Large-scale lithium hydride hydrolysis hydrogen release device and method

Abstract

The invention discloses a large-scale lithium hydride hydrolysis hydrogen release device and method, and the device comprises a hydrolysis reaction unit which is used for the hydrolysis reaction of lithium hydride to generate hydrogen; a hydrogen treatment unit for purifying, storing, pressurizing and drying hydrogen; and the liquid phase treatment unit is used for treating a liquid phase product of the hydrolysis reaction of the lithium hydride. Through interaction among the hydrolysis reaction unit, the hydrogen treatment unit and the liquid phase treatment unit, continuous and stable external supply of hydrogen and hot water is realized, generation of waste gas and waste water is reduced, and reduction of environmental pollution is facilitated.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrogen energy and hydrogen storage and release of solid hydrogen storage materials, and relates to a large-scale lithium hydride water hydrogenation device and method. Background Art

[0002] Hydrogen energy refers to an energy form that uses hydrogen as an energy carrier. It is a secondary energy source that is abundant in source, green, low-carbon, and widely used. It can be produced and stored in a variety of ways. During the combustion process, it only produces water vapor, without the emission of greenhouse gases such as carbon dioxide. This makes hydrogen an environmentally friendly and renewable energy option that can be applied in many fields, including transportation, energy storage and supply, industrial production, and power generation.

[0003] In recent years, there have been many reports on methods related to hydrogen storage and hydrogen release of chemical hydrogen storage materials, but how to enable the chemical hydrogen storage material to continuously and stably release the hydrogen inside remains a top priority in this field.

[0004] For example, the existing technology has realized the electrochemical storage and release of hydrogen by hydrogen peroxide at room temperature and pressure, and complemented the coupling with the renewable energy grid to "cut peaks and fill valleys", connecting and integrating hydrogen energy with multi-energy systems; but its system is complex, both the cathode and the anode require precious metal catalysts, and it is also necessary to add a variety of additives such as binders, hydrophobic additives, and hydrophilic additives. The equipment investment is large and it is not suitable for large-scale production. There is also the use of magnesium hydride hydrolysis to produce hydrogen. While the rate of magnesium hydride hydrolysis reaction is high, the reaction is also relatively stable and the hydrolysis efficiency is high; but the introduction of ammonium salt and magnesium salt composite catalysts is not conducive to the recycling and reuse of magnesium hydroxide, the product of magnesium hydride hydrolysis.

[0005] Therefore, there is an urgent need to study a large-scale green hydrogen release device. Summary of the invention

[0006] In order to overcome the above problems, the present invention proposes a large-scale lithium hydride hydrolysis hydrogenation device and method, the device includes a hydrolysis reaction unit, which is used for lithium hydride hydrolysis reaction to produce hydrogen; a hydrogen treatment unit, which is used to purify, store, pressurize and dry hydrogen; a liquid phase treatment unit, which is used to treat the liquid phase product of the lithium hydride hydrolysis reaction. Through the interaction between the hydrolysis reaction unit, the hydrogen treatment unit and the liquid phase treatment unit, continuous and stable external supply of hydrogen and hot water is achieved, and the generation of waste gas and wastewater is reduced, which helps to reduce pollution to the environment.

[0007] Specifically, the purpose of the present invention is to provide the following aspects: In a first aspect, a lithium hydride water hydrogenation device is provided, the device comprising: A hydrolysis reaction unit, which is used for the hydrolysis reaction of lithium hydride to produce hydrogen; A hydrogen processing unit for purifying, storing, pressurizing and drying hydrogen; A liquid phase treatment unit is used to treat the liquid phase product of the lithium hydride hydrolysis reaction.

[0008] Wherein, the hydrolysis reaction unit comprises a hydrolysis reactor, and the hydrolysis reactor is used for performing lithium hydride hydrolysis reaction.

[0009] Wherein, the hydrogen processing unit comprises: A first hydrogen purifier, which is used to preliminarily purify the hydrogen generated by the hydrolysis reaction of lithium hydride; The second hydrogen purifier is used to deeply purify hydrogen and improve its purity.

[0010] Wherein, the hydrogen processing unit further comprises: A hydrogen tank, which is used to store purified hydrogen; A hydrogen autoclave, which is used to pressurize hydrogen to 400-800 kPaG; Hydrogen dryer, which is used to remove moisture from hydrogen.

[0011] The hydrogen dryer is filled with a desiccant, and the desiccant is selected from any one or more of molecular sieves, silicon dioxide, calcium chloride, and calcium oxide.

[0012] Wherein, the height of the desiccant filled in the hydrogen dryer is 0.4~8m.

[0013] The hydrogen processing unit includes a first hydrogen purifier, a second hydrogen purifier, a hydrogen tank, a hydrogen autoclave and a hydrogen dryer in sequence along the flow direction of hydrogen.

[0014] Wherein, the liquid phase processing unit comprises: The reactor discharge pump is used to transport the liquid product of the lithium hydride hydrolysis reaction.

[0015] Wherein, the liquid phase processing unit further comprises: A settling tank, which is used for secondary hydrolysis of lithium hydride and collection of lithium hydroxide slurry; The supernatant circulation pump circulates the water produced by the secondary hydrolysis reaction of lithium hydride to the hydrolysis reactor.

[0016] In a second aspect, a method for performing hydrogen separation with lithium hydride water according to the device of the first aspect is provided, the method comprising: Step 1, hydrolyzing lithium hydride to produce hydrogen; Step 2, purifying, storing, pressurizing and drying hydrogen; Step 3, treating the liquid product of the lithium hydride hydrolysis reaction The beneficial effects of the present invention include: (1) The lithium hydride hydrolysis hydrogenation device provided by the present invention realizes continuous and stable external supply of hydrogen and hot water through the interaction between the hydrolysis reaction unit, the hydrogen treatment unit and the liquid phase treatment unit. The purity of hydrogen reaches 99.97~99.999% (v), and the external hydrogen supply flow rate reaches 0.31~53.76Nm 3 / min, the amount of 55℃ hot water supplied to the outside is 0.71~204m 3 / h.

[0017] (2) The lithium hydride aqueous hydrogenation device provided by the present invention does not require a catalyst and / or an auxiliary agent, is green and environmentally friendly, and does not cause environmental pollution.

[0018] (3) The method for preparing hydrogen by hydrolysis of lithium hydride provided by the present invention has a simple process flow and convenient control and operation. Through efficient hydrogen purification and recycling of washing liquid, the generation of waste gas and wastewater is reduced, which helps to reduce the impact on the environment. The amount of lithium hydroxide slurry produced as a by-product of hydrolysis is small and does not introduce new impurities, which is easy to recover and recycle, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] By reading the detailed description of the preferred specific embodiments below, various other advantages and benefits of the present invention will become clear to those of ordinary skill in the art. The drawings in the specification are only used for the purpose of illustrating the preferred embodiments and are not considered to be limitations of the present invention. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative work.

[0020] In the attached picture: Figure 1 A schematic structural diagram of a lithium hydride aqueous hydrogenation device according to a preferred embodiment of the present invention is shown; Description of reference numerals: 1-hydrolysis reactor; 111-a first stirring subunit; 112-jacket; 113-Hydrogen outlet; 2- the first hydrogen purifier; 3- Second hydrogen purifier; 4- Hydrogen tank; 41-First entrance; 42- third exit; 5-Hydrogen pressure autoclave; 6- Hydrogen dryer; 7- Sedimentation tank; 71-Exit 4; 72-Exit 5; 73- second stirring sub unit; 8-reactor discharge pump; 9-supernatant circulation pump; 10-Washing liquid circulation pump; 11- Washing liquid cooler; 21- first feeding port; 22-discharging port; 23-First pipeline; 24-First exit; 25-liquid phase outlet; 26- Second pipeline; 27-Second exit; 28-Hydrogen pressurization outlet; 29- Second entrance. DETAILED DESCRIPTION

[0021] The specific embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. Although the specific embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present invention and to enable the scope of the present invention to be fully communicated to those skilled in the art.

[0022] It should be noted that certain words are used in the specification and claims to refer to specific components. Those skilled in the art should understand that technicians may use different nouns to refer to the same component. This specification and claims do not use the difference in nouns as a way to distinguish components, but use the difference in the functions of the components as the criterion for distinction. As mentioned throughout the specification and claims, "including" or "comprising" is an open term, so it should be interpreted as "including but not limited to". The subsequent description of the specification is a preferred embodiment of the present invention, but the description is based on the general principles of the specification and is not intended to limit the scope of the present invention. The scope of protection of the present invention shall be determined by the attached claims.

[0023] In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "front", "rear", etc. indicate positions or positional relationships based on the working state of the present invention, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first", "second", "third", and "fourth" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0024] To facilitate understanding of the embodiments of the present invention, further explanation will be given below by taking specific embodiments as examples in conjunction with the accompanying drawings, and each of the accompanying drawings does not constitute a limitation on the embodiments of the present invention.

[0025] On the one hand, a lithium hydride water hydrogenation device is provided according to the present invention, the device comprising: A hydrolysis reaction unit, which is used for the hydrolysis reaction of lithium hydride to produce hydrogen; A hydrogen processing unit for purifying, storing, pressurizing and drying hydrogen; A liquid phase treatment unit is used to treat the liquid phase product of the lithium hydride hydrolysis reaction.

[0026] In the present invention, Figure 1 As shown, the hydrolysis reaction unit comprises a hydrolysis reactor 1 , and a first stirring subunit 111 is arranged in the hydrolysis reactor 1 .

[0027] In the present invention, the hydrolysis reactor 1 is used to carry out lithium hydride hydrolysis reaction, and the temperature of the hydrolysis reactor 1 (i.e., the temperature of the lithium hydride hydrolysis reaction) is controlled to be -40~95°C, preferably 70~90°C, such as 70°C.

[0028] Among them, the hydrolysis reaction of lithium hydride is a highly exothermic process and the reaction is relatively violent. Although the reaction can be carried out at room temperature, in order to improve industrial production efficiency and output, the temperature is usually increased to speed up the reaction. Considering the safety of the reaction, the industrial reaction temperature is suitable for -40~95℃, and 70~90℃ is better. Higher temperature is conducive to the generation and escape of hydrogen, thereby promoting the reaction in the direction of generating hydrogen.

[0029] In the present invention, the pressure of the hydrolysis reactor 1 (ie, the pressure of the lithium hydride hydrolysis reaction) is controlled to be -10 to 60 kPaG, preferably 15 to 20 kPaG, such as 20 kPaG.

[0030] Among them, lithium hydride hydrolysis reaction can occur at -10~60 kPaG. A pressure slightly higher than normal pressure is conducive to the release of hydrogen and improves the collection efficiency of hydrogen. Excessive pressure may make the reaction too violent and difficult to control, and even cause safety accidents. Considering the promotion of hydrogen release and maintaining the stability of the reaction, 15~20 kPaG is more appropriate.

[0031] In the present invention, there is no strict restriction on the stirring rate of the first stirring subunit 111 in the hydrolysis reactor 1. Stirring helps to maximize the contact area between the reactants, thereby improving the reaction efficiency. The stirring rate is usually 80-500 rpm, for example 80 rpm.

[0032] In the present invention, a jacket 112 is provided outside the hydrolysis reactor 1, and hot water flows in the jacket 112. During the reaction, the hot water flowing in the jacket 112 exchanges heat with the material in the hydrolysis reactor 1 to remove the heat generated by the hydrolysis of lithium hydride and maintain a stable hydrolysis reaction temperature. The heated hot water can be sent to household radiators for heating. After releasing the heat, it is pumped into the jacket 112 of the hydrolysis reactor 1 for recycling.

[0033] In the present invention, the amount of lithium hydride added to the hydrolysis reactor 1 is not limited, and can be 7 kg or 1200 kg, depending on the amount required for the reaction.

[0034] During the reaction, firstly, hot water at 40-45° C. is introduced into the jacket 112 of the hydrolysis reactor 1, and then a saturated lithium hydroxide solution is added into the hydrolysis reactor 1. Then, the reaction material, namely lithium hydride, is added through the first feed port 21 of the hydrolysis reactor 1. The lithium hydride reacts with water to generate lithium hydroxide and hydrogen.

[0035] Furthermore, after the hot water absorbs heat, the temperature rises to 55~56℃ and is supplied to the outside. The hot water flow rate here is positively correlated with the amount of LiH and saturated lithium hydroxide solution, the raw materials for the hydrogen release reaction. The larger the amount of raw materials, the more hot water is needed to take away the heat generated by the hydrogen release reaction. For example, when the raw material for the reaction is 7 kg of lithium hydride, the hot water flow rate is set to 0.7~0.8m 3 / h; when the raw material of the reaction is 1200 kg lithium hydride, the hot water flow rate is set to 204~205m 3 / h. Of course, in order to realize the hydrolysis reaction of lithium hydride in larger batches, a plurality of hydrolysis reactors 1 can be arranged in parallel at the same time, for example, two can be arranged in parallel.

[0036] In the present invention, the hydrogen processing unit includes a first hydrogen purifier 2, a second hydrogen purifier 3, a hydrogen tank 4, a hydrogen autoclave 5 and a hydrogen dryer 6 in sequence along the flow direction of hydrogen.

[0037] Among them, the first hydrogen purifier 2 is used for preliminary purification of hydrogen produced by the hydrolysis reaction of lithium hydride; the second hydrogen purifier 3 is used for deep purification of hydrogen to improve the purity of hydrogen; the hydrogen tank 4 is used to store the purified hydrogen; the hydrogen pressure kettle 5 is used to pressurize the hydrogen to 400~800kPaG; the hydrogen dryer 6 is used to remove moisture from the hydrogen.

[0038] Furthermore, due to the low density of hydrogen, according to the principle that hydrogen enters from the bottom of each unit and is discharged from the top after being processed, the hydrolysis reactor 1, the first hydrogen purifier 2, the second hydrogen purifier 3, the hydrogen tank 4, the hydrogen pressure reactor 5 and the hydrogen dryer 6 have the following specific connection relationship: the upper end of the hydrolysis reactor 1 is provided with a hydrogen outlet 113, and the hydrogen outlet 113 is connected to the lower end inlet of the first hydrogen purifier 2; the upper end of the first hydrogen purifier 2 is provided with a first outlet 24, and the first outlet 24 is connected to the The lower end inlet of the second hydrogen purifier 3 is connected, and the upper end of the second hydrogen purifier 3 is provided with a second outlet 27, and the second outlet 27 is connected to the first inlet 41 at the lower end of the hydrogen tank 4. The upper end of the hydrogen tank 4 is provided with a third outlet 42, and the third outlet 42 is connected to the lower inlet of the outer wall of the hydrogen pressure kettle 5. The upper part of the hydrogen pressure kettle 5 is provided with a hydrogen pressurization outlet 28, and the hydrogen pressurization outlet 28 is connected to the lower end inlet of the hydrogen dryer 6. The hydrogen is discharged along the upper end outlet of the hydrogen dryer 6 after drying to realize hydrogen supply.

[0039] In the present invention, the first hydrogen purifier 2 is a pipeline element, and is filled with a wire mesh, a rectangular saddle ring filler, a θ ring filler, an asbestos rope or a random packing. Since the hydrogen produced by the hydrolysis reactor 1 is mixed with water vapor, liquid droplets and dust, the hydrogen containing water vapor, liquid droplets and dust enters the first hydrogen purifier 2, and the liquid droplets and dust are initially removed by the wire mesh, the rectangular saddle ring filler, the θ ring filler, the asbestos rope or the random packing.

[0040] In the present invention, the height of the filler filled in the first hydrogen purifier 2 is 0.05-0.5m, preferably 0.05-0.4m, for example 0.2m. If the height of the filler filled in the first hydrogen purifier 2 is too high, the hydrogen flow resistance will increase, and the improvement of mass transfer efficiency will no longer be significant. 0.05-0.5m can provide sufficient surface area and contact time to ensure that most of the droplets and dust in the hydrogen are effectively captured and removed.

[0041] In the present invention, the second hydrogen purifier 3 is a packed tower, which has 0 to 3 sections of packing, and the packing is used to adsorb impurities such as droplets and dust in the hydrogen. The packed tower preferably has 0 to 2 sections of packing, for example, 2 sections of packing; the height of each section of packing is 0 to 4 m, preferably 1 to 4 m, for example, 2.5 m. The contact time and contact area of ​​hydrogen are increased by multi-section packing, thereby improving the efficiency of separating droplets and dust from the gas. The type and configuration of the multi-section packing can also be adjusted according to different purification requirements; the 0 to 4 m height packing ensures that a higher purification efficiency is achieved without excessively increasing the pressure drop. The inventors found that even without using packing, the final purity of hydrogen reached more than 99.9%.

[0042] Furthermore, the filler is selected from ball rings, step rings or saddle rings. The ball rings are made of metal, plastic and porcelain. The step rings are made of metal, plastic and porcelain. The saddle rings are made of metal and porcelain.

[0043] In the present invention, the hydrogen pressure reactor 5 is used to pressurize the hydrogen to 400-800 kPaG, preferably 450-800 kPaG, such as 600 kPaG. 400-800 kPaG is suitable for various applications of hydrogen such as fuel cell vehicles, hydrogen fuel cell power plants, industrial synthesis processes, etc., and can also reduce storage space.

[0044] The hydrogen pressure autoclave 5 is also used to adjust the temperature of the hydrogen to 30-40° C., such as 40° C., for ease of use.

[0045] Further, the pressure entering the hydrogen pressure autoclave 5 is controlled to be 5-10 kPaG lower than the pressure of the lithium hydride hydrolysis reaction in the hydrolysis reactor 1. For example, if the pressure of the lithium hydride hydrolysis reaction in the hydrolysis reactor 1 is 20 kPaG, the pressure entering the hydrogen pressure autoclave 5 is controlled to be 15 kPaG; and the temperature entering the hydrogen pressure autoclave 5 is controlled to be 30-40°C, for example, 40°C.

[0046] In the present invention, the hydrogen dryer 6 is filled with a desiccant, which is selected from any one or more of molecular sieves, silicon dioxide, calcium chloride, and calcium oxide, such as molecular sieves. The desiccant is used to absorb moisture in the hydrogen to ensure that the output hydrogen is dry, and in particular, the molecular sieve has a high-efficiency adsorption capacity and regenerable characteristics.

[0047] Furthermore, the height of the desiccant filled in the hydrogen dryer 6 is 0.4-8m, preferably 0.4-4m, for example 4m. The height of the desiccant affects the contact time between the gas and the hydrogen, thereby affecting the drying efficiency. A higher height of the desiccant provides a larger adsorption capacity and can handle a larger flow of hydrogen.

[0048] Furthermore, the lower inlet of the hydrogen dryer 6 is arranged below the desiccant.

[0049] According to a preferred embodiment, a liquid phase outlet 25 is provided at the bottom of the second hydrogen purifier 3, and the liquid phase outlet 25 is connected to the washing liquid circulation pump 10 and the washing liquid cooler 11 in sequence. The washing liquid cooler 11 is connected to the second hydrogen purifier 3 in one way and to the hydrolysis reactor 1 in the other way. The washing liquid circulation pump 10 provides washing liquid for the second hydrogen purifier 3 and ensures that the washing liquid circulates between the second hydrogen purifier 3 and the washing liquid cooler 11; the washing liquid cooler 11 is used to cool the washing liquid, and the cooled washing liquid is mixed with hydrogen in the second hydrogen purifier 3 for mass transfer and heat transfer, and hydrogen carrying dust, trace lithium hydride and droplets of water enters the washing liquid, and is cooled after heat transfer. At this time, hydrogen enters the hydrogen tank 4 from the second outlet 27 due to its low density. The washing liquid is recycled between the second hydrogen purifier 3, the washing liquid circulation pump 10 and the washing liquid cooler 11, reducing medium consumption and waste generation.

[0050] In the present invention, water needs to be added to the second hydrogen purifier 3 during the reaction to maintain the water balance of the entire hydrogen release system. The amount of water added here is the sum of the amount of water required for the lithium hydride hydrolysis reaction and the saturated water carried in the hydrogen at the second outlet 27 of the second hydrogen purifier 3.

[0051] During the reaction, the hydrogen is first preliminarily purified in the first hydrogen purifier 2. At this time, the hydrogen still contains water vapor, droplets and dust. Then, it enters the second hydrogen purifier 3 for deep purification. In the second hydrogen purification 3, the hydrogen containing water vapor, droplets and dust, and the water added to the second hydrogen purifier 3 are in contact with the washing liquid. The washing liquid assists the filler in the second hydrogen purifier 3 to remove the water vapor, droplets and dust in the hydrogen. The washing liquid containing water vapor, all droplets and dust and the water added to the second hydrogen purifier 3 form a mixed liquid and circulate along the liquid phase outlet 25 to the washing liquid. The washing liquid circulation pump 10 is then divided into two paths after being cooled by the washing liquid cooler 11. Part of the mixed liquid enters the second hydrogen purifier 3 along the second pipeline 26 again to be recycled, and the other part of the mixed liquid enters the hydrolysis reactor 1 along the first pipeline 23, so that the concentration of impurities in the washing liquid is maintained within a suitable range to ensure the purification effect of the second hydrogen purifier 3; the washing liquid cooler 11 is also connected to circulating water, and the circulating water comes from the refrigerator. The circulating water circulates between the refrigerant and the washing liquid cooler 11 to ensure the cooling effect of the washing liquid cooler 11.

[0052] After being cooled by the washing liquid cooler 11, the temperature of the mixed liquid is as low as ~35°C.

[0053] In the present invention, the washing liquid is preferably water, and no new substances are introduced and no waste liquid is generated. In particular, the washing liquid after washing the hydrogen in the second hydrogen purifier 3 enters the hydrolysis reactor 1 as supplementary water to participate in the reaction.

[0054] In the present invention, the bottom of the hydrogen autoclave 5 is connected to circulating water, and the circulating water comes from a refrigerator. The temperature of hydrogen will increase during the pressurization process of the hydrogen autoclave 5, and the circulating water is used to cool the hydrogen.

[0055] In the present invention, the liquid phase treatment unit includes a reactor discharge pump 8, a sedimentation tank 7 and a supernatant liquid circulation pump 9 in sequence along the liquid flow direction.

[0056] Among them, the reactor discharge pump 8 is used to transport the liquid phase product of the lithium hydride hydrolysis reaction; the sedimentation tank 7 is used for the lithium hydride secondary hydrolysis reaction and the collection of lithium hydroxide slurry; the supernatant circulation pump 9 is used to circulate the water generated by the lithium hydride secondary hydrolysis reaction to the hydrolysis reactor 1.

[0057] Furthermore, an outlet is provided at the bottom of the hydrolysis reactor 1, a second inlet 29 is provided on one side of the upper end of the settling tank 7, a fourth outlet 71 is provided on the other side of the upper end, a discharge port 22 is provided at the bottom, and a fifth outlet 72 is provided in the middle of the side wall. The outlet at the bottom of the hydrolysis reactor 1 is connected to the second inlet 29 of the settling tank 7 through a reactor discharge pump 8, and the fifth outlet 72 is connected to the hydrolysis reactor 1 through a supernatant circulation pump 9. The discharge port 22 is used to collect lithium hydroxide slurry for subsequent recycling.

[0058] Furthermore, a secondary hydrolysis reaction of lithium hydride occurs in the sedimentation tank 7 , and the generated hydrogen is transported to the hydrogen tank 4 through the fourth outlet 71 .

[0059] Furthermore, a second stirring subunit 73 is provided in the settling tank 7 to promote the hydrolysis reaction of lithium hydride. The stirring rate is 30-1000 rpm, for example, 100 rpm.

[0060] During the reaction, since the liquid phase products of the lithium hydride hydrolysis reaction in the hydrolysis reactor 1 contain a small amount of lithium hydride and water, the liquid phase products such as lithium hydride, water and lithium hydroxide are all transmitted to the settling tank 7 through the reactor discharge pump 8, and the unreacted lithium hydride and water further react in the settling tank 7 to generate lithium hydroxide and hydrogen. The hydrogen is transported to the hydrogen tank 4 along the fourth outlet 71 at the upper end, and the saturated lithium hydroxide solution in the settling tank 7 is sent to the hydrolysis reactor 1 through the supernatant circulation pump 9. The lithium hydroxide slurry with higher purity at the bottom of the settling tank 7 is gravity-flowed into barrels through the discharge port 22 and subsequently recycled and reused.

[0061] Among them, the number of settling tanks 7 is consistent with the number of hydrolysis reactors 1. At this time, one hydrolysis reactor 1 is connected to a corresponding settling tank 7 and a reactor discharge pump 8. Multiple hydrolysis reactors 1 are simultaneously connected to the first purifier 2, and the hydrogen produced by multiple hydrolysis reactors 1 simultaneously enters the first purifier 2 for preliminary purification, multiple settling tanks 7 are simultaneously connected to the hydrogen tank 4, and the hydrogen produced in multiple settling tanks 7 simultaneously enters the hydrogen tank 4, and multiple settling tanks 7 are simultaneously connected to the supernatant circulation pump 9, and the saturated lithium hydroxide solution is simultaneously sent to the hydrolysis reactor 1 through the supernatant circulation pump 9.

[0062] In the present invention, the interaction among the hydrolysis reaction unit, the hydrogen treatment unit and the liquid phase treatment unit is used to realize continuous and stable external supply of hydrogen and hot water, the purity of hydrogen reaches 99.97-99.999% (v), and the external hydrogen supply flow rate reaches 0.31-53.76 Nm 3 / min, the amount of 55℃ hot water supplied to the outside is 0.71~204m 3 / h.

[0063] Of course, the amount of lithium hydride used determines the amount of hydrogen and hot water supplied to a certain extent. For example, 1200kg of lithium hydride can ultimately achieve a hydrogen purity of 99.999% (v) and an external hydrogen flow rate of 53.76Nm 3 / min, the external hot water supply of 55℃ is 204m 3 / h; 7kg lithium hydride, the final hydrogen purity is 99.97% (v), and the external hydrogen flow rate is 0.31Nm 3 / min, the amount of 55℃ hot water supplied to the outside is 0.71m 3 / h.

[0064] On the other hand, according to the method for performing hydrogenation by lithium hydride hydrolysis by the device of the first aspect provided by the present invention, the method comprises: Step 1, hydrolyzing lithium hydride to produce hydrogen; Step 2, purifying, storing, pressurizing and drying hydrogen; Step 3, treating the liquid product of the lithium hydride hydrolysis reaction.

[0065] In step 1, a hydrolysis reaction of lithium hydride is carried out by a hydrolysis reaction unit.

[0066] In step 2, hydrogen is purified, stored, pressurized and dried using a hydrogen processing unit.

[0067] In step 3, a liquid phase treatment unit is used to treat the liquid phase product of the lithium hydride hydrolysis reaction.

[0068] The present invention is further described below through specific examples, but these examples are merely exemplary and do not constitute any limitation to the scope of protection of the present invention.

[0069] Example 1 like Figure 1 As shown in the figure, the first hydrogen purifier 2 used is filled with 0.1m high asbestos rope; the second hydrogen purifier 3 is an empty tower; the hydrogen dryer 6 is filled with 1m high silicon dioxide; the reaction temperature of the hydrolysis reactor 1 is set to 70°C, the pressure is 20kPaG, and the stirring speed is 500rpm; the inlet temperature of the hydrogen pressure reactor 5 is 40°C, the inlet pressure is 15kPaG, the outlet temperature is 40°C, and the outlet pressure is 450kPaG; the stirring speed of the sedimentation tank 7 is 1000rpm; a saturated lithium hydroxide solution is added to the hydrolysis reactor 1 through the supernatant circulation pump 9, and 30kg of lithium hydride is added at 20°C through the first feed port 21 (addition is completed within 1 hour, quantitative feeding), and 5.1m 3 Hot water at 40°C is introduced at a hot water flow rate of / h; the washing liquid used is water.

[0070] The hydrogen containing water vapor, liquid droplets and dust generated by the reaction in the hydrolysis reactor 1 enters the first hydrogen purifier 2 through the hydrogen outlet 113 and the lower inlet of the first hydrogen purifier 2 to remove most of the liquid droplets and dust; then the hydrogen enters the second hydrogen purifier 3 along the first outlet 24 at the upper end of the first hydrogen purifier 2 and the lower inlet of the second hydrogen purifier 3 at 22.93 kg / h, and the hydrogen contacts the water and washing liquid added to the second hydrogen purifier 3. The washing liquid containing water vapor, liquid droplets and dust and the water added to the second hydrogen purifier 3 form a mixed liquid, and circulates to the washing liquid circulation pump 10 along the liquid phase outlet 25 at the bottom of the second hydrogen purifier 3 at 635.84 kg / h. After the liquid cooler 11 is cooled to 35°C, part of the mixed liquid enters the second hydrogen purifier 3 along the second pipeline 26 at 245.36kg / h for recycling, and the other part of the mixed liquid enters the hydrolysis reactor 1 along the first pipeline 23 at 384.72kg / h for utilization; hydrogen flows along the second outlet 27 of the second hydrogen purifier 3 through the first inlet 41 at the lower end of the hydrogen tank 4 to enter the hydrogen tank 4 at 11.08kg / h, and then is discharged from the third outlet 42 of the hydrogen tank 4 to the hydrogen pressure kettle 5, and is pressurized to 450kPaG. The hydrogen at a temperature of 40°C enters the hydrogen dryer 6 at 8.07kg / h to remove trace water in the hydrogen, thereby realizing continuous and stable external hydrogen supply; At the same time, the liquid product discharged from the bottom of the hydrolysis reactor 1 is transmitted to the settling tank 7 along the second inlet 29 through the reactor discharge pump 8 at a rate of 621.92 kg / h, and the unreacted lithium hydride in the liquid product further reacts with water in the settling tank 7 to generate lithium hydroxide and hydrogen. The hydrogen at 50°C is transported to the hydrogen tank 4 along the fourth outlet 71 at the upper end at a rate of 0.63 kg / h, and the saturated lithium hydroxide solution in the settling tank 7 is sent into the hydrolysis reactor 1 through the fifth outlet 72 and the supernatant circulation pump 9, and the discharge port 22 collects the lithium hydroxide slurry at a rate of 391.16 kg / h.

[0071] Finally, the purity of hydrogen from hydrogen dryer 6 to the user is 99.997% (v), and the external hydrogen flow rate is 1.344Nm 3 / min, meeting the hydrogen demand of 100kW fuel cell, and supplying 55℃ hot water to the outside with a capacity of 5.1m 3 / h.

[0072] Example 2 like Figure 1 As shown, the first hydrogen purifier 2 used in the figure is filled with a 0.2m high wire mesh; the second hydrogen purifier 3 is equipped with two sections of polypropylene ball rings (DN16) fillers, each section of fillers is 2.5m high; the hydrogen dryer 6 is filled with a 4m high molecular sieve; the reaction temperature of the hydrolysis reactor 1 is set to 70°C, the pressure is 20kPaG, and the stirring speed is 80rpm; the inlet temperature of the hydrogen pressure reactor 5 is 40°C, the inlet pressure is 15kPaG, the outlet temperature is 40°C, and the outlet pressure is 600kPaG; the stirring speed of the sedimentation tank 7 is 100rpm; a saturated lithium hydroxide solution is added to the hydrolysis reactor 1 through the supernatant circulation pump 9, and 1200kg of lithium hydride is added at 20°C through the first feed port 21 (addition is completed within 1 hour, quantitative feeding), and 204m 3 Hot water at 40°C is introduced at a hot water flow rate of / h; the washing liquid used is water.

[0073] The hydrogen containing water vapor, liquid droplets and dust generated by the reaction in the hydrolysis reactor 1 enters the first hydrogen purifier 2 through the hydrogen outlet 113 and the lower inlet of the first hydrogen purifier 2 to remove most of the liquid droplets and dust; then the hydrogen enters the second hydrogen purifier 3 along the first outlet 24 at the upper end of the first hydrogen purifier 2 and the lower inlet of the second hydrogen purifier 3 at 917.2kg / h, and the hydrogen contacts the water and washing liquid added to the second hydrogen purifier 3 for mass transfer and heat transfer. The washing liquid containing water vapor, liquid droplets and dust and the water added to the second hydrogen purifier 3 form a mixed liquid, and circulate together along the liquid phase outlet 25 at the bottom of the second hydrogen purifier 3 to the washing liquid circulation pump 10 at 25433.6kg / h, and then passes through the washing liquid circulation pump 10. After the washing liquid cooler 11 is cooled to 35°C, part of the mixed liquid enters the second hydrogen purifier 3 along the second pipeline 26 at 9814.4 kg / h for recycling, and the other part of the mixed liquid enters the hydrolysis reactor 1 along the first pipeline 23 at 15388.8 kg / h for utilization; hydrogen flows along the second outlet 27 of the second hydrogen purifier 3 through the first inlet 41 at the lower end of the hydrogen tank 4 to enter the hydrogen tank 4 at 443.2 kg / h, and then is discharged from the third outlet 42 of the hydrogen tank 4 to the hydrogen pressure kettle 5, and the pressure is increased to 600 kPaG. The hydrogen at a temperature of 40°C enters the hydrogen dryer 6 at 322.8 kg / h to remove trace water in the hydrogen, thereby realizing continuous and stable external hydrogen supply; At the same time, the liquid product discharged from the bottom of the hydrolysis reactor 1 is transmitted to the settling tank 7 along the second inlet 29 through the reactor discharge pump 8 at 24876.8 kg / h, and the unreacted lithium hydride in the liquid product further reacts with water in the settling tank 7 to generate lithium hydroxide and hydrogen. The hydrogen at 50°C is transported to the hydrogen tank 4 along the fourth outlet 71 at the upper end at 25.2 kg / h, and the saturated lithium hydroxide solution in the settling tank 7 is sent into the hydrolysis reactor 1 through the fifth outlet 72 and the supernatant circulation pump 9, and the discharge port 22 collects the lithium hydroxide slurry at 15646.4 kg / h.

[0074] Finally, the purity of hydrogen from hydrogen dryer 6 to the user is 99.999% (v), and the external hydrogen flow rate is 53.76Nm 3 / min, the external hot water supply of 55℃ is 204m 3 / h.

[0075] Example 3 like Figure 1As shown, the first hydrogen purifier 2 used in the figure is filled with a 0.05m high rectangular saddle ring filler; the second hydrogen purifier 3 is equipped with a section of glass fiber reinforced polypropylene ladder ring (DN25) filler, the filler height is 1m; the hydrogen dryer 6 is filled with 2.5m high calcium oxide; the reaction temperature of the hydrolysis reactor 1 is set to 90°C, the pressure is 15kPaG, and the stirring speed is 150rpm; the inlet temperature of the hydrogen pressure reactor 5 is 40°C, the inlet pressure is 10kPaG, the outlet temperature is 40°C, and the outlet pressure is 700kPaG; the stirring speed of the step-down tank 7 is 30rpm; a saturated lithium hydroxide solution is added to the hydrolysis reactor 1 through the supernatant circulation pump 9, and 7 kg of lithium hydride is added at 20°C through the first feed port 21 (addition is completed within 1 hour, quantitative feeding), and 0.71m 3 Hot water at 40°C is introduced at a hot water flow rate of / h; the washing liquid used is water.

[0076] The hydrogen containing water vapor, liquid droplets and dust generated by the reaction in the hydrolysis reactor 1 enters the first hydrogen purifier 2 through the hydrogen outlet 113 and the lower inlet of the first hydrogen purifier 2 to remove most of the liquid droplets and dust; then the hydrogen enters the second hydrogen purifier 3 along the first outlet 24 at the upper end of the first hydrogen purifier 2 and the lower inlet of the second hydrogen purifier 3 at 24.23kg / h, and the hydrogen contacts the water and washing liquid added to the second hydrogen purifier 3 for mass transfer and heat transfer. The washing liquid containing water vapor, liquid droplets and dust and the water added to the second hydrogen purifier 3 form a mixed liquid, and circulate together along the liquid phase outlet 25 at the bottom of the second hydrogen purifier 3 to the washing liquid circulation pump 10 at 204.12kg / h. After being cooled to 35°C by the washing liquid cooler 11, part of the mixed liquid enters the second hydrogen purifier 3 along the second pipeline 26 at 101.34kg / h for recycling, and the other part of the mixed liquid enters the hydrolysis reactor 1 along the first pipeline 23 at 102.78kg / h for utilization; hydrogen flows along the second outlet 27 of the second hydrogen purifier 3 through the first inlet 41 at the lower end of the hydrogen tank 4 to enter the hydrogen tank 4 at 2.6kg / h, and then is discharged from the third outlet 42 of the hydrogen tank 4 to the hydrogen pressure kettle 5, and the pressure is increased to 700kPaG. The hydrogen at a temperature of 40°C enters the hydrogen dryer 6 at 1.74kg / h to remove trace water in the hydrogen, thereby realizing continuous and stable external hydrogen supply; At the same time, the liquid product discharged from the bottom of the hydrolysis reactor 1 is transmitted to the settling tank 7 along the second inlet 29 through the reactor discharge pump 8 at a rate of 136.64 kg / h, and the unreacted lithium hydride in the liquid product further reacts with water in the settling tank 7 to generate lithium hydroxide and hydrogen. The hydrogen at 50°C is transported to the hydrogen tank 4 along the fourth outlet 71 at the upper end at a rate of 0.11 kg / h, and the saturated lithium hydroxide solution in the settling tank 7 is sent into the hydrolysis reactor 1 through the fifth outlet 72 and the supernatant circulation pump 9, and the discharge port 22 collects the lithium hydroxide slurry at a rate of 86.42 kg / h.

[0077] Finally, the purity of hydrogen from hydrogen dryer 6 to the user is 99.97% (v), and the external hydrogen flow rate is 0.31Nm 3 / min, the amount of 55℃ hot water supplied to the outside is 0.71m 3 / h.

[0078] Example 4 like Figure 1 As shown, the first hydrogen purifier 2 used in the figure is filled with 0.4m high θ ring filler; the second hydrogen purifier 3 is equipped with two sections of 316L rectangular saddle ring (DN50) filler, each section of filler is 4m high; the hydrogen dryer 6 is filled with 3m high calcium chloride; the reaction temperature of the hydrolysis reactor 1 is set to 80℃, the pressure is 15kPaG, and the stirring speed is 110rpm; the inlet temperature of the hydrogen pressure reactor 5 is 40℃, the inlet pressure is 10kPaG, the outlet temperature is 40℃, and the outlet pressure is 800kPaG; the stirring speed of the sedimentation tank 7 is 60rpm; a saturated lithium hydroxide solution is added to the hydrolysis reactor 1 through the supernatant circulation pump 9, and 690kg of lithium hydride is added at 20℃ through the first feed port 21 (addition is completed within 1 hour, quantitative feeding), and 107m 3 Hot water at 40°C is introduced at a hot water flow rate of / h; the washing liquid used is water.

[0079] The hydrogen containing water vapor, liquid droplets and dust generated by the reaction in the hydrolysis reactor 1 enters the first hydrogen purifier 2 through the hydrogen outlet 113 and the lower inlet of the first hydrogen purifier 2 to remove most of the liquid droplets and dust; then the hydrogen enters the second hydrogen purifier 3 along the first outlet 24 at the upper end of the first hydrogen purifier 2 and the lower inlet of the second hydrogen purifier 3 at 1090.2kg / h, and the hydrogen contacts the water and washing liquid added to the second hydrogen purifier 3 for mass transfer and heat transfer. The washing liquid containing water vapor, liquid droplets and dust and the water added to the second hydrogen purifier 3 form a mixed liquid, and circulates to the washing liquid circulation pump 10 along the liquid phase outlet 25 at the bottom of the second hydrogen purifier 3 at 27221.6kg / h. After the liquid cooler 11 is cooled to 35°C, part of the mixed liquid enters the second hydrogen purifier 3 along the second pipeline 26 at 17931.62 kg / h for recycling, and the other part of the mixed liquid enters the hydrolysis reactor 1 along the first pipeline 23 at 9289.98 kg / h for utilization; hydrogen flows along the second outlet 27 of the second hydrogen purifier 3 through the first inlet 41 at the lower end of the hydrogen tank 4 to enter the hydrogen tank 4 at 256.76 kg / h, and then is discharged from the third outlet 42 of the hydrogen tank 4 to the hydrogen pressure kettle 5, and the pressure is increased to 800 kPaG. The hydrogen at a temperature of 40°C enters the hydrogen dryer 6 at 179.37 kg / h to remove trace water in the hydrogen, thereby realizing continuous and stable external hydrogen supply; At the same time, the liquid product discharged from the bottom of the hydrolysis reactor 1 is transmitted to the settling tank 7 along the second inlet 29 through the reactor discharge pump 8 at a rate of 14143.9 kg / h, and the unreacted lithium hydride in the liquid product further reacts with water in the settling tank 7 to generate lithium hydroxide and hydrogen. The hydrogen at 50°C is transported to the hydrogen tank 4 along the fourth outlet 71 at the upper end at a rate of 10.83 kg / h, and the saturated lithium hydroxide solution in the settling tank 7 is sent into the hydrolysis reactor 1 through the fifth outlet 72 and the supernatant circulation pump 9, and the discharge port 22 collects the lithium hydroxide slurry at a rate of 8946.3 kg / h.

[0080] Finally, the purity of hydrogen from hydrogen dryer 6 to the user is 99.98% (v), and the external hydrogen flow rate is 30.89Nm 3 / min, the external hot water supply volume of 55℃ is 107m 3 / h.

[0081] From the above, it can be seen that after the lithium hydride hydrolysis reaction is carried out in the lithium hydride hydrolysis hydrogenation device, a continuous and stable hydrogen release rate and large-scale external hydrogen supply can be achieved by adjusting the amount of solid lithium hydride added; and no catalyst and / or auxiliary agent is needed to be added in the reaction; the amount of lithium hydride used determines the amount of external hydrogen supply and the amount of hot water to a certain extent, among which the hydrogen purity, hydrogen supply flow rate and hot water amount finally achieved with the lithium hydride amount of 1200 kg in Example 2 are the highest.

[0082] The present invention is described in detail above in combination with preferred embodiments and exemplary examples. However, it should be noted that these specific embodiments are only illustrative explanations of the present invention and do not constitute any limitation on the protection scope of the present invention. Without exceeding the spirit and protection scope of the present invention, various improvements, equivalent substitutions or modifications may be made to the technical content of the present invention and its embodiments, which all fall within the protection scope of the present invention. The protection scope of the present invention shall be subject to the attached claims.

Claims

1. A lithium hydride aqueous hydrogenation device, characterized in that: The device comprises: A hydrolysis reaction unit, which is used for the hydrolysis reaction of lithium hydride to produce hydrogen; A hydrogen processing unit for purifying, storing, pressurizing and drying hydrogen; A liquid phase treatment unit is used to treat the liquid phase product of the lithium hydride hydrolysis reaction.

2. The device according to claim 1, characterized in that Preferably, the hydrolysis reaction unit comprises a hydrolysis reactor (1), and the hydrolysis reactor (1) is used for performing a lithium hydride hydrolysis reaction.

3. The device according to claim 1, characterized in that The hydrogen processing unit comprises: A first hydrogen purifier (2) is used to preliminarily purify hydrogen generated by the hydrolysis reaction of lithium hydride; The second hydrogen purifier (3) is used to deeply purify the hydrogen and improve the purity of the hydrogen.

4. The device according to claim 3, characterized in that The hydrogen processing unit also includes: A hydrogen tank (4), which is used to store purified hydrogen; A hydrogen autoclave (5), which is used to pressurize hydrogen to 400-800 kPaG; The hydrogen dryer (6) is used to remove moisture from the hydrogen.

5. The device according to claim 4, characterized in that The hydrogen dryer (6) is filled with a desiccant, which is selected from any one or more of molecular sieves, silicon dioxide, calcium chloride, and calcium oxide.

6. The device according to claim 4, characterized in that The height of the desiccant filled in the hydrogen dryer (6) is 0.4-8 m.

7. The device according to claim 4, characterized in that The hydrogen processing unit comprises, in sequence along the hydrogen flow direction, a first hydrogen purifier (2), a second hydrogen purifier (3), a hydrogen tank (4), a hydrogen pressure kettle (5) and a hydrogen dryer (6).

8. The device according to claim 1, characterized in that The liquid phase processing unit comprises: The reactor discharge pump (8) is used to transport the liquid phase product of the lithium hydride hydrolysis reaction.

9. The device according to claim 8, characterized in that The liquid phase processing unit also includes: A settling tank (7), which is used for secondary hydrolysis of lithium hydride and collection of lithium hydroxide slurry; The supernatant liquid circulation pump (9) circulates the water generated by the secondary hydrolysis reaction of lithium hydride to the hydrolysis reactor (1).

10. A method for hydrogenation of lithium hydride by aqualysis using a device according to any one of claims 1 to 9, characterized in that: The method comprises: Step 1, hydrolyzing lithium hydride to produce hydrogen; Step 2, purifying, storing, pressurizing and drying hydrogen; Step 3, treating the liquid product of the lithium hydride hydrolysis reaction.

Images