Clean liquid fuel hydrogen carrier process

Abstract

The present disclosure, in one embodiment, refers to a process for producing and transporting clean hydrogen fuel. The process may include hydrotreating, hydrocracking, or both hydrotreating and hydrocracking an aromatic feedstock under conditions to obtain a liquid hydrocarbon fuel. The liquid hydrocarbon fuel is hydrogenated to obtain a hydrogen-rich fuel that is transported to a dehydrogenation facility, which may also be at or near a hydrogen station. The hydrogen-rich fuel is used to obtain hydrogen and a second liquid hydrocarbon fuel.

Description

【Technical Field】 【0001】 Cross - reference to Related Applications This application claims priority to U.S. Patent Application No. 17 / 516,049, filed November 1, 2021, the entire disclosure of which is incorporated herein by reference. 【0002】 This disclosure relates to a clean liquid fuel hydrogen carrier process. 【Background Art】 【0003】 Hydrogen is widely considered a clean fuel because, for example, when consumed in a fuel cell, water is the only by - product. Hydrogen can be produced from a variety of processes and from readily available resources including, for example, natural gas, biomass, and nuclear power. Thus, hydrogen can potentially be used in automotive and power generation applications. Unfortunately, the world is mainly lagging in the introduction of hydrogen applications because storing and transporting it from its production sites, for example, to hydrogen gas stations, is very costly. 【0004】 What is needed is a new way to produce and / or transport hydrogen. Such a method would be advantageous if it were cost - effective. Also, it would be advantageous if such a method could be adopted using existing refinery processes and equipment. It would be even more advantageous if the produced hydrogen had a relatively low amount of impurities such as sulfur, light hydrocarbon gases such as C1 - C4 hydrocarbons, and / or CO. Additionally or alternatively, it would be desirable if the new process did not require, for example, recycling of hydrogen carriers and / or if hydrogen could be transported using, for example, existing distribution infrastructure (such as transport ships, trucks, etc.). 【0005】 This application relates to a novel method for producing and / or transporting hydrogen. Advantageously, the method may be cost-effective and / or may be employed using existing refinery processes and equipment. Furthermore, the hydrogen produced may contain relatively small amounts of impurities such as sulfur. Also, in many embodiments, the process does not require the recycling of hydrogen carriers, which would otherwise be sold as a product. Moreover, the hydrogen produced by the method described herein may be transported, for example, using existing distribution infrastructure. 【0006】 This application relates in one embodiment to a process comprising hydrogenating, hydrocracking, or both hydrogenating and hydrocracking an aromatic feedstock under conditions to obtain a liquid hydrocarbon fuel containing less than about 30 ppm of sulfur and about 13.5% by weight of hydrogen. The liquid hydrocarbon fuel is hydrogenated under conditions to obtain a hydrogen-rich fuel containing less than about 5 ppm of sulfur and more than about 13.5% by weight of hydrogen. The hydrogen-rich fuel is transported to a dehydrogenation facility, where it is dehydrogenated under conditions to obtain a second liquid hydrocarbon fuel containing hydrogen and less than about 5 ppm of sulfur and less than 13.5% by weight of hydrogen. 【0007】 In another embodiment, the application relates to a process comprising hydrogenating an aromatic feedstock containing less than 50 ppm of sulfur under conditions to obtain a hydrogen-rich fuel containing less than 1 ppm of sulfur and more than 13.5% by weight of hydrogen. The hydrogen-rich fuel is transported to a dehydrogenation facility, where it is dehydrogenated under conditions to obtain a second liquid hydrocarbon fuel containing hydrogen and less than 5 ppm of sulfur and less than 13.5% by weight of hydrogen. 【0008】 These and other purposes, features, and advantages of the exemplary embodiments of this disclosure will become apparent when read in conjunction with the appended claims and the following detailed description of the exemplary embodiments of this disclosure. 【0009】 Various embodiments of this disclosure, along with further objectives and advantages, can be best understood by referring to the following description in conjunction with the accompanying drawings. [Brief explanation of the drawing] 【0010】 [Figure 1] This illustrates typical production and delivery of hydrogen to hydrogen stations or other desired facilities. [Modes for carrying out the invention] 【0011】 The following description of embodiments provides non-limiting representative examples to illustrate the features and teachings of different embodiments of the Invention. It should be recognized that the embodiments described are implementable separately or in combination with other embodiments from the description of embodiments. Those skilled in the art, reviewing the description of embodiments, should be able to learn and understand the different described embodiments of the Invention. The description of embodiments should facilitate understanding of the Invention to the extent that, within the scope of the knowledge of those skilled in the art who have read the description of embodiments, other implementations should be understood to be consistent with the application of the Invention. 【0012】 definition Unless otherwise specified, the following terms, technical terms, and definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from IUPAC Compendium of Chemical Terminology, 2nd ed (1997) may be applied, provided that such definition does not conflict with any other disclosure or definition applicable herein, or obscure or invalidate any claim to which such definition applies. If any definition or usage shown in any document incorporated herein by reference conflicts with any definition or usage shown herein, the definition or usage shown herein shall prevail. 【0013】 "Processed," "processed," "upgraded," "upgraded," and "upgraded" describe a hydrogenated or hydrogenated feedstock, or the resulting material or crude product, which, when used in conjunction with an oil feedstock, has a reduction in the molecular weight of the feedstock, a reduction in the boiling point range of the feedstock, a reduction in the concentration of asphaltenes, a reduction in the concentration of hydrocarbon free radicals, and / or a reduction in the amount of impurities such as sulfur, nitrogen, oxygen, halides, and metals. 【0014】 Hydrogenation refers to the process of contacting carbonaceous raw materials with hydrogen and a catalyst at higher temperatures and pressures for the purpose of removing undesirable impurities and / or converting the raw materials into desired products. Examples of hydrogenation processes include hydrocracking, hydrogenation, catalytic dewaxing, and hydrogenation finishing. 【0015】 Hydrocracking refers to the process in which hydrogenation and dehydrogenation are involved in the breakdown / fragmentation of hydrocarbons, for example, converting heavier hydrocarbons into lighter hydrocarbons, or converting aromatic compounds and / or cycloparaffins (naphthenes) into acyclic branched paraffins. 【0016】 Hydrogenation refers to a process that converts a sulfur and / or nitrogen-containing hydrocarbon feedstock into hydrocarbon products with reduced sulfur and / or nitrogen content, typically in conjunction with hydrocracking, and produces hydrogen sulfide and / or ammonia (respectively) as byproducts. Such processes or steps carried out in the presence of hydrogen include hydrodesulfurization, hydrodenitrification, hydrodemetallation, and / or hydrodearomatization of components (e.g., impurities) of the hydrocarbon feedstock, and / or hydrogenation of unsaturated compounds in the feedstock. Depending on the type of hydrogenation and reaction conditions, improvements in viscosity, viscosity index, saturation content, low-temperature properties, volatility, and depolarization may be observed in the products of the hydrogenation process. 【0017】 The terms "hydrocarbonaceous," "hydrocarbon," and similar terms refer to compounds containing only carbon and hydrogen atoms. If a specific group is present in a hydrocarbon, other identifiers may be used to indicate its presence (for example, halogenated hydrocarbons indicate the presence of one or more halogen atoms replacing an equal number of hydrogen atoms in the hydrocarbon). 【0018】 The term “periodic table” refers to the version of the IUPAC periodic table of elements as of June 22, 2007, and the numbering scheme for the periodic table groups is as described in Chem.Eng.News, 63(5), 26-27 (1985). “Group 2” refers to the IUPAC Group 2 elements, for example, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and combinations thereof, in their elemental, compound, or ionic form. “Group 6” refers to the IUPAC Group 6 elements, for example, chromium (Cr), molybdenum (Mo), and tungsten (W). “Group 7” refers to the IUPAC Group 7 elements, for example, manganese (Mn), rhenium (Re), and combinations thereof, in their elemental, compound, or ionic form. "Group 8" refers to the IUPAC Group 8 elements, such as iron (Fe), ruthenium (Ru), osmium (Os), and combinations thereof, in their elemental, compound, or ionic form. "Group 9" refers to the IUPAC Group 9 elements, such as cobalt (Co), rhodium (Rh), iridium (Ir), and combinations thereof, in their elemental, compound, or ionic form. "Group 10" refers to the IUPAC Group 10 elements, such as nickel (Ni), palladium (Pd), platinum (Pt), and combinations thereof, in their elemental, compound, or ionic form. "Group 14" refers to the IUPAC Group 14 elements, such as germanium (Ge), tin (Sn), lead (Pb), and combinations thereof, in their elemental, compound, or ionic form. The term "support," particularly when used in the context of "catalyst support," refers to a conventional material, typically a solid with a high surface area, to which a catalytic material is attached. The support material may be inert, or it may participate in the catalytic reaction, and it may be porous or non-porous.Typical catalyst supports include materials obtained by adding various types of carbon, alumina, silica, and silica-alumina, such as amorphous silicaaluminate, zeolites, alumina-boria, silica-alumina-magnesia, silica-alumina-titania, and other zeolites and other composite oxides. 【0019】 A "molecular sieve" refers to a material having pores of uniform molecular size within a framework structure, where, depending on the type of molecular sieve, only certain molecules can access the pore structure of the molecular sieve, while other molecules are excluded, for example, due to their molecular size and / or reactivity. The terms "molecular sieve" and "zeolite" are synonymous and include (a) intermediates and (b) the final or desired molecular sieve, as well as molecular sieves produced by (1) direct synthesis or (2) post-crystallization treatment (secondary modification). Secondary synthesis methods allow for the synthesis of the desired material from intermediate materials by heteroatomic lattice substitution or other methods. For example, aluminosilicates can be synthesized from intermediate borosilicates by post-crystallization heteroatomic lattice substitution of Al for B. Such techniques are known, for example, as described in U.S. Patent No. 6,790,433. Zeolites, crystalline aluminophosphates, and crystalline silicoaluminophosphates are typical examples of molecular sieves. 【0020】 In this disclosure, compositions and methods or processes are often described in terms of "including" various components or steps, but unless otherwise specified, compositions and methods may also "essentially consist of" or "consist of" various components or steps. 【0021】 The terms “a,” “an,” and “the” are intended to include multiple substitutes, e.g., at least one. For example, the disclosure of “transition metal” or “alkali metal” means, unless otherwise specified, to include one transition metal or alkali metal, or a mixture or combination of multiple transition metals or alkali metals. 【0022】 All numerical values ​​in the detailed description and claims of this specification are modified by values ​​indicated as "approximately" or "about," taking into account experimental errors and variations that can be expected by those skilled in the art. 【0023】 General process The process of this application varies depending on the available feedstock, equipment, and desired product. While many different feedstocks can be used, the process typically utilizes aromatic feedstocks from refinery aromatic streams, i.e., light cycle oil from a fluid catalytic cracking process stream. The properties of aromatic feedstocks such as light cycle oil may vary depending on the origin of the stream and its previous treatment (if any). Other aromatic-rich hydrocarbons include diesel products from cokers, residual desulfurization (RDS), etc. In one embodiment, the aromatic-rich hydrocarbon feedstock contains at least 50% cyclic compounds (e.g., aromatics and naphthenes). In one embodiment, it contains at least 60% cyclic compounds. Preferably, it contains at least 65% cyclic compounds. That is, the preferred density, sulfur content, cetane number, boiling point, aromatic content, and other properties of aromatic feedstocks such as light cycle oil may vary depending on the feedstock. The preferred density of aromatic feedstocks varies, and in the case of light cycle oil or other aromatic feedstocks, the density is about 900 to about 960 kg / m³. 3 (Approximately 56-60 lbs / ft) 3) It can be. Depending on the nature of the aromatic feedstock, it may contain sulfur or sulfur compounds. In some embodiments, a lower sulfur content may be desirable, but light cycle oil or other aromatic feedstocks can contain more than about 1000 ppm, or more than about 2000 ppm, or even more than about 5,000 ppm. In some embodiments, light cycle oil or other aromatic feedstocks can contain nitrogen or nitrogen compounds. In some embodiments, light cycle oil or other aromatic feedstocks can contain a cetane number greater than about 20, or greater than about 25, up to about 30, or up to about 35, or up to about 40. The boiling point of light cycle oil or other aromatic feedstocks varies depending on the particular process used, but in some embodiments, the boiling point can be less than about 430 °C (about 806 °F) or less than about 400 °C (about 752 °F) according to ASTM D - 86. 【0024】 Hydrotreating / Hydrocracking The aromatic feedstock can be subjected to hydrotreating, hydrocracking, or both hydrotreating and hydrocracking under conditions to obtain a clean liquid hydrocarbon fuel that can meet the specifications for use as, for example, diesel or aviation fuel. The properties of the resulting liquid hydrocarbon fuel can vary, but often contain less than about 60 ppm, less than about 50 ppm, or less than about 40 ppm, or less than about 30 ppm, or less than about 20 ppm of sulfur, and / or less than about 10 ppm, or less than about 5 ppm, or less than 10 ppm of N, or less than about 13.5 wt% of hydrogen. The liquid hydrocarbon fuel can, in some cases, be referred to as a clean liquid HC fuel as shown in Figure 1. In some cases, the aromatic feedstock already contains properties sufficiently similar to the desired liquid hydrocarbon fuel, such as less than 50 ppm of sulfur, so hydrotreating and / or hydrocracking may not be necessary. In such cases, the aromatic feedstock may be hydrogenated directly without hydrotreating and / or hydrocracking of the liquid hydrocarbon fuel. 【0025】 Typically, for either hydrotreating or hydrocracking, the reaction temperature is from about 250 °C (482 °F) to about 500 °C (932 °F), the pressure is from about 3.5 MPa (500 psi) to about 24.2 MPa (3,500 psi), and the feed rate is from about 0.1 to about 20 hr -1 (oil volume / catalyst volume hr). The hydrogen recycle rate generally ranges from about 350 standard liters H2 / kg oil (2,310 standard cubic feet / barrel; SCF / B) to 1,780 standard liters H2 / kg oil (11,750 standard cubic feet / barrel). Preferred reaction temperatures can range from about 340 °C (644 °F) to about 455 °C (851 °F). Preferred total reaction pressures can range from about 7.0 MPa (1,000 psi) to about 20.7 MPa (3,000 psi). The reactor can also be operated in any suitable catalyst bed configuration mode, such as a fixed bed, slurry bed, or ebulating bed, but a fixed bed, co-current downflow is often utilized. 【0026】 In one embodiment, the process is operated by introducing a feedstock that may contain high levels of sulfur and nitrogen into a first hydrotreating reaction stage and converting a substantial amount of the sulfur and nitrogen in the feed to an inorganic form, the primary purpose of this step being to reduce the sulfur content of the feedstock. Of course, if hydrotreating is not required, the feed may be passed directly to hydrocracking or hydrotreating. 【0027】 The hydrogenation process is typically carried out in one or more reaction zones (catalyst beds) in the presence of hydrogen and a hydrogenation catalyst. The conditions used are suitable for hydrodesulfurization and / or denitrification, depending on the feed characteristics. When hydrocracking is used, the product stream is passed through a hydrocracking step that affects the boiling range conversion. If desired, the stream of hydrogenated and / or hydrocrackled liquid hydrocarbons may be passed through a separator such as a distillation column, along with the hydrogenation gas and other hydrogenation / hydrocracking reaction products that may contain hydrogen sulfide and ammonia, to remove hydrogen, light end, and inorganic nitrogen and hydrogen sulfide from the hydrocrackled liquid product stream. The recycled hydrogen gas can be washed to remove ammonia and subjected to an amine scrub to remove hydrogen sulfide to improve the purity of the recycled hydrogen and reduce the sulfur level of the product. If desired, a bed of hydrodesulfurization catalyst, such as a bulk polymetallic catalyst, may be provided at some point before hydrogenation. 【0028】 Hydrogenation catalyst The conventional hydrogenation catalyst may be any suitable catalyst. Typical conventional hydrogenation catalysts include a catalyst comprising at least one group VIII metal, preferably Fe, Co, or Ni, more preferably Co and / or Ni, and most preferably Ni, and at least one group VIB metal, preferably Mo or W, more preferably Mo, on a relatively high surface area support material, preferably alumina. Other suitable hydrogenation desulfurization catalyst supports include zeolites, amorphous silica-alumina, and titania-alumina. Preferably, a noble metal catalyst may also be used when the noble metal is selected from Pd and Pt. Two or more hydrogenation desulfurization catalysts may be used on different beds in the same reaction vessel. The group VIII metal is typically present in an amount ranging from about 2 to about 20% by weight, preferably about 4 to about 12% by weight. The group VIB metal is typically present in an amount ranging from about 5 to about 50% by weight, preferably about 10 to about 40% by weight, and more preferably about 20 to about 30% by weight. All metal weight percentages are based on the weight of the catalyst. 【0029】 Hydrocracking catalyst Examples of conventional hydrocracking catalysts that may be used include nickel, nickel-cobalt-molybdenum, nickel-cobalt-tungsten, nickel-molybdenum-tungsten, cobalt-molybdenum and nickel-tungsten, and / or nickel-molybdenum, with the latter two being preferred. Non-limiting examples of noble metal catalysts include those based on platinum and / or palladium. Porous support materials that can be used for both noble metal and non-noble metal catalysts include refractory oxide materials such as alumina, silica, alumina-silica, diatomaceous earth (kieselguhr), magnesia, or zirconia, with alumina, silica, and alumina-silica being preferred and most common. Zeolite supporters, particularly large-pore faujasite such as USY and beta-zeolite, may also be used. 【0030】 Numerous hydrocracking catalysts are available from different commercial suppliers and may be used according to the requirements of the supplied raw materials and products, and their functionalities may be determined empirically. The selection of the hydrocracking catalyst is not critical. Any catalyst having the desired hydrocracking functionalities under selected operating conditions, including conventional hydrocracking catalysts, can be used. As described above, the hydrotreatment and / or hydrocracking is carried out under conditions suitable for obtaining liquid hydrocarbon fuels having the aforementioned properties, which may, if present, contain, for example, less than about 30 ppm of sulfur and less than about 13.5% by weight of hydrogen. 【0031】 Hydrogenation Next, the liquid hydrocarbon fuel having the properties described above is hydrogenated. Hydrogenation conditions can vary, but are typically selected to obtain a hydrogen-rich fuel containing less than about 5 ppm, less than about 2 ppm, less than about 1 ppm, or about 0 ppm of sulfur, which has more hydrogen than the starting liquid hydrocarbon fuel. Hydrogenation generally does not change the ring structure, but rather converts aromatic compounds into naphthenic compounds. The amount of hydrogen in the resulting hydrogen-rich fuel may be more than about 13.5% by weight, more than about 13.8% by weight, more than about 14.0% by weight, more than about 14.5% by weight, or even more hydrogen. 【0032】 Hydrogenation can be achieved by any means necessary to obtain a hydrogen-rich fuel of the desired type. In one embodiment, a liquid hydrocarbon fuel can be hydrogenated by the reaction of a catalyst with hydrogen gas under conditions that allow for hydrogenation. 【0033】 In one embodiment, the hydrogenation catalyst may contain or essentially consist of supported group 7, 8, 9, and 10 metals. In some embodiments, the hydrogenation catalyst may be selected from the group consisting of one or more of Ni, Cu, Ag, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Sn, Mo, and W, supported on silica, alumina, silica-alumina, clay, titania, zirconia, or a mixed metal oxide support. In other embodiments, the hydrogenation catalyst may be nickel supported on diatomaceous earth, platinum and / or palladium supported on alumina, or nickel and / or platinum and / or palladium supported on alumina, alternatively, nickel supported on diatomaceous earth, alternatively, nickel and / or platinum and / or palladium supported on silica, or alternatively, cobalt-molybdenum supported on alumina. In yet another embodiment, the hydrogenation catalyst may be one or more of the group consisting of diatomaceous earth, silica, alumina, clay, or nickel supported on silica-alumina. 【0034】 In general, hydrogenation can be carried out in any type of process and / or reactor capable of hydrogenating hydrogen-rich fuels to desired properties. In one embodiment, hydrogenation can be carried out in a batch process, a continuous process, or any combination thereof, alternatively in a batch process, or alternatively in a continuous process. In some embodiments, hydrogenation can be carried out in a slurry reactor, a continuous stirred tank reactor, a fixed-bed reactor, or any combination thereof, alternatively in a slurry reactor, alternatively in a continuous stirred tank reactor, or alternatively in a fixed-bed reactor. 【0035】 If desired, the hydrogen-rich fuel can be filtered to separate the hydrogenation catalyst and / or catalyst particles from the hydrogen-rich fuel. Furthermore, the hydrogen-rich fuel can be further purified or distilled to separate the highly hydrogen-rich fuel. 【0036】 The amount of hydrogenation catalyst used may depend on the identity of the hydrogenation catalyst and the specific hydrogenation process used. Generally, the amount of hydrogenation catalyst used may be any amount that can produce the desired hydrogen-rich fuel. In non-fixed-bed hydrogenation processes (e.g., slurry reactors or continuous stirred tank reactors), the amount of hydrogenation catalyst used for hydrogenation may range from 0.001% to 20% by weight, 0.01% to 15% by weight, 0.1% to 10% by weight, or 1% to 5% by weight. The weight percentage of the hydrogenation catalyst is based on the total weight of the hydrogenation catalyst and the hydrogenated liquid hydrocarbon fuel. 【0037】 In general, the conditions under which liquid hydrocarbon fuels can be hydrogenated include hydrogen pressure, temperature, contact time, or any combination thereof, alternatively, hydrogen pressure and temperature, alternatively, hydrogen pressure, temperature, and contact time, alternatively, hydrogen pressure, alternatively, temperature, or alternatively, contact time. In one embodiment, the hydrogenation temperatures that can be utilized may be in the range of 25°C (77°F) to 350°C (662°F), 50°C (122°F) to 300°C (572°F), 60°C (140°F) to 250°C (482°F), or 70°C (158°F) to 200°C (392°F). In one embodiment, the available hydrogen pressures may range from 100 kPa (14 psi) to 30 MPa (4351 psi), 250 kPa (36 psi) to 20 MPa (2901 psi), 500 kPa (72 psi) to 10 MPa (1450 psi), or 750 kPa (109 psi) to 5 MPa (725 psi). In one embodiment, the available contact times may range from 1 minute to 100 hours, 2 minutes to 50 hours, 5 minutes to 25 hours, or 10 minutes to 10 hours. In a fixed-bed process, the WHSV (weight space velocity) of the liquid hydrocarbon fuel on the hydrogenation catalyst may range from 0.1 to 20, 0.5 to 10, or 1 to 5. 【0038】 In some embodiments, the hydrogenation process generates significantly more heat than a standard hydrogenation process. Therefore, at least a portion of the heat may be recycled and used, for example, in a hydrogenation / hydrocracking process(s). 【0039】 Next, if desired, a hydrogen-rich fuel produced by hydrogenation may be transported. 【0040】 transportation If desired, hydrogen-rich fuels are typically transported to dehydrogenation facilities in any convenient manner. Advantageously, hydrogen-rich fuels can be transported using existing distribution infrastructure, for example. Such existing distribution infrastructure includes tankers (for oil or chemicals), container ships, trucks, rail tank cars, pipelines, and / or any combination thereof. 【0041】 dehydrogenation After transport, hydrogen-rich fuel is dehydrogenated to obtain hydrogen and a second liquid hydrocarbon fuel. Typically, dehydrogenation is carried out under conditions to obtain hydrogen and a second liquid hydrocarbon fuel containing less than 13.5% by weight of hydrogen and less than 5 ppm, or less than 2 ppm, or less than 1 ppm, or about 0 ppm of sulfur, and a considerable amount of heat must be added to achieve dehydrogenation. 【0042】 Hydrogen-rich fuels are typically brought into contact with a catalyst complex in a dehydrogenation reactor under dehydrogenation conditions. This contact can be achieved in a fixed catalyst bed system, a movable catalyst bed system, a fluidized bed system, or a batch-type operation. The dehydrogenation reactor itself may include one or more separate reactor zones with heating means between them to ensure that the temperature can be maintained at the inlet to each reaction zone to obtain the desired conversion. The hydrogen-rich fuel may be brought into contact with the catalyst complex in the manner of an upward, downward, or radial flow. When in contact with the catalyst, the hydrogen-rich fuel may be in the liquid phase, a mixed gas-liquid phase, or a gas phase. 【0043】 Dehydrogenation conditions vary, ranging from a temperature of approximately 300°F (149°C) to approximately 1500°F (816°C), a pressure of approximately 0.1 kPa (0.01 psi) to approximately 2533 kPa (367 psi), and a duration of approximately 0.01 to 50 hours. -1 This may include the liquid space velocity (LHSV). Preferred temperatures may be about 350°F (177°C) to about 900°F (482°C), more preferably about 400°F (204°C) to about 800°F (427°C), and more preferably 450°F (232°C) to 700°F (371°C). Preferred pressures may range from about 10 kPa (1.5 psi) to about 507 kPa (74 psi). Atmospheric pressure is very suitable for most processes, and generally, the pressure in the dehydrogenation zone is kept as low as feasible, consistent with equipment limitations, to maximize the benefits of chemical equilibrium. Preferred LHSV values ​​are about 0.05 hr -1 ~approximately 10 hours -1The range is, or more preferably, about 0.1 to about 5hr-1. Naturally, those skilled in the art will select the desired temperature, pressure, and LHSV depending on the characteristics of the hydrogen-rich fuel and catalyst system being used. 【0044】 If desired, hydrogen-rich fuel may be mixed with a diluent gas before, during, or after passing through the dehydrogenation zone. The diluent material may be hydrogen, vapor, methane, carbon dioxide, nitrogen, argon, or a mixture thereof. If a diluent gas is used, it should be in sufficient quantity to ensure a molar ratio of diluent gas to hydrocarbons of approximately 0.1 to approximately 20, with best results obtained when the molar ratio ranges from approximately 1 to 10. The diluted hydrogen stream passing through the dehydrogenation zone is typically recycled after hydrogen has been separated from the dehydrogenation zone effluent within a hydrogen separation zone. 【0045】 Dehydrogenation catalyst complexes can exhibit high activity, high selectivity, and good stability. The dehydrogenation catalyst may be the same as or different from the hydrogenation catalysts described above. Particularly preferred catalyst complexes of this disclosure include those comprising a Group VIII noble metal and a solid inorganic support. Such catalyst complexes are well known to those skilled in the art, as represented by U.S. Patents 3,531,543, 3,631,215, 3,864,284, 3,584,060, 4,191,846, 4,716,143, 4,786,625, 4,827,072, and 4,902,849, the contents of which are incorporated herein by reference. Particularly preferred catalyst complexes may include platinum, palladium, nickel, tin, and any combination thereof on an alumina catalyst. 【0046】 A dehydrogenated hydrogen-rich fuel yields hydrogen and a second liquid hydrocarbon fuel. If desired, the hydrogen and the second liquid hydrocarbon fuel can be separated. The hydrogen may be stored at a field hydrogen station or transported to a hydrogen station. The resulting second liquid hydrocarbon fuel can be recycled in any convenient manner. In one embodiment, recycling the second liquid hydrocarbon fuel involves mixing the second liquid hydrocarbon fuel with a liquid hydrocarbon fuel and then hydrogenating the mixed liquid hydrocarbon fuel. 【0047】 Example 1: Characteristics of LCO Table 1 shows the physical properties of the LCO supply material used in this study, namely ABQ3034. This LCO contains approximately 63% by volume of aromatic compounds. Approximately 80% by volume of the molecule has a ring structure. Its hydrogen content is approximately 10.7%, and therefore it is a good supply material for hydrogen storage and transport. [Table 1] 【0048】 Example 2: LCO Hydrogenation and Hydrocracking for the Production of Clean Liquid Fuel CGQ7699 As shown in Table 1, LCO ABQ3034 contains more than 2000 ppm of sulfur and more than 600 ppm of nitrogen. Both nitrogen and sulfur impurities are removed by hydrotreatment to produce a clean liquid fuel. Hydrodenitrification and hydrodesulfurization were performed in a single-pass standard hydrotreatment unit filled with an ISOCRACKING® catalyst system containing the conversion commercial hydrocracking pretreatment catalyst ICR 514 / 1001 and the hydrocracking catalyst ICR 183, under hydrotreatment conditions of 0.88 LHSV, 8000 SCF / B, a hydrogen partial pressure of 1400 psia (9653 kPa), and a catalyst mean bed temperature of 675°F (357°C). 【0049】 The hydrogenation product was distilled into two fractions. The diesel range product (boiling point 380°F+, CGQ7699) was selected for the clean liquid fuel hydrogen carrier study. Its physical properties are shown in Table 1. The results in Table 1 show that the clean liquid fuel CGQ7699 produced from LCO contained <0.3 ppm N and <5 ppm S. Its hydrogen content was approximately 13.2% by weight. Approximately 75% by volume of the hydrocarbons are molecules with a ring structure suitable for carrying hydrogen. 【0050】 Example 3: Clean liquid fuel as a hydrogen carrier [Table 2] 【0051】 The results in Table 2 show that ICR 419 further saturates the aromatics in the clean liquid fuel CGQ7699 to less than 1 wt% in the resulting liquid fuel containing ≥13.9 wt% hydrogen. Furthermore, ICR 419 also shows that it can produce hydrogen from a hydrogen-rich liquid fuel through dehydrogenation, resulting in a liquid fuel containing ≤13.2 wt% hydrogen under process conditions. 【0052】 Example 4: Clean liquid fuel as a hydrogen carrier [Table 3-1] [Table 3-2] 【0053】 The results in Table 3 show that ICR 731 can saturate the aromatics in clean liquid fuel CGQ7699 to less than 1% by weight. The resulting liquid fuel contained ≥13.9% by weight of hydrogen. Furthermore, ICR 731 also shows that it can produce hydrogen from clean liquid fuel, resulting in a liquid fuel containing ≤13.0% by weight of hydrogen. 【0054】 Figure 1 shows an embodiment of the present invention in which light cycle oil is hydrotreated and / or hydrocracked into a liquid hydrocarbon fuel that is hydrogenated into a hydrogen-rich clean fuel. The hydrogen-rich clean fuel can then be transported without the need for recycling required by a liquid organic hydrogen carrier, such as a liquid organic hydrogen carrier (e.g., dibenzyltoluene). After transport, the hydrogen and clean liquid hydrocarbon fuel are produced by dehydrogenation. 【0055】 Various embodiments are described in the aforementioned specification. However, it will be apparent that various modifications and changes may be made, and additional embodiments may be implemented, without departing from the broader scope of the invention as described in the following claims. Accordingly, this specification and the drawings should be considered illustrative rather than restrictive. The invention described in the original claims of this application is as follows: [Section 1] It is a process, Hydrogenating, hydrocracking, or both hydrogenating and hydrocracking aromatic feedstocks under conditions to obtain liquid hydrocarbon fuels containing less than approximately 30 ppm of sulfur and less than approximately 13.5% by weight of hydrogen. Hydrogenating the liquid hydrocarbon fuel under conditions to obtain a hydrogen-rich fuel containing less than approximately 5 ppm of sulfur and more than approximately 13.5% by weight of hydrogen, Transporting the hydrogen-rich fuel to a dehydrogenation facility, Dehydrogenating a hydrogen-rich fuel under conditions for obtaining a second liquid hydrocarbon fuel containing hydrogen, less than 5 ppm of sulfur, and less than 13.5% by weight of hydrogen, To separate the hydrogen and the second liquid hydrocarbon fuel, Recycling the aforementioned second liquid hydrocarbon fuel, The process including the process described above. [Section 2] The process according to claim 1, wherein the aromatic feedstock includes hydrocarbons from a fluid catalytic decomposition process. [Section 3] The process according to item 1, wherein the aromatic feedstock includes light cycle oil. [Section 4] The process according to item 3, wherein the light cycle oil contains more than approximately 2,000 ppm of sulfur. [Section 5] The aforementioned light cycle oil has a load of approximately 900 to 960 kg / m³. 3 The process described in item 4, including the density of. [Section 6] The process according to item 4, wherein the light cycle oil has a cetane number of approximately 20 to approximately 35. [Section 7] The process according to item 4, wherein the light cycle oil has a boiling point of less than approximately 400°C according to ASTM D-86. [Section 8] The process according to item 1, further comprising transporting the hydrogen to a hydrogen station. [Item 9] The process according to claim 1, wherein the recycling of the second liquid hydrocarbon fuel comprises mixing the second liquid hydrocarbon fuel with a liquid hydrocarbon fuel and then hydrogenating the mixed liquid hydrocarbon fuel. [Item 10] The process according to item 1, wherein the conditions used for hydrogenation, hydrocracking, or both hydrogenation and hydrocracking include conditions suitable for removing nitrogen. [Item 11] The process according to claim 1, further comprising recycling at least a portion of any heat generated in the hydrogenation step. [Item 12] It is a process, Hydrogenating an aromatic feedstock containing less than 50 ppm of sulfur under conditions to obtain a hydrogen-rich fuel containing less than approximately 5 ppm of sulfur and more than approximately 13.5% by weight of hydrogen, Transporting the hydrogen-rich fuel to a dehydrogenation facility, Dehydrogenating a hydrogen-rich fuel under conditions for obtaining a second liquid hydrocarbon fuel containing hydrogen, less than 5 ppm of sulfur, and less than 13.5% by weight of hydrogen, To separate the hydrogen and the second liquid hydrocarbon fuel, Recycling the aforementioned second liquid hydrocarbon fuel, The process including the process described above. [Item 13] The process according to claim 12, wherein the aromatic feedstock includes hydrocarbons from a fluid catalytic decomposition process. [Item 14] The process according to item 12, wherein the aromatic feedstock includes light cycle oil. [Item 15] The process according to item 14, wherein the light cycle oil contains more than approximately 2,000 ppm of sulfur. [Item 16] The aforementioned light cycle oil has a load of approximately 900 to 960 kg / m³. 3 The process described in item 14, including the density of. [Item 17] The process according to item 14, wherein the light cycle oil has a cetane number of about 20 to about 35. [Item 18] The process according to item 14, wherein the light cycle oil has a boiling point of less than approximately 400°C according to ASTM D-86.

Claims

[Claim 1] It is a process, Hydrocracking aromatic feedstock under conditions to obtain a liquid hydrocarbon fuel containing less than approximately 30 ppm of sulfur and less than approximately 13.5% by weight of hydrogen. Hydrogenating the liquid hydrocarbon fuel under conditions to obtain a hydrogen-rich fuel containing less than approximately 5 ppm of sulfur and more than approximately 13.5% by weight of hydrogen, Transporting the hydrogen-rich fuel to a dehydrogenation facility, Dehydrogenating a hydrogen-rich fuel under conditions for obtaining a second liquid hydrocarbon fuel containing hydrogen, less than 5 ppm of sulfur, and less than 13.5% by weight of hydrogen, To separate the hydrogen and the second liquid hydrocarbon fuel, Recycling the second liquid hydrocarbon fuel, The process including the process described above. [Claim 2] The process according to claim 1, wherein the aromatic feedstock includes hydrocarbons from a fluid catalytic decomposition process. [Claim 3] The process according to claim 1, wherein the aromatic supply material includes light cycle oil. [Claim 4] The process according to claim 3, wherein the light cycle oil contains more than approximately 2,000 ppm of sulfur. [Claim 5] The aforementioned light cycle oil has a viscosity of approximately 900 to 960 kg / m³. ３ The process according to claim 4, comprising the density of . [Claim 6] The process according to claim 4, wherein the light cycle oil has a cetane number of about 20 to about 35. [Claim 7] The process according to claim 4, wherein the light cycle oil has a boiling point of less than approximately 400°C according to ASTM D-86. [Claim 8] The process according to claim 1, further comprising transporting the hydrogen to a hydrogen station. [Claim 9] The process according to claim 1, wherein the recycling of the second liquid hydrocarbon fuel comprises mixing the second liquid hydrocarbon fuel with a liquid hydrocarbon fuel and then hydrogenating the mixed liquid hydrocarbon fuel. [Claim 10] The process according to claim 1, wherein the conditions used for hydrocracking include conditions suitable for removing nitrogen. [Claim 11] The process according to claim 1, further comprising recycling at least a portion of any heat generated in the hydrogenation step.

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