribution of Figure 2 The hydrogen release rate curve of magnesium hydride at 80℃ is shown in Figure 3 The hydrolysis conversion rate of magnesium hydride is 95%, and the hydrogen production per unit mass of magnesium hydride is 1.46L.

[0124] The magnesium hydride feed rate to the reactor is:

[0125] 100L(H2) / min÷1.46L(H2) / g(MgH2)=68.5g(MgH2) / min

[0126] According to the three-stage reactor design, the amount of hydrogen released by magnesium hydride in the first reaction tube (first stage reactor), the second reaction tube (second stage reactor), and the third reaction tube (third stage reactor) must be consistent. Figure 3 The time points corresponding to the 1 / 3, 2 / 3, and 3 / 3 total volume values ​​on the cumulative flow curve were selected as the residence time for each zone. That is, the residence time for the first reactor was 30 minutes, the residence time for the second reactor was 15 minutes, and the residence time for the third reactor was 30 minutes. The residual magnesium hydride was converted in the product storage bin.

[0127] The inner diameter of the ribbon stirring shaft is 20 mm, the outer diameter of the screw pitch is 4 cm, and the length is 1.2 m. According to the residence time requirement, the rotation speeds of the three-stage reactor are 1 r / min, 2 r / min, and 1 r / min respectively.

[0128] The filling volume of the material in the reactor is:

[0129] 30min×68.5g(MgH2) / min÷650g / L=3.2L

[0130] The stirring shaft occupies a small proportion of the space inside the reaction tube and is not included in the calculation of the reaction tube cavity.

[0131] Calculated based on a filling volume of 60%, the inner diameter of the reaction tube is:

[0132]

[0133] Therefore, the stirring shaft can be 2 mm thick and 25 mm high.

[0134] See the schematic diagram of the reaction tube cross-section dimensions for Figure 4 .

[0135] The total water intake from the pump is 2-3 times the amount of magnesium hydride reacted at 90% of the reaction volume. As designed, the three reactors produce equal amounts of hydrogen, achieving a 30% conversion rate. The theoretical water flow rate is 76.4 mg / min. Therefore, the first injection point receives three times the amount of water, or 229 ml / min; the second injection point receives two times the amount of water, or 152.8 ml / min; and the third injection point receives two times the amount of water, or 152.8 ml / min.

[0136] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor, characterized in that: Including water circulation system, reaction system, hydrogen purification system and control system; The water circulation system comprises an electric heating water tank (1), a circulation pump (2), a constant temperature water tank (3), an electric three-way valve (4), a radiator (5) and a temperature sensor (20); the outlet of the electric heating water tank (1) is connected to the inlet of the constant temperature water tank (3) through the circulation pump (2); the outlet of the constant temperature water tank (3) is connected to the inlet of the electric heating water tank (1) and the heat medium inlet of the radiator (5) through the electric three-way valve (4); the heat medium outlet of the radiator (5) is connected to the inlet of the electric heating water tank (1); the temperature sensor (20) is provided in both the electric heating water tank (1) and the constant temperature water tank (3); The reaction system comprises a motor (6), a reducer (7), a gear set (8), a silo (9), a feed regulating device (10), a reaction tube (11), a ribbon stirring shaft (12), a water inlet pump (13), a water intake pipe (14), a water injection pipe (15) and a product storage bin (17); the reaction tubes (11) are multiple, and the multiple reaction tubes (11) are arranged side by side from top to bottom, and the discharge port of the upper reaction tube is connected to the feed port of the lower reaction tube; the silo (9) is connected to the uppermost reaction tube through the feed regulating device (10). The feed port of the reaction tube (11) is connected, and the discharge port of the lowest reaction tube is connected to the product storage bin (17); the inlet of the water intake pipe (14) is located in the constant temperature water tank (3), the outlet of the water intake pipe (14) is connected to the inlet of the water injection pipe (15) through the outlet of the water inlet pump (13), and the outlet of the water injection pipe (15) is connected to the reaction tube (11); the motor (6), the reducer (7), the gear set (8) and the spiral stirring shaft (12) are connected in sequence, and the spiral stirring shaft (12) is arranged in the reaction tube (11); The hydrogen purification system includes a condenser (18) and a dryer (19), the reaction tube (11) and the product storage bin (17) are respectively connected to the condenser (18), and the top outlet of the condenser (18) is connected to the dryer (19); The electric heating water tank (1), the circulation pump (2), the electric three-way valve (4), the motor (6), the feed regulating device (10), the water inlet pump (13) and the temperature sensor (20) are all communicatively connected to the control system (21).

2. The continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor according to claim 1, characterized in that: The feed regulating device (10) is a spiral feed structure or an adjustable valve; And / or, a filter layer (16) is provided at one end of the reaction tube (11) close to the condenser (18); And / or, the outlet of the water injection pipe (15) is located near the feed port and the discharge port of the reaction tube (11).

3. The continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor according to claim 1, characterized in that: A flap is provided on the spiral ribbon stirring shaft between adjacent spirals.

4. The continuous hydrolysis hydrogen production device based on a multi-stage ribbon reactor according to claim 3, characterized in that: The angle between the adjacent extended surfaces of the flaps is 60-120°; And / or, the flap is a rectangular plate, the width of the flap is 1 / 2 to 2 / 3 of the screw pitch, and the height is flush with the screw belt.

5. A continuous hydrolysis hydrogen production method, characterized in that: The following steps are involved: The water circulation system ensures that the reaction system is maintained within the set temperature range through preheating and heat extraction processes; Solid hydrogen production material enters the reaction tube from the feed port through the feed regulating device from the feed silo; The water in the constant temperature water tank is injected into the reaction tube through the water intake pipe, water inlet pump and water injection pipe; The spiral ribbon stirring shaft in the reaction tube rotates under the drive of the motor, stirring the solid hydrogen-producing material and water, and at the same time, pushing the mixture toward the discharge port. During the process of the mixture moving toward the discharge port, a chemical reaction occurs to generate hydrogen and release a large amount of heat; A large amount of heat causes water to vaporize into water vapor, and the water vapor and hydrogen flow through the filter layer, condenser and dryer in sequence and are sent to the subsequent process; The control unit can realize the automatic operation of the continuous hydrolysis hydrogen production device.

6. The method according to claim 5, characterized in that The preheating and heat extraction of the water circulation system comprises the following steps: 1) During the reaction preparation phase, the water in the electric heating water tank is heated to a set temperature of 70°C-90°C; then, a circulating pump injects high-temperature water into the constant-temperature water tank to preheat the reaction tubes; 2) At the initial stage of the reaction, the water in the constant temperature water tank acts as one of the reactants, raising the overall temperature of the reactants; 3) During the reaction, heat is exchanged between the constant temperature water tank and the reaction tube to quickly remove the heat released by the reaction and regulate the temperature of the reaction system; When the temperature sensor detects that the temperature in the constant temperature water tank is lower than the set value, the circulating water directly flows back to the electric heating water tank; When it is higher than the set value, the circulating water flows through the radiator to cool down and then flows back to the electric heating water tank. The electric three-way valve controls the replacement of the return path. The working flow rate of the circulating pump is 60% of the maximum flow rate. When the temperature in the thermostatic water tank is higher than the set upper limit or lower than the set lower limit, the flow rate is gradually increased to the maximum value.

7. The method according to claim 5, characterized in that The feed rate q of the solid hydrogen production material is: q = (V / 22.4*2) / k (Equation 1); Where: q is the feed rate of solid hydrogen production material, g / min; V——target hydrogen release rate, L / min; k——the amount of hydrogen released per unit mass of solid hydrogen-generating material, g(H2) / g; l——The distance the ribbon agitator shaft advances per revolution, m / r.

8. The method according to claim 5, characterized in that The amount of water injected into the reaction tube is 2-4 times the theoretical amount of water required for the solid hydrogen storage material to undergo hydrogen production reaction.

9. The method according to claim 5, characterized in that: The residence time T of the mixture of the solid hydrogen-producing material and water in the reaction tube is: T = L / (r × l) (Formula 2); Where: T - residence time in the reaction tube, min; L——reaction tube length, m; r——Speed ​​of the ribbon stirring shaft, r / min; l——The distance the ribbon agitator shaft advances per revolution, m / r.

10. The method according to claim 5, characterized in that: The filling amount of the solid hydrogen-producing material in the reaction tube is 40%-70%.

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