Integrated method for naphtha reforming and benzyl toluene production

Abstract

The present invention relates to an integrated method and related system for naphtha reforming and benzyl toluene production. The method comprises the steps of providing a first toluene stream and a chlorine gas stream to a halogenation reactor to produce a benzyl chloride stream and a first HCl effluent stream, and subsequently providing the benzyl chloride stream, the second toluene stream, and a Lewis acid stream to an alkylation reactor to produce a benzyl toluene stream and a second HCl effluent stream via a Friedel-Crafts reaction. The method further comprises the steps of providing naphtha to a catalytic reforming unit to produce a reformed stream and a spent catalyst stream, and subsequently providing at least one of the first HCl effluent stream and the second HCl effluent stream and the spent catalyst stream to a catalyst regenerator to regenerate the spent catalyst stream.

Description

Technology Field

[0001] Cross-reference regarding related applications

[0002] This application claims the benefit of U.S. Patent Application 18 / 530,454 filed December 6, 2023, the full text of which is incorporated into the present invention by reference.

[0003] Technology field

[0004] The present invention relates to an integrated method and related system for naphtha reforming and benzyl toluene production. Background Technology

[0005] Aromatic compounds and olefins, such as BTX (benzene, toluene, and xylene), are high-value chemicals frequently utilized in the production of numerous materials and the manufacture of many consumer goods. For example, BTX compounds are frequently used in the processing or production of petroleum products and in the production of consumer goods such as paints and lacquers, thinners, fuels, rubber products, adhesives, inks, cosmetics, and pharmaceuticals. Similarly, light olefins are basic raw materials for many modern plastic products. One of the most common ways to produce BTX compounds is through naphtha reforming. Therefore, naphtha reforming methods are typically incorporated into hydrocarbon refineries.

[0006] In addition, benzyl toluene is one of the most promising carriers for hydrogen transport due to its high boiling point, low melting point, low flammability, high ignition point, and high hydrogen storage density. Therefore, the demand for benzyl toluene is expected to increase steadily in the future. Accordingly, the production of benzyl toluene is expected to gradually expand in hydrocarbon purification facilities.

[0007] Considering the current and anticipated increase in demand for these high-value-added chemicals, it is desirable to efficiently produce BTX and benzyl toluene. However, conventional purification systems and methods fail to maximize the economic synergy effects that can be obtained by integrating these methods.

[0008] Therefore, there has been a clear and long-standing need to provide an efficient and economical method for producing both BTX and benzyltoluene. The method and system of the present invention address this clear and long-standing need by utilizing a method and system that integrates the two production methods to mutually benefit the use of a waste stream from one method as a feed for the other method. Specifically, the regeneration of the reforming catalyst used in the naphtha reforming method requires a continuous supply of chlorine, which can incur costs for production, storage, and / or transportation. However, the integrated method of the present invention allows waste HCl to be delivered directly to the catalyst regenerator without the need for expensive purchase and / or transportation, and without the generation of excess carbon dioxide. Similarly, toluene produced as part of naphtha reforming can be directly utilized in the benzyltoluene production method, thereby eliminating or reducing production, storage, and / or transportation costs.

[0009] According to one or more aspects of the present invention, an integrated method for naphtha reforming and benzyl toluene production is described. The method comprises the steps of: (i) providing a first toluene stream and a chlorine gas stream to a halogenation reactor; (ii) operating the halogenation reactor to produce a benzyl chloride stream and a first HCl effluent stream; (iii) providing the benzyl chloride stream, the second toluene stream, and a Lewis acid stream to an alkylation reactor; (iv) operating the alkylation reactor to produce a benzyl toluene stream and a second HCl effluent stream through a Friedel-Crafts reaction; (v) providing naphtha to a catalytic reforming unit in which a reforming catalyst is placed; and (vi) operating the catalytic reforming unit to produce a reformed stream and a spent catalyst stream, wherein the spent catalyst stream represents the used reforming catalyst. (vii) providing at least one of the first HCl effluent stream and the second HCl effluent stream and the spent catalyst stream to a catalyst regenerator; (viii) operating the catalyst regenerator to regenerate the reforming catalyst and form a regenerated reforming catalyst stream; and (ix) providing the regenerated reforming catalyst stream to the catalyst reforming unit as a recirculation stream.

[0010] In a further embodiment, the reforming stream is provided to an aromatic complex to separate and capture benzene, toluene, and mixed xylene; and the toluene captured in the aromatic complex is provided, at least partially, to at least one of a halogenation reactor and an alkylation reactor instead of the first toluene stream and the second toluene stream.

[0011] According to one or more aspects of the present invention, an integrated system for naphtha reforming and benzyl toluene production is described. The system comprises: (i) a catalytic reforming unit comprising an inlet receiving a naphtha feed stream, a reforming catalyst disposed within the catalytic reforming unit, and two or more outlets discharging a spent catalyst stream and a reformer stream, configured to reform the naphtha feed stream to produce a reformer stream and a spent catalyst stream; (ii) a catalytic regenerator fluidically connected to the catalytic reforming unit to receive a spent catalyst stream and configured to regenerate the spent catalyst; and (iii) a halogenation reactor comprising an inlet receiving a first toluene stream, an inlet receiving a chlorine stream, an outlet discharging a first HCl effluent stream, and an outlet discharging a benzyl chloride stream. (iv) an alkylation reactor comprising an inlet receiving a benzyl chloride stream from a halogenation reactor, an inlet receiving a Lewis acid stream, an inlet receiving a second toluene stream, an outlet discharging a benzyl toluene stream, and an outlet discharging a second HCl effluent stream, and operating based on a Friedel-Crafts reaction; and (v) one or more HCl recirculation lines comprising a catalyst regenerator fluidly connected to the halogenation reactor and the alkylation reactor to transfer the first HCl effluent stream and the second HCl effluent stream to the inlet of the catalyst regenerator.

[0012] In a further embodiment, the system comprises: an aromatic complex, configured to receive a reforming stream and separate it into a benzene stream, a third toluene stream, and a mixed xylene stream; and a fluid connection between a halogenation reactor and an alkylation reactor, further comprising a fluid connection for transferring the third toluene stream from the aromatic complex to at least one of the halogenation reactor and the alkylation reactor, at least partially instead of the first toluene stream and the second toluene stream.

[0013] Additional features and benefits of the described embodiments are set forth in the following detailed description. These additional features and benefits of the described embodiments will, in part, become readily apparent to those skilled in the art from the description or will be recognized by practicing the described embodiments, including the detailed description and the following drawings and claims. Brief explanation of the drawing

[0014] The following detailed description of specific embodiments of the present disclosure is best understood when read together with the drawings. FIG. 1 is a schematic diagram of one or more embodiments of the integrated method for naphtha reforming and benzyl toluene production of the present invention; FIG. 2 is a schematic diagram of the production of benzyl chloride according to one or more aspects of the present invention; FIG. 3 is a schematic diagram of the production of benzyl toluene according to one or more embodiments of the present invention; FIG. 4 is a schematic diagram of a catalyst regenerator according to one or more embodiments of the present invention; FIG. 5 is a schematic diagram of one or more embodiments of the integrated method for naphtha reforming and benzyl toluene production of the present invention, comprising a parallel naphtha reforming unit; FIG. 6 is a schematic diagram of one or more embodiments of the integrated method for naphtha reforming and benzyl toluene production of the present invention, including an aromatic complex facility; FIG. 7 is a schematic diagram of one or more embodiments of the integrated method for naphtha reforming and benzyl toluene production illustrated in FIG. 6, including toluene recycling; FIG. 8 is a schematic diagram of one or more embodiments of the naphtha reforming and benzyl toluene production integrated method illustrated in FIG. 6, comprising reverse-transalkylation of benzene and mixed xylene for toluene production; FIG. 9 is a schematic diagram of one or more embodiments of the naphtha reforming and benzyl toluene production integrated method illustrated in FIG. 6, including the hydrogenation of benzyl toluene for the production of perhydrobenzyl toluene. For the sake of these simplified schematics and descriptions, numerous valves, temperature sensors, electronic controllers, etc., which are customarily used in specific refining facility operations and are well known to those skilled in the art, are not included. Additionally, components associated with conventional refining facility operations, such as air supplies, nitrogen supplies, hydrogen supplies, catalyst hoppers, and flue gas handling, are not necessarily depicted. Additionally, arrows in the drawing refer to pipes, conduits, channels, or other physical transmission lines connecting one or more system units to one or more other system units by fluidic communication. Furthermore, arrows connecting to system units define the inlets and outlets of each provided system unit. Various embodiments will be described in more detail, some of which are exemplified in the attached drawings. Where possible, the same reference numbers have been used throughout the drawings to refer to identical or similar parts. Specific details for implementing the invention

[0015] Aspects of the integrated method for naphtha reforming and benzyl toluene production and the related system of the present invention will be described in detail below. Although the integrated system for naphtha reforming and benzyl toluene production shown in the attached drawings is provided as an example, it should be understood that the system and method of the present invention may also include other configurations.

[0016] The method and system of the present invention provide an integrated method and system for naphtha reforming and benzyl toluene production. Specifically, the method and system of the present invention utilizes HCl, which is generated as a byproduct during benzyl toluene production, for the regeneration of a reforming catalyst used in naphtha reforming. The synergy generated from the integration of different hydrocarbon treatment operations reduces the costs, waste, and pollution of each individual method by converting waste stream products into high-value feedstocks.

[0017] In one or more embodiments, the integrated method for naphtha reforming and benzyl toluene production comprises the step of providing a first toluene stream (101) and a chlorine gas stream (103) to a halogenation reactor (10) and operating the halogenation reactor (10) to produce a benzyl chloride stream (115) and a first HCl effluent stream (117). The method further comprises the step of providing the benzyl chloride stream (115), a second toluene stream (111), and a Lewis acid stream (113) to an alkylation reactor (20) and operating the alkylation reactor (20) to produce a benzyl toluene stream (125) and a second HCl effluent stream (127) via a Friedel-Crafts reaction. The method also comprises the step of providing a naphtha stream (105) to a catalytic reforming unit (30), wherein a reforming catalyst (32) is placed within the catalytic reforming unit (30). Additionally, the method comprises the step of operating a catalyst reforming unit (30) to generate a reformed material stream (132) and a spent catalyst stream (134), wherein the spent catalyst stream (134) represents a used reforming catalyst (32). The method further comprises the step of providing at least one of a first HCl effluent stream (117) and a second HCl effluent stream (127) and the spent catalyst stream (134) to a catalyst regenerator (40), and operating the catalyst regenerator (40) to regenerate the reforming catalyst (32) and form a regenerated reforming catalyst stream (136). Finally, the method comprises the step of providing the regenerated reforming catalyst stream (136) to the catalyst reforming unit (30) as a recirculation stream to replenish the reforming catalyst (32).

[0018] In one or more embodiments, an integrated system (100) for naphtha reforming and benzyl toluene production comprises a catalyst reforming unit (30) comprising an inlet receiving a naphtha feed stream (105), a reforming catalyst (32) disposed within a catalyst reforming unit (30), and two or more outlets discharging a spent catalyst stream (134) and a reformed product stream (132), wherein the catalyst reforming unit (30) is configured to reform the naphtha feed stream (105) to produce a reformed product stream (132) and a spent catalyst stream (134). The system (100) further comprises a catalyst regenerator (40) fluidically connected to the catalyst reforming unit (30) to receive the spent catalyst stream (134), wherein the catalyst regenerator (40) is configured to regenerate the spent catalyst from the spent catalyst stream (132). Additionally, the system (100) comprises a halogenation reactor (10) comprising an inlet receiving a first toluene stream (101), an inlet receiving a chlorine stream (103), an outlet discharging a first HCl effluent stream (117), and an outlet discharging a benzyl chloride stream (117). Additionally, the system (100) comprises an alkylation reactor (20) comprising an inlet receiving a benzyl chloride stream (115) from the halogenation reactor (10), an inlet receiving a Lewis acid stream (113), an inlet receiving a second toluene stream (111), an outlet discharging a benzyl toluene stream (125), and an outlet discharging a second HCl effluent stream (127), wherein the alkylation reactor (20) operates based on a Friedel-Crafts reaction. Finally, the system (100) includes one or more HCl recirculation lines (138) that fluidly connect the catalyst regenerator (40) to the halogenation reactor (10) and the alkylation reactor (20) to deliver the first HCl effluent stream (117) and the second HCl effluent stream (127) to the inlet of the catalyst regenerator (40).

[0019] Basic operations of the integrated method and related system for naphtha reforming and benzyl toluene production have been described, and each step and unit operation of the embodiment of the integrated method and related system is now provided in additional detail.

[0020] Benzyl toluene formation

[0021] The production of benzyl toluene is generally achieved through a two-step method. In the first step, benzyl chloride is synthesized by reacting toluene with chlorine. Subsequently, in the second step, benzyl chloride is reacted with toluene via Friedel-Crafts alkylation to form benzyl toluene. This method and related unit operations are discussed herein, along with separate discussions regarding the production of benzyl chloride and benzyl toluene.

[0022] Benzyl chloride can be produced according to an embodiment of the present invention using any method known to those skilled in the art. Benzyl chloride is typically produced on an industrial scale using thermal or photochemical chlorination of toluene. Specifically, irradiation using ultraviolet light or beta rays and elevated temperature conditions, such as 65 to 100°C, promote a reaction between toluene and chlorine gas to produce benzyl chloride. Due to this irradiation, chlorine molecules are excited and decomposed into two chloride ions, which can react with toluene. Specifically, hydrogen is removed from the methyl group of toluene and replaced by a chloride ion. Additionally, the hydrogen ion removed from the methyl group of toluene can react with the remaining chloride ion to form HCl. The entire reaction is exemplified in Reaction Scheme 1 provided below. This reaction is carried out in a halogenation reactor (10).

[0023] Reaction Equation 1

[0024] Next, according to an embodiment of the present invention, benzyl toluene can be produced from benzyl chloride using any method known to those skilled in the art. The production of benzyl toluene from benzyl chloride is typically carried out via a Friedel-Crafts reaction. Specifically, benzyl chloride reacts with toluene in the presence of a Lewis acid. The entire reaction is exemplified in Reaction Scheme 2 provided below. This reaction is carried out in an alkylation reactor (20).

[0025] Reaction Equation 2

[0026] Halogenation reactor

[0027] Benzyl chloride is produced from toluene and chlorine gas in a halogenation reactor (10). In one or more embodiments, the halogenation reactor (10) comprises an inlet receiving a first toluene stream (101), an inlet receiving a chlorine stream (103), an outlet discharging a first HCl effluent stream (117), and an outlet discharging a benzyl chloride stream (115). In one or more embodiments, the first HCl effluent stream (117) and the benzyl chloride stream (115) may be discharged from the halogenation reactor (10) as a single stream, which may then be separated by any conventional method known to those skilled in the art to produce separate first HCl effluent stream (117) and benzyl chloride stream (115). For brevity, such separation is not illustrated in the drawings provided herein, but will be fully understood by those skilled in the art.

[0028] In one or more embodiments, the halogenation reactor (10) utilizes the thermal chlorination of toluene to produce benzyl chloride. For example, the halogenation reactor (10) may operate at 65°C to 200°C, 100°C to 200°C, or 65°C to 100°C to excite chlorine in the chlorine stream (103) to produce chloride ions for reaction with the toluene provided as the first toluene stream (101).

[0029] In one or more embodiments, the halogenation reactor (10) utilizes the photochemical chlorination of toluene to produce benzyl chloride. For example, the halogenation reactor (10) may include a lamp emitting radiation in the ultraviolet region to excite chlorine in the chlorine stream (103) to produce chloride ions for reaction with the toluene provided in the first toluene stream (101). In various embodiments, the light may be provided from a light-emitting diode (LED) bank, a mercury vapor lamp, or other light source. For example, the LED may emit radiation of a wavelength of 395 nm or 365 nm in the ultraviolet region. Likewise, the mercury vapor lamp may emit light in the wavelength range of 300 to 500 nm, corresponding to the region where the absorption band of chlorine exists.

[0030] In one or more embodiments, the halogenation reactor (10) is operated substantially at atmospheric pressure. When operated at atmospheric pressure and temperature within the range discussed above, toluene is maintained in a liquid state and chlorine is maintained in a gaseous state. However, at other temperatures within the range discussed above, both toluene and chlorine are in a gaseous state and benzyl chloride is in a liquid state. Specifically, benzyl chloride has a boiling point of 179°C and toluene has a boiling point of 110.6°C, creating an operating range between these boiling points where benzyl chloride is liquid and toluene is gas. Under these conditions, benzyl chloride can be removed from the halogenation reactor (10) as it forms and condenses.

[0031] In one or more embodiments, with reference to FIG. 2, the halogenation reactor (10) comprises a chlorination unit (12) and a toluene recirculation unit (14). The chlorination unit (12) converts a first toluene stream (101) into a chlorinated compound in the chlorination unit effluent (119) and into HCl in the first HCl effluent stream (117). The toluene recirculation unit (14) receives the chlorination unit effluent (119) from the chlorination unit (12) and separates unreacted toluene (144) from the chlorinated compound in the chlorination unit effluent (119). The unreacted toluene (144) is recirculated as a feed to the chlorination unit (12), and the chlorinated compound is discharged for utilization or further treatment.

[0032] It will be known that by reacting chlorine and toluene to form benzyl chloride, benzyl chloride can be further chlorinated to form highly chlorinated compounds such as benzoyl chloride or benzotrile chloride. To minimize the formation of these highly chlorinated compounds, toluene may be provided to the chlorination unit (12) in excess of the chlorine provided to the chlorine gas stream (103). Specifically, the excess toluene causes most of the chlorine to be consumed in the formation of benzyl chloride, thereby minimizing or eliminating the formation of highly chlorinated compounds. Specifically, benzyl chloride is formed first and then reacts with additional Cl2 to form benzoyl chloride. Since this is a chain reaction, consuming more chlorine in the first step inhibits the second reaction to form benzoyl chloride. Accordingly, in one or more embodiments, the conversion of a toluene stream into a chlorinated compound, comprising both the first toluene stream (103) and unreacted toluene (144) supplied to the chlorination unit (12), may be limited to 20 to 40% of the toluene inflow. However, depending on various embodiments, the collection and recirculation of unreacted toluene (144) causes the conversion of the first toluene stream (103) initially supplied to the chlorination unit (12) to reach 50%, 60%, 70%, 80%, 90%, 50 to 95%, 60 to 95%, 70 to 95%, 80 to 95%, or 85 to 95%.

[0033] In one or more embodiments, the chlorination reactor (12) may be operated at the same temperature and pressure as generally described in detail for the halogenation reactor (10). For example, the chlorination reactor (12) may be operated at a temperature of 65 to 100°C and at atmospheric pressure.

[0034] The toluene recirculation unit (14) receives the chlorination unit effluent (119) from the chlorination unit (12) and separates unreacted toluene (144) from the chlorination compounds in the chlorination unit effluent (119). Chlorination compounds that boil at a higher temperature than toluene are discharged as a chlorination compound stream (146). Additionally, compounds that boil at a lower temperature than toluene may be discharged from the toluene recirculation unit (14) as toluene separation off-gas (142). Since the toluene separation off-gas (142) contains mostly HCl, small amounts of hydrocarbons or other chloride chemical species are combusted when introduced into the catalyst regenerator (40), so there is no need to purify this stream. Accordingly, the toluene recirculation unit (14) produces a stream of toluene separation off-gas (142), a stream of unreacted toluene (144), and a chlorinated compound stream (146).

[0035] The toluene recirculation unit (14) may include any unit operation or system known to those skilled in the art for separating a hydrocarbon stream by vapor pressure. An example of the toluene recirculation unit (14) is an atmospheric distillation unit. The atmospheric distillation unit separates the feed streams using fractional distillation, which heats the feed to a temperature at which one or more fractions of the mixture vaporize and another fraction remains liquid. Additionally, in various embodiments, the toluene recirculation unit (14) may be a simple flash column or a true boiling point distillation having 15 or more theoretical stages.

[0036] In one or more embodiments, the toluene recirculation unit (14) comprises a plurality of separation units. For ease of illustration, the provided FIG. 2 illustrates a single unit operation, but it is understood that such unit operation may include several individual separator units to produce the described product stream.

[0037] In one or more embodiments, unreacted toluene (144) is provided to a toluene storage tank (148) to store unreacted toluene (144) before being transferred to a chlorination unit (12). The toluene storage tank (148) enables steady-state supply to the chlorination unit (12) while providing a buffer to compensate for fluctuations in the recovery rate of unreacted toluene (144) from the chlorination unit effluent (119).

[0038] In one or more embodiments, the chlorinated compound is discharged from the toluene recirculation unit (14) as a chlorinated compound stream (146). The chlorinated compound stream (146) may be supplied to a benzyl chloride separation unit (16) for the separation of benzyl chloride to form a benzyl chloride stream (115). Specifically, the benzyl chloride separation unit (16) may separate the benzyl chloride stream (115) from a light fraction and a highly chlorinated fraction (164) of a benzyl chloride separation off-gas (162). The benzyl chloride separation off-gas (162) contains a fraction that boils at a lower temperature than benzyl chloride, and the highly chlorinated fraction (164) contains a chemical species that boils at a higher temperature than benzyl chloride. The highly chlorinated fraction may include benzoyl chloride and benzotrile chloride, each representing toluene having two or three chlorinations.

[0039] The benzyl chloride separation unit (16) may comprise any unit operation or system known to those skilled in the art for separating a hydrocarbon stream by vapor pressure. An example of the benzyl chloride separation unit (16) is an atmospheric distillation unit. Additionally, in various embodiments, the benzyl chloride separation unit (16) may be a simple flash column having 15 or more theoretical stages or a true boiling point distillation. Additionally, in one or more embodiments, the benzyl chloride separation unit (16) comprises separation units. For ease of illustration, the provided FIG. 2 illustrates a single unit operation, but it is understood that such a unit operation may comprise several individual separator units for producing the described product stream.

[0040] alkylation reactor

[0041] Benzyl toluene is produced from toluene and benzyl chloride together with a Lewis acid in an alkylation reactor (20). In one or more embodiments, the alkylation reactor (20) comprises an inlet receiving a benzyl chloride stream (115) from a halogenation reactor (10), an inlet receiving a Lewis acid stream (113), an inlet receiving a second toluene stream (111), an outlet discharging a benzyl toluene stream (125), and an outlet discharging a second HCl effluent stream (127). Additionally, the alkylation reactor (20) operates based on a Friedel-Crafts reaction to produce a benzyl toluene stream (125). Since the mechanism of the Friedel-Crafts reaction is well known, a detailed description of the mechanism is omitted. It will be understood that in one or more embodiments, the second HCl effluent stream (127) and the benzyl toluene stream (125) may be discharged from the alkylation reactor (20) as a single stream, which may then be separated by any conventional method known to those skilled in the art to produce separate second HCl effluent stream (127) and benzyl chloride stream (125). For brevity, such separation is not illustrated in the drawings provided herein, but will be fully understood by those skilled in the art.

[0042] In one or more embodiments, with reference to FIG. 3, the alkylation reactor (20) comprises a benzylation unit (22) and a toluene recovery unit (24). The benzylation unit (22) converts the benzyl chloride stream (115) into benzyl toluene in the benzylation unit effluent (222) and into HCl in the second HCl effluent stream (127). The toluene recovery unit (24) receives the benzylation unit effluent (222) from the benzylation unit (22) and separates residual toluene (242) from the benzyl toluene in the benzylation unit effluent (222). The residual toluene (242) may be recycled as a feed to the halogenation reactor (10) or the benzylation unit (22), and the benzyl toluene is discharged as a benzyl toluene stream (125) for utilization or further treatment.

[0043] In one or more embodiments, the benzylation unit (22), which completes the Friedel-Crafts reaction of the benzyl chloride stream (115) to produce benzyl toluene in the benzylation unit effluent (222) and HCl in the second HCl effluent stream (127), is operated at a temperature in the range of 50°C to 150°C. In various additional embodiments, the benzylation unit (22) may be operated at 70°C to 150°C, 90°C to 150°C, 120°C to 140°C, or approximately 130°C.

[0044] The Friedel-Crafts reaction of the benzyl chloride stream (115) to produce benzyl toluene in the benzylation unit effluent (222) and HCl in the second HCl effluent stream (127) is completed with the provision of a Lewis acid stream (113). The Lewis acid acts as a catalyst to promote the Friedel-Crafts reaction. In one or more embodiments, the Lewis acid stream (113) comprises one or more of ZnCl2, FeCl3, AlCl3, SnCl3, and TiCl4. Thus, in one or more embodiments, the Lewis acid provided to the alkylation reactor (20), more particularly to the benzylation unit (22), may be selected from ZnCl2, FeCl3, AlCl3, SnCl3, and TiCl4.

[0045] In one or more embodiments, the Lewis acid is supplied to the benzylation unit (22) of the alkylation reactor (20) at 50 ppm to 50 weight percent of the total feed to the benzylation unit (22). In one or more additional embodiments, a solid catalyst is charged into the alkylation reactor (20) so that the Lewis acid stream (113) is not required.

[0046] To minimize the formation of dibenzyltoluene and other higher-order products, the total toluene provided to the benzylation unit (22) may be in excess compared to the benzyl chloride provided to the benzyl chloride stream (115) required for the completion of the Friedel-Crafts reaction. Specifically, because benzyltoluene is more reactive than benzyl chloride and toluene, overalkylation may be an issue. Alkylation can be controlled by providing an excess of toluene to consume all chloride species.

[0047] The toluene recovery unit (24) may include any unit operation or system known to those skilled in the art for separating a hydrocarbon stream by vapor pressure. An example of the toluene recovery unit (24) is an atmospheric distillation unit. Additionally, in various embodiments, the toluene recovery unit (24) may be a simple flash column having 15 or more theoretical stages or a true boiling point distillation. The residual toluene (242) removed by the toluene recovery unit (24) may be recycled as a feed to the halogenation reactor (10) or the benzylation unit (22) to reduce the demand for fresh toluene for these unit operations.

[0048] In one or more embodiments, the benzylation unit effluent (222) essentially consists of a benzyltoluene oligomer and excess toluene, which may contain chlorinated organic compounds such as chlorotoluene, chlorobenzyltoluene, and, generally, a benzyltoluene oligomer having one or more chlorine atoms in a benzene nucleus. These compounds may be introduced or formed from impurities of benzyl chloride or Lewis acids. After removing excess toluene in the toluene recovery unit (24), the resulting benzyltoluene stream (125) may be further treated to remove chlorinated organic compounds. For example, the benzyltoluene stream (125) may be treated with an alcoholate and heated with stirring to a temperature in the range of 220°C to 320°C. After dechlorination treatment, a single distillation may be performed to recover a benzyltoluene oligomer with a low chlorine content. The heavy fraction containing residues of the dechlorination agent, NaCl, iron salts, and heavy benzyltoluene oligomers remains as the bottom of the distillation column.

[0049] Catalytic reforming unit

[0050] Catalytic reforming is a chemical method that converts low-octane petroleum refining naphtha, distilled from crude oil, into a high-octane liquid product called a reformer. The reformer is used as a premium blending feedstock for high-octane gasoline. Specifically, catalytic reforming converts low-octane linear hydrocarbons, such as paraffins, into branched alkanes, such as isoparaffins and cyclic naphthenes, which are then partially dehydrogenated to produce high-octane aromatic hydrocarbons. Therefore, it is common to include catalytic reforming within hydrocarbon refining facilities.

[0051] In one or more embodiments, the catalytic reforming unit (30) comprises an inlet receiving a naphtha feed stream (105), a reforming catalyst (32) disposed within the catalytic reforming unit (30), and two or more outlets discharging a spent catalyst stream (134) and a reformed product stream (132). The catalytic reforming unit (30) is configured to reform the naphtha feed stream (105) to produce a reformed product stream (132) and a spent catalyst stream (134) as a byproduct of the operation.

[0052] In one or more embodiments, the naphtha feed stream (105) is pretreated to remove impurities, contaminants, and other chemical species that may adversely affect the operation of the catalytic reforming unit (30). Such pretreatment may include hydrotreatment or filtering. Such operations are within the scope and knowledge of those skilled in the art based on the specific characteristics of the naphtha feed stream (105).

[0053] The operation of the catalyst reforming unit (30) and specific processing parameters of the naphtha feed stream (105) are excluded from the scope of the invention. Specifically, the invention relates to achieving synergistic benefits by integrating the naphtha reforming process and related methods for regenerating the spent catalyst generated as part of the naphtha reforming process with the production of benzyl toluene. Accordingly, the catalyst reforming unit (30) may operate at the temperature, pressure, liquid-time-space velocity, or other operating parameters desired or required for the catalytic reforming of naphtha, as understood by those skilled in the art.

[0054] The catalytic reforming unit (30) includes a reforming catalyst (32) disposed within the catalytic reforming unit (30). The catalyst bed reactor of the catalytic reforming unit (30) may operate as a moving bed reactor in one or more embodiments. In an additional embodiment, the catalyst bed reactor of the catalytic reforming unit (30) may operate as a fixed bed reactor.

[0055] The catalyst reforming unit (30) can operate as a continuous regenerative reformer, a semi-continuous regenerative reformer, or a circulating regenerative reformer. For the purposes of this invention, the continuous regenerative reformer operates continuously while continuously removing the spent catalyst and replacing it with a regenerated catalyst or a new catalyst, the semi-continuous regenerative reformer operates continuously for a certain period before stopping the naphtha-reforming operation and regenerating the catalyst in the same reaction system, and the circulating regenerative reformer operates multiple reactors in parallel while the remaining reactors continue to operate and can be periodically shut down for regeneration.

[0056] As used herein, "spent catalyst" refers to a catalyst that reacts with naphtha to produce at least partially coke. Additionally, as used herein, "regenerated catalyst" refers to a catalyst discharged from a catalyst regenerator from which at least partially or substantially the coke has been removed, and "fresh catalyst" refers to a catalyst newly introduced into the system (100) from which at least partially or substantially the coke has been removed.

[0057] The catalyst used in the naphtha reforming method is typically binary functional and contains a metal for dehydrogenation and hydrogenation functionality and a metal for acid-catalyzed isomerization functionality. The metal sites are provided by platinum and metal promoters such as rhenium, tin, germanium, and iridium. Additionally, an alumina support and a chloride typically provide acid-catalyzed isomerization functionality for the catalyst. In one or more embodiments, the reforming catalyst (32) is platinum on an alumina catalyst. In further embodiments, a zeolite and a metal catalyst may be utilized with a zeolite provided at the acid site.

[0058] Catalyst regenerator

[0059] The catalyst regenerator (40) receives the spent catalyst stream (134) and regenerates the spent catalyst to produce a regenerated reformed catalyst stream (136). As previously described, the reformed catalyst (32) can be regenerated continuously or periodically. The purpose of catalyst regeneration is to restore the reformed catalyst (32) to a state similar to that of a new catalyst, in which the metal and acid portions function as before the coke deposition for use. Accordingly, catalyst regeneration typically involves burning the deposited coke in a controlled manner, reprocessing the platinum and promoter metals, and restoring the catalyst chloride levels.

[0060] In one or more embodiments, with reference to FIG. 4, the catalyst regenerator (40) can operate while continuously regenerating the reforming catalyst (32). The continuously regenerating catalyst regenerator (40) can operate in three separate zones: a catalyst regeneration zone, a chlorination zone, and a drying zone. A spent catalyst stream (134) is provided to the top of the catalyst regenerator (40), and the spent catalyst passes through each zone sequentially and is discharged to the bottom of the catalyst regenerator as a regenerated reforming catalyst stream (136).

[0061] The catalyst regeneration zone removes carbonaceous material and coke from the spent catalyst. Carbonaceous material or coke is an undesirable byproduct of the naphtha reforming method and is deposited on the reforming catalyst (32), and the amount of carbonaceous deposition increases depending on the operating time, feed quality, and catalyst condition. Consequently, as platinum and acidic areas become covered with coke, the catalyst activity and selectivity performance are also degraded. Therefore, it is necessary to remove the coke during the catalyst regeneration process. In one or more embodiments, the spent catalyst is heated to a coke removal temperature of 500°C to 600°C in an environment with controlled oxygen levels to produce a decoke catalyst. For example, in one or more embodiments, a nitrogen stream containing 0.8 to 1.3 wt.% oxygen is provided to provide a controlled oxygen environment to produce the decoke catalyst. Controlled combustion of the catalyst coke during the regeneration process is possible through the control of temperature and oxygen concentration.

[0062] In one or more embodiments, the spent catalyst stream (134) may pass through a separating hopper (not shown) to remove the catalyst before being supplied to the catalyst regenerator (40). Additionally, supplying the spent catalyst to the catalyst regenerator (40) includes hydrogen purging to remove associated hydrocarbons and gases, thereby enabling safe catalyst heating and regeneration within the catalyst regenerator (40).

[0063] After decoking, the decoking catalyst is moved to a chlorination zone. In the chlorination zone, platinum is redispersed and chlorine is replenished in the alumina support. Even if controlled coking is performed, metal crystal grains within the modified catalyst (32) can be calcined during the regeneration process. As the diameter of the metal crystal grains increases, the activity of the modified catalyst (32) decreases. Therefore, it is desired to redisperse metals such as platinum through an oxychlorination method. Typically, due to transportation and storage issues, instead of directly providing HCl according to the present invention, HCl and Cl2 are produced using organic chlorides such as dichloroethane, dichloropropane, or tetrachloroethylene as precursors. For example, in the case of dichloroethane, HCl is produced as an intermediate product through Deacon equilibrium to obtain chlorine. Then, redispersion is achieved by the chlorine reacting with Pt oxide to form volatile chemical species. However, if HCl is supplied directly from an HCl recirculation line (138) that fluidly connects the catalyst regenerator (40) to the halogenation reactor (10) and the alkylation reactor (20) for transporting the first HCl effluent stream (117) and the second HCl effluent stream (127), the initial step of oxychlorination can be skipped.

[0064] The redistribution of platinum and the replenishment of chlorine in the reforming catalyst (32) are achieved according to reaction formula 3 within the catalyst regeneration zone of the catalyst regenerator (40), and subsequently according to reaction formulas 4 and 5 within the chlorination zone of the catalyst regenerator (40). Specifically, platinum oxide is produced according to reaction formula 3, Cl2 is produced according to reaction formula 4, and then platinum oxide and Cl2 react to produce a regenerated reforming catalyst. Reaction formulas 4 and 5 within the chlorination zone of the catalyst regenerator (40) for achieving oxychlorination can be performed at an operating temperature of 450°C to 550°C, 475°C to 550°C, 450°C to 525°C, 475°C to 525°C, or approximately 500°C.

[0065] Pt x + xO2↔ (PtO2) x Reaction Equation 3

[0066] 2HCl + 1 / 2O2 ↔ Cl2 + H2O (Decon equilibrium) Equation 4

[0067] (PtO2) x + Cl2↔ (PtO2) x-1 + Pt(O-Cl)2 reaction equation 5

[0068] In one or more embodiments, the reforming catalyst (32) passing through the chlorination zone of the catalyst regenerator (40) is further provided to the drying zone of the catalyst regenerator (40). The drying zone removes moisture adsorbed on the reforming catalyst (32) and then recirculates the reforming catalyst (32) to the catalyst reforming unit (30). Since water is a product of reaction 4, it is desirable to remove it. Drying is achieved by flowing nitrogen provided from the nitrogen supply (152). Since the temperature of the reforming catalyst (32) moving from the chlorination zone of the catalyst regenerator (40) is 450°C to 550°C, it will be seen that the temperature of the drying zone changes in such a way that it is higher at the inlet of the drying zone and lower at the outlet of the drying zone.

[0069] You will see that carbon dioxide emissions from the method can be reduced because carbon dioxide is generated as waste during the conversion process. Additionally, costs can be directly reduced by eliminating the need to purchase HCl by providing it directly from benzyl toluene production. Furthermore, when using the continuous regeneration method, the need for transportation or storage is eliminated because the waste stream from benzyl toluene production is consumed directly.

[0070] Naphtha reforming may also be achieved using multiple reactors. Accordingly, in one or more embodiments, with reference to FIG. 5, two or more catalyst reforming units (30) and two or more catalyst regenerators (40) may be provided in parallel to enable cyclic operation of each method line. Specifically, this arrangement allows the first catalyst reforming unit (30A) to be operated while regenerating the reforming catalyst (32) of the second catalyst reforming unit (40B), and the second catalyst reforming unit (30B) to be operated while regenerating the reforming catalyst (32) of the first catalyst reforming unit (40A).

[0071] Aromatic composite equipment

[0072] Referring to FIGS. 6 to 9 in one or more embodiments, the system (100) may include an aromatic complex facility (60) configured to receive a modified stream (132) and separate it into a benzene stream (162), a third toluene stream (164), and a mixed xylene stream (166).

[0073] In an aromatic complex facility (60), various systems and technologies can be utilized to separate the modified stream (132) into several fractions, and the present invention is not intended to be limited to a specific arrangement of the aromatic complex facility (60). Generally, the aromatic complex facility (60) produces a benzene stream (162), a third toluene stream (164), a mixed xylene stream (166), and an aromatic bottom fraction (168).

[0074] In some embodiments, the benzene stream (162) may comprise benzene and a cyclic aromatic hydrocarbon of the formula C6H6. In some embodiments, the benzene stream (162) may comprise at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of benzene based on the total weight of the benzene stream (162). In some embodiments, the third toluene stream (164) may comprise toluene and a substituted cyclic aromatic hydrocarbon of the formula C6H5CH3. In some embodiments, the third toluene stream (164) may comprise at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of toluene based on the total weight of the third toluene stream (164). In some embodiments, the mixed xylene stream (166) may comprise a xylene mixture. Xylene is a group of substituted cyclic aromatic hydrocarbons of the chemical formula (CH3)2C6H4. In some embodiments, the mixed xylene stream (166) may comprise at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of xylene based on the total weight of the mixed xylene stream (166).

[0075] In one or more embodiments, the reforming stream (132) passes through an aromatic extraction unit (70) to separate the reforming stream (132) into a non-aromatic fraction (172) and an aromatic fraction (170). Thus, the aromatic fraction (170) can be transferred to an aromatic complex (60) instead of the entire reforming stream (132). Although the non-aromatic fraction (172) is depicted as a single stream in FIGS. 6 through 9 to reduce complexity, it will be noted that the non-aromatic fraction (172) can be further separated into individual streams of various components. Likewise, although the aromatic bottom fraction (168) is depicted as a single stream in FIGS. 6 through 9 to reduce complexity, it will be noted that the aromatic bottom fraction (168) can be further separated into individual streams of various components.

[0076] In one or more embodiments, the aromatic fraction (170) is provided to a clay treatment unit (80) to remove unsaturated hydrocarbons from the aromatic fraction (170). The clay treatment unit (80) can be operated to purify the aromatic fraction (170). In one or more embodiments, the clay treatment unit (80) can be operated to remove at least non-aromatic olefin compounds from the aromatic fraction (170) by reacting non-aromatic olefin compounds by acid-catalyzed alkylation. Generally, these non-aromatic olefin compounds can contaminate downstream units (e.g., p-xylene extraction units) or degrade the purity of the generated aromatic streams (benzene stream (162), third toluene stream (164), and mixed xylene stream (166)). The clay treatment unit (80) can be operated by contacting the aromatic fraction (170) with a Lewis acid catalyst, such as active clay. The clay treatment unit (80) may contact the aromatic fraction (170) with a Lewis acid catalyst at a temperature greater than 165°C, e.g. greater than 170°C, greater than 180°C, 165°C to 250°C, 170°C to 230°C, 180°C to 22°C, 190°C to 210°C, or any of these sub-items. The resulting clay-treated stream (182) may be provided to the aromatic complex facility (60) instead of the whole modified stream (132) or the aromatic fraction (170).

[0077] In one or more embodiments, the clay-treated stream (182) may contain benzene, toluene, xylene, and C9+ aromatic compounds. In an embodiment, the clay-treated stream (182) may have a lower concentration of benzene and a higher concentration of toluene and xylene than the aromatic fraction (170). In an embodiment, the clay-treated stream (182) may contain a combined weight of at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, or at least 99 wt.% of benzene, toluene, xylene, and C9+ aromatic compounds based on the total weight of the clay-treated stream (182). In one or more embodiments, the clay-treated stream (182) may contain less than 5 wt.%, e.g., less than 2.5 wt.%, less than 1 wt.%, less than 0.5 wt.%, less than 0.25 wt.%, less than 0.1 wt.%, less than 0.01 wt.%, or even less than 0.001 wt.% of olefinic non-aromatic hydrocarbons based on the total weight of the clay-treated stream (182).

[0078] The configuration of an aromatic recovery complex is generally varied. In one or more embodiments, the aromatic complex (60) may include, for example, a dehexanizer distillation column that removes lighter components and discharges a bottom product stream. The bottom product stream may be fed to a benzene distillation column that removes the benzene top and discharges a bottom stream having, for example, toluene, mixed xylene, ethylbenzene, and C9+ aromatic compounds. In some cases, the top effluent may be introduced into an absorption and stripping column to purify the benzene. The bottom stream from the benzene distillation column may be processed in the absorption and stripping column to further remove lighter components from the distillation column. The aforementioned absorption and stripping column may include solvent extraction.

[0079] These bottom streams from the benzene distillation column can be finally processed in a distillation column to separate and recover toluene and various mixed xylenes. The distillation column may include toluene distillation column(s) and xylene distillation column(s). The toluene distillation column can separate and discharge the toluene top. The xylene distillation column can receive the bottom effluent from the toluene distillation column, separate and discharge the xylene top, and discharge a heavy aromatic (C9+) bottom stream such as the aromatic bottom fraction (168).

[0080] By integrating the aromatic complex facility (60), in one or more embodiments with reference to FIG. 7, the toluene captured in the aromatic complex facility (60) can be supplied to at least one of the halogenation reactor (10) and the alkylation reactor (20). Specifically, supplying the third toluene stream (164) to the halogenation reactor (10) and the alkylation reactor (20) can at least partially offset the demand for toluene from the first toluene stream (101) and the second toluene stream (111), respectively. Based on the toluene production rate in the aromatic complex plant (60) and the demand for toluene for each of the halogenation reactor (10) and the alkylation reactor (20), in one or more embodiments, the third toluene stream (164) may provide supplementary toluene to only one of the halogenation reactor (10) and the alkylation reactor (20) and provide an alternative toluene source to the other. In one or more embodiments, it should be noted that both the halogenation reactor (10) and the alkylation reactor (20) may be supplied from a single toluene supply line comprising valves and other standard piping equipment designed to supply a defined flow rate to each of the halogenation reactor (10) and the alkylation reactor (20). The third toluene stream (164) can be mixed with a single toluene supply line to combine all toluene sources for the halogenation reactor (10) and the alkylation reactor (20).

[0081] Reverse trans-alkylation reactor

[0082] In one or more embodiments, with reference to FIG. 8, at least a portion of the benzene stream (162) and mixed xylene stream (166) captured in the aromatic complex facility (60) may be supplied to a reverse trans-alkylation reactor (90) to convert the benzene and mixed xylene into toluene. The toluene produced in the reverse trans-alkylation reactor (90) is discharged as a trans-alkylation reactor effluent stream (192).

[0083] In one or more embodiments, the trans-alkylation reactor effluent stream (192) is recirculated as a feed to the aromatic complex (60). Specifically, the trans-alkylation reactor effluent stream (192) is toluene-rich, and this toluene can be recovered within the aromatic complex (60). Additional toluene is generated in the trans-alkylation reactor (90) and subsequently recovered in the aromatic complex (60), enabling further integration of naphtha reforming and benzyl toluene production methods and further reducing the demand for supplemental toluene.

[0084] Hydrogenation unit

[0085] In one or more embodiments, with reference to FIG. 9, a benzyl toluene stream (125) produced in an alkylation reactor (20) may be supplied to a hydrogenation unit (95). When the benzyl toluene stream (125) passes into the hydrogenation unit (95), the benzyl toluene in the benzyl toluene stream (125) is converted into perhydro benzyl toluene in the perhydro benzyl toluene stream (196).

[0086] In one or more embodiments, hydrogen generated in the catalytic reforming unit (30) may be supplied to the hydrogenation unit (95). Specifically, a hydrogen source is required for the operation of the hydrogenation unit (95), and the utilization of the hydrogen stream (194) generated as a waste stream through the normal operation of the catalytic reforming unit (30) further incorporates naphtha reforming and benzyl toluene production methods. This treatment may reduce or eliminate the need to obtain hydrogen for the operation of the hydrogenation unit (95).

[0087] Various aspects of integrated methods and systems for converting crude oil into high-value-added petrochemical products have been described, and it should be understood that these aspects can be utilized in conjunction with various other aspects.

[0088] According to the first aspect, an integrated method for naphtha reforming and benzyl toluene production comprises: (i) providing a first toluene stream and a chlorine gas stream to a halogenation reactor; (ii) operating the halogenation reactor to produce a benzyl chloride stream and a first HCl effluent stream; (iii) providing the benzyl chloride stream, a second toluene stream, and a Lewis acid stream to an alkylation reactor; (iv) operating the alkylation reactor to produce a benzyl toluene stream and a second HCl effluent stream via a Friedel-Crafts reaction; (v) providing naphtha into a catalytic reforming unit in which a reforming catalyst is placed; (vi) operating the catalytic reforming unit to produce a reforming stream and a spent catalyst stream, wherein the spent catalyst stream represents a used reforming catalyst; (vii) providing at least one of the first HCl effluent stream and the second HCl effluent stream and the spent catalyst stream to a catalyst regenerator; (viii) operating a catalyst regenerator to regenerate the reforming catalyst and form a regenerated reforming catalyst stream; and (ix) providing the regenerated reforming catalyst stream to a catalyst reforming unit as a recirculation stream.

[0089] A second aspect includes the method of the first aspect, which provides both the first HCl effluent stream and the second HCl effluent stream to a catalyst regenerator.

[0090] A third aspect includes a method of the first or second aspect, which provides a reformed stream to an aromatic complex facility to separate and capture benzene, toluene, and mixed xylene.

[0091] A fourth aspect includes a method of a third aspect, wherein the toluene captured in an aromatic complex is provided, at least partially, to at least one of a halogenation reactor and an alkylation reactor instead of a first toluene stream and a second toluene stream.

[0092] A fifth aspect includes a method of a third aspect, which provides the toluene captured in an aromatic complex facility to both a halogenation reactor and an alkylation reactor, at least partially, instead of the first toluene stream and the second toluene stream.

[0093] The sixth aspect includes a method of any one of the third to fifth aspects, wherein at least a portion of the benzene and mixed xylene captured in an aromatic complex is provided to a reverse trans-alkylation reactor to convert the benzene and mixed xylene into toluene within the trans-alkylation reactor effluent stream.

[0094] A seventh aspect includes the method of a sixth aspect, in which a trans-alkylation reactor effluent stream is recirculated as a feed to an aromatic complex.

[0095] The eighth aspect includes a method of any one of the first to seventh aspects, wherein benzyl toluene produced in an alkylation reactor is provided to a hydrogenation unit, hydrogen produced in a catalytic reforming unit is provided to a hydrogenation unit, and benzyl toluene is converted into perhydrobenzyl toluene.

[0096] The ninth aspect includes a method of any one of the first to eighth aspects in which a halogenation reactor produces benzyl chloride by thermal chlorination of toluene.

[0097] The 10th aspect includes a method of any one of the 1st to 9th aspects, wherein a halogenation reactor produces benzyl chloride by photochemical chlorination of toluene.

[0098] The 11th aspect comprises a method of any one of the 1st to 10th aspects, wherein a halogenation reactor comprises a chlorination unit and a toluene recirculation unit, wherein the chlorination unit converts toluene into a chlorinated compound and the toluene recirculation unit separates unreacted toluene from the chlorinated compound in the effluent of the chlorination unit; and the unreacted toluene is recirculated to the chlorination unit as a feed to achieve a benzyl chloride yield of at least 90% based on the toluene feed to the halogenation reactor.

[0099] The 12th aspect comprises a method of any one of the 1st to 11th aspects, wherein the Lewis acid provided to the alkylation reactor is selected from ZnCl2, FeCl3, AlCl3, SnCl3, and TiCl4.

[0100] The 13th aspect includes a method of any one of the 1st to 12th aspects, which provides an excess amount of toluene to an alkylation reactor to consume chloride chemical species and limit alkylation.

[0101] The 14th aspect includes a method of any one of the 1st to 13th aspects in which the catalyst regenerator operates in continuous regeneration.

[0102] The 15th aspect comprises a method of any one of the first to 13 aspects, wherein two or more catalyst reforming units and two or more catalyst regenerators are provided in parallel, and the method further comprises the step of alternately operating the first catalyst reforming unit while regenerating the reforming catalyst of the second catalyst reforming unit and operating the second catalyst reforming unit while regenerating the reforming catalyst of the first catalyst reforming unit.

[0103] The 16th aspect includes a method of any one of the 1st to 15th aspects, wherein a spent catalyst is heated to a coke removal temperature of 500°C to 600°C in a nitrogen stream containing 0.8 to 1.3 wt.% oxygen in a catalyst regenerator to produce a decoke catalyst.

[0104] The 17th aspect includes the method of the 16th aspect, in which the reforming catalyst is platinum on an alumina catalyst.

[0105] The 18th aspect includes the method of the 17th aspect, which passes a decoke catalyst through the chlorination zone of a catalyst regenerator and combines it with one or both of a first HCl effluent stream and a second HCl effluent stream in the presence of oxygen at an operating temperature of 475°C to 525°C to redistribute platinum from an alumina support of a reforming catalyst and replenish chlorine.

[0106] The 19th aspect includes a method of any one of the 1st to 18th aspects, wherein the reforming catalyst is further provided to a drying zone of a catalyst regenerator to remove moisture adsorbed on the catalyst and subsequently the reforming catalyst is recirculated back to a catalyst reforming unit.

[0107] According to the 20th aspect, an integrated system for naphtha reforming and benzyl toluene production comprises: (i) a catalytic reforming unit comprising an inlet receiving a naphtha feed stream, a reforming catalyst disposed within the catalytic reforming unit, and two or more outlets discharging a spent catalyst stream and a reformer stream, configured to reform the naphtha feed stream to produce a reformer stream and a spent catalyst stream; (ii) a catalyst regenerator fluidically connected to the catalytic reforming unit to receive a spent catalyst stream and configured to regenerate the spent catalyst; (iii) a halogenation reactor comprising an inlet receiving a first toluene stream, an inlet receiving a chlorine stream, an outlet discharging a first HCl effluent stream, and an outlet discharging a benzyl chloride stream; (iv) an alkylation reactor comprising an inlet receiving a benzyl chloride stream from a halogenation reactor, an inlet receiving a Lewis acid stream, an inlet receiving a second toluene stream, an outlet discharging a benzyl toluene stream, and an outlet discharging a second HCl effluent stream, and operating based on a Friedel-Crafts reaction; and (v) one or more HCl recirculation lines comprising a catalyst regenerator fluidly connected to the halogenation reactor and the alkylation reactor to transfer the first HCl effluent stream and the second HCl effluent stream to the inlet of the catalyst regenerator.

[0108] The 21st aspect includes a system of the 20th aspect further comprising an aromatic complex facility configured to receive a reforming stream and separate it into a benzene stream, a third toluene stream, and a mixed xylene stream.

[0109] The 22nd aspect comprises a system of the 21st aspect further comprising a fluid connection between a system halogenation reactor and an alkylation reactor, for transferring a third toluene stream from an aromatic complex to at least one of the halogenation reactor and the alkylation reactor, at least partially instead of the first toluene stream and the second toluene stream.

[0110] It will be obvious to those skilled in the art that various modifications and variations of the embodiments described herein are possible without departing from the essence and scope of the claimed subject matter. Accordingly, this specification is intended to encompass modifications and variations of the various embodiments described, and such modifications and variations are included within the scope of the claims and their equivalents.

[0111] For the purposes of this disclosure, the indication that a stream or effluent is delivered or provided explicitly refers to the manner in which the stream or effluent is delivered directly, as well as the manner in which an intermediate system or unit exists that can substantially alter the composition of the stream or effluent between the units. As used in the present invention, "directly" delivering a stream or effluent from one unit to another refers to moving a stream or effluent from a first unit to a second unit without moving the stream or effluent through an intervening reaction system or separation system that substantially alters the composition of the stream or effluent. Likewise, the indication that two systems are "fluidically connected" indicates that a stream can be delivered directly between the systems. 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 devices are not considered as intervening systems that alter the composition of the stream or effluent. Furthermore, combining two streams or effluents together is not considered to include an intervening system that alters the composition of one or both of the streams or effluents being combined.

[0112] It should be further understood that a stream may be named for a component of the stream, and that the named component of the stream may be a major component of the stream (e.g., comprising 50 wt.%, 70 wt.%, 90 wt.%, 95 wt.%, 99 wt.%, 99.5 wt.%, or even 99.9 wt.% to 100 wt.% of the stream contents). Additionally, it should be understood that a component of the stream is disclosed as moving from one system component to another system component when the stream containing said component is disclosed as moving from said system component to another system component. For example, a “hydrocarbon stream” disclosed as moving to a first system component or from a first system component to a second system component should be understood as equivalently disclosing “hydrocarbon” moving to the first system component or moving from a first system component to a second system component.

[0113] The singular form includes the plural form unless the context clearly specifies otherwise.

[0114] A range is provided throughout the entire disclosure. Each discontinuous value included in the range is also considered to be included. Furthermore, a range that can be formed by each discontinuous value included in the explicitly disclosed range is also considered to be likewise. Briefly, the same content following each disclosed range is not explicitly indicated, and a general description of the invention is provided.

[0115] The words “comprising,” “having,” and “containing,” and all grammatical variations thereof as used in this application and the claims, are each intended to have an open and non-restrictive meaning that does not exclude additional elements or steps.

Claims

Claim 1 An integrated method for naphtha reforming and benzyl toluene production, wherein the method comprises: (i) providing a first toluene stream and a chlorine gas stream to a halogenation reactor; (ii) operating the halogenation reactor to produce a benzyl chloride stream and a first HCl effluent stream; (iii) providing the benzyl chloride stream, the second toluene stream, and a Lewis acid stream to an alkylation reactor; (iv) operating the alkylation reactor to produce a benzyl toluene stream and a second HCl effluent stream via a Friedel-Crafts reaction; (v) providing naphtha to a catalytic reforming unit in which a reforming catalyst is placed; (vi) operating the catalytic reforming unit to produce a reforming stream and a spent catalyst stream, wherein the spent catalyst stream represents the used reforming catalyst; (vii) providing at least one of the first HCl effluent stream and the second HCl effluent stream and the spent catalyst stream to a catalyst regenerator. A method comprising: (viii) operating the catalyst regenerator to regenerate the reforming catalyst and form a regenerated reforming catalyst stream; and (ix) providing the regenerated reforming catalyst stream to the catalyst reforming unit as a recirculation stream. Claim 2 A method according to claim 1, wherein both the first HCl effluent stream and the second HCl effluent stream are provided to the catalyst regenerator. Claim 3 A method according to claim 1 or 2, wherein the modified stream is provided to an aromatic complex facility to separate and capture benzene, toluene, and mixed xylene. Claim 4 A method according to claim 3, wherein the toluene captured in the aromatic complex is provided, at least partially, to at least one of the halogenation reactor and the alkylation reactor instead of the first toluene stream and the second toluene stream. Claim 5 A method according to claim 3 or 4, wherein at least a portion of the benzene and the mixed xylene captured in the aromatic complex is provided to a reverse trans-alkylation reactor to convert the benzene and the mixed xylene into toluene in the trans-alkylation reactor effluent stream. Claim 6 A method according to claim 5, wherein the trans-alkylation reactor effluent stream is recirculated as a feed to the aromatic complex facility. Claim 7 A method according to any one of claims 1 to 6, wherein the benzyl toluene produced in the alkylation reactor is provided to a hydrogenation unit; hydrogen produced in the catalyst reforming unit is provided to the hydrogenation unit; and the benzyl toluene is converted into perhydrobenzyl toluene. Claim 8 A method according to any one of claims 1 to 7, wherein the halogenation reactor comprises a chlorination unit and a toluene recirculation unit, wherein the chlorination unit converts toluene into a chlorinated compound and the toluene recirculation unit separates unreacted toluene from the chlorinated compound in the effluent of the chlorination unit; and the unreacted toluene is recirculated to the chlorination unit as a feed. Claim 9 A method according to any one of claims 1 to 8, wherein the Lewis acid provided to the alkylation reactor is selected from ZnCl2, FeCl3, AlCl3, SnCl3, and TiCl4. Claim 10 A method according to any one of claims 1 to 9, wherein an excess amount of toluene is provided to an alkylation reactor to consume chloride chemical species and limit alkylation. Claim 11 A method according to any one of claims 1 to 10, wherein a spent catalyst is heated to a coke removal temperature of 500°C to 600°C in a nitrogen stream containing 0.8 to 1.3 wt.% oxygen in the catalyst regenerator to produce a decoke catalyst. Claim 12 A method according to claim 11, wherein the reforming catalyst is platinum on an alumina catalyst, and the decoking catalyst is passed through the chlorination zone of the catalyst regenerator and combined with one or both of the first HCl effluent stream and the second HCl effluent stream in the presence of oxygen at an operating temperature of 475°C to 525°C to redistribute platinum on the alumina support of the reforming catalyst and replenish chlorine. Claim 13 A method according to claim 12, wherein the modified catalyst is further provided to a drying zone of the catalyst regenerator to remove moisture adsorbed on the catalyst and subsequently the modified catalyst is recirculated back to the catalyst modification unit. Claim 14 An integrated system for naphtha reforming and benzyl toluene production, comprising: (i) a catalyst reforming unit comprising an inlet receiving a naphtha feed stream, a reforming catalyst disposed within the catalyst reforming unit, and two or more outlets discharging a spent catalyst stream and a reformed product stream, configured to reform the naphtha feed stream to produce the reformed product stream and the spent catalyst stream; (ii) a catalyst regenerator fluidically connected to the catalyst reforming unit to receive the spent catalyst stream and configured to regenerate the spent catalyst; (iii) a halogenation reactor comprising an inlet receiving a first toluene stream, an inlet receiving a chlorine stream, an outlet discharging a first HCl effluent stream, and an outlet discharging a benzyl chloride stream; (iv) an alkylation reactor comprising an inlet receiving the benzyl chloride stream from the halogenation reactor, an inlet receiving a Lewis acid stream, an inlet receiving a second toluene stream, an outlet discharging a benzyl toluene stream, and an outlet discharging a second HCl effluent stream, and an alkylation reactor operating based on a Friedel-Crafts reaction; and (v) a system comprising one or more HCl recirculation lines, wherein the catalyst regenerator is fluidly connected to the halogenation reactor and the alkylation reactor to transfer the first HCl effluent stream and the second HCl effluent stream to the inlet of the catalyst regenerator. Claim 15 A system according to claim 14, comprising: an aromatic complex, configured to receive the reforming stream and separate it into a benzene stream, a third toluene stream, and a mixed xylene stream; and a fluid connection between the halogenation reactor and the alkylation reactor, further comprising a fluid connection for transferring the third toluene stream from the aromatic complex to at least one of the halogenation reactor and the alkylation reactor, at least partially, instead of the first toluene stream and the second toluene stream.

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