KR20240030339A - Complex energy system producing clean fuel and hydrogen using reforming process and liquid organic hydrogen carrier - Google Patents

Abstract

The present invention controls the molar ratio of H ₂ /CO by converting and storing excess hydrogen that does not participate in the Fischer-Tropsch reaction in the synthesis gas produced through the reforming process into a liquid organic hydrogen carrier (LOHC), and the separated hydrogen is used in the upgrading process. The Compact-GTL process can be configured to supply hydrocarbons with 1 to 2 carbon atoms generated during the process as fuel in the reforming section, and the heat from the reforming section is used as reaction heat in the dehydrogenation reaction section, making it economical and environmentally useful. It is about complex energy systems that can be significantly increased. Specifically, the complex energy system includes a gas/liquid separation unit that separates condensate material with a carbon number of 5 or more from the raw material gas containing at least hydrocarbons; A gas separation unit that separates substances with carbon numbers of 1 to 2 and 3 to 4 from the raw material gas; A pre-reformer that receives raw material gas and performs a reforming reaction on part of it; A reformer that receives preheated raw material gas and causes a steam reforming reaction of hydrocarbons contained in the raw material gas; A synthesis gas control unit that separates water in the synthesis gas and then separates a certain amount of CO ₂ ; A hydrogenation reaction control unit that stores some of the hydrogen in the raw material gas in a liquid organic hydrogen carrier through a hydrogenation reaction and controls the H ₂ /CO molar ratio; and a dehydrogenation reaction unit that separates and discharges hydrogen from the liquid organic hydrogen carrier.

Description

Complex energy system for clean fuel and hydrogen production using reforming process and liquid organic hydrogen carrier {COMPLEX ENERGY SYSTEM PRODUCING CLEAN FUEL AND HYDROGEN USING REFORMING PROCESS AND LIQUID ORGANIC HYDROGEN CARRIER}

The present invention produces clean fuel using a reforming process, and stores excess hydrogen in the synthesis gas produced through the reforming process in a liquid organic hydrogen carrier (LOHC) to produce H ₂ /CO for clean fuel. It relates to a complex energy system characterized by controlling the molar ratio and producing hydrogen.

Republic of Korea Patent Publication No. 10-2163578 (Patent Document 1) discloses a methanation reaction unit that produces methane by reacting hydrogen and carbon dioxide, and a methanation reaction unit that burns some of the methane produced in the methanation reaction unit to provide rotational power with the generated combustion gas. It combines a power generation unit that generates electricity and a dehydrogenation unit that separates hydrogen from liquid organic matter in which hydrogen is stored, and the heat of reaction (endotherm) for the needs of the dehydrogenation unit is converted into the heat of reaction (exotherm) of the methanation reaction unit and the combustion of the power generation unit. A methane production combined power generation system combining the methanation process and dehydrogenation process provided by gas waste heat and an operation method of the methane production combined power generation system were presented.

Republic of Korea Patent Publication No. 10-2020-0076094 (Patent Document 2) simultaneously produces hydrogen (H ₂ ) and dimethyl ether (DME) from synthetic gas (syngas) obtained by reforming natural gas using carbon dioxide (CO ₂ ) as a raw material. A separation process was presented. H ₂ and dimethyl ether can be produced simultaneously by separating high purity H ₂ from synthesis gas with an H ₂ /CO molar ratio of more than 1 through a separation membrane and synthesizing dimethyl ether from the remaining synthesis gas with a H ₂ /CO molar ratio of 1.

Republic of Korea Patent Publication No. 10-2163578 Republic of Korea Patent Publication No. 10-2020-0076094

The present invention stores excess hydrogen in synthetic gas produced through a reforming process in a liquid organic hydrogen carrier (LOHC) to control the molar ratio of H ₂ /CO for synthetic fuel production and simultaneously produces hydrogen required in the upgrading process. This is possible, and surplus hydrogen can be supplied to hydrogen stations, etc., making it possible to implement a Compact GTL process, and to create a clean fuel and hydrogen production complex energy system that can economically produce the target product by upgrading the product at the back end. The purpose is to provide

The object of the present invention is not limited to the objects mentioned above. The object of the present invention will become clearer from the following description and may be realized by means and combinations thereof as set forth in the claims.

A complex system for clean fuel and hydrogen production according to an embodiment of the present invention includes a gas/liquid separation unit that separates raw material gas containing at least hydrocarbons into hydrocarbons having 1 to 4 carbon atoms and hydrocarbons having 5 or more carbon atoms; A gas separation unit that receives hydrocarbons having 1 to 4 carbon atoms from the gas/liquid separation unit and separates them into hydrocarbons having 1 to 2 carbon atoms and hydrocarbons having 3 to 4 carbon atoms; A pre-reforming unit that receives hydrocarbons having 1 to 2 carbon atoms from the gas separation unit and performs a reforming reaction with steam; A reforming unit that receives the product of the pre-reforming unit and performs an additional reforming reaction to produce a synthesis gas containing hydrogen and carbon monoxide; A synthesis gas control unit that removes the synthesis gas heavy matter (H ₂ O) and then removes a certain amount of carbon dioxide (CO ₂ ); A hydrogenation reaction control unit that controls the H ₂ /CO molar ratio by storing excess hydrogen in the synthesis gas control unit in a liquid organic hydrogen carrier (LOHC); and a Fischer-Tropsch reaction unit that receives synthesis gas with an adjusted H ₂ /CO/CO ₂ molar ratio from the synthesis gas control unit and the hydrogenation reaction unit and causes a Fischer-Tropsch reaction.

The raw material gas is natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), liquid condensate of C ₅₊ (C ₅₊ condensate), and combinations thereof. It may include at least one selected from the group consisting of

The complex energy system includes a liquid hydrogen storage unit for separating/storing the liquid organic hydrogen carrier supplied from the hydrogenation reaction unit; and a dehydrogenation reaction unit that receives the liquid organic hydrogen carrier from the liquid hydrogen storage unit and separates hydrogen from the liquid organic hydrogen carrier using waste heat generated in the reforming unit.

The complex energy system receives hydrocarbons with a carbon number of 5 or more from the gas/liquid separation unit, separates and stores C5+ condensate, and the wax component separated in the gas/liquid/solid separation unit of the Fischer-Tropsch reactor is stored in the LOHC. It may further include an upgrading unit that reacts with the extracted hydrogen after storage to produce clean fuel.

The upgrading unit may react wax among the products of the Fischer-Tropsch reaction unit with hydrogen supplied from the hydrogenation reaction unit to produce clean fuels of desired components such as gasoline, diesel, and LPG.

The synthesis gas control unit adjusts the H ₂ /CO molar ratio of the synthesis gas supplied from the reforming unit to 2 or less than 2 through LOHC, and stores the excess hydrogen generated in the process in the LOHC and separates it into hydrogen again for the upgrading process. It can be utilized, supplied to hydrogen cars, fuel cells, etc., or compressed into liquid hydrogen and supplied to consumers as compressed hydrogen.

The complex system may further include a gas/liquid/solid separation unit that separates the product of the Fischer-Tropsch reaction unit into LPG, gasoline, middle oil, and wax.

The complex system may further include an LPG storage unit for storing the LPG, a gasoline storage unit for storing the gasoline, an intermediate oil storage unit for storing the intermediate oil, and a wax storage unit for storing the wax.

Hydrocarbons with 3 to 4 carbon atoms separated in the gas separation unit can be stored in the LPG storage unit, and hydrocarbons with 1 to 2 carbon atoms can be supplied as fuel to maintain the reaction temperature of the reforming unit.

The complex energy system for clean fuel and hydrogen production using a reforming process and a liquid organic hydrogen carrier according to the present invention can reduce storage costs by converting hydrogen gas into a liquid organic hydrogen carrier with a volume of 1/800, and waste heat from the reformer It can be supplied as reaction heat in the dehydrogenation process, and the hydrogen produced in the dehydrogenation process is used in the upgrading process of the wax product of the Fischer-Tropsch reaction, and the material with 1 to 2 carbon atoms generated in the upgrading process is It is believed to be an alternative to the next-generation Compact GTL and GTL-FPSO processes, which can be supplied as fuel to the reformer and can significantly increase the economic and environmental usefulness of the process.

The effects of the present invention are not limited to the effects mentioned above. The effects of the present invention should be understood to include all effects that can be inferred from the following description.

Figure 1 shows a combined energy system for clean fuel and hydrogen production according to the present invention.

The above objects, other objects, features and advantages of the present invention will be easily understood through the following preferred embodiments related to the attached drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content will be thorough and complete and so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art.

While describing each drawing, similar reference numerals are used for similar components. In the attached drawings, the dimensions of the structures are enlarged from the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, a first component may be named a second component, and similarly, the second component may also be named a first component without departing from the scope of the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof. Additionally, when a part of a layer, membrane, region, plate, etc. is said to be “on” another part, this includes not only being “directly above” the other part, but also cases where there is another part in between. Conversely, when a part of a layer, membrane, region, plate, etc. is said to be "underneath" another part, this includes not only being "immediately below" the other part, but also cases where there is another part in between.

Unless otherwise specified, all numbers, values and/or expressions used herein expressing amounts of ingredients, reaction conditions, organic matter and formulations mean that such numbers, among other things, are inherently measurements taken to obtain these values. Since they are approximations that reflect various uncertainties, in all cases, they should be understood as being modified by the term “about.” Additionally, where a numerical range is disclosed herein, such range is continuous and, unless otherwise indicated, includes all values from the minimum to the maximum of such range inclusively. Furthermore, when such range refers to an integer, all integers from the minimum value up to and including the maximum value are included, unless otherwise indicated.

Figure 1 schematically shows a clean fuel and hydrogen production complex energy system using a reforming process and a liquid organic hydrogen carrier according to the present invention. With reference to this, the complex system includes a gas/liquid separation unit 20 that separates raw material gas 10 containing at least hydrocarbons into hydrocarbons with a carbon number of 1 to 4 and hydrocarbons with a carbon number of 5 or more, the gas/liquid separation unit A gas separation unit (30) that receives hydrocarbons with a carbon number of 1 to 4 from (20) and separates them into hydrocarbons with a carbon number of 1 to 2 and hydrocarbons with a carbon number of 3 to 4, from the gas separation unit to a hydrocarbon with a carbon number of 1 to 2. A pre-reforming unit 40 that receives phosphorus hydrocarbons and performs a reforming reaction with steam, a reforming unit 50 that receives the products of the pre-reforming unit and performs an additional reforming reaction to produce a synthetic gas containing hydrogen and carbon monoxide, the synthetic gas A synthesis gas control unit 60 that removes water ( _H2O ) and then removes a certain amount of carbon dioxide (CO ₂ ), and stores excess hydrogen in the synthesis gas control unit in a liquid organic hydrogen carrier (LOHC) to produce H ₂ A hydrogenation reaction control unit 70 that controls the /CO molar ratio, a liquid hydrogen storage unit 80 that stores the liquid organic hydrogen carrier supplied from the hydrogenation reaction unit, and a reforming unit that receives the liquid organic hydrogen carrier from the liquid hydrogen storage unit. Synthetic gas adjusted to a specific H ₂ /CO/CO ₂ molar ratio is supplied from the dehydrogenation reaction unit 90, which separates hydrogen from the liquid organic hydrogen carrier using waste heat as reaction heat, and the synthesis gas control unit and hydrogenation reaction control unit. It includes a Fischer-Tropsch reaction unit 100 that produces clean raw materials by causing a Fischer-Tropsch reaction.

Hereinafter, each configuration of the complex energy system will be described in detail.

The raw material gas 10 may include at least one selected from the group consisting of natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), and combinations thereof. You can. In addition, the raw material gas 10 may be natural gas (Associated Gas or Stranded gas) held in a marginal gas field.

The raw material gas 10 passes through the gas/liquid separation unit 20 and the gas separation unit 30 to produce hydrocarbons having a carbon number of 5 or more (C ₅₊ condensate), hydrocarbons having a carbon number of 3 to 4 (LPG), and carbon. It is separated into hydrocarbons of numbers 1 to 2 (methane, ethane).

The hydrocarbons having a carbon number of 5 or more are stored as liquid condensate (C ₅₊ condensate), the hydrocarbons having a carbon number of 3 to 4 are stored in an LPG storage unit to be described later, and the hydrocarbons having a carbon number of 1 to 2 are used for the production of hydrogen. It is provided in the wire reforming unit 40 for this purpose.

The pre-reforming unit 40 includes a water vapor supply line that supplies moisture and/or water vapor, and when a reforming reaction of some of the hydrocarbons having 1 to 2 carbon atoms is carried out in the rear reforming unit 50, more than necessary It can contribute to reducing the amount of water vapor and the production of carbon.

The reforming unit 50 is configured to receive the product of the pre-reforming unit 40 and cause a steam reforming reaction of additional hydrocarbons as described below. The synthesis gas discharged from the reforming unit 50 may include at least hydrogen (H ₂ ), carbon monoxide (CO), carbon dioxide (CO ₂ ), methane (CH ₄ ), and water vapor (H ₂ O).

C _m H _n + mH ₂ O → mCO + (m+n)/2H ₂ --- (1)

CO + 3H ₂ ↔ CH ₄ + H ₂ O --- (2)

CO + H ₂ O ↔ CO ₂ + H ₂ --- (3)

The reforming unit 50 contacts the hydrocarbon having 1 to 2 carbon atoms on a reforming catalyst and causes a steam reforming reaction to produce hydrogen-rich synthesis gas containing a high concentration of hydrogen. The reforming catalyst is a catalyst in which a metal such as nickel or ruthenium is supported on a carrier having a special shape such as alumina, silica, and magnesium aluminate or a spherical shape. It may include etc.

In order to increase the hydrogen production rate of the steam reforming reaction of hydrocarbons, it may be desirable to maintain the temperature of the reforming unit 50 at 600°C to 900°C. When the synthesis gas passes through the reforming unit 50, the temperature is preferably between 750°C and 850°C.

The synthesis gas passes through a heat exchanger, lowers its temperature, and is supplied to the synthesis gas control unit 60. The heat obtained from the heat exchanger is provided to the hydrogenation reaction control unit 70 and the dehydrogenation reaction unit 90 and can be used as reaction heat.

The pre-reforming unit 40 and the reforming unit 50 may be reactors of an integrated structure. However, the present invention is not limited to this, and the pre-reforming unit 40 and the reforming unit 50 may be physically separate devices.

The synthesis gas control unit 60 removes water (H ₂ O) and a certain amount of CO ₂ to be suitable for the Fischer-Tropsch reaction and supplies it to the hydrogenation reaction control unit 70, and H from the hydrogenation reaction control unit 70. Synthesis gas with a controlled ₂ /CO molar ratio can be received and supplied to the Fischer-Tropsch reaction unit 100.

The synthesis gas control unit 60 may remove water (H ₂ O) and a certain amount of CO ₂ to suit the Fischer-Tropsch reaction, and then adjust the H ₂ /CO molar ratio of the synthesis gas to 0.5 to 2. (0.5~1.5 on Fe-based catalyst, 2 on Co-based catalyst). Excess hydrogen in the synthesis gas may flow into the hydrogenation reaction control unit 70 and be converted to a liquid compound state and stored.

In order to control the H ₂ /CO molar ratio for the Fischer-Tropsch reaction, the hydrogenation reaction control unit 70 converts excess hydrogen into a liquid phase through the LOHC process and separates/stores it to control the H ₂ /CO molar ratio, and then synthesizes it again. It can be sent to the gas control unit and used as a raw material for the Fischer-Tropsch reaction. Hydrogen stored in liquid form can undergo a dehydrogenation reaction again and be used in the upgrading process or supplied to hydrogen consumers (hydrogen stations, fuel cells, liquid hydrogen, etc.). Therefore, the H ₂ /CO molar ratio can be controlled and stored by efficiently separating hydrogen in less space and with less energy cost than the H ₂ /CO molar ratio control process by the existing PSA process.

The hydrogenation reaction control unit 70 supplies hydrogen or synthesis gas to the liquid organic hydrogen carrier (H ₀ LOHC) in a state capable of storing hydrogen, so that the liquid organic hydrogen carrier (H _n LOHC) whose hydrogen acceptance level has reached a predetermined level is The H ₂ /CO molar ratio can be controlled by performing a hydrogenation reaction until it is achieved, and other gases can be circulated to the synthesis gas control unit.

The hydrogen acceptance value of the liquid organic hydrogen carrier may be 50 to 100% of the maximum hydrogen storage capacity. The predetermined level of hydrogen acceptance can be flexibly designed according to the configuration of the system of the present invention.

The liquid organic hydrogen carrier (H _n LOHC) whose hydrogen acceptance value has reached a predetermined level in the hydrogenation reaction control unit 70 may be moved to the liquid hydrogen storage unit 80.

The liquid organic hydrogen carrier containing hydrogen stored in the liquid hydrogen storage unit 80 flows into the dehydrogenation reaction unit 90 when demand for hydrogen occurs, compresses the stored hydrogen, and is then used in the upgrading process or in a liquid hydrogen state. It can be moved to other demand sources (hydrogen station, fuel cell power generation and on-site power generation, liquid hydrogen plant, etc.).

The dehydrogenation reaction unit 90 may be configured to cause an endothermic dehydrogenation reaction under an operating temperature of 250°C to 300°C, a pressure of 1 bar to 5 bar, and a catalytic environment. Through the dehydrogenation reaction, hydrogen is released from the liquid organic hydrogen carrier (H _n LOHC) containing hydrogen, and can be converted into a liquid organic hydrogen carrier (H ₀ LOHC) capable of storing hydrogen.

In addition, the hydrogenation reaction control unit 70 and the dehydrogenation reaction unit 90 can receive heat necessary for the reaction from the heat generated in the reforming unit 50. Since the reaction between hydrogen and carbon monoxide that occurs in the reforming unit 50 is an endothermic reaction, heat can be supplied through the combustion reaction of hydrocarbons and waste heat can be used for the latter reaction. The method of heat exchange is not particularly limited, and the reforming unit 50, the hydrogenation reaction control unit 70, and the dehydrogenation reaction unit 90 may be placed in spatially adjacent positions, or a fluid capable of transferring heat between the two components may be used. You can use it.

The metal-containing catalyst used for hydrogenation and dehydrogenation in the hydrogenation reaction control unit 70 and the dehydrogenation reaction unit 90 includes palladium, nickel, platinum, iridium, ruthenium, which are metals finely distributed on a porous non-polar carrier. The same or different solid catalysts containing one or more of cobalt, rhodium, copper, gold, rhenium, and iron.

The Fischer-Tropsch reaction unit 100 receives synthesis gas adjusted to an optimal H ₂ /CO/CO ₂ molar ratio from the synthesis gas control unit 60 and the hydrogenation reaction control unit 70, thereby causing a Fischer-Tropsch reaction. It is designed to produce clean fuel.

The products of the Fischer-Tropsch reaction unit 100 are separated into final products in the gas/liquid/solid separation unit 110 and stored and/or supplied to specific needs. Specifically, the gas/liquid/solid separation unit 110 can separate the product into LPG, gasoline, middle oil, and wax.

In addition, the combined energy system includes an LPG storage unit 120 for storing LPG discharged from the gas/liquid/solid separation unit 110, a gasoline storage unit 130 for storing the gasoline, and a storage unit for storing the intermediate oil. It may include an intermediate oil storage unit 150 and a wax storage unit 170 for storing the wax.

The LPG storage unit 120 can receive and store not only LPG flowing in from the gas/liquid/solid separation unit 110 but also hydrocarbons having 3 to 4 carbon atoms separated in the above-mentioned gas separation unit 30.

Gasoline stored in the gasoline storage unit 130 can be supplied to demand sources such as gas stations 140, and the middle oil stored in the middle oil storage unit 150 can be used as a raw material for producing high value-added products 160. You can.

The combined energy system receives wax among the products of the Fischer-Tropsch reaction unit 100 from the wax storage unit 170 and reacts it with hydrogen supplied from the dehydrogenation reaction unit 90 to produce LPG, gasoline, and It may include an upgrading unit 180 that produces clean fuel such as heavy oil.

Clean fuel discharged from the upgrading unit 180 may be stored in each storage unit (120, 130, 150, and 170). At this time, hydrocarbons having 1 to 2 carbon atoms can be used as fuel to maintain the reaction temperature of the reforming unit 50.

The overall process of producing and storing clean fuel and hydrogen through the complex energy system is explained in terms of the flow of raw material gas 10 as follows.

The raw material gas 10 is supplied to the gas/liquid separation unit 20 to separate hydrocarbons with a carbon number of 5 or more from the raw material gas 10, and the hydrocarbons with a carbon number of 3 to 4 are separated through the gas separation unit 30. . Steam is added to cause some hydrocarbons to participate in the reforming reaction through the pre-reforming unit 40, and then additional steam is added and sent to the reforming unit 50 to complete the additional reforming reaction. The synthesis gas produced in the reforming unit 50 adjusts the H ₂ /CO molar ratio to 2 or 1 or less, then causes a Fischer-Tropsch reaction in the Fischer-Tropsch reaction unit 100 to produce clean fuel and store it. and/or supply to specific needs. Excess hydrogen generated in the process can be stored in LOHC and then separated into hydrogen and used in the upgrading process, supplied to hydrogen vehicles, fuel cells, etc., or compressed in liquid hydrogen form and supplied to consumers as compressed hydrogen. Additionally, the hydrogen released from the dehydrogenation reaction unit 90 can be used to cause a hydrogenolysis reaction of wax among the products of the Fischer-Tropsch reaction, thereby upgrading it into clean fuel.

As the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited to the above-described embodiments, and various modifications and modifications by those skilled in the art using the basic concept of the present invention as defined in the following patent claims are made. Improved forms are also included in the scope of the present invention.

10: Raw material gas 20: Gas/liquid separation unit 30: Gas separation unit
40: pre-reforming unit 50: reforming unit 60: synthesis gas control unit
70: Hydrogenation reaction control unit 80: Liquid hydrogen storage unit 90: Dehydrogenation reaction unit
100: Fischer-Tropsch reaction unit 110: Gas/liquid/solid separation unit
120: LPG storage unit 130: Gasoline 140: Gas station 150: Intermediate oil storage unit
160: High value-added product 170: Wax storage unit 180: Upgrade unit

Claims (10)

A gas/liquid separation unit that separates raw material gas containing at least hydrocarbons into hydrocarbons having 1 to 4 carbon atoms and hydrocarbons having 5 or more carbon atoms;
A gas separation unit that receives hydrocarbons having 1 to 4 carbon atoms from the gas/liquid separation unit and separates them into hydrocarbons having 1 to 2 carbon atoms and hydrocarbons having 3 to 4 carbon atoms;
A pre-reforming unit that receives hydrocarbons having 1 to 2 carbon atoms from the gas separation unit and performs a reforming reaction with a portion of the hydrocarbons with steam;
A reforming unit that receives the product of the pre-reforming unit and performs an additional reforming reaction to produce a synthesis gas containing hydrogen and carbon monoxide;
a synthesis gas control unit that separates water from the synthesis gas, then adjusts the H ₂ /CO molar ratio and removes a certain amount of carbon dioxide (CO ₂ );
A hydrogenation reaction control unit that stores excess hydrogen in the synthesis gas control unit in a liquid organic hydrogen carrier (LOHC) to control the H ₂ /CO molar ratio; and
A clean fuel and hydrogen production complex energy system comprising a Fischer-Tropsch reaction unit that receives synthesis gas with the H ₂ /CO/CO ₂ molar ratio adjusted from the synthesis gas control unit and causes a Fischer-Tropsch reaction. According to paragraph 1,
The raw material gas is selected from the group consisting of natural gas, liquefied natural gas (LNG), liquefied petroleum gas (LPG), liquid condensate (C ₅₊ condensate), and combinations thereof. A clean fuel and hydrogen production complex energy system including at least one selected. According to paragraph 1,
a liquid hydrogen storage unit that stores the liquid organic hydrogen carrier supplied from the hydrogenation reaction unit; and
A clean fuel and hydrogen production complex energy system further comprising a dehydrogenation reaction unit that receives the liquid organic hydrogen carrier from the liquid hydrogen storage unit and separates hydrogen from the liquid organic hydrogen carrier using waste heat accompanying the reforming unit. According to paragraph 3,
An upgrading unit that reacts the hydrogen supplied from the dehydrogenation reaction unit with the Wax product of the Fischer-Tropsch reaction to produce clean fuel such as LPG, gasoline, and middle oil. A complex energy system for producing clean fuel and hydrogen, further comprising a. According to paragraph 1,
The synthesis gas control unit is a hydrogenation reaction control unit that controls the H ₂ /CO molar ratio by storing excess hydrogen in LOHC in the process to control the H ₂ /CO molar ratio of the synthesis gas supplied from the reforming unit to 2 or 1 or less. A clean fuel and hydrogen production energy complex system characterized by providing. According to paragraph 1,
A clean fuel and hydrogen production complex energy system further comprising a gas/liquid/solid separation unit for separating the products of the Fischer-Tropsch reaction unit into LPG, gasoline, middle oil, and wax. According to clause 6,
An LPG storage unit that stores the LPG,
A gasoline storage unit that stores the gasoline,
An intermediate oil storage unit that stores the intermediate oil and
A clean fuel and hydrogen production complex energy system further comprising a wax storage unit for storing the wax. In clause 7,
A clean fuel and hydrogen production complex energy system in which hydrocarbons with 3 to 4 carbon atoms separated in the gas separation unit are stored in the LPG storage unit. According to claim 1 or 5,
A clean fuel and hydrogen production complex energy system characterized in that hydrogen separated from LOHC is supplied to an upgrading process or supplied to a hydrogen user. According to paragraph 1,
The H ₂ /CO molar ratio of the synthesis gas is adjusted in the synthesis gas control unit and supplied to the Fischer-Tropsch reaction unit, and the remaining excess hydrogen is converted to LOHC in the hydrogenation reaction control unit or synthesized gas from which a certain amount of water and carbon dioxide has been removed in the synthesis gas control unit. A clean fuel and hydrogen production complex energy system that is controlled by performing a hydrogenation reaction in the hydrogenation reaction control unit and storing a certain amount of hydrogen in liquid form.