Process for treating liquid organic hydrogen carriers

Abstract

One or more liquid organic hydrogen carriers can be processed by a method comprising the following steps: feeding one or more hydrogen-lean liquid organic hydrogen carriers and hydrogen to a hydrotreating reactor to form a hydrotreating reactor effluent. The hydrotreating reactor effluent may include one or more hydrogen-rich liquid organic hydrogen carriers and unreacted hydrogen. The method may further include feeding the hydrotreating reactor effluent from the hydrotreating reactor to a separation unit, whereby at least one or more hydrogen-rich liquid organic hydrogen carriers are separated from the unreacted hydrogen. The method may further include feeding at least a naphtha feed and the unreacted hydrogen to a naphtha hydrotreating processor to produce a hydrotreating processor effluent comprising hydrotreated naphtha.

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. non-provisional application serial number 18 / 517,939, filed November 22, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] The embodiments disclosed herein generally relate to chemical processing, and more specifically, to methods and systems for processing liquid organic hydrogen carriers. Background Technology

[0003] Currently, hydrogen demand is experiencing significant growth, driven by its crucial role in addressing global energy and environmental challenges. With increasing emphasis on decarbonization and reducing greenhouse gas emissions, hydrogen is gaining popularity as a clean and versatile energy carrier. It is increasingly being used in transportation, industry, and power generation to replace fossil fuels and reduce carbon footprints. This demand is particularly evident in the development of fuel cell vehicles and the integration of hydrogen into industries including steel and chemical production. Furthermore, hydrogen's potential in energy storage and grid stabilization, especially when combined with renewable energy sources, enhances its appeal. As countries worldwide commit to achieving ambitious sustainable development goals, the current demand for hydrogen reflects its critical role in realizing a greener and more sustainable energy future. Summary of the Invention

[0004] The transportation and storage of hydrogen present several challenges to its efficient use as a clean energy carrier. One major issue is its low volumetric energy density, meaning that large quantities of hydrogen need to be transported to meet energy demands. Hydrogen is also highly flammable. Furthermore, leakage can be a problem due to the small molecular size of hydrogen, making it prone to escaping from storage and transport containers. However, the embodiments disclosed herein utilize a liquid organic hydrogen carrier (LOHC) capable of efficiently storing and transporting hydrogen, releasing it via a chemical process when needed, thus providing a practical and efficient way to utilize hydrogen as an energy source. Specifically, in the embodiments disclosed herein, the hydrogenation of the LOHC is integrated with naphtha hydrotreating (a process that can be used in crude oil refineries). Conventional naphtha hydrotreating processors typically utilize a portion of the hydrogen recovered after use in the hydrotreating processor, and another portion added to the system as supplementary hydrogen. It has been found that efficiency improvements can be achieved when this additional hydrogen portion is first used for LOHC hydrogenation upstream of the naphtha hydrotreating process. In particular, the integration of LOHC hydrogenation and naphtha hydrogenation has been found to have synergistic effects, as LOHC hydrogenation and naphtha hydrogenation can be carried out at relatively similar temperatures and pressures. Furthermore, in one or more embodiments, the hydrogenated LOHC can be readily separated from hydrogen after LOHC hydrogenation. These aspects enable the integration of LOHC hydrogenation and naphtha hydrogenation, thereby reducing capital and operating expenditures.

[0005] According to one or more embodiments, a liquid organic hydrogen carrier can be processed by a method comprising the following steps: feeding one or more hydrogen-lean liquid organic hydrogen carriers and hydrogen to a hydrotreating reactor to form a hydrotreating reactor effluent. The hydrotreating reactor effluent may contain one or more hydrogen-rich liquid organic hydrogen carriers and unreacted hydrogen. The method may further include feeding the hydrotreating reactor effluent from the hydrotreating reactor to a separation unit, and separating at least the one or more hydrogen-rich liquid organic hydrogen carriers from the unreacted hydrogen in the separation unit. The method may further include feeding at least a naphtha feed and the unreacted hydrogen to a naphtha hydrotreating processor to produce a hydrotreating processor effluent containing hydrotreated naphtha.

[0006] These and other embodiments are described in more detail in the specific embodiments. It should be understood that the foregoing general description and the subsequent detailed description present embodiments of the subject matter and are intended to provide an overview or framework for understanding the nature and characteristics of the claimed technology. The accompanying drawings are included to provide a further understanding of the technology disclosed herein and are incorporated into and form part of this specification. The drawings illustrate various embodiments and, together with the description, serve to explain the principles and operation of the technology described herein. Furthermore, the drawings and description are illustrative only and are not intended to limit the scope of the claims in any way. Attached Figure Description

[0007] The best understanding of this disclosure can be obtained by reading the following detailed description of specific embodiments in conjunction with the accompanying drawings, wherein the same structures are indicated by the same reference numerals, and wherein: Figure 1 A schematic illustration depicts a liquid organic hydrogen processing system according to one or more embodiments described in this disclosure.

[0008] Reference will now be made in more detail to various embodiments, some of which are illustrated in the accompanying drawings. Throughout the drawings, the same reference numerals are used wherever possible to denote the same or similar parts.

[0009] For the purpose of illustrating the simplified diagrams in the accompanying figures, numerous valves, temperature sensors, electronic controllers, etc., which are well-known and likely to be used by those skilled in the art in certain chemical processing operations, are not included. Furthermore, ancillary components typically included in typical chemical processing operations, such as air supply, catalyst hoppers, and flue gas treatment systems, are not depicted. Ancillary components in the hydrotreating unit, such as exhaust streams, spent catalyst discharge subsystems, and catalyst replacement subsystems, are also not shown. It should be understood that these components are within the spirit and scope of the embodiments disclosed herein. However, operating components (such as those described in this disclosure) may be added to the embodiments described herein.

[0010] It should also be noted that the arrows in the accompanying drawings represent process streams. However, arrows can also represent transport lines used to transfer process streams between two or more system components. Furthermore, arrows connected to system components define the inlet or outlet of each given system component. The direction of the arrow generally corresponds to the primary direction of movement of the stream material contained within the physical transport line indicated by the arrow. Additionally, arrows not connected to two or more system components represent product streams leaving the system or system inlet streams entering the system. Product streams may be further processed in an associated chemical processing system or may be commercialized as a final product. System inlet streams may be streams delivered from an associated chemical processing system or may be unprocessed raw material streams. Some arrows may represent recirculated streams, which are outflow streams from system components that are recycled back into the system. However, it should be understood that in some embodiments, any recirculated stream shown may be replaced by a system inlet stream of the same material, and a portion of the recirculated stream may leave the system as a system product.

[0011] Furthermore, the arrows in the accompanying drawings may schematically depict the process steps of transferring material from one system component to another. For example, an arrow pointing from one system component to another may indicate the "transfer" of effluent from one system component to another, which may include "draining" or "removing" the contents of the process material from one system component and "introducing" the contents of that product material into another system component. It should be understood that the arrows in the relevant accompanying drawings do not represent necessary or required steps.

[0012] It should be understood that, according to the embodiments presented in the relevant figures, the arrow between two system components may indicate that the material flow is not processed between the two system components. In other embodiments, the material flow indicated by the arrow may have substantially the same composition throughout its transport between the two system components. Furthermore, it should be understood that in one or more embodiments, the arrow may indicate that at least 75% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, at least 99.9% by weight, or even 100% by weight of the material flow is transported between the system components. Therefore, in some embodiments, less than the total material flow indicated by the arrow may be transported between the system components, for example, if a diversion occurs.

[0013] It should be understood that when two or more lines intersect in the schematic flow diagram of the relevant figures, two or more process streams are "mixed" or "combined". Mixing or combining may also include mixing by directly introducing the two streams into the same reactor, separation unit, or other system component. For example, it should be understood that when two streams are depicted as being directly combined before entering a separation unit or reactor, in some embodiments, these streams may be equivalently introduced into the separation unit or reactor and mixed in the reactor. Detailed Implementation

[0014] This disclosure relates to a method for processing one or more liquid organic hydrogen carriers (LOHCs) in a system integrated with naphtha hydrotreating. Typically, in the embodiments described herein, hydrogen-lean LOHCs are co-fed with hydrogen into a hydrotreating reactor. The hydrogen and hydrogen-lean LOHCs are contacted with each other under conditions sufficient to produce a hydrotreating reactor effluent containing hydrogen-rich LOHCs and unreacted hydrogen. In such an arrangement, it has been found that unreacted hydrogen from the hydrotreating reactor effluent can be fed as supplemental hydrogen to a naphtha hydrotreating processor to produce hydrotreated naphtha for further processing. As described herein, the similarity in pressure and / or temperature between the hydrotreating and hydrotreating reactions allows for minimal handling of the hydrogen between the hydrotreating and hydrotreating processes.

[0015] As used in this disclosure, "directly" transferring a stream or effluent from one unit to another generally means transferring the stream or effluent from the first unit to the second unit without passing the stream or effluent through an intermediate reaction system or separation system that substantially alters its composition. Heat transfer devices (such as heat exchangers, preheaters, coolers, condensers, or other heat transfer equipment) and pressure devices (such as pumps, pressure regulators, compressors, or other pressure equipment) are not considered intermediate systems that alter the composition of the stream or effluent. Combining two streams of stream or effluent is also not considered an intermediate system that alters the composition of one or both streams of stream or effluent. Simply splitting a stream into two streams with the same composition is also not considered an intermediate system that alters the composition of that stream.

[0016] As used herein, a "reactor" (e.g., a naphtha hydrotreating reactor) refers to a vessel or series of vessels in which one or more reactants may optionally undergo one or more chemical reactions in the presence of one or more catalysts. For example, a reactor may include a tank reactor, a tubular reactor, or a fixed-bed reactor. A reactor described herein may include a series of separate reactors. Furthermore, a reactor may include separation devices, such as those that separate the catalyst from the reaction products. As will be understood by those skilled in the art, such reactors may also include a catalyst regeneration section.

[0017] As used herein, "catalyst" means any substance that can increase the rate of a particular chemical reaction. The catalysts described herein can be used to promote a variety of reactions, such as, but not limited to, hydrotreatment reactions. As used herein, a "hydrotreatment catalyst" can increase the rate of a hydrotreatment reaction, which can reduce sulfur, nitrogen, metals, or other substances in the process stream. In some embodiments, such catalysts may have dual functions. The methods described herein should not necessarily be limited to specific catalytic materials. As described herein, catalysts can be of a fixed configuration and utilize gaseous reactants. However, other configurations are also contemplated.

[0018] As used in this disclosure, a "separation unit" means any separation device or system of separation devices that at least partially separates one or more chemicals mixed in a process stream from each other. For example, a separation unit may selectively separate materials of different chemicals, phases, or sizes to form one or more chemical fractions. Examples of separation units include, but are not limited to: distillation columns, flash tanks, separators, centrifuges, cyclone separators, filters, traps, scrubbers, expansion devices, membranes, solvent extraction devices, etc. It should be understood that the separation processes described in this disclosure may not completely separate all one chemical component from all another chemical component. It should be understood that the separation processes described in this disclosure "at least partially" separate different chemical components from each other, and even if not explicitly stated, separation may involve only partial separation.

[0019] As used in this disclosure, a "liquid organic hydrogen carrier" (commonly referred to as "LOHC") is a chemical compound or substance capable of reversibly absorbing and releasing hydrogen atoms from molecular hydrogen (H2). LOHCs typically act as carriers for storing and transporting hydrogen in liquid form. LOHCs generally undergo hydrogenation to store hydrogen and dehydrogenation to release hydrogen when needed. In some embodiments, LOHCs can retain and / or expel hydrogen atoms by converting an aromatic ring to a non-aromatic cycloalkane moiety. As understood in the art, sometimes, converting an aromatic moiety to a cycloalkane moiety can be described as "hydrogenating" the LOHC with hydrogen. Examples of LOHCs include, but are not limited to: benzyltoluene, dibenzyltoluene, N-ethylcarbazole, tetrahydronaphthalene, decahydronaphthalene, methylcyclohexane, diethylcyclohexane, etc. "Hydrogen-rich" refers to a LOHC that retains hydrogen, for example by having one or more saturated rings (i.e., cyclohexane moieties). "Hydrogen-poor" refers to a LOHC that does not retain hydrogen, for example by having one or more aromatic moieties that can be subsequently hydrogenated. In some embodiments, hydrogen-poor LOHCs may include aromatic and / or alkenyl functional groups, while hydrogen-rich LOHCs include alkyl functional groups, wherein these aromatic and / or alkenyl functional groups are originally present in a hydrogen-poor state.

[0020] As used in this disclosure, the term "effluent" can refer to the stream discharged from a reactor, reaction zone, or separation unit after a specific reaction or separation. Typically, the composition of the effluent differs from the stream entering the separation unit, reactor, or reaction zone. It should be understood that when the effluent is transferred to another system unit, only a portion of that system stream may be transferred.

[0021] As described herein, a "naphtha hydrotreating unit" generally refers to a unit within a refinery designed for the hydrotreating of naphtha fractions. Naphtha is a hydrocarbon feedstock with a wide boiling range, commonly used in the production of gasoline, petrochemicals, and other high-value products, as understood by those skilled in the art. As described herein, naphtha can be heavy naphtha, light naphtha, or any naphtha fraction. In some embodiments, the naphtha can be heavy naphtha with a minimum boiling point in the range of 80°C to 100°C and a maximum boiling point in the range of 180°C to 220°C. The naphtha hydrotreating unit is designed to remove impurities and contaminants, such as sulfur, nitrogen, and olefins, from naphtha by subjecting it to high-temperature, high-pressure conditions in the presence of hydrogen and a hydrotreating catalyst.

[0022] The method described herein for treating one or more liquid organic hydrogen carriers can utilize... Figure 1 The processing system. The method in Figure 1 This description is made within the context of a specific system, but it is anticipated that many other systems are applicable to the methods described herein. In particular, besides those concerning... Figure 1 In addition to those described, other systems and methods may also be suitable, such as, but not limited to, alternative separation schemes, alternative logistics handling, and the sequence of the disclosed separation and / or handling steps. In particular, this document will... Figure 1 Detailed description in the context of the system Figure 1 This document will describe the various logistics and processes described herein. However, the steps, logistics, or other characteristics of the disclosed methods are independent of... Figure 1 It exists for the system and provides Figure 1 This is merely to illustrate one or more suitable systems currently conceived.

[0023] Now for reference Figure 1 A hydrogenation system 101 is depicted within existing refinery infrastructure, comprising a hydrogenation reactor 110, a separation unit 120, and a naphtha hydrogenation processor 130. These system components will be described in detail herein.

[0024] According to one or more embodiments, lean hydrogen LOHC and hydrogen can be fed into hydrogenation reactor 110 via hydrogenation reactor feed 102 to form hydrogenation reactor effluent 114. Hydrogenation reactor effluent 114 may contain one or more hydrogen-rich LOHCs and unreacted hydrogen. Figure 1As shown, the hydrogenation reactor feed 102 can be fed to the hydrogenation reactor 110. The hydrogenation reactor feed 102 may contain lean LOHC and hydrogen. The hydrogen in the hydrogenation reactor feed 102 may be additional hydrogen added to system 101 (e.g., not from the recycled hydrogen of the heat-exchanged hydrogenation treatment effluent 164 described below). The hydrogen fed to the hydrogenation reactor 110 may be from any hydrogen source, such as hydrogen produced by electrolysis from any fuel source (e.g., fossil fuels, wind power, or solar energy).

[0025] The hydrotreating reactor feed 102 may contain 1% to 99% by weight of lean hydrogen LOHC and 1% to 99% by weight of hydrogen. In one embodiment, the hydrotreating reactor feed 102 may contain greater than or equal to 1% by weight, greater than or equal to 10% by weight, greater than or equal to 20% by weight, greater than or equal to 30% by weight, or greater than or equal to 40% by weight of lean hydrogen LOHC. In other embodiments, the hydrotreating reactor feed 102 may contain greater than or equal to 1% by weight, greater than or equal to 10% by weight, greater than or equal to 20% by weight, greater than or equal to 30% by weight, or greater than or equal to 40% by weight of hydrogen. It is anticipated that the amounts of lean hydrogen liquid organic hydrogen carrier and hydrogen in the hydrotreating reactor feed 102 may fluctuate depending on industrial demand and the amount of hydrogen ultimately desired to be supplied as supplemental hydrogen to the naphtha hydrotreating processor 130.

[0026] like Figure 1 As shown, the hydrotreating reactor feed 102 can be fed to the hydrotreating reactor 110. The hydrotreating reactor 110 is operable to at least partially hydrogenate lean LOHC to produce a hydrotreating reactor effluent 114 containing hydrogen-rich LOHC and unreacted hydrogen. The lean LOHC can be benzyltoluene. It is anticipated that benzyltoluene can be produced by the refinery where system 101 is located, for example, in an aromatics complex of the refinery.

[0027] In reaction I shown below, benzyltoluene reacts with hydrogen to produce perhydrobenzyltoluene. This reaction can be carried out using a catalyst, such as, but not limited to, cobalt-molybdenum (Co-Mo), nickel-molybdenum (Ni-Mo), nickel-tungsten (Ni-W), and / or noble metal catalysts. In embodiments, the catalyst may be supported on alumina. Without being bound by any theory, sulfide catalysts such as cobalt-molybdenum (Co-Mo) and nickel-molybdenum (Ni-Mo) can be used because they may contain active metal sites, enabling the hydrogenation reaction and potentially outperforming other catalysts.

[0028]

[0029] As described herein, in embodiments, the hydrogenation reactor 110 can operate at temperatures and pressures sufficient for hydrogen-lean LOHC hydrogenation. For example, in embodiments where the hydrogen-lean liquid organic hydrogen carrier is benzyltoluene, the operating temperature of the hydrogenation reactor 110 can be from 200°C to 260°C, such as 200°C to 220°C, 220°C to 240°C, 240°C to 260°C, or any combination of these ranges. It is contemplated that the operating temperature difference between the hydrogenation reactor 110 and the naphtha hydrogenation processor 130 can be less than or equal to 25°C (e.g., less than or equal to 20°C, less than or equal to 15°C, less than or equal to 10°C, or even less than or equal to 5°C). In the implementation, the operating pressure of the hydrotreating reactor 110 can be from 2.5 MPa (25 bar) to 4.5 MPa (45 bar), for example, 2.5 MPa to 3 MPa, 3 MPa to 3.5 MPa, 3.5 MPa to 4 MPa, 4 MPa to 4.5 MPa, or any combination of one or more of these ranges. It is anticipated that the operating pressure difference between the hydrotreating reactor 110 and the naphtha hydrotreating processor 130 can be less than or equal to 1.0 MPa (10 bar) (e.g., less than or equal to 0.8 MPa, less than or equal to 0.6 MPa, less than or equal to 0.4 MPa, or even less than or equal to 0.2 MPa).

[0030] According to one or more embodiments, the effluent 114 from the hydrogenation reactor 110 can be conveyed to a separation unit 120, where it is separated into at least one or more hydrogen-rich LOHC gases and unreacted hydrogen. Figure 1 As shown, the effluent 114 from the hydrogenation reactor can be conveyed to the separation unit 120. In some embodiments, such as... Figure 1 As shown, the effluent 114 from the hydrogenation reactor is separated into two streams: an unreacted hydrogen stream 124 and a hydrogen-rich LOHC stream 126. The hydrogen-rich LOHC stream 126 can be transported downstream for storage or transportation. Such hydrogen-rich LOHC can later be dehydrogenated to form hydrogen in different facilities at different geographical locations. In this way, hydrogen from the hydrogenation reactor feed 102 can be transported to its destination in liquid form, rather than as compressed hydrogen.

[0031] In one or more embodiments, separation unit 120 may be a flash tank or a distillation column. Perhydrobenzyltoluene has a boiling point of 260°C to 280°C at atmospheric pressure, which makes it relatively easy to separate from hydrogen by boiling point under the various pressures that may be present in separation unit 120.

[0032] According to one or more embodiments, naphtha feed 132 and unreacted hydrogen stream 124 can be fed to naphtha hydrotreating processor 130 to produce hydrotreating processor effluent 158 ​​containing hydrotreated naphtha. The naphtha feed can be a fraction from an atmospheric distillation column processing crude oil (e.g., from a refinery). Figure 1 As shown, unreacted hydrogen stream 124 can be fed to naphtha hydrotreating processor 130. According to one or more embodiments, unreacted hydrogen stream 124 can be combined with naphtha feed 132 before being fed to naphtha hydrotreating processor 130 to form hydrotreating processor feed 134. In some embodiments, the pressure change of unreacted hydrogen stream 124 from separation unit 120 after it leaves hydrotreating reactor 110 and separation unit 120 does not exceed 10 bar. Therefore, unreacted hydrogen stream 124 does not need to be recompressed after separation in separation unit 120. For example, the pressure of unreacted hydrogen stream 124 can be approximately the same as the pressure of hydrotreating reactor 110 (e.g., a difference of less than or equal to 10 bar), and hydrotreating reactor 110 can operate at a pressure within 10 bar of the naphtha hydrotreating processor 130, as explained in more detail below. Therefore, the unreacted hydrogen stream 124 does not need to be repressurized before the unreacted hydrogen is combined with the naphtha feed 132 upstream of the naphtha hydrotreating processor 130.

[0033] like Figure 1 As shown, the hydroprocessor feed 134 can be heated in a heat exchanger 140 via the hydroprocessor effluent 158. This preheats the hydroprocessor feed 134 upstream of the naphtha hydroprocessor 130, forming a preheated hydroprocessor feed 144. In some embodiments, the preheated hydroprocessor feed 144 can be further heated by a heater 150 (e.g., a furnace, flame heater, etc.). The heater 150 can heat the preheated hydroprocessor feed 144 to form a heated hydroprocessor feed 154. It should be understood that some embodiments may not include the heat exchanger 140, and the hydroprocessor feed 134 can be fed to the heater 150 upstream of the naphtha hydroprocessor 130. In embodiments including the heat exchanger 140, the hydroprocessor feed 134 can be heated in the heat exchanger 140 and then fed to the naphtha hydroprocessor 130 via the heated hydroprocessor feed 154. According to Figure 1 In other embodiments not shown, the hydrotreating feed 134 may be further heated, for example, but not limited to, through an additional heat exchanger, furnace, flame heater, etc., before entering the naphtha hydrotreating processor 130.

[0034] Continue to refer to Figure 1The heated hydrotreating feed 154 can be fed to the naphtha hydrotreating processor 130. The naphtha hydrotreating processor 130 may contain at least one hydrotreating catalyst. It is contemplated that the at least one hydrotreating catalyst may be a cobalt-molybdenum (Co-Mo), nickel-molybdenum (Ni-Mo), nickel-tungsten (Ni-W), and / or a noble metal catalyst. In an embodiment, the catalyst may be supported on alumina. The naphtha hydrotreating processor 130 may operate to at least partially reduce the content of metals, sulfur, or nitrogen in the heated hydrotreating feed 154 to produce a hydrotreating effluent 158. For example, the amount of one or more of sulfur, metals, or nitrogen in the hydrotreating effluent 158 ​​discharged from the naphtha hydrotreating processor 130 may be at least 25%, at least 50%, or even at least 75% less than that in the heated hydrotreating feed 154.

[0035] As described herein, in embodiments, the naphtha hydrotreating processor 130 can operate at temperatures and pressures sufficient for hydrotreating naphtha. For example, the operating temperature of the naphtha hydrotreating processor 130 can be from 225°C to 275°C, such as 225°C to 235°C, 235°C to 245°C, 245°C to 255°C, 255°C to 265°C, 265°C to 275°C, or any combination of these ranges. It is anticipated that the operating temperature difference between the naphtha hydrotreating processor 130 and the hydrotreating reactor 110 can be less than or equal to 25°C (e.g., less than or equal to 20°C, less than or equal to 15°C, less than or equal to 10°C, or even less than or equal to 5°C). In the implementation, the operating pressure of the naphtha hydrotreating processor 130 may be from 2.5 MPa (25 bar) to 4.5 MPa (45 bar), for example, 2.5 MPa to 3 MPa, 3 MPa to 3.5 MPa, 3.5 MPa to 4 MPa, 4 MPa to 4.5 MPa, 4.5 MPa to 5 MPa, or any combination of one or more of these ranges. It is anticipated that the operating pressure difference between the naphtha hydrotreating processor 130 and the hydrotreating reactor 110 will be less than or equal to 1.0 MPa (10 bar) (e.g., less than or equal to 0.8 MPa, less than or equal to 0.6 MPa, less than or equal to 0.4 MPa, or even less than or equal to 0.2 MPa).

[0036] According to some embodiments, the catalyst-to-feed ratio of the heated hydrogenation processor feed 154 can be from 5 to 100. For example, the catalyst-to-feed ratio of the heated hydrogenation processor feed 154 can be 5 to 10, 10 to 20, 20 to 30, 30 to 40, 40 to 50, 50 to 60, 60 to 70, 70 to 80, 80 to 90, or 90 to 100. Unless otherwise stated herein, the catalyst-to-feed ratio is described in weight / weight form.

[0037] After the heated hydrogenation processor feed 154 undergoes hydrogenation treatment to form hydrogenation processor effluent 158, the hydrogenation processor effluent 158 ​​can exchange heat with the hydrogenation processor feed 134 to form heat-exchanged hydrogenation processor effluent 164. According to... Figure 1 In some embodiments not shown, the hydrotreating processor effluent 164 after heat exchange can be separated into multiple streams to form hydrogen and hydrotreated naphtha. The hydrotreated naphtha can be transported downstream for further processing (e.g., reforming) and ultimately used in a gasoline blending tank. The hydrogen separated from the hydrotreating processor effluent 164 can be reintroduced into system 101 as a recycled hydrogen stream 166. It is anticipated that the recycled hydrogen stream 166 can be combined with unreacted hydrogen stream 124 to form a mixed hydrogen stream 172. The mixed hydrogen stream 172 can be combined with the naphtha feed 132 upstream of the naphtha hydrotreating processor 130. In this way, hydrogen can be circulated in the system, with the unreacted hydrogen stream 124 serving as supplemental hydrogen required for hydrotreating.

[0038] This disclosure includes several aspects. A first aspect is a method for processing one or more liquid organic hydrogen carriers, the method comprising: feeding one or more hydrogen-poor liquid organic hydrogen carriers and hydrogen to a hydrotreating reactor to form a hydrotreating reactor effluent, wherein the hydrotreating reactor effluent comprises one or more hydrogen-rich liquid organic hydrogen carriers and unreacted hydrogen; feeding the hydrotreating reactor effluent from the hydrotreating reactor to a separation unit, and separating at least the one or more hydrogen-rich liquid organic hydrogen carriers from the unreacted hydrogen in the separation unit; and feeding at least a naphtha feed and the unreacted hydrogen to a naphtha hydrotreating processor to produce a hydrotreating processor effluent comprising hydrotreated naphtha.

[0039] The second aspect of this disclosure may include the first aspect, wherein the operating pressure difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 10 bar.

[0040] A third aspect of this disclosure may include any of the foregoing aspects, wherein the operating pressure of the hydrogenation reactor is 25 bar to 50 bar, and the operating pressure of the naphtha hydrogenation processor is 25 bar to 45 bar.

[0041] The fourth aspect of this disclosure may include any of the foregoing aspects, wherein the operating pressure difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 10 bar; and the operating pressure of the hydrogenation reactor is 25 bar to 50 bar, and the operating pressure of the naphtha hydrogenation processor is 25 bar to 45 bar.

[0042] The fifth aspect of this disclosure may include any of the foregoing aspects, wherein the operating temperature difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 25°C.

[0043] The sixth aspect of this disclosure may include any of the foregoing aspects, wherein the hydrogenation reactor operates at a temperature of 200°C to 260°C and the hydrogenation processor operates at a temperature of 225°C to 275°C.

[0044] The seventh aspect of this disclosure may include any of the foregoing aspects, wherein the operating temperature difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 25°C; and the operating temperature of the hydrogenation reactor is 200°C to 260°C, and the operating temperature of the hydrogenation processor is 225°C to 275°C.

[0045] The eighth aspect of this disclosure may include any of the foregoing aspects, wherein the operating pressure difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 10 bar; and the operating temperature difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 25°C.

[0046] The ninth aspect of this disclosure may include any of the foregoing aspects, wherein the one or more hydrogen-poor liquid organic hydrogen carriers comprise benzyltoluene, and the one or more hydrogen-rich liquid organic hydrogen carriers comprise perhydrobenzyltoluene.

[0047] The tenth aspect of this disclosure may include any of the foregoing aspects, wherein the naphtha feed has a minimum boiling point in the range of 80°C to 100°C and a maximum boiling point in the range of 180°C to 220°C.

[0048] The eleventh aspect of this disclosure may include any of the foregoing aspects, wherein the hydrogenation reactor comprises a catalyst.

[0049] The twelfth aspect of this disclosure may include any of the foregoing aspects, and further includes combining the naphtha with the unreacted hydrogen upstream of the naphtha hydrotreating processor.

[0050] The thirteenth aspect of this disclosure may include any of the foregoing aspects, wherein the hydrogenation processor effluent further comprises hydrogen.

[0051] The fourteenth aspect of this disclosure may include the thirteenth aspect, further comprising separating hydrogen from the hydrotreated naphtha in the hydrotreating processor effluent to generate a circulating hydrogen stream.

[0052] The fifteenth aspect of this disclosure may include the fourteenth aspect, further comprising combining the circulated hydrogen stream with the unreacted hydrogen to form a mixed hydrogen stream; and combining the mixed hydrogen stream with the naphtha feed upstream of the hydrotreating processor.

[0053] The sixteenth aspect of this disclosure may include any of the foregoing aspects, wherein the amount of one or more of sulfur, metals or nitrogen in the hydrotreating processor effluent is less than that in the naphtha feed.

[0054] The seventeenth aspect of this disclosure may include any of the foregoing aspects, and further includes heat exchange of the unreacted hydrogen, the naphtha, or both with the hydrotreated naphtha to form a preheated hydrotreating feed.

[0055] The eighteenth aspect of this disclosure may include the seventeenth aspect, further comprising heating the preheated hydrotreating processor feed upstream of the naphtha hydrotreating processor via a heating furnace.

[0056] The nineteenth aspect of this disclosure may include any of the foregoing aspects, and further includes heating the unreacted hydrogen, the naphtha, or both upstream of the naphtha hydrotreating processor via a heating furnace.

[0057] The twentieth aspect of this disclosure may include any of the foregoing aspects, wherein at least one hydrogen-rich liquid organic hydrogen carrier has a boiling point of 260°C to 280°C.

[0058] The subject matter of this disclosure has been described in detail through specific embodiments. It should be understood that any detailed description of the components or features of an embodiment does not necessarily imply that such component or feature is necessary for that particular embodiment or any other embodiment. Furthermore, it will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments without departing from the spirit and scope of the claimed subject matter.

[0059] It should be noted that one or more of the following claims use the term "wherein" as a transitional phrase. In defining this technology, it should be noted that this term is introduced in the claims as an open-ended transitional phrase to introduce a description of a series of structural features, and should be interpreted in a similar manner to the more commonly used open-ended preposition "comprising".

[0060] It should be understood that any two quantitative values ​​assigned to a characteristic can constitute a range for that characteristic, and all combinations of ranges formed by all described quantitative values ​​of a given characteristic are considered in this disclosure. It should be understood that in some embodiments, the compositional range of a chemical component in the composition should be understood as including a mixture of isomers of that component. In other embodiments, the chemical compound may be present in alternative forms, such as derivatives, salts, hydroxides, etc.

[0061] It should also be noted that the descriptions of “at least one” components, elements, etc. in this article should not be used to infer that the alternative use of the article “a or an” should be limited to a single component, element, etc.

[0062] It should also be understood that a logistics stream can be named after its components, and the components named after the logistics stream can be the main components of the logistics stream (e.g., accounting for 50% to 100% by weight, 70% to 100% by weight, 90% to 100% by weight, 95% to 100% by weight, 99% to 100% by weight, 99.5% to 100% by weight, or even 99.9% to 100% by weight of the contents of the logistics stream). It should also be understood that when a logistics stream containing a certain component is disclosed as being transported from one system component to another system component, the component of that logistics stream is also disclosed as being transported from one system component to another system component. For example, a disclosed "naphtha logistics stream" being transported from a first system component to a second system component should be understood as equivalently disclosing the transport of "naphtha" from the first system component to the second system component, and so on.

Claims

1. A method for treating one or more liquid organic hydrogen carriers, the method comprising: One or more hydrogen-poor liquid organic hydrogen carriers and hydrogen are fed into a hydrogenation reactor to form a hydrogenation reactor effluent, wherein the hydrogenation reactor effluent comprises one or more hydrogen-rich liquid organic hydrogen carriers and unreacted hydrogen. The effluent from the hydrogenation reactor is transported from the hydrogenation reactor to a separation unit, where at least one or more hydrogen-rich liquid organic hydrogen carriers are separated from unreacted hydrogen. as well as At least the naphtha feed and the unreacted hydrogen are fed to the naphtha hydrotreating processor to produce a hydrotreating processor effluent containing hydrotreated naphtha.

2. The method according to claim 1, wherein the operating pressure difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 10 bar.

3. The method according to claim 1 or 2, wherein the operating pressure of the hydrogenation reactor is 25 bar to 50 bar, and the operating pressure of the naphtha hydrogenation processor is 25 bar to 45 bar.

4. The method according to any of the preceding claims, wherein the operating temperature difference between the hydrogenation reactor and the naphtha hydrogenation processor is less than or equal to 25°C.

5. The method according to any of the preceding claims, wherein the operating temperature of the hydrogenation reactor is 200°C to 260°C, and the operating temperature of the hydrogenation processor is 225°C to 275°C.

6. The method according to any of the preceding claims, wherein the one or more hydrogen-poor liquid organic hydrogen carriers comprise benzyltoluene, and the one or more hydrogen-rich liquid organic hydrogen carriers comprise perhydrobenzyltoluene.

7. The method according to any of the preceding claims, wherein the naphtha feed has a minimum boiling point in the range of 80°C to 100°C and a maximum boiling point in the range of 180°C to 220°C.

8. The method according to any of the preceding claims, wherein the hydrogenation reactor comprises a catalyst.

9. The method of claim 1, further comprising combining the naphtha with the unreacted hydrogen upstream of the naphtha hydrotreating processor.

10. The method according to any of the preceding claims, wherein the hydrogenation processor effluent further comprises hydrogen.

11. The method of claim 10, further comprising separating hydrogen from the hydrotreated naphtha in the hydrotreating processor effluent to generate a circulating hydrogen stream.

12. The method of claim 11, further comprising: The circulating hydrogen stream is combined with the unreacted hydrogen to form a mixed hydrogen stream; as well as The mixed hydrogen stream is combined with the naphtha feed upstream of the hydrotreating processor.

13. The method according to any of the preceding claims, wherein the amount of one or more of sulfur, metals or nitrogen in the hydrotreating processor effluent is less than that in the naphtha feed.

14. The method according to any of the preceding claims further comprises exchanging heat between the unreacted hydrogen, the naphtha, or both with the hydrotreated naphtha to form a preheated hydrotreating feed.

15. The method according to any of the preceding claims, wherein at least one hydrogen-rich liquid organic hydrogen carrier has a boiling point of 260°C to 280°C.

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