Plant and hydrogen utilization methods

Abstract

To provide a new technique for producing hydrogen from organic hydride.SOLUTION: A plant 1 comprises: a modified raw material oil tank 8 for storing a modified raw material oil; an organic hydride tank 16 for storing organic hydride; and a catalytic reforming apparatus 10 in which the modified raw material oil in the modified raw material oil tank 8 and the organic hydride in the organic hydride tank 16 are directly or indirectly supplied to produce a reformed product, a dehydrogenate of the organic hydride, and hydrogen from the modified raw material oil and the organic hydride by a catalytic reaction.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a plant and a hydrogen production method.

Background Art

[0002] In recent years, organic hydrides have attracted attention as energy carriers for large-scale transportation and storage of hydrogen. For example, Patent Document 1 discloses a hydrogen transportation and storage system in which an aromatic compound is hydrogenated to produce an organic hydride, the produced organic hydride is transported to a dehydrogenation reactor, and the organic hydride is dehydrogenated in the dehydrogenation reactor to extract hydrogen.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In a conventional hydrogen transportation and storage system, a dedicated dehydrogenation reactor has been used to extract hydrogen from an organic hydride, that is, to produce hydrogen. In contrast, as a result of intensive studies, the present inventor has found a new technique for producing hydrogen from an organic hydride without using a dedicated dehydrogenation reactor.

[0005] The present invention has been made in view of such a situation, and an object thereof is to provide a new technique for producing hydrogen from an organic hydride.

Means for Solving the Problems

[0006] One aspect of the present invention is a plant. This plant comprises a feedstock tank for storing feedstock oil, an organic hydride tank for storing organic hydrides, and a catalytic reforming apparatus to which the feedstock oil in the feedstock tank and the organic hydrides in the organic hydride tank are supplied directly or indirectly, and which generates a reformed product, a dehydrogenated organic hydride, and hydrogen from the feedstock oil and organic hydrides through a catalytic reaction.

[0007] Another aspect of the present invention is a method for producing hydrogen. This method for producing hydrogen includes supplying organic hydrides directly or indirectly to a catalytic reforming unit for reformed feedstock oil, and producing hydrogen by dehydrogenating the organic hydrides through a catalytic reaction in the catalytic reforming unit.

[0008] Any combination of the above components, as well as any conversion of the expressions of this disclosure between methods, apparatus, systems, etc., are also valid forms of this disclosure. [Effects of the Invention]

[0009] According to the present invention, a new technology for producing hydrogen from organic hydrides can be provided. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic diagram of a plant according to an embodiment. [Figure 2] This is a schematic diagram of the plant in a modified form. [Modes for carrying out the invention]

[0011] The present invention will be described below with reference to the drawings, based on preferred embodiments. The embodiments are illustrative and not limiting, and not all features or combinations thereof described in the embodiments are necessarily essential to the invention. The same or equivalent components, members, and processes shown in each drawing are denoted by the same reference numerals, and redundant explanations are omitted as appropriate. Furthermore, the scale and shape of each part shown in each drawing are set for convenience to facilitate explanation and are not to be interpreted restrictively unless otherwise specified. In addition, when terms such as "first," "second," etc. are used in this specification or claims, these terms do not indicate any order or importance, but are used to distinguish one configuration from another. Furthermore, some components that are not important for explaining the embodiments are omitted in each drawing.

[0012] The inventors of this invention sought to utilize existing equipment instead of dedicated dehydrogenation reactors as a method for producing hydrogen from organic hydrides. They then conceived of using a catalytic reforming unit at an oil refinery. In the petroleum refining process, catalytic reforming units are used to reform feedstocks such as naphtha to produce reformed products such as high-octane reformed gasoline.

[0013] More specifically, in a catalytic reforming unit, cyclization dehydrogenation of paraffins and dehydrogenation of naphthenes in the reformed feedstock oil occur. This produces a reformed product containing reformed gasoline rich in aromatic compounds such as benzene, toluene, and xylene (so-called BTX), as well as hydrogen as a by-product. Therefore, by using a catalytic reforming unit, it is possible to perform dehydrogenation of organic hydrides simultaneously with the reforming of the reformed feedstock oil.

[0014] Figure 1 is a schematic diagram of Plant 1 according to an embodiment. Plant 1 in this embodiment is a petroleum refining plant and includes a crude oil tank 2, an atmospheric distillation unit 4, a hydrodesulfurization unit 6, a reforming feedstock tank 8, a catalytic reforming unit 10, a hydrogen utilization unit 12, a hydrogen production unit 14, etc. Depending on the scale of the refinery, some equipment may be omitted or other equipment may be added. Since these pieces of equipment in Plant 1 are publicly known, detailed explanations will be omitted as appropriate.

[0015] Crude oil is stored in crude oil tank 2. The crude oil in crude oil tank 2 is subjected to treatments such as desalination, dehydration, and removal of solids, heated to a predetermined temperature, and supplied to atmospheric distillation unit 4. Atmospheric distillation unit 4 separates the supplied crude oil into various fractions such as off-gas, LPG, naphtha, kerosene, light oil, and heavy oil. The naphtha fractionated in atmospheric distillation unit 4 is supplied to hydrodesulfurization unit 6. The naphtha supplied to hydrodesulfurization unit 6 is mainly heavy naphtha.

[0016] Hydrodesulfurization unit 6 performs desulfurization treatment on naphtha. The desulfurization treatment is carried out, for example, in the presence of hydrogen, at a reaction temperature of 280-350°C, a hydrogen partial pressure of 0.5-10 MPaG, and a liquid space velocity (LHSV) of 1.0-8.0 h. -1 One such process involves contacting naphtha with a hydrogenation catalyst under reaction conditions of a hydrogen / oil ratio of 10 to 150 NL / L. The desulfurized naphtha is stored in a reformed feedstock tank 8 as a feedstock for reforming.

[0017] Furthermore, the feedstock oil stored in the feedstock oil tank 8 may also contain catalytic cracked gasoline (CCG). Catalytic cracked gasoline includes light catalytic cracked gasoline with a boiling point range of approximately 30 to 100°C and heavy catalytic cracked gasoline with a boiling point range of approximately 100 to 200°C. Catalytic cracked gasoline can be produced, for example, by a fluid catalytic cracking apparatus connected to the atmospheric distillation apparatus 4 and supplied to the feedstock oil tank 8. The method for producing catalytic cracked gasoline is not particularly limited, and known catalytic cracking apparatuses, raw materials, operating conditions, etc., can be used. As an example, a method is exemplified in which catalytic cracking is performed on petroleum fractions from light oil to vacuum light oil, intermittently desulfurized light oil obtained from an indirect heavy oil desulfurization apparatus, directly desulfurized heavy oil obtained from a direct heavy oil desulfurization apparatus, atmospheric residual oil, etc., using a catalyst such as amorphous silica alumina or zeolite to produce catalytic cracked gasoline. Furthermore, catalytic cracked gasoline may be used alone as the feedstock oil.

[0018] The reformed raw material oil in the reformed raw material oil tank 8 is supplied to the catalytic reformer 10. In this embodiment, the reformed raw material oil is supplied directly to the catalytic reformer 10, that is, without passing through other processing devices. However, the reformed raw material oil may also be supplied indirectly to the catalytic reformer 10, that is, via other processing devices. The catalytic reformer 10 performs a reforming treatment on the reformed raw material oil to produce reformed products, hydrogen, etc. The catalytic reformer 10 has a platinum-alumina catalyst or a bimetallic alumina catalyst in which a second metal such as rhenium, germanium, tin, or iridium is added to platinum. The reaction temperature in the reforming treatment is preferably 400 to 600°C, and more preferably 450 to 550°C. The LHSV (liquid space velocity) is preferably 0.5 to 5 h -1 , comfortably 1-2 hours -1 The reaction pressure is preferably 0.1 to 2 MPa, and more preferably 0.2 to 1.5 MPa. The hydrogen / oil ratio (molar ratio) is preferably 0.5 to 10, and more preferably 1 to 5. The operating conditions of the catalytic reforming apparatus 10 and the type of catalyst are not particularly limited.

[0019] The reformate produced by the catalytic reforming unit 10 contains aromatic compounds such as BTX. The reformate is used as a high-octane gasoline base material (reformate gasoline) or a chemical raw material (aromatic compounds such as BTX) either as it is or after passing through a separation process. Furthermore, a part of the aromatic compounds can also be used as an organic hydride raw material described later.

[0020] The hydrogen produced by the catalytic reforming unit 10 is supplied to the hydrogen utilization unit 12. The hydrogen utilization unit 12 includes a hydrorefining unit, a hydrocracking unit, etc. The hydrorefining unit includes a device for removing impurities such as sulfur, nitrogen, and oxygen from the base material used in petroleum products. The base material may be naphtha, kerosene, gas oil, etc. separated by the atmospheric distillation unit 4. That is, the hydrodesulfurization unit 6 can also be included in the hydrogen utilization unit 12.

[0021] In addition, the hydrorefining unit may also include a device for saturating unnecessary unsaturated hydrocarbons contained in the base material of petroleum products to stabilize the properties of the base material, a device for subjecting compounds other than the base material of petroleum products to a hydrogenation treatment, etc. The hydrocracking unit includes a device for hydrocracking the heavy fraction separated by the atmospheric distillation unit 4 to convert it into a light fraction.

[0022] The hydrogen utilization unit 12 may be provided outside the plant 1. Also, the hydrogen produced by the catalytic reforming unit 10 may be used for hydrogen power generation or supplied to a hydrogen station. That is, the hydrogen utilization unit 12 may be a hydrogen power generation device, a hydrogen station, etc. A hydrogen station is a facility for supplying hydrogen to a fuel cell vehicle that uses hydrogen as fuel. When supplying the hydrogen produced by the catalytic reforming unit 10 to a hydrogen station, the hydrogen obtained from the catalytic reforming unit 10 may be purified according to the required hydrogen purity.

[0023] Furthermore, some of the hydrogen produced in the catalytic reforming unit 10 can be used in the catalytic reforming unit 10. Catalytic reforming is a dehydrogenation reaction. Therefore, a lower hydrogen partial pressure is advantageous for the reaction to proceed. However, by supplying hydrogen to the catalytic reforming unit 10, the deposition of coke on the reforming catalyst can be suppressed, thereby preventing the deactivation of the catalyst. In addition, fractions other than naphtha produced in the atmospheric distillation unit 4 are also subjected to various refining treatments, including desulfurization, as needed, and used as is as a product or as a raw material for other products (including reforming feedstock). Furthermore, as in gasoline production, multiple fractions (including those that have undergone refining treatments, etc.) may be mixed to produce a product with desired properties.

[0024] The hydrogen utilization device 12 is supplied with hydrogen not only from the catalytic reforming device 10 but also from the hydrogen production device 14. The hydrogen production device 14 is supplied with off-gas, LPG, naphtha, etc. as raw materials and off-gas, etc. as fuel. The hydrogen production device 14 reforms the raw materials into hydrogen and carbon monoxide by a steam reforming reaction. The generated carbon monoxide is converted to carbon dioxide by a shift reaction, and hydrogen is produced in the process. The generated hydrogen is supplied from the hydrogen production device 14 to the hydrogen utilization device 12. This makes it possible to compensate for the shortage of hydrogen supply when the hydrogen consumption of the hydrogen utilization device 12 exceeds the amount of hydrogen supplied from the catalytic reforming device 10. Alternatively, the amount of hydrogen produced in the hydrogen production device 14 can be reduced by supplying hydrogen from the catalytic reforming device 10 to the hydrogen utilization device 12.

[0025] Furthermore, the plant 1 of this embodiment includes an organic hydride tank 16, an O2 stripper 18, and a raw material tank 20.

[0026] The organic hydride tank 16 stores the organic hydride. The organic hydride and its dehydrogenated product used in this embodiment are not particularly limited as long as they are organic compounds that can remove / add hydrogen by reversibly undergoing a dehydrogenation / hydrogenation reaction, and a wide range of acetone-isopropanol systems, benzoquinone-hydroquinone systems, aromatic hydrocarbon systems, etc., can be used. Among these, aromatic hydrocarbon systems are preferred from the viewpoint of transportability during energy transport.

[0027] Aromatic hydrocarbon compounds used as dehydrogenated products of organic hydrides are compounds containing at least one aromatic ring, such as benzene, alkylbenzene, naphthalene, alkylnaphthalene, anthracene, and diphenylethane.

[0028] Alkylbenzenes include compounds in which the 1st to 4th hydrogen atoms of an aromatic ring are substituted with a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of such compounds include toluene, xylene, mesitylene, ethylbenzene, and diethylbenzene. Alkylnaphthalenes include compounds in which the 1st to 4th hydrogen atoms of an aromatic ring are substituted with a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of such compounds include methylnaphthalene. The preferred dehydrogenated product is at least one of toluene and benzene.

[0029] Furthermore, nitrogen-containing heterocyclic aromatic compounds such as pyridine, pyrimidine, pyrazine, quinoline, isoquinoline, N-alkylpyrrole, N-alkylindole, and N-alkyldibenzopyrrole can also be used as dehydrogenated products. Additionally, the organic hydride may be used individually or in combination of multiple types.

[0030] The organic hydride in the organic hydride tank 16 may contain a large amount of oxygen. In particular, if the organic hydride is supplied to the organic hydride tank 16 from outside the plant 1 by sea transport or the like, it is highly likely to contain a large amount of oxygen. Oxygen can act as a catalytic poison for the catalytic reforming catalyst. For this reason, the organic hydride is supplied to the catalytic reforming apparatus 10 after the oxygen has been removed in the O2 stripper 18. The O2 stripper 18 has a known structure. Therefore, in this embodiment, the organic hydride is supplied to the catalytic reforming apparatus 10 indirectly, that is, via the O2 stripper 18. However, if the amount of oxygen contained in the organic hydride is below the permissible amount, the O2 stripper 18 may be omitted. In this case, the organic hydride will be supplied directly to the catalytic reforming apparatus 10.

[0031] In Plant 1 shown in Figure 1, the organic hydride line (transport pipe) is connected to a line that connects the reformed feed oil tank 8 and the catalytic reformer 10. Therefore, the reformed feed oil and organic hydride are mixed in the line by a line blending method and supplied to the catalytic reformer 10. For example, if the organic hydride is methylcyclohexane, the reformed feed oil also contains methylcyclohexane, but by supplying methylcyclohexane from the organic hydride tank 16 to the catalytic reformer 10, the proportion of methylcyclohexane in the reactants can be increased. Note that the mixing method of the reformed feed oil and organic hydride is not limited to the line blending method.

[0032] The catalytic reformer 10 generates a reformed product and hydrogen from the feedstock oil through a catalytic reaction, and also generates a dehydrogenated product and hydrogen from the organic hydride. The operating conditions of the catalytic reformer 10, including temperature, pressure, LHSV, etc., are adjusted as appropriate according to the composition of the reactants supplied to the catalytic reformer 10 and the type of product to be produced. The catalytic reformer 10 may also be operated in a way that adjusts the reaction temperature by changing the amount of fuel gas supplied according to the amount of organic hydride added from the organic hydride tank 16.

[0033] A catalytic reaction in the catalytic reforming unit 10 generates organic hydride raw materials. At least a portion of the organic hydride raw materials generated in the catalytic reforming unit 10 is recovered from the catalytic reforming unit 10 for the production of organic hydrides and stored in the raw material tank 20. A portion of the organic hydride raw materials stored in the raw material tank 20 may be used as a gasoline base material or a raw material for chemicals. The organic hydride raw materials to be recovered can be recovered by subjecting the products obtained from the catalytic reforming unit 10 to known treatments such as distillation separation, extraction separation, membrane separation, and adsorption separation.

[0034] The organic hydride raw materials produced in the catalytic reforming unit 10 include the dehydrogenated organic hydride supplied from the organic hydride tank 16. A portion of the dehydrogenated organic hydride supplied from the organic hydride tank 16 is not recovered into the raw material tank 20, meaning it can be used as a raw material for gasoline or chemicals without passing through the raw material tank 20. Furthermore, the same compounds as these dehydrogenated organic hydride can also be produced by the catalytic reforming reaction of the reformed feedstock oil. In other words, organic hydride raw materials can be produced not only by the dehydrogenation reaction of organic hydride but also by the catalytic reforming reaction of the reformed feedstock oil.

[0035] For example, the organic hydride may be methylcyclohexane, and the organic hydride raw material to be recovered may be toluene. In this case, toluene is produced in the catalytic reforming unit 10 by both the dehydrogenation reaction of the organic hydride (methylcyclohexane) and the catalytic reforming reaction of the reforming raw material oil. Therefore, the raw material tank 20 stores a mixture of toluene derived from the organic hydride and toluene derived from the reforming raw material oil.

[0036] Furthermore, the organic hydride raw material can be any compound that becomes an organic hydride through a hydrogenation reaction. Therefore, the organic hydride raw material recovered in the raw material tank 20 is not limited to the dehydrogenated organic hydride (let's call it compound A) supplied from the organic hydride tank 16 and the same compound A produced by the catalytic reforming reaction of the reformed feedstock oil. For example, if compound B, which is different from the dehydrogenated organic hydride (compound A) supplied from the organic hydride tank 16 and becomes an organic hydride through a hydrogenation reaction, is produced by the catalytic reforming reaction of the reformed feedstock oil, compound B may be recovered in the raw material tank 20 alone or together with compound A. In other words, when methylcyclohexane is supplied as an organic hydride from the organic hydride tank 16, the organic hydride raw material recovered in the raw material tank 20 is not limited to toluene (corresponding to compound A) derived from the organic hydride and the reformed feedstock oil, but may also include benzene, xylene (corresponding to compound B), etc., produced by the catalytic reforming reaction of the reformed feedstock oil. As described above, the organic hydride raw material may include a dehydrogenated organic hydride (compound A) supplied from the organic hydride tank 16 and a compound B different from the same compound (compound A) derived from the reformed feedstock oil. However, it is preferable that the organic hydride raw material recovered in the raw material tank 20 consists of a dehydrogenated organic hydride (compound A) supplied from the organic hydride tank 16 and the same compound (compound A) derived from the reformed feedstock oil.

[0037] The organic hydride raw materials stored in the raw material tank 20 are supplied to the organic hydride production apparatus 22. The organic hydride production apparatus 22 produces organic hydride from the organic hydride raw materials. Preferably, an amount of organic hydride raw materials equivalent to the amount of organic hydride supplied to the catalytic reforming apparatus 10 is supplied from the raw material tank 20 to the organic hydride production apparatus 22 and used for the production of organic hydride.

[0038] As the organic hydride production apparatus 22, a known apparatus capable of performing hydrogenation treatment on organic hydride raw materials can be employed. For example, the organic hydride production apparatus 22 may be an apparatus that produces hydrogen by water electrolysis or the like, and then produces organic hydrides by hydrogenation treatment such as chemical hydrogenation. Furthermore, the source of hydrogen used in the production of organic hydrides is not particularly limited. For example, the hydrogen may be derived from fossil fuels such as natural gas or coal. Alternatively, it may be by-product hydrogen generated in steel manufacturing processes such as coke production, or by-product hydrogen generated in caustic soda production processes.

[0039] Another example of the organic hydride production apparatus 22 is an electrolytic reduction apparatus that hydrogenates organic hydride raw materials by an electrochemical reduction reaction. The electrolytic reduction apparatus comprises an electrolyte membrane, a cathode, and an anode. The electrolyte membrane is placed between the cathode and the anode and moves protons from the anode side to the cathode side. The electrolyte membrane is composed of, for example, a solid polymer electrolyte membrane having proton conductivity. The cathode has a cathode catalyst layer. The cathode catalyst layer hydrogenates the organic hydride raw materials with protons to produce organic hydrides. The cathode catalyst layer has platinum, ruthenium, or the like as the cathode catalyst. The anode oxidizes water to produce protons. The anode has, for example, a metal such as iridium, ruthenium, or platinum, or an oxide of these metals, as the anode catalyst.

[0040] The reaction that occurs when toluene (TL) is used as an example of an organic hydride raw material in an electrolytic reduction apparatus is as follows: <Electrode reaction at the anode> 3H2O → 3 / 2O2 + 6H + +6e - <Electrode reaction at the cathode> TL+6H + +6e - →MCH

[0041] The electrode reactions at the cathode and anode proceed in parallel. Protons produced by the electrolysis of water at the anode are supplied to the cathode catalyst layer via the electrolyte membrane. Electrons produced by the electrolysis of water are also supplied to the cathode catalyst layer via an external circuit. The protons and electrons supplied to the cathode catalyst layer are used for the hydrogenation of toluene in the cathode catalyst layer, thereby producing methylcyclohexane (MCH).

[0042] The power source for the organic hydride production apparatus 22 is preferably renewable energy obtained from solar, wind, hydroelectric, or geothermal power generation. By producing organic hydrides with electricity derived from renewable energy, carbon dioxide emissions during the hydrogen production process can be suppressed. In other words, so-called CO2-free hydrogen can be produced. Note that the amount of electricity generated by renewable energy power generation varies depending on climatic conditions, and may exceed the electricity demand. Therefore, the organic hydride production apparatus 22 may be used in an operational manner that effectively utilizes surplus electricity, such as operating only when surplus electricity is generated at such power plants. Furthermore, even if renewable energy is not used, carbon dioxide capture and storage (CCS) or enhanced oil recovery (EOR) can be combined to capture and store the carbon dioxide generated during hydrogen production, thereby reducing carbon dioxide emissions. Therefore, hydrogen produced in combination with CCS or EOR may also be used. Enhanced recovery is a method of recovering remaining crude oil from an oil field that has stopped flowing naturally or whose reservoir water content has increased, by injecting carbon dioxide into the field.

[0043] The location of the organic hydride production apparatus 22 is not restricted. When renewable energy is used, the organic hydride production apparatus 22 may be installed near a power plant located in a place with high renewable energy generation efficiency. Also, when by-product hydrogen is used or when CCS and EOR are combined, it may be installed near such facilities. Therefore, the organic hydride production apparatus 22 may be installed in a remote location relative to Plant 1. Organic hydrides produced at the remote organic hydride production apparatus 22 may be transported to Plant 1 by sea or other means. In this case, the combination of Plant 1 and the organic hydride production apparatus 22 can be considered as a hydrogen production system. The power source for the organic hydride production apparatus 22 is not limited to renewable energy. Furthermore, the organic hydride production apparatus 22 may be installed within Plant 1.

[0044] As described above, the plant 1 according to this embodiment comprises a reformed raw material oil tank 8 for storing reformed raw material oil, an organic hydride tank 16 for storing organic hydrides, and a catalytic reforming apparatus 10 to which the reformed raw material oil in the reformed raw material oil tank 8 and the organic hydrides in the organic hydride tank 16 are supplied directly or indirectly, and which generates a reformed product, a dehydrogenated organic hydride, and hydrogen from the reformed raw material oil and organic hydrides through a catalytic reaction.

[0045] In this way, by producing hydrogen from organic hydrides using an existing catalytic reforming unit 10, a new hydrogen production technology that makes effective use of existing equipment can be provided. Furthermore, since the installation of a dedicated dehydrogenation reactor is not required, hydrogen production costs and production equipment can be reduced.

[0046] In particular, if a decline in oil demand leads to a decrease in the operating rate of the refinery's catalytic reforming unit 10, this system can improve the operating rate of the catalytic reforming unit 10. In other words, it can effectively utilize the surplus processing capacity of the refinery. Furthermore, since the catalytic reforming reaction of the feedstock is carried out to produce gasoline base materials and chemical raw materials while simultaneously performing the dehydrogenation reaction of organic hydrides, it becomes possible to increase hydrogen production without significantly impacting the overall operating plan of the refinery. In addition, the increase in hydrogen production in the catalytic reforming unit 10 makes it possible to reduce the scale or even eliminate the hydrogen production equipment 14. These factors can enhance the competitiveness of the refinery.

[0047] Furthermore, when organic hydrides are produced using electricity derived from renewable energy sources, or by combining CCS and EOR, carbon dioxide emissions associated with hydrogen production can be reduced. In addition, if the scale of the hydrogen production equipment 14 is reduced or the hydrogen production equipment 14 is omitted, the consumption of fuel and raw materials in the hydrogen production equipment 14 can be reduced, and further reductions in carbon dioxide emissions can be expected.

[0048] Furthermore, the plant 1 of this embodiment includes a raw material tank 20 for storing organic hydride raw materials recovered from the catalytic reforming unit 10 and used in the production of organic hydrides. This allows the organic hydrides to be repeatedly used as hydrogen carriers.

[0049] The embodiments of the present invention have been described in detail above. The embodiments described above are merely examples of how to implement the present invention. The content of the embodiments does not limit the technical scope of the present invention, and many design changes, such as changes, additions, and deletions of components, are possible as long as they do not depart from the spirit of the invention as defined in the claims. The new embodiments to which design changes have been made combine the effects of the respective embodiments and modifications. In the embodiments described above, the content in which such design changes are possible is emphasized with notations such as "in this embodiment" or "in this embodiment," but design changes are also permitted even if there are no such notations. Any combination of the above components is also valid as an embodiment of the present invention.

[0050] (modified version) This modified version has a configuration common to Embodiment 1, except for the connection method of the organic hydride tank 16. Below, this modified version will be described focusing on the configurations that differ from Embodiment 1, and the common configurations will not be described. Figure 2 is a schematic diagram of the plant 1 according to the modified version. In the plant 1 according to the modified version, the organic hydride line extending from the organic hydride tank 16 is connected to the crude oil tank 2. Therefore, the organic hydride is mixed with crude oil in the crude oil tank 2 by a tank blending method.

[0051] When a mixture of crude oil and organic hydride is supplied to the atmospheric distillation unit 4, a mixed fraction of naphtha and organic hydride is obtained by the atmospheric distillation unit 4. This mixed fraction is stored in the reforming feedstock tank 8 and used as reforming feedstock. Therefore, in this modified example, the organic hydride is supplied indirectly to the catalytic reformer 10, that is, via the crude oil tank 2, atmospheric distillation unit 4, hydrodesulfurization unit 6, and reforming feedstock tank 8. After the mixed fraction is supplied to the catalytic reformer 10, reformed products, dehydrogenated organic hydride products, and hydrogen are produced, similar to Embodiment 1. In addition, a portion of the products is recovered in the feedstock tank 20.

[0052] By supplying the organic hydride to the crude oil tank 2, even if the organic hydride contains a large amount of oxygen, this oxygen can be separated from the organic hydride in the atmospheric distillation unit 4. Therefore, according to this modified example, the O2 stripper 18 can be omitted even if the amount of oxygen contained in the organic hydride exceeds the permissible limit. The organic hydride line may also be connected to the line connecting the crude oil tank 2 and the atmospheric distillation unit 4.

[0053] The embodiments may be specified by the items described below. [Item 1] Organic hydrides are supplied directly or indirectly to the catalytic reforming unit (10) for reformed raw material oil. A method for producing hydrogen, comprising producing hydrogen by dehydrogenating an organic hydride through a catalytic reaction in a catalytic reforming apparatus (10). [Item 2] A method for producing hydrogen according to item 1, comprising recovering organic hydride raw materials used in the production of organic hydrides from a catalytic reforming apparatus (10). [Explanation of Symbols]

[0054] 1 plant, 8 reformed raw material tanks, 10 catalytic reforming units, 16 organic hydride tanks, 20 raw material tanks, 22 organic hydride production units.

Claims

1. A tank for storing reformed feedstock oil, A catalytic reforming apparatus that generates hydrogen from the reformed raw material oil, A hydrogen production device that generates hydrogen from raw materials, A hydrogen utilization device that utilizes the hydrogen produced in the catalytic reforming apparatus and the hydrogen produced in the hydrogen production apparatus, It includes an organic hydride tank for storing organic hydrides, The catalytic reforming apparatus receives the organic hydride directly or indirectly along with the reforming feed oil, and generates hydrogen from the reforming feed oil and the organic hydride. plant.

2. The catalytic reforming apparatus generates a reformed product and hydrogen from the reformed raw material oil by a catalytic reaction. The plant according to claim 1.

3. The catalytic reforming apparatus has at least one catalyst selected from the group consisting of platinum-alumina catalysts and bimetallic alumina catalysts in which a second metal is added to platinum. The plant according to claim 2.

4. The reformed feedstock oil comprises at least one selected from the group consisting of naphtha and catalytic cracking gasoline. The plant according to any one of claims 1 to 3.

5. The raw material supplied to the hydrogen production apparatus includes at least one selected from the group consisting of off-gas and LPG. The plant according to any one of claims 1 to 4.

6. The hydrogen utilization apparatus includes at least one selected from the group consisting of a hydrogenation and purification apparatus, a hydrocracking apparatus, a hydrogen power generation apparatus, and a hydrogen station. The plant according to any one of claims 1 to 5.

7. A catalytic reforming device generates hydrogen from the reformed raw material oil. Hydrogen is produced from raw materials using a hydrogen production device. Utilizing the hydrogen produced in the catalytic reforming apparatus and the hydrogen produced in the hydrogen production apparatus, The process includes supplying the organic hydride directly or indirectly to the catalytic reforming apparatus together with the reformed raw material oil, and generating hydrogen from the reformed raw material oil and the organic hydride in the catalytic reforming apparatus. Methods of hydrogen utilization.

8. The catalytic reforming apparatus generates a reformed product and hydrogen from the reformed raw material oil by a catalytic reaction. The hydrogen utilization method according to claim 7.

9. The catalytic reforming apparatus has at least one catalyst selected from the group consisting of platinum-alumina catalysts and bimetallic alumina catalysts in which a second metal is added to platinum. The hydrogen utilization method according to claim 8.

10. The raw material supplied to the hydrogen production apparatus includes at least one selected from the group consisting of off-gas and LPG. A method for utilizing hydrogen according to any one of claims 7 to 9.

11. A hydrogen utilization apparatus selected from the group consisting of a hydrogenation and purification apparatus, a hydrocracking apparatus, a hydrogen power generation apparatus, and a hydrogen station, which includes utilizing hydrogen produced in the catalytic reforming apparatus and hydrogen produced in the hydrogen production apparatus, A method for utilizing hydrogen according to any one of claims 7 to 10.

12. The contact reforming apparatus is provided in the plant, The hydrogen utilization device includes at least one selected from the group consisting of the hydrogen power generation device and the hydrogen station, which is located outside the plant. The hydrogen utilization method according to claim 11.

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