KR20210126491A - Process for Storing and Releasing Hydrogen Using Liquid Organic Hydrogen Carriers - Google Patents

Abstract

According to the present disclosure, disclosed is a process capable of effectively storing/releasing hydrogen through a hydrogenation/dehydrogenation reaction using a liquid organic hydrogen carrier (LOHC), unlike a conventional hydrogen compression storage method, and further providing high-purity hydrogen.

Description

Process for Storing and Releasing Hydrogen Using Liquid Organic Hydrogen Carriers

The present invention relates to a hydrogen storage and release process using a liquid organic hydrogen carrier. More specifically, the present invention performs efficient storage/release of hydrogen through hydrogenation/dehydrogenation reaction using a liquid organic hydrogen carrier (LOHC), unlike the conventional hydrogen compression storage method, and furthermore, it is possible to provide high-purity hydrogen. It's about the process.

As environmental pollution problems such as reduction of fossil fuel reserves, global warming caused by pollutants generated during combustion, and carbon dioxide have become serious, global interest in and demand for alternative energy development is increasing explosively.

As an alternative energy source, renewable energy such as wind power, tidal power, geothermal heat, hydrogen energy, solar energy, etc. is in the spotlight, and each energy source has advantages and disadvantages. Renewable energy is difficult to supply and demand smoothly due to the instability of energy sources according to time and natural environment. Therefore, in order to effectively replace conventional fossil fuels, the technology for storing and supplying surplus energy to stably supply energy is required. development is needed for

In this regard, hydrogen energy is: (i) the most energy efficient per unit mass, (ii) only water is generated during combustion, no other harmful by-products, and (iii) water, the main source of hydrogen, is abundant in nature and used After conversion to water, it is advantageous in terms of reuse, and (iv) it is receiving particular attention because it is suitable for securing competitiveness in the precision industry and IT industry as a distributed power source using hydrogen as a fuel. Moreover, hydrogen can be produced using other renewable energy such as solar energy, wind power, etc., and can be widely applied not only in various energy sources but also in other industrial fields (eg, various petrochemical fields), etc. at home and abroad. It is emerging as a key energy source of the future.

In general, research and development of hydrogen energy is largely divided into the production field, transport (transport) field, and storage field of hydrogen. Hydrogen has an excellent energy storage capacity relative to mass, but low energy storage capacity versus volume, so hydrogen can be efficiently used The storage technology is acting as the biggest obstacle to the practical use of hydrogen energy. Therefore, research on a technology for storing as much hydrogen as possible in a storage medium as light as possible and having a small volume and discharging it efficiently is being actively conducted.

Conventionally, a method of mainly compressing hydrogen and storing it in a high-pressure tank has been adopted, but this high-pressure storage method has a high risk of hydrogen explosion and is difficult to store in a large capacity.

As an alternative to this, as a material having a hydrogen storage capacity, research on various inorganic materials, inorganic-organic complexes, etc. is in progress, but recently, reversible catalytic hydrogenation using organic materials, specifically liquid organic hydrogen carriers (LOHCs; Liquid Organic Hydrogen Carrier) / Hydrogen storage technology by dehydrogenation has been developed (US Patent No. 7,901,491, etc.). LOHC technology has the advantages of being able to operate in a low pressure range, easily regenerating stored materials, etc., and also, because of the advantages of liquid fossil fuels, such as handleability and high energy density, the existing liquid fuel transportation and storage infrastructure. It is possible to provide a practical hydrogen storage system that can efficiently transport and store using Substances such as offene, quinaldine, and carbazole have also been developed. In this regard, as a hydrogen storage material, a technique using a compound having a pi-conjugated double bond is known (eg, US Pat. No. 7,351,395, etc.), but it is difficult to secure uniform reactivity due to pi-conjugation, mostly solid phase It exists as a mixture, so it is used in the form of a mixture. In particular, when N-ethylcarbazole (NEC)/hydrogenated N-ethylcarbazole (H12-NEC) is used, the theoretical hydrogen storage capacity is 5.8% by weight, but due to the high melting point (68° C.) of NEC, the solid phase at room temperature is As such, transport and storage are limited.

In order to alleviate this problem, a technique using benzyltoluene and dibenzyltoluene (DBT) as a hydrogen storage material is also known (eg, Korean Patent Publication No. 2015-97558, etc.). It is known that the hydrogen storage material exists in a liquid phase at room temperature and has a boiling point of 280° C. or higher, so there is no limitation in terms of utilization.

As such, in the past, research has been focused on the selection of LOHC materials and the development of catalysts for hydrogenation/dehydrogenation reactions accompanying hydrogen storage/release, and it remains at the level of examining the applicability in actual laboratory scale or pilot facilities. . Therefore, research on a process or system essential for the commercialization of LOHC-based hydrogen storage technology is relatively slow.

In particular, in order to effectively perform the hydrogenation/dehydrogenation reaction by LOHC, the catalyst, hydrogen molecules, and the LOHC compound must be in contact at the same time, but in general, a catalyst in pellet form is used in consideration of handling and recovery. have. In this regard, in order to effectively promote the hydrogenation/dehydrogenation reaction, as it is desirable to increase the surface area of the catalyst, it is preferable to use a catalyst in powder form having a small particle size, but as the particle size decreases, the catalyst and It is difficult to isolate LOHC. This point acts as a factor hindering the commercialization of the LOHC-based process.

Therefore, for the commercialization of the LOHC-based hydrogen storage/release process or system, a catalyst in powder form (ie, a heterogeneous catalyst) is used, but the hindering factors of commercialization caused therefrom are alleviated, and the hydrogen stored in the LOHC is converted to a hydrogen consumer. There is a need for a method capable of providing high-purity hydrogen while releasing hydrogen by a dehydrogenation reaction after being transferred to the furnace.

In one embodiment of the present invention, it is an object of the present invention to provide a process or system capable of effectively commercializing LOHC-based technology that has been conventionally performed on a laboratory or pilot facility scale.

Another embodiment of the present invention is to provide a method for providing high-purity hydrogen in a hydrogen transport process using a liquid organic hydrogen carrier.

According to one embodiment of the present invention,

a) By supplying a liquid organic hydrogen carrier (LOHC) and hydrogen to a first reactor in which a flange-type first filter is detachably mounted on the lower side of the reactor, and hydrogenation reaction in the presence of a hydrogenation catalyst in powder form, LOHC is converted to LOHC in hydrogenated form, and the hydrogenated product is filtered through the first filter and discharged from the first reactor, while retaining the hydrogenation catalyst in powder form in the first reactor;

b) transferring the hydrogenated product discharged from the first reactor to a predetermined distance;

c) supplying the transferred hydrogenation product to a second reactor in which a flange-type second filter is detachably mounted on the lower side of the reactor to dehydrogenate in the presence of a dehydrogenation catalyst in powder form. The conversion of LOHC to LOHC produces a hydrogen-containing gas, and the dehydrogenation product is filtered through a second filter and discharged from the second reactor while retaining the dehydrogenation catalyst in powder form in the second reactor, while the hydrogen-containing gas discharging from the second reactor;

d) cooling the discharged hydrogen-containing gas by heat exchange in a condenser; and

e) purifying the cooled hydrogen-containing gas to recover purified hydrogen;

There is provided a hydrogen storage and release process comprising:

According to an exemplary embodiment, the hydrogen-containing gas produced in step c) may contain hydrocarbons produced during the LOHC and/or dehydrogenation reaction in addition to hydrogen.

According to an exemplary embodiment, after condensing and separating the LOHC in the hydrogen-containing gas in step d), the method may further include recovering.

According to an exemplary embodiment, the method may further include recycling the recovered LOHC to a second reactor.

According to an exemplary embodiment, step e) may include adsorbing and removing hydrocarbons in the hydrogen-containing gas.

According to an exemplary embodiment, a plurality of support members serving as a bridge may be provided on the periphery of each of the first flange filter and the second flange filter.

In the hydrogen storage/release process and system according to the present invention, most of the existing LOHC-based hydrogen storage/release technologies are limited to confirming the possibility of implementation in laboratory scale or pilot facilities, and hydrogenation/dehydrogenation catalyst in the form of pellets It is possible to effectively solve the problem of limitations in achieving an effective hydrogenation / dehydrogenation reaction by using In particular, it is possible to increase hydrogen storage efficiency and shorten reaction time by maximizing the contact between the reactant LOHC and hydrogen by using a catalyst in powder (particle) form rather than in pellet form, which is a suitable factor for commercialization. Furthermore, by providing a flange-type filter in the hydrogenation reactor and the dehydrogenation reactor to perform filtering (filtration) in the reactor, it provides the advantage of effectively suppressing the deterioration (oxidation, etc.) phenomenon caused by exposure of the catalyst to the outside of the reactor. . Therefore, a wide range of applications is expected in the future.

1 is a process flow diagram schematically illustrating a LOHC-based hydrogen storage/release process according to one embodiment;
2A and 2B are each a cross-sectional view showing a schematic structure of a hydrogenation reactor and a movement path of a material, and a schematic structure inside a hydrogenation reactor, according to an exemplary embodiment;
3A and 3B are each a cross-sectional view showing a schematic structure of a dehydrogenation reactor and a movement path of a material, and a schematic structure inside a dehydrogenation reactor, in an exemplary embodiment of the present invention;
4 is a diagram showing a schematic structure of a condenser for separating hydrogen from a hydrogen-containing gas discharged from a dehydrogenation reactor and a movement path of materials according to an exemplary embodiment of the present invention; and
5 is a diagram illustrating a schematic structure of an adsorption tower for further purifying hydrogen separated from a condenser and a movement path of a material in an exemplary embodiment of the present invention.

The present invention can all be achieved by the following description. It is to be understood that the following description describes preferred embodiments of the present invention, but the present invention is not necessarily limited thereto. In addition, the accompanying drawings are provided to aid understanding, the present invention is not limited thereto, and details regarding individual configurations may be properly understood by the specific purpose of the related description to be described later.

In this specification, the terms “located on the upper side” or “located on the lower side” may be understood to represent a relative positional relationship in a state in which a specific object is not in contact as well as in a state in contact with a specific object.

In the present specification, a specific numerical range may be understood to include any combination between the lower limit and the upper limit thereof, for example, "1 to 10" means 1, 2, 3, 4, 5, 6, 7, Subcombinations using any two values of 8, 9 and 10 as the lower limit and the upper limit may be included.

In this specification, when any component or member is described as “connected” or “in communication with” another component or member, unless otherwise stated, the component or member is directly connected or in communication with the other component or member. It can be understood that not only the case, but also the case of being connected or connected under the intervening of other components or members is included.

Similarly, it may be understood that the term “contacting” may also include a case of making direct contact as well as a case of making contact with the presence of other components or members.

In the present specification, when a component is "included", it means that other components may be further included, unless otherwise stated.

1 schematically shows a LOHC-based hydrogen storage/release process according to an embodiment of the present invention.

According to the illustrated embodiment, in step (a), a liquid organic hydrogen carrier (LOHC) is supplied to the hydrogenation reactor, and hydrogen (H ₂ ) is supplied to the hydrogenation reactor through a separate line in order to store hydrogen in a manner of hydrogenating the LOHC. is supplied with

According to the illustrated embodiment. An inert gas, for example, nitrogen (N ₂ ) gas may be supplied to the hydrogenation reactor through a separate line, and the nitrogen gas is (i) nitrogen purge for discharging residual gas remaining in the reactor before and after the hydrogenation reaction and/or (ii) transporting the hydrogenated LOHC to a subsequent step, and further providing a pressure (filtration pressure) necessary for filtration of a flange filter provided in the reactor in a pressurized state. have.

In an exemplary embodiment, any type known in the art may be used for the LOHC without particular limitation. In this regard, LOHC may be a compound having a π-conjugated double bond, and typically may be selected from aromatic compounds (specifically, aromatic compounds capable of maintaining a liquid phase as much as possible during dehydrogenation), in which case the hydrogenation reaction While the conjugated double bond in the compound is hydrogenated by this, it can be converted back to a conjugated double bond by the dehydrogenation reaction. In this case, the “hydrogenation reaction” refers to saturating the unsaturated bond by adding hydrogen, and in principle, cleavage of a molecule by hydrogen or cleavage of a carbon-carbon bond or a bond between carbon-heteroelements is not included. In this embodiment, the transport of hydrogen may be carried out in the form of hydrogenated LOHC. On the other hand, "dehydrogenation reaction" refers to the release of hydrogen as the hydrogenated LOHC is converted to the initial LOHC (that is, unsaturated bonds are formed between atoms other than hydrogen present in the molecule), and between the existing elements in the molecule. Reactions in which new single bonds are formed are not included in principle.

In this embodiment, it may be advantageous to select the LOHC from a type having properties that can minimize loss during process performance, for example, dibenzyl toluene (DBT) may be used. DBT can be advantageous because it has good hydrogen storage density (about 6.2 wt. %), as well as properties suitable for existing fuel supply systems.

In this regard, hydrogen storage (hydrogenation) and hydrogen release (dehydrogenation) when DBT is applied as LOHC can be performed as in Scheme 1 below.

[Scheme 1]

According to the illustrated embodiment, the hydrogenation reaction is typically exothermic (about 65.4 kJ/mol for DBT), resulting in an increase in the temperature of the product (LOHC in hydrogenated form) as the reaction proceeds. In addition, the reaction may be carried out under a relatively high hydrogen partial pressure condition, for example, may be controlled within the range of about 30 to 80 barg, specifically about 40 to 70 barg, more specifically about 45 to 60 barg. Taking the above into consideration, the hydrogenation reactor may have a design pressure of approximately 100 barg to withstand high pressure. According to an exemplary embodiment, the reaction temperature may be set, for example, in the range of about 100 to 180° C., specifically about 120 to 170° C., and more specifically about 140 to 160° C., wherein the reactor design temperature is approximately 200 °C. In addition, _{the volume ratio of H 2} /LOHC is adjustable within, for example, about 3 to 10 Nm3/m3, specifically about 4 to 7 Nm3/m3, more specifically about 5 to 6 Nm3/m3. do. In addition, the reaction time may be, for example, about 4 to 12 hours, specifically about 6 to 10 hours, and more specifically about 7 to 9 hours. However, the above-described reaction conditions may be understood by way of example and may be changed according to LOHC.

FIG. 2A shows a schematic structure of a hydrogenation reactor and a material movement path, and FIG. 2B shows a schematic structure inside a hydrogenation reactor according to an exemplary embodiment of the present invention.

According to the illustrated embodiment, the hydrogenation reactor (A) is equipped with a hydrogen line and a stirrer for hydrogenating the LOHC by largely bubbling hydrogen. At this time, the hydrogen line is introduced into the reactor (A) from the hydrogen source 103 through the line 104 by valve operation, and the stirrer 109 is, in the hydrogenation process, for example, about 800 to 2000 rpm, specifically It may be configured to rotate at about 1000 to 1500 rpm, more specifically, at about 1100 to 1300 rpm.

In this regard, in the case of hydrogen introduced via line 104, for hydrogen purging purposes, it may be, for example, a pressure level of about 1 to 5 barg (specifically about 2 to 3 barg), and for the hydrogenation reaction may be, for example, a pressure level of about 40 to 90 barg (specifically about 50 to 80 barg). To this end, a bypass line may be installed in the supply line from the hydrogen source 103 to the reactor A, and hydrogen may be supplied at a pressure required for each of the hydrogen purge and the hydrogenation reaction through valve operation.

In addition, referring to FIGS. 2A and 2B , nitrogen is introduced into the reactor A from the nitrogen source 101 through the line 102 by valve operation for the purpose of nitrogen purging and/or liquid transfer by pressurized nitrogen. do. The nitrogen flow introduced in this way serves to discharge excess gas after the reaction as well as nitrogen purging before and after the hydrogenation reaction as described above. As an example, the pressure of the nitrogen flow introduced into the reactor for the purpose of purging or evacuating excess gas as described above may be, for example, in the range of about 1 to 4 barg (specifically, about 2 to 3 barg). On the other hand, the nitrogen pressure (ie, nitrogen boosting pressure) for the purpose of liquid transport (specifically, providing and transporting the filtration pressure of the hydrogenated LOHC) is, for example, about 5 to 15 barg (specifically, about 8 to 12 barg) barg) within the range. However, such nitrogen gas transport conditions may be understood as exemplary.

Meanwhile, according to an exemplary embodiment, in order to raise the temperature to a temperature (or operating temperature) required for the hydrogenation reaction, a reactor heater (not shown) may be used. In this case, the heater may be a flange-type heater. Illustratively, the flange heater may be composed of a hairpin or a bent tube member, and may be manufactured by welding or brazing the heating member onto the flange. The flange-type heater has an advantage of good thermal efficiency as it can be used by directly inputting the heating member to the object to be heated, and the material thereof may be stainless steel or the like.

In addition, since the hydrogenation reaction is an exothermic reaction, a cooling line for temperature control may be provided for the purpose of appropriately controlling the temperature rise in the reactor due to this. Water may be supplied through a water cooling line (eg, in the form of a cooling coil) installed inside the reactor. Alternatively, a thermal medium oil known in the art may be used instead of water to maintain a temperature range suitable for the hydrogenation reaction.

In the illustrated embodiment, the hydrogenation reactor may be designed in the form of a dip pipe so that bubbling and reaction can easily occur. In addition, a double check valve may be provided to prevent backfire in the reactor.

According to an exemplary embodiment, the hydrogenation reaction may be performed in the presence of a heterogeneous catalyst, specifically, a transition metal-based heterogeneous catalyst (ie, a transition metal supported catalyst). In this case, the hydrogenation catalyst may be in a form in which a hydrogenation metal is supported on a porous inorganic oxide support, and the porous inorganic oxide support is, for example, alumina (specifically, gamma-alumina), silica, silica-alumina, titania, silicon carbide. It may be at least one selected from and the like. In addition, the metal hydride may be at least one transition metal selected from Groups 5 to 10 on the periodic table, and specifically may be at least one selected from nickel, platinum, palladium, rhodium, iridium and ruthenium. The metal component in the catalyst may be supported on a support in the form of nano-sized particles or clusters, wherein the size of the metal particles is, for example, about 1 to 30 nm, specifically about 2 to 15 nm, more specifically about 4 to 10 nm, but this is to be understood as illustrative.

In addition, in certain embodiments, the metal hydride may be a noble metal, and in particular, when DBT is used as LOHC, it may be advantageous to use a ruthenium (Ru) supported catalyst, specifically, a catalyst in which ruthenium is supported on an alumina support. . However, the present disclosure is not limited to the catalyst exemplified above, and an appropriate catalyst may be selected according to the LOHC used. The above-mentioned catalyst may be prepared by a method known in the art, for example, an impregnation method, and the like. As such a catalyst preparation method is known in the art, it will not be described separately in the present specification.

According to an exemplary embodiment, a powdered catalyst may be used as the hydrogenation catalyst, because it can provide a high reaction area, and when using a conventional pellet or block-shaped catalyst, the reaction area is reduced and the hydrogenation reaction time is shortened. increase can be effectively suppressed. In this case, the size (diameter) of the powdery catalyst may be, for example, about 100 to 900 nm, specifically about 300 to 700 nm, and more specifically about 400 to 600 nm. In this regard, if the size of the powder catalyst is too small, the hydrogenated LOHC and the catalyst may be discharged from the reactor together, whereas if it is too large, excessive filtration pressure is required or the hydrogenated LOHC (liquid phase) is blocked by clogging the filter. may impede the release of Accordingly, the size of the powder catalyst may be determined in consideration of the size of the flange filter, which will be described later.

It may also be advantageous for the powdery catalyst particles to be dispersed in the LOHC to have a density suitable for increasing the hydrogenation reaction efficiency, wherein the density range is, for example, about 4 to 5 g/cm 3 , specifically about 4.2 to 4.7 g/cm 3 , more specifically, may be in the range of about 4.4 to 4.5 g/cm 3 , but this may be changed depending on the LOHC used and the like.

2a and 2b, when the internal pressure exceeds an appropriate level (eg, 50 barg) on the upper side of the reactor (A), a relief valve for lowering the pressure in order to secure safety (a flow path above a specific pressure is A valve that opens to reduce the pressure, while automatically closing again at a certain pressure) may be provided. As a result, when an abnormal pressure is reached during the reaction, the valve is opened so that the hydrogen can be automatically discharged through the discharge line 107 (ie, the automatic opening venting line).

According to an exemplary embodiment, in order to increase the hydrogenation reaction efficiency, the hydrogenation reaction can be performed by configuring two stages, for example, performing the first stage reaction at about 30 to 50 barg, and about 50 to 80 barg A second stage reaction can be performed in For this, a pressure control valve (PCV) may be provided.

In addition, in order to sample the hydrogenated LOHC, a sampling port (not shown) may be installed at one point of the reactor (A) to recover the sample through an automatic valve during the hydrogenation reaction process or after the reaction.

On the other hand, when a powder catalyst is used as described above, unlike the pellet catalyst, it exists in a dispersed form in the liquid LOHC. Moreover, it is subjected to continuous shearing force by the stirrer during the reaction, so that it can be further subdivided. Therefore, when a powdery catalyst is used, it is difficult to separate and recover the catalyst from the hydrogenated LOHC after the hydrogenation reaction.

In order to solve this problem, in this embodiment, a flange-type filter (B) in one area at the bottom of the hydrogenation reactor (specifically, the lower central portion of the vertical cross-section of the hydrogenation reactor having an inverted pentagonal shape as shown in FIG. 2B) ) is installed.

At this time, the flange-type filter (B) may have a mesh structure of a metal material (eg, stainless steel, etc.), the mesh size is, for example, about 0.1 to 0.9 μm, specifically about 0.3 to 0.7 ㎛, more specifically, may be in the range of about 0.4 to 0.6 ㎛, such a flange type filter may be manufactured to be detachable from the reactor. However, the mesh size of the aforementioned filter may be understood as an exemplary meaning, and may be changed in consideration of the particle size of the catalyst used, the degree of pressure increase of the supplied nitrogen, and the like. In particular, when pressurized nitrogen is used, safety can be secured according to the use of an inert gas, and system operation costs can be reduced because a pump is not used to filter the liquid. Moreover, it is noteworthy that, when a pump is used, it is difficult to transport the hydrogenated LOHC to the reactor external line due to the small mesh size of the filter described above.

According to an exemplary embodiment, the first flange filter B may have a plurality of supporting members (eg, leg-foot shape) that function as a leg at the periphery (periphery) of the metal mesh filter. Such a support structure can facilitate the circulation of the surrounding fluid flow. When a straight paddle-shaped structure is used, the catalyst particles around the filter cannot circulate due to the interference of the metal filter, which reduces the hydrogenation reaction efficiency. can be solved

According to an exemplary embodiment, as the hydrogenation reaction proceeds, the viscosity of the LOHC at the reaction temperature is significantly reduced to have high fluidity, and the pressurized nitrogen flow pushes the liquid hydrogenated LOHC into contact with the flange filter (B). and pass through the filter, while the solid (powder-type) catalyst particles do not pass through the flange filter (B) and remain inside the reactor. In the illustrated embodiment, the catalyst used is not exposed to an external environment (eg, an oxidizing atmosphere) because it exists as a residual state after being filtered through a filter installed inside the reactor. As a result, it can be used continuously or repeatedly in the reactor while suppressing deterioration such as oxidation, the operation time of the entire process can be shortened, and energy consumption due to catalyst separation can be reduced. In addition, the hydrogenation catalyst captured by the flange filter (B) can be reused again, and when the catalyst life is reached, the deactivated catalyst can be recovered because the flange filter can be simply removed from the reactor. As such, when the replacement cycle of the hydrogenation catalyst is reached, catalyst recovery and filter replacement also provide the advantage of easy.

On the other hand, according to an exemplary embodiment, the hydrogenated LOHC may be discharged or recovered from the reactor after the hydrogenation reaction is completed, or alternatively, it may be recovered by valve operation (eg, automatic valve) during the hydrogenation reaction. .

In addition, during the hydrogenation reaction, hydrogen not participating in the reaction is discharged to the outside of the reactor through the line 107, while the LOHC in the hydrogenated form is discharged from the hydrogenation reactor through the line 108 and can be transferred to a desired predetermined position. . At this time, the hydrogenated LOHC may be transported through a pipe, or may be transported to a destination by various transport means (eg, a vehicle equipped with a storage tank, etc.). As such, the advantage of using LOHC to transport in hydrogenated form is that it can utilize the existing fuel supply or transport system based on liquid hydrocarbon-fuel. In addition, it is possible to minimize the energy cost due to pressurization, which has been a problem in the conventional technology for transporting or storing hydrogen as a low-temperature liquid or compressed gas.

According to the illustrated embodiment, the transferred hydrogenated LOHC is subjected to a dehydrogenation reaction step (C) to separate hydrogen from the LOHC.

Figure 3a shows a schematic structure of a dehydrogenation reactor and a material movement path, and Figure 3b shows a schematic structure inside the dehydrogenation reactor in an exemplary embodiment of the present invention.

In this regard, the structure of the dehydrogenation reactor (C) may be similar to the structure of the hydrogenation reactor described above except for the flow line of the fluid. In the illustrated example, the dehydrogenation reactor (C) is equipped with a stirrer 110 to produce hydrogen by dehydrogenation by contacting with a catalyst while bubbling the hydrogenated form of LOHC.

In this case, the stirrer 112 may be configured to rotate at, for example, about 150 to 400 rpm, specifically about 180 to 350 rpm, and more specifically, about 200 to 300 rpm in the dehydrogenation process.

According to an exemplary embodiment, since the dehydrogenation reaction is typically an endothermic reaction, it is necessary to supply thermal energy during the dehydrogenation reaction as well as during the process of raising the temperature to the initial operating temperature. To this end, it may be advantageous to use a flange-type heater (not shown) similarly to the hydrogenation reaction.

In addition, the dehydrogenation reaction may be carried out under a relatively low pressure condition, for example, it may be controlled within the range of about 0.3 to 3 barg, specifically about 0.5 to 2 barg, more specifically about 0.8 to 1.3 barg, where The dehydrogenation reactor may have a design pressure of approximately 20 barg. In addition, the reaction temperature may be, for example, about 200 to 350 ° C., specifically about 250 to 330 ° C., more specifically about 290 to 310 ° C. The bar may be set in the range, wherein the reactor design temperature is higher than that of the hydrogenation reactor. , specifically about 350°C. In addition, the dehydrogenation reaction time may be, for example, about 4 to 12 hours, specifically about 6 to 10 hours, and more specifically about 7 to 9 hours. However, the above-described reaction conditions may be understood by way of example and may be changed according to the LOHC. In order to maintain the dehydrogenation reaction temperature at an appropriate level, a simple jacket (not shown) may be installed in the reactor to release heat through this when excessive heat is supplied.

Referring to FIGS. 3A and 3B , nitrogen is introduced into the reactor C from the nitrogen source 101 via the line 111 by a valve operation for the purpose of nitrogen purging and/or liquid transfer by pressurized nitrogen. The nitrogen flow introduced in this way not only purifies nitrogen before and after the dehydrogenation reaction, but also serves to discharge excess gas after the reaction. Residual gas in the reactor removed by nitrogen purging or the like may be discharged through the line 114 through a valve operation. In the case of nitrogen purging, the pressure of the nitrogen flow may be, for example, in the range of about 1-4 barg (specifically about 2-3 barg). Meanwhile, the nitrogen pressure (ie, nitrogen boosting pressure) for the purpose of liquid transport is adjustable within, for example, about 5 to 15 barg (specifically, about 8 to 12 barg).

On the other hand, when the internal pressure exceeds an appropriate level (eg, about 1.17 barg) on the upper side of the reactor (C), a relief valve for lowering the pressure is provided to ensure safety, and when the abnormal pressure is reached, the inside of the reactor Allows automatic pressure adjustment.

In the illustrated embodiment, the dehydrogenation reaction may be performed in the presence of a heterogeneous catalyst, specifically, a transition metal-based heterogeneous catalyst (ie, a transition metal supported catalyst). As an example, the dehydrogenation catalyst may be selected within the scope of the hydrogenation catalyst. Specifically, the dehydrogenation catalyst may be a catalyst in which a metal (specifically, a transition metal, more specifically, a noble metal) is supported on a porous inorganic oxide support. According to a specific embodiment, when DBT is used as the LOHC, it may be advantageous to use a catalyst in which platinum (Pt) is supported on an alumina (specifically, gamma-alumina) support as a dehydrogenation catalyst. However, the present disclosure is not limited to the catalyst exemplified above, and an appropriate catalyst may be selected according to the LOHC used.

However, in this embodiment, a powder-type catalyst may be used to provide a high reaction area similar to the hydrogenation catalyst. In this case, the size (diameter) of the powdery catalyst may be, for example, about 100 to 900 nm, specifically about 300 to 700 nm, and more specifically about 400 to 500 nm. In addition, it may be advantageous for the powdery catalyst particles to be appropriately dispersed in the hydrogenated form of the LOHC to have an appropriate density to promote the dehydrogenation reaction, wherein the density range is, for example, about 4.5 to 5.5 g/cm 3 , specifically to about 4.7 to 5.2 g/cm 3 , more specifically, about 4.8 to 5 g/cm 3 , but this catalyst density can be changed depending on the LOHC used, etc.

In addition, in order to sample the dehydrogenated LOHC, a sampling port (not shown) is installed at one point of the reactor (C) so that the sample can be recovered through an automatic valve during the reaction process or after the reaction.

On the other hand, as a result of using the powder-type dehydrogenation catalyst, the catalyst particles exist in a dispersed form in the liquid LOHC, and it is difficult to recover them after the dehydrogenation reaction. Therefore, as shown in Fig. 3b, in one region at the bottom of the dehydrogenation reactor (C) (specifically, the lower central portion of the vertical cross section of the inverted pentagonal hydrogenation reactor as shown in Fig. 3b) of the flange type A filter (B') can be installed.

In this case, the flange-type filter (B') may be substantially the same as the detailed description of the flange-type filter (B) provided in the hydrogenation reactor, and may be manufactured to be separable from the reactor (C). In addition, the LOHC, which has undergone dehydrogenation by performing filtering using pressurized nitrogen, may be discharged through the reactor external line 113 .

As described above, the hydrogen generated through the dehydrogenation reaction is discharged from the reactor in the form of a hydrogen-containing gas through the hydrogen discharge line 112 . At this time, the discharged hydrogen-containing gas is discharged at a high temperature. At this time, due to the relatively high dehydrogenation reaction temperature, at least a part of the LOHC may be vaporized, and further, various hydrocarbons (cyclohexane) that are inevitably generated during the dehydrogenation reaction. , benzene, toluene, methane, etc.). Considering that it is desirable to recover high-purity hydrogen, components other than hydrogen correspond to impurities, and it may be desirable to recover them.

4 shows a schematic structure of a condenser for separating hydrogen from a hydrogen-containing mixed gas discharged from a dehydrogenation reactor and a movement path of materials in an exemplary embodiment of the present invention.

Referring to the figure, the hydrogen-containing gas (mainly containing hydrogen and LOHC) discharged along line 112 from the dehydrogenation reactor is disposed on one side of a condenser D, for example a transversely extending cylindrical condenser. It is introduced through an inlet of the hydrogen-containing gas formed at the end, and a first port 115 is provided at a position around the opposite (or opposite) end (or an outlet to be described later) to supply condensed water. The hydrogen-containing gas introduced through the inlet in the condenser D is cooled by transferring heat to the condensed water, while the condensed water is discharged in an elevated state through the second port 116 formed around the inlet. In addition, when the high-temperature hydrogen-containing gas flows into the condenser, a pressure relief valve (PSV) may be provided in case the pressure rises more than necessary. On the other hand, the cooled hydrogen-containing gas is transferred through a line 118 through a hydrogen-containing gas outlet formed at the opposite end of the inlet 112 .

In the illustrated example, LOHC vaporized in the hydrogen-containing gas (which may additionally contain hydrocarbons produced by decomposition of a portion of the LOHC during the dehydrogenation reaction) is condensed by cooling to a condenser intermediate region (specifically, the first port may be discharged through a third port 117 disposed in the region between 115 and second port 116), where the condensed LOHC is to be reused in the hydrogen storage (hydrogenation)/release (dehydrogenation) process. can For example, as shown in FIG. 1 , the LOHC discharged through the third port 117 may be recycled to the dehydrogenation reactor.

As a result of the heat exchange in the condenser, the temperature of the hydrogen-containing gas may be reduced, for example, in the range of about 40 to 80 °C, specifically about 50 to 70 °C, more specifically about 55 to 65 °C. Also, the heat duty inside the condenser may be, for example, in the range of about 4000 to 7000 kcal/h, specifically about 5000 to 6500 kcal/h.

On the other hand, a significant amount of the LOHC and hydrocarbon components in the hydrogen-containing gas 118 are separated and removed through the condenser, but may still exist in the form of uncondensed impurities (especially hydrocarbons lighter than LOHC).

In consideration of the above, the hydrogen purification step through the adsorption tower (E) may be performed as in FIG. 1 . In this regard, FIG. 5 shows a schematic structure of an adsorption tower for further purifying hydrogen separated from the condenser and a movement path of materials in an exemplary embodiment of the present invention.

Referring to the drawings, the hydrogen-containing gas supplied through the line 118 is introduced into the lower side of the adsorption tower E and is filled with an adsorbent, for example, activated carbon, zeolite, alumina, silica alumina, etc. by an adsorbent. Hydrocarbon-based impurities and the like may be adsorbed and removed. In this regard, the type of the adsorbent is not limited to the above type, and as long as it is a type capable of adsorbing gaseous hydrocarbons in the pores, other types may be used.

According to a specific embodiment, activated carbon may be used as the adsorbent. In this case, the specific surface area (BET) of the activated carbon may be, for example, about 800 to 1500 cm 2 /g, specifically, about 900 to 1200 cm 2 /g. Also, the particle size of the activated carbon may be, for example, in the range of about 1 to 5 mm, specifically, about 2 to 4 mm.

According to an exemplary embodiment, the pressure of the hydrogen-containing gas entering the adsorption tower (E) may be, for example, about 0.7 to 1.2 barg, specifically about 0.8 to 1.1 barg, more specifically about 0.9 to 1.1 barg. In addition, the adsorption temperature may be controlled, for example, in the range of about 40 to 70 °C, specifically about 50 to 65 °C.

Referring to FIG. 5, in the case of the hydrogen stream 119 passing through the adsorption tower, fine dust of activated carbon as an adsorbent may be included. can be recovered In this case, the filter 120 may be, for example, an in-line filter type, and the filter size may be, for example, in the range of about 3 to 10 μm, specifically, about 6 to 8 μm.

In another exemplary embodiment, the pressure at the back end of the adsorption tower may be increased if the user does not want to supply hydrogen. In this case, the pressure sensor and the automatic valve are provided, and a signal is transmitted to the automatic valve to open the automatic valve to release hydrogen to the outside, thereby improving safety.

In addition, when some components are discharged in an unadsorbed state despite passing through the adsorption tower, it may cause air pollution and odor. In order to solve this problem, a venting line (not shown) is installed in the adsorption tower, and a small filter (specifically, an activated carbon filter) is provided to additionally purify the discharged gas component, and then it can be discharged into the atmosphere. In addition, a backfire preventer (not shown) for suppressing a phenomenon in which the gas discharged from the adsorption tower flows back into the adsorption tower may be additionally installed.

The concentration of hydrogen recovered through the above-described process may be, for example, at least about 99%, more specifically, at least about 99.5%, and more specifically, at least about 99.9%.

All simple modifications or changes of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be made clear by the appended claims.

Claims (16)

a) By supplying a liquid organic hydrogen carrier (LOHC) and hydrogen to a first reactor in which a flange-type first filter is detachably mounted on the lower side of the reactor, and hydrogenation reaction in the presence of a hydrogenation catalyst in powder form, LOHC is converted to LOHC in hydrogenated form, and the hydrogenated product is filtered through the first filter and discharged from the first reactor, while retaining the hydrogenation catalyst in powder form in the first reactor;
b) transferring the hydrogenated product discharged from the first reactor to a predetermined distance;
c) supplying the transferred hydrogenation product to a second reactor in which a flange-type second filter is detachably mounted on the lower side of the reactor to dehydrogenate in the presence of a dehydrogenation catalyst in powder form. The conversion of LOHC to LOHC produces a hydrogen-containing gas, and the dehydrogenation product is filtered by a second filter and discharged from the second reactor while retaining the dehydrogenation catalyst in powder form in the second reactor, while the hydrogen-containing gas discharging from the second reactor;
d) cooling the discharged hydrogen-containing gas by heat exchange in a condenser; and
e) purifying the cooled hydrogen-containing gas to recover purified hydrogen;
A hydrogen storage and release process comprising a. The hydrogen storage and release process according to claim 1, wherein the hydrogen-containing gas produced in step c) contains, in addition to hydrogen, vaporized LOHC and/or hydrocarbons produced during the dehydrogenation reaction. The hydrogen storage and release process according to claim 2, wherein step d) further comprises condensing and separating the LOHC in the hydrogen-containing gas and recovering the LOHC. The process of claim 3 further comprising recycling the recovered LOHC to a second reactor. 4. The process of claim 3, wherein step e) comprises adsorbing and removing hydrocarbons in the hydrogen-containing gas. 2. Hydrogen storage according to claim 1, wherein step a) includes introducing nitrogen gas at a pressure for purging before and after the hydrogenation reaction and nitrogen gas at a pressure to move the hydrogenation product in a liquid state. and release processes. The method of claim 1, wherein step c) comprises introducing nitrogen gas at a pressure for purging before and after the dehydrogenation reaction, and nitrogen gas at a pressure for moving the dehydrogenation product in a liquid state. Hydrogen storage and release process. The hydrogen storage according to claim 1, wherein the hydrogenation reaction is carried out under conditions of a temperature of 100 to 180° C., a pressure of 30 to 80 barg, and _{a volume ratio of H 2 /LOHC of 3 to 10 Nm 3 /m 3 .} and release processes. The hydrogen storage and release process according to claim 1, wherein the dehydrogenation reaction is performed at a temperature of 200 to 350 °C and a pressure of 0.3 to 3 barg. The hydrogen storage and release process according to claim 1, wherein each of the first filter and the second filter has a metal mesh structure and a mesh size ranges from 0.1 to 0.9 μm. The hydrogen storage and release process according to claim 10, wherein each of the hydrogenation catalyst in powder form and the dehydrogenation catalyst in powder form is defined in the range of 100 to 900 nm. 11. A process according to claim 10, comprising a plurality of support members functioning as a bridge at the periphery of each of the first filter and the second filter. The hydrogen storage and release process according to claim 5, wherein step e) is performed using an adsorption tower, wherein activated carbon is filled as an adsorbent. The method according to claim 3, wherein step d) is performed using a transversely extending cylindrical condenser,
Here, the hydrogen-containing gas is introduced through an inlet formed at one end of the condenser and discharged in a cooled state through an outlet formed at the opposite end,
The condensed water is supplied through a first port formed at a position around the outlet and discharged at an elevated temperature through a second port formed at a position around the inlet, and
Hydrogen storage and release process, characterized in that the vaporized LOHC and/or hydrocarbons generated during the dehydrogenation reaction are condensed and discharged through a third port formed between the first port and the second port. The hydrogen storage and release process according to claim 13, wherein a filter for removing fine dust is provided at a rear end of the adsorption tower. The method of claim 1, wherein DBT is used as LOHC,
In this case, the hydrogenation catalyst is a catalyst in which ruthenium is supported on an alumina support, and the dehydrogenation catalyst is a catalyst in which platinum is supported on an alumina support.

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