Hydrogen production method and hydrocarbon mixture processing method

Abstract

A hydrogen production method including: a hydrogenation step for obtaining a hydrogenated hydrocarbon compound by subjecting a mixture containing an aromatic compound and an unsaturated hydrocarbon compound to hydrogenation and a process including at least one selected from the group consisting of desulfurization processes, denitrification processes, demetallization processes, and hydrocracking in an environment exceeding 250°C; a transport step for transporting the hydrogenated hydrocarbon compound from a first site to a second site; and a dehydrogenation step for recovering hydrogen from the transported hydrogenated hydrocarbon compound.

Description

Method for producing hydrogen and method for treating hydrocarbon mixtures

[0001] The present invention relates to a method for producing hydrogen and a method for treating a hydrocarbon mixture.

[0002] In recent years, the development and practical application of hydrogen energy utilization technologies, such as fuel cell vehicles, has progressed, and the development of hydrogen purification, storage, and transportation technologies has been vigorously pursued. For example, Patent Document 1 discusses a hydrogen purification method in which a fossil fuel, such as naphtha, is hydrogenated in the presence of a hydrogenation catalyst to obtain a hydrogenated aromatic compound (organic hydride), and then the hydrogenated aromatic compound is dehydrogenated in the presence of a dehydrogenation catalyst, and the hydrogen obtained by this dehydrogenation is recovered.

[0003] Japanese Patent Application Laid-Open No. 2006-052110

[0004] To date, hydrogen carriers such as ammonia, a type of hydrogen derivative, and inorganic and organic hydrides have been considered as a medium for transporting energy from areas suitable for clean energy supply to areas with clean energy demand. When using these hydrogen carriers, not only are there energy losses during the production, transportation, and hydrogen production of the substance, but degradation and loss of the hydrogen carrier occur throughout the process, resulting in high costs and limited actual environmental value. Furthermore, all of the equipment involved in this process would need to be newly built, requiring huge investments, which has hindered progress in social implementation.

[0005] In view of the above circumstances, one aspect of the present invention aims to provide a novel hydrogen production method including a step of transporting a hydrogen carrier. Another aspect of the present invention aims to provide a hydrogen production method including a step of transporting a hydrogen carrier, which utilizes existing facilities, reduces problems of deterioration and loss of the hydrogen carrier, and has excellent energy efficiency.

[0006] One aspect of the present invention includes, for example, the following [1] to

[26] . [1] A method for producing hydrogen, comprising: a hydrogenation step of performing hydrogenation and at least one treatment selected from the group consisting of desulfurization, denitrification, demetallization, and hydrocracking on a mixture containing aromatic compounds and unsaturated hydrocarbon compounds in an environment of above 250°C to obtain hydrogenated hydrocarbon compounds; a transport step of transporting the hydrogenated hydrocarbon compounds from a first location to a second location; and a dehydrogenation step of recovering hydrogen from the transported hydrogenated hydrocarbon compounds. [2] A method for producing hydrogen according to [1], wherein the hydrogenation is performed using clean hydrogen. [3] The method for producing hydrogen according to [1] or [2], further comprising, before the hydrogenation step, at least one step selected from the group consisting of: Step A of electrolyzing water to obtain hydrogen; Step B including steam reforming methane to produce hydrogen and carbon dioxide and separating the produced carbon dioxide and storing it underground; and Step C of thermally decomposing a methane-containing gas to obtain hydrogen, wherein the hydrogenation step is a step of hydrogenation using the hydrogen obtained in any of Steps A to C. [4] The method for producing hydrogen according to any one of [1] to [3], wherein the unsaturated hydrocarbon compound is an olefin. [5] The method for producing hydrogen according to any one of [1] to [4], wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 90% volume distillation temperature of 360°C or higher and an RVP of 13 psi or lower, and wherein the total mass concentration of aromatic compounds among compounds having an NBP of 300°C or lower contained in the hydrocarbon mixture is one-tenth or less of the total mass concentration of cyclic alkanes. [6] The method for producing hydrogen according to any one of [1] to [4], wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D86 End Boiling Point of 230°C or less, the total mass concentration of benzene, toluene, xylene, and ethylbenzene is one-tenth or less of the total mass concentration of cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane in the hydrocarbon mixture, and the total mass concentration of paraffin compounds including hexane and heptane is one-tenth or more of the total mass concentration of the hydrogenated hydrocarbon mixture.[7] The method for producing hydrogen according to any one of [1] to [4], wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 5% by volume distillation temperature of 300°C or higher, and wherein the total mass concentration of aromatic compounds contained in the hydrocarbon mixture is half or less of the total mass concentration of cyclic alkanes. [8] The method for producing hydrogen according to any one of [1] to [6], wherein the dehydrogenation step is carried out using at least one apparatus selected from the group consisting of a catalytic reformer, an ethylene production apparatus, a thermal cracker, and a catalytic cracker. [9] The method for producing hydrogen according to any one of [1] to [8], wherein the dehydrogenation step is carried out using at least one apparatus selected from the group consisting of an ethylene production apparatus, a thermal cracker, and a catalytic cracker, and further comprising, after the dehydrogenation step, a separation step of purifying the hydrogen by at least one separation process selected from the group consisting of membrane separation, adsorption separation, and cryogenic separation.

[10] The method for producing hydrogen according to any one of [1] to [9], wherein the dehydrogenation step is a step of recovering hydrogen from the transported hydrogenated hydrocarbon compound and another hydrogenated hydrocarbon compound other than the transported hydrogenated hydrocarbon compound, and further comprises: a calculation step of calculating a mass ratio of hydrogen generated from the transported hydrogenated hydrocarbon compound among the recovered hydrogen; and a step of dividing the recovered hydrogen after the dehydrogenation step based on the mass ratio.

[11] The method for producing hydrogen according to any one of [1] to

[10] , wherein the dehydrogenation step is a step of producing a mixture containing at least one selected from the group consisting of ethylene, propylene, benzene, toluene, xylene, and solid carbon together with the hydrogen.

[12] A method for treating a hydrocarbon mixture, comprising: a hydrogenation step of subjecting a mixture containing aromatic compounds and unsaturated hydrocarbon compounds to hydrogenation and at least one treatment selected from the group consisting of desulfurization, denitrification, demetallization, and hydrocracking in an environment of above 250°C to obtain hydrogenated hydrocarbon compounds, and a transport step of transporting the hydrogenated hydrocarbon compounds from a first location to a second location.

[13] The method for treating a hydrocarbon mixture according to

[12] , wherein the hydrogenation is performed using clean hydrogen.

[14] The method for treating a hydrocarbon mixture according to

[12] or

[13] , further comprising, prior to the hydrogenation step, at least one step selected from the group consisting of: Step A of obtaining hydrogen by electrolyzing water, Step B comprising steam reforming methane to produce hydrogen and carbon dioxide and separating the produced carbon dioxide and storing it underground, and Step C of obtaining hydrogen by thermal decomposition of a gas containing methane, wherein the hydrogenation step is a step of carrying out hydrogenation using the hydrogen obtained in any of Steps A to C.

[15] The method for treating a hydrocarbon mixture according to any one of

[12] to

[14] , wherein the unsaturated hydrocarbon compound is an olefin.

[16] The method for treating a hydrocarbon mixture according to any one of

[12] to

[15] , wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 90% volume distillation temperature of 360°C or higher and an RVP of 13 psi or lower, and wherein the total mass concentration of aromatic compounds among compounds having an NBP of 300°C or lower contained in the hydrocarbon mixture is one-tenth or less of the total mass concentration of cyclic alkanes.

[17] The method for treating a hydrocarbon mixture according to any one of

[12] to

[15] , wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D86 End Boiling Point of 230°C or lower, and wherein the total mass concentration of benzene, toluene, xylene, and ethylbenzene is one-tenth or less of the total mass concentration of cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane in the hydrocarbon mixture, and wherein the concentration of paraffin compounds including hexane and heptane is one-tenth or more of the total mass concentration of the hydrogenated hydrocarbon mixture.

[18] The method for treating a hydrocarbon mixture according to any one of

[12] to

[15] , wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 5% by volume distillation temperature of 300°C or higher, and the total mass concentration of aromatic compounds contained in the hydrocarbon mixture is half or less of the total mass concentration of cyclic alkanes.

[19] A method for producing hydrogen, comprising: a transporting step of transporting the hydrogenated hydrocarbon compound from a first location to a second location; and a dehydrogenation step of recovering hydrogen from the transported hydrogenated hydrocarbon compound.

[20] The method for producing hydrogen according to

[19] , wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 90% volume distillation temperature of 360°C or higher and an RVP of 13 psi or lower, and wherein the total mass concentration of aromatic compounds among compounds having an NBP of 300°C or lower contained in the hydrocarbon mixture is one-tenth or less of the total mass concentration of cyclic alkanes.

[21] The method for producing hydrogen according to

[19] , wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D86 End Boiling Point of 230°C or lower, and wherein the total mass concentration of benzene, toluene, xylene, and ethylbenzene is one-tenth or less of the total mass concentration of cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane in the hydrocarbon mixture, and the total mass concentration of paraffin compounds including hexane and heptane is one-tenth or more of the total mass concentration of the hydrogenated hydrocarbon mixture.

[22] The method for producing hydrogen according to

[19] , wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 5% by volume distillation temperature of 300°C or higher, and wherein the total mass concentration of aromatic compounds contained in the hydrocarbon mixture is half or less of the total mass concentration of cyclic alkanes.

[23] The method for producing hydrogen according to any one of

[19] to

[22] , wherein the dehydrogenation step is carried out using at least one apparatus selected from the group consisting of a catalytic reformer, an ethylene production apparatus, a thermal cracker, and a catalytic cracker.

[24] The method for producing hydrogen according to any one of

[19] to

[23] , wherein the dehydrogenation step is carried out using at least one apparatus selected from the group consisting of an ethylene production apparatus, a thermal cracker, and a catalytic cracker, and further comprising, after the dehydrogenation step, a separation step of purifying the hydrogen by at least one separation process selected from the group consisting of membrane separation, adsorption separation, and cryogenic separation.

[25] The method for producing hydrogen according to any one of

[19] to

[24] , wherein the dehydrogenation step is a step of recovering hydrogen from the transported hydrogenated hydrocarbon compound and another hydrogenated hydrocarbon compound other than the transported hydrogenated hydrocarbon compound, and further comprises a calculation step of calculating a mass ratio of hydrogen generated from the transported hydrogenated hydrocarbon compound among the recovered hydrogen, and a step of dividing the recovered hydrogen based on the mass ratio after the dehydrogenation step.

[26] The method for producing hydrogen according to any one of

[19] to

[25] , wherein the dehydrogenation step is a step of producing a hydrocarbon mixture containing at least one selected from the group consisting of ethylene, propylene, benzene, toluene, xylene, and solid carbon together with the hydrogen.

[0007] According to one aspect of the present invention, a novel hydrogen production method including a step of transporting a hydrogen carrier can be provided. Also, according to another aspect of the present invention, a hydrogen production method including a step of transporting a hydrogen carrier can be provided, which utilizes existing facilities, reduces problems of deterioration and loss of the hydrogen carrier, and is highly energy efficient.

[0008] FIG. 1 is a configuration diagram showing a hydrogen production facility according to one embodiment of the present invention.

[0009] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description, the same or corresponding parts will be designated by the same reference numerals, and duplicated explanations will be omitted.

[0010] [Hydrogen Production Facility] Fig. 1 is a configuration diagram showing a hydrogen production facility according to one embodiment of the present invention. The hydrogen production facility 100 shown in Fig. 1 is divided into a first location side and a second location side, with a hydrogenation facility 10 on the first location side and a dehydrogenation facility 20 on the second location side.

[0011] The hydrogenation equipment 10 is located at the first location and includes a processing device 11, a hydrogenation device 12, and a hydrogen generation device 13.

[0012] The hydrocarbon mixture is transferred to a processing unit 11 through a transfer pipe L11. Examples of the hydrocarbon mixture include crude oil and naphtha. The processing unit 11 adjusts the properties of the processed oil supplied to a hydrogenation unit 12 through a transfer pipe L12. The processing unit 11 may be a distillation unit or a cracking reaction facility, or a combination thereof.

[0013] When the processing device 11 is a distillation device, the distillation may be carried out under conditions of, for example, a pressure at the top of the distillation column of 1 to 1500 kPa and a temperature at the bottom of the column of 150 to 400° C. Furthermore, the processing device 11 may be a combination of a plurality of distillation columns.

[0014] When the processing device 11 is a decomposition reaction device, the decomposition reaction may be carried out under conditions such as a thermal decomposition reaction using heat of 400° C. or higher, or a reaction using a catalyst or a solid equivalent thereto. The processing device 11 may be a combination of multiple reaction devices, and may be equipped with a distillation column in either the upstream or downstream stage of the reaction device, or both.

[0015] The processing oil is a mixture containing aromatic compounds, unsaturated hydrocarbon compounds, or both. Aromatic compounds include benzene, toluene, xylene, naphthalene, phenanthrene, anthracene, etc. Unsaturated hydrocarbon compounds include hexene, heptene, octene, etc.

[0016] Examples of processed oils include naphtha (gasoline feedstock) containing hydrocarbons having 5 to 12 carbon atoms produced using a distillation apparatus, kerosene (light oil) containing hydrocarbons having 10 to 12 carbon atoms, diesel (light oil) containing hydrocarbons having 12 to 20 carbon atoms, vacuum gas oil (vacuum gas oil), and residue (heavy oil) having 20 or more carbon atoms, and any combination of these may be used. Processed oils produced by cracking reactions are called cracked naphtha, cracked kerosene, cracked diesel, cracked vacuum gas oil, and cracked residue, respectively, and any combination of these may be used.

[0017] Naphtha includes, for example, chain alkanes such as pentane, hexane, octane, etc.; chain alkenes (olefins) such as ethylene, propylene, butene, etc.; cyclic alkanes such as cyclohexane, etc.; and aromatic hydrocarbons such as benzene, toluene, etc. The boiling point range of naphtha may be, for example, 30 to 200°C.

[0018] Kerosene includes, for example, chain alkanes such as decane, dodecane, tetradecane, etc., cyclic alkanes such as cyclododecane, etc., and aromatic hydrocarbons such as naphthalene, etc. The boiling point range of kerosene may be, for example, 150 to 275°C.

[0019] Diesel contains, for example, chain alkanes such as dodecane, hexadecane, octadecane, etc., and aromatic hydrocarbons such as phenanthrene, anthracene, etc. The boiling point range of diesel may be, for example, 250 to 350°C.

[0020] The residue may include, for example, chain alkanes such as eicosane, triacontane, pentacontane, etc., and aromatic hydrocarbons such as asphaltenes, etc. The boiling point of the residue may be, for example, 350° C. or higher.

[0021] The vacuum gas oil contains hydrocarbons having 20 to 40 carbon atoms. The boiling point of the vacuum gas oil may be 350 to 550°C. The vacuum residue contains hydrocarbons having 40 or more carbon atoms. The boiling point of the vacuum residue may be 550°C or higher.

[0022] Vacuum gas oils include, for example, chain alkanes such as eicosane, docosane, triacontane, isoeicosane, and isodocosane; cyclic alkanes such as cyclohexadecane and cyclooctadecane; and aromatic hydrocarbons such as phenanthrene, anthracene, and benzopyrene.

[0023] A transfer pipe L12 and a transfer pipe L13 are connected to the treatment device 11. The transfer pipe L12 transfers the treated oil, and the transfer pipe L13 transfers other fractions.

[0024] The treated oil is transferred to the hydrogenation unit 12 through the transfer pipe L12. The hydrogenation unit 12 is an apparatus that hydrogenates the treated oil (a mixture containing aromatic compounds and unsaturated hydrocarbon compounds) transferred through the transfer pipe L12 using hydrogen transferred through the transfer pipe L14 to obtain hydrogenated hydrocarbon compounds (e.g., hydrogenated naphtha). The hydrogen transferred through the transfer pipe L14 is produced in the hydrogen generation unit 13. The hydrogenated hydrocarbon compounds are transported to a second location by transportation means T1, and by-products and impurities in the hydrogenation unit 12 are discharged through L15. In other words, the hydrogenated hydrocarbon compounds transported from the first location to the second location by transportation means T1 are hydrogen carriers.

[0025] The hydrogenation of the treated oil is carried out in an environment above 250°C. By carrying out the hydrogenation at above 250°C, the hydrogenation reaction is promoted and impurities (such as nitrogen and sulfur) that are not acceptable for inclusion in products from downstream equipment can be completely removed. The hydrogenation of the treated oil may be carried out at a temperature of 250 to 400°C and at a pressure of 2 to 20 MPa. The hydrogenation of the treated oil may be carried out in the presence of a catalyst, which may be a metal such as nickel supported on a substrate such as alumina.

[0026] The hydrogen used in the hydrogenation of the treated oil may be clean hydrogen. Clean hydrogen is hydrogen produced by an environmentally friendly method, and refers to hydrogen in which the amount of harmful substances such as greenhouse gases released into the atmosphere during the production process is reduced. The carbon intensity in the production of this clean hydrogen is, for example, 3.0 kg-CO ２ / kg-H ２ It may be the following:

[0027] The clean hydrogen may be green hydrogen produced by electrolyzing water, blue hydrogen produced by obtaining a mixture of hydrogen and carbon dioxide through steam reforming (steam methane reforming) or the like, separating the carbon dioxide from the mixture, and storing it underground, or turquoise hydrogen produced by thermally decomposing a gas containing hydrocarbons (e.g., methane), such as natural gas. The hydrogen used in the hydrogenation of processed oil may be a combination of these clean hydrogens. A storage battery may be used to accommodate fluctuations in the power load during hydrogen production. That is, the hydrogen generator 13 may be a device that produces green hydrogen produced by electrolyzing water, a device that produces blue hydrogen produced by obtaining a mixture of hydrogen and carbon dioxide through steam reforming (steam methane reforming) or the like, separating the carbon dioxide from the mixture, and storing it underground, or a device that produces turquoise hydrogen produced by thermally decomposing a gas containing hydrocarbons (e.g., methane), such as natural gas. The hydrogen used in the hydrogenation of processed oil may be a combination of these clean hydrogens. A storage battery may be used to accommodate fluctuations in the power load during hydrogen production. Furthermore, the electricity used to produce these hydrogen may be electricity with low carbon intensity (for example, electricity derived from renewable energy sources).

[0028] By using clean hydrogen to hydrogenate the processed oil, the by-product hydrogen produced when the dehydrogenation reaction is carried out at the second location to manufacture products can also be considered clean hydrogen, making it a high-value-added product. This series of steps is essentially equivalent to the process of transporting crude oil and its derivatives from a first location to a second location and processing the transported crude oil and its derivatives at the second location to manufacture fuel, chemical raw materials, etc., from the transported crude oil and its derivatives. Therefore, the energy consumed for transporting hydrogen is the same energy required in conventional processes, and there is essentially no cost involved. The hydrogen used in the hydrogenation of the processed oil has a carbon strength of 3.0 kg-CO before transportation. ２ / kg-H ２ It may also include hydrogen produced by the following methods.

[0029] Hydrogenated hydrocarbon compounds include chain alkanes such as hexane, octane, decane, dodecane, hexadecane, and octadecane; and cyclic alkanes such as cyclohexane and cyclododecane. Because hydrogenated hydrocarbon compounds are equivalent to hydrocarbon compounds generally available on the market, there is no need to install new facilities for producing hydrogen carriers, as opposed to producing organic hydrides, and existing facilities can be used. To produce a hydrogen carrier, only existing facilities may be used, or new facilities may be used as needed.

[0030] When the treated oil supplied through the transfer pipe L12 contains residue derived from crude oil, the hydrogenated hydrocarbon compounds obtained in the hydrogenation unit 12 may be a hydrocarbon mixture having an ASTM D1160 90% by volume distillation temperature of 360°C or higher and an RVP of 13 psi or lower, and the total mass concentration of aromatic compounds among compounds having an NBP of 300°C or lower contained in the hydrocarbon mixture may be one-tenth or less of the total mass concentration of cyclic alkanes.

[0031] When the treated oil supplied through transfer pipe L12 is naphtha or cracked naphtha, the hydrogenated hydrocarbon compounds obtained in hydrogenation unit 12 may be a hydrocarbon mixture having an ASTM D86 End Boiling Point of 230°C or less, in which the total mass concentration of benzene, toluene, xylene, and ethylbenzene in the hydrocarbon mixture is one-tenth or less of the total mass concentration of cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane, and the total mass concentration of paraffin compounds including hexane and heptane is one-tenth or more of the total mass concentration of the hydrogenated hydrocarbon mixture.

[0032] When the treated oil supplied through the transfer pipe L12 is vacuum gas oil or an equivalent cracked gas oil, the hydrogenated hydrocarbon compound obtained in the hydrogenation unit 12 may be a hydrocarbon mixture having an ASTM D1160 5% by volume distillation temperature of 300°C or higher, and the total mass concentration of aromatic compounds contained in the hydrocarbon mixture may be half or less of the total mass concentration of cyclic alkanes.

[0033] In the hydrogenation unit 12, the processed oil may be subjected to processes such as desulfurization, denitrification, and demetallization. By performing the desulfurization, denitrification, and demetallization processes in the first location, the amount of clean hydrogen obtained in the second location can be increased, and the energy consumed in producing products in the second location can be minimized, thereby maximizing overall energy efficiency.

[0034] In the desulfurization process, sulfur compounds (e.g., thiophene, benzothiophene) are removed from the treated oil. By removing the sulfur compounds from the treated oil in the first location, the amount of clean hydrogen obtained in the second location can be increased and energy efficiency can be maximized. The desulfurization process is carried out, for example, under conditions of a temperature of 300 to 400°C and a pressure of 3 to 10 MPa. In the desulfurization process, sulfur compounds are converted into hydrogen sulfide using a cobalt-molybdenum catalyst or a nickel-molybdenum catalyst. The hydrogen sulfide produced in the desulfurization process may be removed, for example, by absorption in an amine.

[0035] In the denitrification process, nitrogen compounds (e.g., pyridine, quinoline) are removed from the treated oil. By removing the nitrogen compounds from the treated oil in the first location, the amount of clean hydrogen obtained in the second location can be increased and energy efficiency can be maximized. The denitrification process is carried out, for example, under conditions of a temperature of 300 to 450°C and a pressure of 3 to 10 MPa. In the denitrification process, the nitrogen compounds are converted into ammonia using a cobalt-molybdenum catalyst or a nickel-molybdenum catalyst. The ammonia produced in the denitrification process may be removed, for example, by absorption in water.

[0036] In demetallization, metal compounds are removed from the treated oil. By removing the metal compounds from the treated oil in a first location, the amount of clean hydrogen obtained in the second location can be increased and energy efficiency can be maximized. The demetallization is carried out, for example, at a temperature of 350 to 450°C and a pressure of 5 to 15 MPa. In the demetallization, for example, a cobalt-molybdenum catalyst is used to decompose the metal compounds, and then the metal compounds are adsorbed and removed.

[0037] In the hydrogenation unit 12, the treated oil may be brought into contact with high-temperature, high-pressure hydrogen gas and subjected to hydrocracking. Hydrocracking breaks C-C bonds to produce low-molecular-weight hydrocarbons. Hydrocracking may be carried out simultaneously with the hydrogenation of the vacuum gas oil.

[0038] The hydrocracking is carried out at a temperature of 350 to 450° C. and a pressure of 7 to 20 MPa. The hydrocracking may be carried out using, for example, a nickel-molybdenum catalyst or a cobalt-molybdenum catalyst.

[0039] The process up to the hydrogenation performed at the first site can be carried out using existing facilities in the oil plant, and therefore the hydrogenation facility 10 may be an existing facility, or may be a partially or entirely new facility.

[0040] The hydrogenated hydrocarbon compounds produced in the hydrogenation device 12 are transported from a first location to a second location by transportation means T1. The hydrogenated hydrocarbon compounds produced in the hydrogenation device 12 may be temporarily stored in a storage tank before and / or after being transported from the first location to the second location. Examples of transportation means T1 include ships, diesel locomotives, railways, trucks, etc. The hydrogenated hydrocarbon compounds may be transported at room temperature and atmospheric pressure, at room temperature and elevated pressure, at low temperature and atmospheric pressure, or at low temperature and elevated pressure. The first location may be, for example, a clean hydrogen production location. The second location may be a hydrogen consumption location or a location where valuable materials produced from the hydrogenated hydrocarbon compounds are used or consumed. The first location may be a region, country, etc. where the production cost of clean hydrogen is lower than that of the second location. The second location may be a region with high demand for clean hydrogen and a higher consumption of petroleum and petrochemical products produced from the hydrogenated hydrocarbon compounds than the first location, or a region, country, etc. where petroleum and petrochemical production facilities are established.

[0041] The hydrogenated hydrocarbon compound transported by transport means T1 is transported to a dehydrogenation facility 20 at a second location. The dehydrogenation facility 20 includes a dehydrogenation device 21.

[0042] The dehydrogenation unit 21 is a unit that produces and recovers hydrogen from hydrogenated hydrocarbon compounds. The produced and recovered hydrogen may be a main product or a by-product. The dehydrogenation unit 21 may be at least one unit selected from the group consisting of a catalytic reformer, an ethylene production unit, a thermal cracker, and a catalytic cracker, or may be a combination of these units. When the dehydrogenation unit 21 is a catalytic reformer, any one unit selected from the group consisting of an ethylene production unit, a hydrocracker, a thermal cracker, and a catalytic cracker may be provided before the dehydrogenation unit 21.

[0043] When the dehydrogenation unit 21 is a catalytic reforming unit, the hydrogenated hydrocarbon compounds are reformed in the presence of an alumina catalyst carrying platinum, rhenium, or the like at a temperature of 450 to 550°C and a pressure of 0.5 to 7 MPa to produce aromatic compounds and hydrogen. Examples of aromatic compounds produced in the catalytic reforming unit include benzene, toluene, and xylene. This series of steps, in which hydrogenated hydrocarbon compounds from naphtha fraction are produced at a first location and then catalytically reformed at a second location, is equivalent to the process of producing benzene, toluene, xylene, and the like at a second location using crude oil-derived naphtha as a feedstock. Therefore, substantially no energy is consumed for the purpose of transporting the hydrogen carrier. Therefore, no additional costs are incurred for producing hydrogen as a by-product such as benzene at the second location, and hydrogen can be supplied inexpensively in areas of demand.

[0044] When the dehydrogenation unit 21 is an ethylene production unit, the hydrogenated hydrocarbon compounds react with high-temperature steam to produce ethylene, hydrogen, and other by-products. Ethylene production is carried out, for example, under conditions of a temperature of 800 to 900°C and a pressure of 0.1 to 0.3 MPa. This series of steps, in which hydrogenated hydrocarbon compounds of naphtha fraction are produced at a first location and then processed in an ethylene production unit at a second location, is equivalent to the process of producing ethylene at a second location using naphtha derived from crude oil as a feedstock, and therefore, substantially no energy is consumed for the purpose of transporting a hydrogen carrier. Therefore, there is no cost for producing hydrogen as a by-product of ethylene, etc., and hydrogen can be supplied inexpensively in areas where hydrogen is in demand.

[0045] When the dehydrogenation device 21 is a thermal cracking device, the hydrogenated hydrocarbon compound containing the residue is decomposed at high temperatures to produce hydrogen and carbon materials such as hydrocarbon gases and solid carbon. Thermal decomposition is performed, for example, at a temperature of 480 to 800°C and a pressure of 0.1 to 0.3 MPa. Examples of hydrocarbon gases include methane, ethane, propane, ethylene, and propylene. Carbon materials are distributed in the market as high-value-added products compared to hydrogenated hydrocarbon compounds, improving the profitability of the thermal cracking facility. Furthermore, the series of processes from producing hydrogenated hydrocarbon compounds containing the residue at a first location to producing carbon materials in a thermal cracking facility at a second location are equivalent to the processes performed to produce carbon materials at a second location using crude oil-derived residues as a feedstock. Therefore, substantially no energy is consumed for the transportation of hydrogen carriers. Therefore, there is no cost for producing hydrogen as a by-product of carbon materials, allowing hydrogen to be supplied inexpensively in areas of demand.

[0046] When the dehydrogenation device 21 is a catalytic cracking device, the hydrogenated hydrocarbon compound containing the residue is catalytically cracked to produce hydrogen, hydrocarbon gas, and a hydrocarbon mixture that can be used as gasoline or diesel feedstock. Catalytic cracking is performed, for example, at a temperature of 500 to 700°C and a pressure of 0.1 to 0.5 MPa. Examples of catalysts include zeolite-based catalysts, platinum-based catalysts, and palladium-based catalysts. Examples of hydrocarbon gases include methane, ethane, propane, ethylene, and propylene. Furthermore, the series of processes from producing hydrogenated hydrocarbon compounds containing the residue at a first location to producing a carbon material using catalytic cracking equipment at a second location is equivalent to the process performed to produce a hydrocarbon mixture that can be used as gasoline or diesel feedstock at a second location using crude oil-derived residue as a feedstock. Therefore, substantially no energy is consumed for the transportation of a hydrogen carrier. Therefore, there is no cost for producing hydrogen as a by-product of the hydrocarbon mixture that can be used as gasoline or diesel feedstock, allowing hydrogen to be supplied inexpensively in areas with a demand for hydrogen.

[0047] A transfer pipe L21 and a transfer pipe L22 are connected to the dehydrogenation device 21. The transfer pipe L21 transfers hydrogen, and the transfer pipe L22 transfers hydrocarbon compounds produced by dehydrogenation (e.g., aromatic compounds produced by a catalytic reforming reaction).

[0048] A separation device may be provided downstream of the dehydrogenation device 21 in order to increase the purity of the hydrogen and / or hydrocarbon compounds discharged from the dehydrogenation device 21. For example, when the dehydrogenation device 21 is at least one device selected from the group consisting of a catalytic reformer, an ethylene production device, a thermal cracking device, and a catalytic cracking device, at least one separation device selected from the group consisting of a membrane separation device, an adsorption separation device, and a cryogenic separation device may be provided downstream of the dehydrogenation device 21 in order to increase the purity of the hydrogen. Note that, conventionally, when the dehydrogenation device is a device other than a catalytic reformer, the amount of hydrogen obtained from the hydrogen carrier is relatively small, and therefore a membrane separation device, an adsorption separation device, and a cryogenic separation device have not been provided downstream of the dehydrogenation device.

[0049] The hydrogen obtained from the dehydrogenation device 21 is CO ２ and CO obtained by the reverse shift reaction with CO to obtain synthetic crude oil (hydrocarbon compounds) by the Fischer-Tropsch process. ２ and the Sabatier reaction to obtain methane, or the Haber-Bosch reaction to obtain ammonia, or CO ２ Methanol may be obtained by reacting CO with CO obtained by the reverse shift reaction with CO ２ Methanol may be obtained by reacting CO ２ may be procured from outside the dehydrogenation facility 20 or may be recovered in the process of the dehydrogenation facility 20.

[0050] The dehydrogenation device 21 may be supplied with the hydrogenated hydrocarbon compounds transported via the hydrogenation device (the hydrogenated hydrocarbon compounds transported by transportation means T1) and other hydrogenated hydrocarbon compounds other than the transported hydrogenated hydrocarbon compounds, and the transported hydrogenated hydrocarbon compounds and the other hydrogenated hydrocarbon compounds may be dehydrogenated simultaneously in the dehydrogenation device 21. Furthermore, when hydrogen is recovered from the transported hydrogenated hydrocarbon compounds and the other hydrogenated hydrocarbon compounds supplied to the dehydrogenation device 21, the mass proportion of hydrogen generated from the transported hydrogenated hydrocarbon compounds may be calculated, and the recovered hydrogen may be divided based on this mass proportion. As a result, for example, when hydrogenation in the hydrogenation device 12 is performed using clean hydrogen, the carbon intensity of part of the hydrogen recovered in the dehydrogenation device 21 will be sufficiently low, and the hydrogen can be divided into hydrogen with a low carbon intensity (clean hydrogen) and the other hydrogen (gray hydrogen). The mass proportion of hydrogen generated from the transported hydrogenated hydrocarbon compounds in the recovered hydrogen can be calculated based on the flow rates and compositions of each component flowing into and out of the dehydrogenation device 21, the reaction rates of each reaction occurring in the dehydrogenation device 21, etc.

[0051] If the second location is a hydrogen consuming area, producing hydrogen at the second location eliminates the need for extra energy and costs for transporting hydrogen. Also, if clean hydrogen is used in the hydrogenation in the hydrogenation device 12, the carbon intensity of the hydrogen recovered in the dehydrogenation device 21 will be sufficiently low, and the hydrogen recovered at the second location will be clean hydrogen.

[0052] The hydrocarbon compounds transported through the transfer pipe L22 are higher value-added products than the hydrogenated hydrocarbon compounds, and are therefore consumed at the second location. Therefore, there is no need to transport the hydrocarbon compounds back to the first location, resulting in less energy loss. Furthermore, there is no need to repeatedly use the hydrogenated hydrocarbon compounds as hydrogen carriers, so there is no deterioration or loss of the hydrogen carrier.

[0053] The process up to dehydrogenation performed at the second location can be carried out using existing equipment in the hydrogen production plant, so dehydrogenation equipment 20 may be an existing equipment, or may be a partially or entirely new equipment.

[0054] [Method for Producing Hydrogen] A method for finally producing hydrogen from a mixture containing aromatic compounds and unsaturated hydrocarbon compounds using the hydrogen production facility 100 will be described. That is, one embodiment of the present invention is a method for producing hydrogen that includes at least the following steps. For the following hydrogen production method, reference can be made to the description of the hydrogen production facility 100 as appropriate. (a) A hydrogenation step in which a mixture containing aromatic compounds and unsaturated hydrocarbon compounds is subjected to hydrogenation and a treatment including at least one treatment selected from the group consisting of desulfurization, denitrification, demetallization, and hydrocracking in an environment above 250°C to obtain a hydrogenated hydrocarbon compound. (b) A transport step in which the hydrogenated hydrocarbon compound obtained in step (a) is transported from a first location to a second location. (c) A dehydrogenation step in which hydrogen is recovered from the hydrogenated hydrocarbon compound transported in step (b).

[0055] <Step (a)> Step (a) is a step of subjecting a mixture containing aromatic compounds and unsaturated hydrocarbon compounds to hydrogenation and at least one treatment selected from the group consisting of desulfurization, denitrification, demetallization, and hydrocracking in an environment above 250°C to obtain hydrogenated hydrocarbon compounds. In step (a), the mixture containing aromatic compounds and unsaturated hydrocarbon compounds may be derived from crude oil or naphtha. In step (a), the aromatic compounds may be monocyclic aromatic compounds or polycyclic aromatic compounds. In step (a), the unsaturated hydrocarbon compounds may be olefins.

[0056] In step (a), the hydrogen used for hydrogenation may be clean hydrogen. Therefore, the process may further include at least one step selected from the group consisting of step A, which electrolyzes water to obtain hydrogen, step B, which includes steam reforming methane to produce hydrogen and carbon dioxide and separating and storing the produced carbon dioxide underground, and step C, which thermally decomposes gas containing hydrocarbons (e.g., methane) such as natural gas to obtain hydrogen, before step (a), and step (a) may be a step in which hydrogenation is performed using the hydrogen obtained in any of steps A to C.

[0057] <Step (b)> Step (b) is a step of transporting the hydrogenated hydrocarbon compound from a first location to a second location. Step (b) may include temporarily storing the hydrogenated hydrocarbon compound in a storage tank container before and / or after transporting the hydrogenated hydrocarbon compound from the first location to the second location. The first location may be, for example, a clean hydrogen production location. The second location may be a hydrogen consumption location, or a location where valuable materials produced from the hydrogenated hydrocarbon compound are used or consumed. The first location may be a region, country, etc. where the production cost of clean hydrogen is lower than that of the second location. The second location may be a region, country, etc. where there is a high demand for clean hydrogen and where there is a higher consumption of petroleum and petrochemical products produced from the hydrogenated hydrocarbon compound than that of the first location, or where petroleum and petrochemical production facilities are in place.

[0058] <Step (c)> The step (c) is a step of recovering hydrogen from the transported hydrogenated hydrocarbon compound. The step (c) may be a step performed using at least one apparatus selected from the group consisting of a catalytic reforming apparatus, an ethylene production apparatus, a thermal cracking apparatus, and a catalytic cracking apparatus.

[0059] When the step (c) is carried out using at least one apparatus selected from the group consisting of an ethylene production apparatus, a thermal cracking apparatus, and a catalytic cracking apparatus, the method for producing hydrogen may further include, after the step (c), a separation step of purifying the hydrogen recovered in the step (c) by at least one separation treatment selected from the group consisting of membrane separation, adsorption separation, and cryogenic separation.

[0060] When step (c) is a step of recovering hydrogen from the transported hydrogenated hydrocarbon compounds and other hydrogenated hydrocarbon compounds other than the transported hydrogenated hydrocarbon compounds, the method may further include a calculation step of calculating the mass proportion of hydrogen generated from the transported hydrogenated hydrocarbon compounds among the recovered hydrogen, and a step of dividing the recovered hydrogen based on the mass proportion after the dehydrogenation step.

[0061] The step (c) may be a step of producing a hydrocarbon mixture containing hydrogen and at least one member selected from the group consisting of ethylene, propylene, benzene, toluene, xylene, and solid carbon.

[0062] Another embodiment of the present invention is a hydrogen production method that does not include the above-mentioned step (a), but includes steps (b) and (c). For example, in a hydrogen production method in which step (a) is not performed but steps (b) and (c) are performed in a certain country, step (a) may be performed in another country. That is, a hydrogen production method according to another embodiment includes at least the following steps. In the hydrogen production method according to another embodiment, hydrogen is produced using the equipment on the second location side of Figure 1. (b) A transporting step of transporting a hydrogenated hydrocarbon compound from a first location to a second location. (c) A dehydrogenation step of recovering hydrogen from the hydrogenated hydrocarbon compound transported in step (b).

[0063] Another embodiment of the present invention is a method for treating a hydrocarbon mixture that does not include the above-mentioned step (c), but does include step (a) and step (b). For example, this method for treating a hydrocarbon mixture may be performed in a certain country, but step (c) is not performed, and step (c) may be performed in another country. That is, the method for treating a hydrocarbon mixture according to another embodiment includes at least the following steps. In the method for treating a hydrocarbon mixture according to another embodiment, the hydrocarbon mixture is treated using the equipment at the first location in Figure 1. (a) A hydrogenation step in which a mixture containing aromatic compounds and unsaturated hydrocarbon compounds is subjected to hydrogenation and at least one treatment selected from the group consisting of desulfurization, denitrification, demetallization, and hydrocracking in an environment above 250°C to obtain hydrogenated hydrocarbon compounds. (b) A transportation step in which the hydrogenated hydrocarbon compounds obtained in step (a) are transported from the first location to a second location.

[0064] 10...hydrogenation equipment, 11...treatment device, 12...hydrogenation device, 13...hydrogen generation device, 20...dehydrogenation equipment, 21...dehydrogenation device, T1...transportation means, 100...hydrogen production equipment

Claims

1. A method for producing hydrogen, comprising: a hydrogenation step in which a mixture containing aromatic compounds and unsaturated hydrocarbon compounds is subjected to hydrogenation and at least one treatment selected from the group consisting of desulfurization, denitrification, demetallization, and hydrocracking in an environment of above 250°C to obtain hydrogenated hydrocarbon compounds; a transport step in which the hydrogenated hydrocarbon compounds are transported from a first location to a second location; and a dehydrogenation step in which hydrogen is recovered from the transported hydrogenated hydrocarbon compounds.

2. The method for producing hydrogen according to claim 1, wherein the hydrogenation is carried out using clean hydrogen.

3. The method for producing hydrogen according to claim 1 or 2, further comprising, prior to the hydrogenation step, at least one step selected from the group consisting of: step A of obtaining hydrogen by electrolyzing water; step B of steam reforming methane to produce hydrogen and carbon dioxide and separating the produced carbon dioxide and storing it underground; and step C of obtaining hydrogen by thermal decomposition of a gas containing methane, wherein the hydrogenation step is a step of performing hydrogenation using the hydrogen obtained in any of steps A to C.

4. The method for producing hydrogen according to claim 1 or 2, wherein the unsaturated hydrocarbon compound is an olefin.

5. The method for producing hydrogen according to claim 1 or 2, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 90% by volume distillation temperature of 360°C or higher and an RVP of 13 psi or lower, and the total mass concentration of aromatic compounds among compounds having an NBP of 300°C or lower contained in the hydrocarbon mixture is one-tenth or less of the total mass concentration of cyclic alkanes.

6. The method for producing hydrogen according to claim 1 or 2, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D86 End Boiling Point of 230°C or less, the total mass concentration of benzene, toluene, xylene, and ethylbenzene is one-tenth or less of the total mass concentration of cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane in the hydrocarbon mixture, and the total mass concentration of paraffin compounds including hexane and heptane is one-tenth or more of the total mass concentration of the hydrogenated hydrocarbon mixture.

7. The method for producing hydrogen according to claim 1 or 2, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 5% by volume distillation temperature of 300°C or higher, and the total mass concentration of aromatic compounds contained in the hydrocarbon mixture is half or less of the total mass concentration of cyclic alkanes.

8. The method for producing hydrogen according to claim 1 or 2, wherein the dehydrogenation step is carried out using at least one apparatus selected from the group consisting of a catalytic reformer, an ethylene production apparatus, a thermal cracker, and a catalytic cracker.

9. The method for producing hydrogen according to claim 1 or 2, wherein the dehydrogenation step is carried out using at least one apparatus selected from the group consisting of an ethylene production apparatus, a thermal cracking apparatus, and a catalytic cracking apparatus, and further comprising, after the dehydrogenation step, a separation step of purifying the hydrogen by at least one separation process selected from the group consisting of membrane separation, adsorption separation, and cryogenic separation.

10. A method for producing hydrogen according to claim 1 or 2, wherein the dehydrogenation step is a step of recovering hydrogen from the transported hydrogenated hydrocarbon compound and other hydrogenated hydrocarbon compounds other than the transported hydrogenated hydrocarbon compound, and further comprising: a calculation step of calculating a mass proportion of hydrogen generated from the transported hydrogenated hydrocarbon compound among the recovered hydrogen; and a step of dividing the recovered hydrogen based on the mass proportion after the dehydrogenation step.

11. The method for producing hydrogen according to claim 1 or 2, wherein the dehydrogenation step is a step of producing a hydrocarbon mixture containing, together with the hydrogen, at least one member selected from the group consisting of ethylene, propylene, benzene, toluene, xylene, and solid carbon.

12. A method for treating a hydrocarbon mixture, comprising: a hydrogenation step of subjecting a mixture containing aromatic compounds and unsaturated hydrocarbon compounds to hydrogenation and at least one treatment selected from the group consisting of desulfurization, denitrification, demetallization, and hydrocracking in an environment of above 250°C to obtain hydrogenated hydrocarbon compounds; and a transport step of transporting the hydrogenated hydrocarbon compounds from a first location to a second location.

13. The method for treating a hydrocarbon mixture according to claim 12, wherein the hydrogenation is carried out using clean hydrogen.

14. The method for treating a hydrocarbon mixture according to claim 12 or 13, further comprising, prior to the hydrogenation step, at least one step selected from the group consisting of: step A of obtaining hydrogen by electrolyzing water; step B of steam reforming methane to produce hydrogen and carbon dioxide and separating the produced carbon dioxide and storing it underground; and step C of obtaining hydrogen by thermal decomposition of a gas containing methane, wherein the hydrogenation step is a step of carrying out hydrogenation using the hydrogen obtained in any of steps A to C.

15. The method for treating a hydrocarbon mixture according to claim 12 or 13, wherein the unsaturated hydrocarbon compound is an olefin.

16. The method for treating a hydrocarbon mixture according to claim 12 or 13, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 90% by volume distillation temperature of 360°C or higher and an RVP of 13 psi or lower, and the total mass concentration of aromatic compounds among compounds having an NBP of 300°C or lower contained in the hydrocarbon mixture is one-tenth or less of the total mass concentration of cyclic alkanes.

17. The method for treating a hydrocarbon mixture according to claim 12 or 13, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D86 End Boiling Point of 230°C or less, the total mass concentration of benzene, toluene, xylene, and ethylbenzene is one-tenth or less of the total mass concentration of cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane in the hydrocarbon mixture, and the concentration of paraffin compounds including hexane and heptane is one-tenth or more of the total mass concentration of the hydrogenated hydrocarbon mixture.

18. A method for treating a hydrocarbon mixture according to claim 12 or 13, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having a 5% by volume distillation temperature according to ASTM D1160 of 300°C or higher, and the total mass concentration of aromatic compounds contained in the hydrocarbon mixture is half or less of the total mass concentration of cyclic alkanes.

19. A method for producing hydrogen, comprising: a transporting step of transporting a hydrogenated hydrocarbon compound from a first location to a second location; and a dehydrogenation step of recovering hydrogen from the transported hydrogenated hydrocarbon compound.

20. The method for producing hydrogen according to claim 19, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D1160 90% by volume distillation temperature of 360°C or higher and an RVP of 13 psi or lower, and the total mass concentration of aromatic compounds among compounds having an NBP of 300°C or lower contained in the hydrocarbon mixture is one-tenth or less of the total mass concentration of cyclic alkanes.

21. The method for producing hydrogen according to claim 19, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having an ASTM D86 End Boiling Point of 230°C or less, the total mass concentration of benzene, toluene, xylene, and ethylbenzene is one-tenth or less of the total mass concentration of cyclohexane, methylcyclohexane, dimethylcyclohexane, and ethylcyclohexane in the hydrocarbon mixture, and the total mass concentration of paraffin compounds including hexane and heptane is one-tenth or more of the total mass concentration of the hydrogenated hydrocarbon mixture.

22. A method for producing hydrogen according to claim 19, wherein the hydrogenated hydrocarbon compound is a hydrocarbon mixture having a 5% by volume distillation temperature according to ASTM D1160 of 300°C or higher, and the total mass concentration of aromatic compounds contained in the hydrocarbon mixture is half or less of the total mass concentration of cyclic alkanes.

23. The method for producing hydrogen according to any one of claims 19 to 22, wherein the dehydrogenation step is carried out using at least one apparatus selected from the group consisting of a catalytic reformer, an ethylene production apparatus, a thermal cracker, and a catalytic cracker.

24. The method for producing hydrogen according to any one of claims 19 to 22, wherein the dehydrogenation step is carried out using at least one type of apparatus selected from the group consisting of an ethylene production apparatus, a thermal cracking apparatus, and a catalytic cracking apparatus, and further comprising, after the dehydrogenation step, a separation step of purifying the hydrogen by at least one type of separation treatment selected from the group consisting of membrane separation, adsorption separation, and cryogenic separation.

25. A method for producing hydrogen according to any one of claims 19 to 22, wherein the dehydrogenation step is a step of recovering hydrogen from the transported hydrogenated hydrocarbon compound and a hydrogenated hydrocarbon compound other than the transported hydrogenated hydrocarbon compound, and further comprising: a calculation step of calculating a mass ratio of hydrogen generated from the transported hydrogenated hydrocarbon compound out of the recovered hydrogen; and a step of dividing the recovered hydrogen based on the mass ratio after the dehydrogenation step.

26. A method for producing hydrogen according to any one of claims 19 to 22, wherein the dehydrogenation step is a step for producing a hydrocarbon mixture containing, together with the hydrogen, at least one member selected from the group consisting of ethylene, propylene, benzene, toluene, xylene, and solid carbon.

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