Process for the manufacture of (di)amino derivatives of aniline and 1-methylbenzene from plastic waste and chemical products based on cyclohexanone manufactured from plastic waste

Abstract

The invention relates to a process and a chemical plant for separating benzene and 1-methylbenzene from a liquid stream comprising at least one pyrolysis oil made from plastic waste and further converting the benzene and 1-methylbenzene into aromatic amines. These aromatic amines are suitable as precursors for diisocyanate and polyisocyanate derivatives of benzene and 1-methylbenzene, which are at least partially based on benzene and 1-methylbenzene made from plastic waste. Furthermore, polyurethanes, thermoplastic polyurethanes, polyisocyanurates and polyureas can be made by the process according to the invention.

Description

Technical Field

[0001] This invention relates to a method for producing aniline and (di)amino derivatives of 1-methylbenzene from plastic waste, and to chemical products based on aniline and (di)amino derivatives of 1-methylbenzene produced from plastic waste. Background Technology

[0002] Aniline and (di)amino derivatives of 1-methylbenzene are important intermediates in the chemical industry for the production of diisocyanates or polyisocyanates of benzene and 1-methylbenzene. These isocyanate derivatives of benzene and 1-methylbenzene are then used as building blocks in the manufacture of polyurethanes and thermoplastic polyurethanes (abbreviated as PU and TPU, respectively, and (T)PU when referring to both types of polyurethane), polyisocyanurates (PIR), and polyureas.

[0003] The common starting material for the manufacture of aniline is benzene, and the common starting material for the manufacture of (di)amino derivatives of 1-methylbenzene is 1-methylbenzene, both of which are derived from fossil sources such as processed crude oil.

[0004] Aniline and (di)amino derivatives of 1-methylbenzene are then produced by nitridation of benzene and 1-methylbenzene followed by hydrogenation of the corresponding nitridation intermediates.

[0005] Future regulations and consumer demands may require a certain percentage of recycled content in aniline, (di)amino derivatives of 1-methylbenzene, and chemical products made from them. Therefore, there is a need for recycling options and recycled feedstocks for polymers such as PU based on mixed plastic waste (e.g., some PU applications go into very small-scale or dispersed applications, such as adhesives and coatings that cannot be collected on a large scale and then recycled in a closed loop).

[0006] The major carbon atom contributors to the building blocks of (T)PU, polyisocyanurate (PIR), and polyurea are aromatic nuclei, namely (di)amino derivatives of aniline and / or 1-methylbenzene and their corresponding isocyanate derivatives. Therefore, aromatic nuclei are also the most important building blocks that need to be recycled.

[0007] US / 2023 / 0016550 A1 discloses the use of pyrolysis oil from plastic waste as a co-raw material for the production of chemicals and plastics. It does not disclose the direct separation of benzene from plastic pyrolysis oil for the manufacture of cyclohexanone without steam cracking.

[0008] US 10513661 B2 discloses a method for separating C6-C8 aromatic hydrocarbons from plastic pyrolysis oil. The method includes a hydroalkylation unit and a steam cracking unit, in which a first “heavy stream” is converted and in which a “treated hydrocarbon stream” is converted. The resulting streams from the two units are then combined in a second separation unit, in which C6-C8 aromatic hydrocarbons can be separated.

[0009] The first object of the present invention is to provide a method for producing aniline and (di)amino derivatives of 1-methylbenzene from plastic waste.

[0010] A second object of the present invention is to provide a method for manufacturing diisocyanates and polyisocyanate derivatives of benzene and 1-methylbenzene, such as 1-isocyano-benzene, 1,1'-methylenebis(4-isocyano-benzene), and 2,4-diisocyano-1-methylbenzene, from plastic waste.

[0011] A third object of the present invention is to provide diisocyanates and polyisocyanate derivatives of benzene (such as 1,1'-methylenebis(4-isocyanophenyl)) and diisocyanates and polyisocyanate derivatives of 1-methylbenzene (such as 2,4-diisocyano-1-methylbenzene) (benzene and 1-methylbenzene are manufactured from plastic waste) for the manufacture of (T)PU, polyisocyanurates and polyureas. Summary of the Invention

[0012] These problems are addressed by a method for producing aromatic amino compounds from benzene and 1-methylbenzene, the method comprising the following steps:

[0013] a) Provide benzene or 1-methylbenzene and a mixture of nitric acid and sulfuric acid,

[0014] b) Contacting benzene or 1-methylbenzene with the mixture of nitric acid and sulfuric acid, thereby forming nitrobenzene or a nitro derivative of 1-methylbenzene.

[0015] c1) Hydrogenating the nitrobenzene or nitro derivative of 1-methylbenzene formed in step b) in the presence of hydrogen and optionally a catalyst, thereby forming aniline or an amino derivative of 1-methylbenzene.

[0016] Characterized in that at least a portion of the benzene or 1-methylbenzene provided in step a) is manufactured by the following manner

[0017] a1) Provides a liquid stream S1 comprising at least one pyrolysis oil, the liquid stream S1 further comprising C6-C8 aromatic hydrocarbons, an organic compound comprising at least one heteroatom, and a compound having a C-C double bond and / or a C-C triple bond.

[0018] a2) Provides a stream S2, which contains H2.

[0019] a3) The liquid stream S1 and the liquid stream S2 are fed into the hydrogenation unit HU1, in which at least a portion of the components of the liquid stream S1 reacts with the liquid stream S2 in a hydrogenation reaction to form a liquid stream S3, wherein the liquid stream S3 is depleted relative to the liquid stream S1 of compounds having C-C double bonds and / or C-C triple bonds, and

[0020] Optionally, at least a portion of the liquid recirculation stream S3' is fed into the hydrogenation unit HU1, and the liquid recirculation stream S3' is separated from the liquid stream S3. Preferably, the mass ratio of "liquid recirculation stream S3' : liquid stream S3" preferably ranges from about 1 : 1 to about 30 : 1, more preferably from about 5 : 1 to about 20 : 1, and most preferably from about 10 : 1 to about 15 : 1.

[0021] a4) subjecting at least a portion or the remainder of the liquid stream S3 to a distillation unit DU, in which at least a portion or the remainder of the liquid stream S3 is separated into a stream S4 containing valuable products and a liquid stream S5, wherein the stream S4 containing valuable products comprises C6-C8 aromatic hydrocarbons and organic compounds containing at least one heteroatom.

[0022] a5) The stream S4 containing the valuable product is subjected to a hydrogenation unit HU2, in which the stream S4 is converted into a stream S6, wherein the stream S6 contains C6-C8 aromatic hydrocarbons and is relatively lean compared to stream S4, containing at least one heteroatom and / or C / C double bond of an organic compound, and

[0023] a6) Separate benzene and / or 1-methylbenzene from stream S6 in the aromatic hydrocarbon extraction unit AEU.

[0024] These problems are further addressed by a chemical apparatus for producing aromatic amino compounds from benzene and 1-methylbenzene from a liquid stream containing at least one pyrolysis oil, the apparatus comprising...

[0025] (i) at least one first hydrogenation processing unit HU1, the at least one first hydrogenation processing unit HU1

[0026] It contains at least one entrance and at least one exit.

[0027] (ii) Optionally, a recirculation unit is located downstream of and fluidly connected to the inlet and outlet of the first hydrogenation treatment unit HU1.

[0028] (iii) A distillation unit DU, which is downstream of and fluidly connected to the outlet of the first hydrogenation treatment unit HU1, the distillation unit DU having a bottom outlet BO and a top outlet HO.

[0029] (iv) A second hydrogenation treatment unit HU2, which is downstream of and fluidly connected to the top outlet HO of the distillation unit DU.

[0030] (v) At least one aromatic hydrocarbon extraction unit AEU, which is downstream of and fluidly connected to the second hydrogenation treatment unit HU2.

[0031] The chemical equipment is suitable for steps a1) to a6) and for providing benzene and / or 1-methylbenzene in step a) of the method according to the invention.

[0032] The method according to the invention provides the following advantages:

[0033] First, aniline or amino derivatives of 1-methylbenzene can be manufactured from plastic waste as raw material, and therefore all benzene or 1-methylbenzene provided in step a) has a 100% recycling content if it is manufactured by steps a1) to a6).

[0034] In cases where not all benzene or 1-methylbenzene provided in step a) is manufactured via steps a1) to a6) and instead is manufactured, for example, from fossil fuels, aniline or amino derivatives of 1-methylbenzene having a recycling content of less than 100% can also be manufactured by the method according to the invention. Therefore, the method according to the invention also enables the manufacture of aniline or amino derivatives of 1-methylbenzene having a desired recycling content of less than 100%.

[0035] Secondly, aniline or 1-methylbenzene amino derivatives manufactured from plastic waste and therefore having a recycling content can be used as raw materials to manufacture diisocyanates or polyisocyanates of benzene and 1-methylbenzene (such as 1,1'-methylenebis(4-isocyanophenyl) (“MDI”) and 2,4-diisocyano-1-methylbenzene (“TDI”)). Therefore, in cases where all aniline or 1-methylbenzene amino derivatives are manufactured from benzene or 1-methylbenzene produced by steps a1) to a6), provided in step a), they also have a recycling content of up to 100%. Diisocyanates or polyisocyanates of benzene and 1-methylbenzene having a recycling content of less than 100% can be manufactured from aniline or 1-methylbenzene amino derivatives having a recycling content of less than 100%. Therefore, the method according to the invention also enables the manufacture of diisocyanates or polyisocyanates of benzene and 1-methylbenzene having a desired recycling content of less than 100%.

[0036] Third, benzene and 1-methylbenzene diisocyanates or polyisocyanate derivatives derived from plastic waste and thus having a recycling content can be used as raw materials to manufacture (T)PU, polyisocyanurate, and polyurea. Therefore, in the case where all benzene and 1-methylbenzene diisocyanates or polyisocyanate derivatives are manufactured from benzene or 1-methylbenzene provided in step a) through steps a1) to a6), it also has a recycling content of up to 100%, and the additional building blocks used in the corresponding polymerization reaction have a recycling content of 100%. (T)PU, polyisocyanurate, and polyurea with a recycling content of less than 100% can be manufactured from benzene and 1-methylbenzene diisocyanates or polyisocyanate derivatives with a recycling content of less than 100%. Therefore, the method according to the invention also enables the manufacture of (T)PU, polyisocyanurate, and polyurea with a desired recycling content of less than 100%.

[0037] Fourth, in cases where plastic waste containing (T)PU, polyisocyanurate, and polyurea with a recycled content is produced therefrom, the method according to the invention is for a closed recycling loop for (T)PU, polyisocyanurate, and / or polyurea.

[0038] Fifth, in the production of benzene or 1-methylbenzene from plastic waste according to steps a1) to a6), undesirable polymerization and scaling are inhibited (see examples). Attached Figure Description

[0039] Figure 1A method is shown in which a recycle stream from the second hydrogenation unit into the first hydrogenation unit is utilized. This recycle stream is used in the method disclosed in AU 2021 / 222788 A1 and is therefore used as a comparative example in the Examples section.

[0040] Figure 2 A method for producing benzene and 1-methylbenzene from plastic waste according to a first embodiment of the present invention is shown.

[0041] Figure 3 A method for producing benzene and 1-methylbenzene from plastic waste according to steps a1) to a6) is shown according to a second embodiment of the present invention. Detailed Implementation

[0042] The present invention is further described below with reference to embodiments, but the present invention is not limited to these embodiments, and any modifications or substitutions to these embodiments or combinations thereof within the basic spirit of the present invention are still within the scope of the present invention as claimed.

[0043] definition:

[0044] In the context of this specification and the appended claims, the term "about" preferably means a deviation of ±10% from the value described herein. In the context of this invention, the term "combination thereof" includes one or more of the listed elements. In the context of this invention, the term "mixture thereof" includes one or more of the listed elements. The term "recycled content" is defined herein as the amount or percentage of recycled material used in a product or material. It indicates the extent to which recycled material has been incorporated into the manufacturing or production process. The term "non-fossil feedstock" is defined herein as a feedstock comprising plastic waste and / or biomass. "Polyisocyanate" is defined herein as a molecule comprising more than two isocyanate residues.

[0045] In step a) of the method according to the invention, benzene or 1-methylbenzene is provided. At least a portion of the benzene or 1-methylbenzene provided in step a) is produced by steps a1) to a6). The benzene and 1-methylbenzene produced by steps a1) to a6) have a 100% recycling content.

[0046] In the context of this invention, the term "pyrolysis" refers to the thermal decomposition or degradation of a feedstock, such as plastic waste, under inert conditions, producing gaseous, liquid, and solid char components. During pyrolysis, the feedstock is converted in a pyrolysis unit into a wide variety of chemicals, including gases such as H2, C1- to C4-alkanes, C2- to C4-olefins, acetylene, propyne, 1-butyne, pyrolysis oil having a boiling temperature of 25°C to 500°C or higher, and char. The direct products from this pyrolysis are "pyrolysis gases" and solid products. The liquid product, "pyrolysis oil," is then separated from the "pyrolysis gases" by condensation. Furthermore, water is formed during pyrolysis, which may be partially dispersed in the pyrolysis oil and may be partially contacted with the pyrolysis oil as a separate phase. The water formed during pyrolysis contains various organic compounds and / or their salts that are also formed during pyrolysis. The term "pyrolysis" includes slow pyrolysis, fast pyrolysis, flash catalytic pyrolysis, and catalytic pyrolysis. These pyrolysis types differ in process temperature, heating rate, residence time, and feed particle size, resulting in varying product qualities. Pyrolysis units can operate adiabatic, isothermal, non-adiabatic, non-isothermal, or combinations thereof. The pyrolysis reaction disclosed herein can be carried out in a single stage or in multiple stages. For example, a pyrolysis unit may comprise two reactor vessels connected in series with fluid connection.

[0047] In the context of this invention, "valuable component" means "C6-C8 aromatic hydrocarbons" (benzene, toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, and ethylbenzene).

[0048] In the context of this invention, the term "pyrolysis oil" should be understood to mean any oil derived from the pyrolysis of plastic waste. The term "plastic waste" includes rubber waste such as scrap tires and raw materials containing plastic waste. Pyrolysis oil is obtained and / or is available from the pyrolysis of such plastic waste.

[0049] In the context of this invention, the term "plastic waste" refers to any plastic material that is discarded after use, i.e., the plastic material has reached the end of its service life and is considered post-consumer waste. Plastic waste can be pure polymer plastic waste, mixed plastic waste, or membrane waste, including sludge, adhesive materials, fillers, residues, etc. Plastic waste may have oxygen content, nitrogen content, sulfur content, halogen content, and optionally heavy metal content. Plastic waste can originate from any source containing plastic materials.

[0050] Therefore, the term "plastic waste" includes industrial and household plastic waste, as well as used tires and agricultural and horticultural plastic materials.

[0051] Typically, plastic waste is a mixture of different plastic materials, including hydrocarbon plastics such as polyolefins such as polyethylene (HDPE, LDPE) and polypropylene, polystyrene and their copolymers, and polymers composed of carbon, hydrogen and other elements such as chlorine, fluorine, oxygen, nitrogen, sulfur, silicon, etc., such as chlorinated plastics such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), nitrogen-containing plastics such as polyamide (PA), polyurethane (PU), acrylonitrile butadiene styrene (ABS), oxygen-containing plastics such as polyesters such as polyethylene terephthalate (PET), polycarbonate (PC), silicone and / or sulfur-bridged crosslinked rubber.

[0052] Typically, plastic materials contain additives such as processing aids, plasticizers, flame retardants, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, antioxidants, etc. These additives may contain elements other than carbon and hydrogen. For example, the presence of bromine is primarily associated with flame retardants. Heavy metal compounds can be used as light-resistant pigments and / or stabilizers in plastics. Cadmium, zinc, and lead may be present in heat stabilizers and slip agents used in plastic manufacturing. Plastic waste may also contain residues. In the context of this invention, residues are contaminants that adhere to plastic waste. Additives and residues are generally present in amounts of less than 50 wt.-%, preferably less than 30 wt.-%, more preferably less than 20 wt.-%, and even more preferably less than 10 wt.-%, based on the total dry weight of the plastic.

[0053] Examples of rubber waste (also considered "plastic waste" in the context of this invention) include end-of-life tires, rubber waste generated during the manufacturing process, and discarded rubber-containing products such as latex inspection gloves and gaskets. End-of-life tires contain additional components, such as textiles, as well as organic and inorganic additives, which can be separated from the rubber portion of the end-of-life tire before pyrolysis. The pyrolysis oil obtained by (primarily) the pyrolysis of end-of-life tires is also known as tire pyrolysis oil (TPO).

[0054] Examples of biological waste that can be included in “plastic waste” include green waste, food waste, human waste, manure, sewage, sewage sludge and slaughterhouse waste.

[0055] To obtain the pyrolysis oil according to the invention, the feedstock is inserted into the pyrolysis reactor using a metering unit such as a screw or extruder, a rotary valve, a pneumatic conveyor, or a liquid injector. The feedstock may optionally be preheated in, for example, a heat exchanger and / or subjected to pre-pyrolysis at a temperature, for example, in the range of about 200°C to about 360°C, before being inserted into the pyrolysis reactor. The feedstock is then heated in the pyrolysis reactor to a temperature in the range of about 350°C to about 900°C, more preferably in the range of 400°C to about 550°C, and a pressure in the range of about 0.5 bar to about 2 bar (absolute value), more preferably in the range of 0.9 bar to about 1.5 bar (absolute value). The pyrolysis reactor is preferably selected from the group consisting of fluidized bed reactors, moving bed reactors, entrained flow reactors, screw reactors, extruders, stirred tank reactors, and rotary kiln reactors. Preferably, the pyrolysis is carried out in the pyrolysis reactor under an inert atmosphere free of oxygen or air.

[0056] Pyrolysis methods are known in themselves. They are described, for example, in EP 0713906 A1 and WO 95 / 03375 A1. Suitable pyrolysis oils are also commercially available. Pyrolysis oils are typically liquid at 15°C or waxy at said temperature. In the terminology of this invention, "liquid at 15°C" means that the pyrolysis oil has a density of up to 1.3 g / ml at 15°C and 1013 mbar, as determined according to DIN EN ISO 12185, for example, a density in the range of 0.65 to 0.98 g / ml.

[0057] The amount of C6-C8 aromatics formed by the pyrolysis reaction of the above-mentioned feedstock can be increased, for example, in the presence of a suitable catalyst. Another suitable method for increasing the amount of C6-C8 aromatics is disclosed in EP 3744814 A1: the pyrolysis gas obtained from the pyrolysis reaction of the above-mentioned feedstock is then subjected to thermal catalytic treatment at about 450°C to about 600°C (at least 50°C lower than the pyrolysis reaction temperature applied in the first step) in the presence of an aromatization catalyst such as ZSM-5, ZSM-11, ZSM-35, ZSM-23, magnesium alkali zeolite, β-zeolite, zeolite Y, zeolite X, mordenite, zeolite A, IM-5, SSZ-20, SSZ-55, MCM-22, TNU-9, metal-treated, exchanged, or impregnated catalysts, and combinations of the aforementioned catalysts and post-treatments. Other suitable catalysts include sand and alumina. Furthermore, combinations of the above-mentioned catalysts can be used for this purpose.

[0058] The amount of C6-C8 aromatics in pyrolysis oil can also be increased by reforming the pyrolysis oil or a mixture of pyrolysis oils (e.g., by catalytic reforming). Such reforming reactions are disclosed, for example, in...

[0059] https: / / www.e-education.psu.edu / fsc432 / content / catalyic-reforming-processes

[0060] And if necessary, adjustments can be made by technicians.

[0061] A liquid stream S1 containing pyrolysis oil or a mixture of pyrolysis oil can also be produced by pyrolysis of a plastic waste stream containing polystyrene. The liquid stream S1 further contains C6-C8 aromatic hydrocarbons, organic compounds containing at least one heteroatom, and compounds having C-C double bonds and / or C-C triple bonds (Maafa, IM Pyrolysis of Polystyrene Waste: A Review. Polymers 2021, 13, 225. https: / / doi.org / 10.3390 / polym13020225).

[0062] The liquid stream S1, more preferably the at least one pyrolysis oil contained in the liquid stream S1, comprises at least 5 wt.-%, or at least 10 wt.-%, or at least 15 wt.-%, or at least 20 wt.-%, or at least 25 wt.-%, or at least 30 wt.-%, or at least 35 wt.-%, or at least 40 wt.-%, or at least 45 wt.-%, or at least 50 wt.-%, or at least 55 wt.-%, or at least 60 wt.-%, or at least 70 wt.-%, or at least 80 wt.-%. Preferably, the C6-C8 aromatic hydrocarbons are selected from the group consisting of benzene, toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, and ethylbenzene.

[0063] The at least one pyrolysis oil contained in liquid stream S1 preferably further has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (as determined by ASTM 1159) and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-% (as determined by ASTM D 5134) and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-% (as determined by ASTM D 5134) and / or a styrene content of about 0.02 wt.-% to about 29.5 wt.-% (as determined by ASTM D 5134) and / or a toluene content of about 4.3 wt.-% to about 71.5 wt.-% (as determined by ASTM D 5134). Such pyrolysis oils are particularly suitable for the methods and chemical equipment according to the invention.

[0064] Optionally, before being used as the liquid stream S1 in the method according to the invention and / or as a feedstock for the chemical equipment according to the invention, the pyrolysis oil or a mixture of pyrolysis oils may be subjected to one or more methods selected from filtration, centrifugation, adsorption, washing, and extraction. Such optional pretreatment methods are described, for example, in WO 2021 / 224287 A1, WO 2023 / 061834 A1, EP0713906 A1, and WO 95 / 03375 A1, which are incorporated herein by reference. Those skilled in the art will understand how and in what circumstances the pretreatment methods disclosed in the aforementioned documents and comparable pretreatment methods disclosed elsewhere may be used.

[0065] Liquid stream S1 comprises at least one pyrolysis oil or a mixture of such pyrolysis oils produced by the above-described feedstock and method. Liquid stream S1 comprises C6-C8 aromatic hydrocarbons, organic compounds containing at least one heteroatom, and compounds having C-C double bonds (olefins, dienes) and / or C-C triple bonds, contributed by the at least one pyrolysis oil optionally included in liquid stream S1 and / or other liquid hydrocarbon feedstocks. Examples of such other liquid hydrocarbon feedstocks are further given below.

[0066] In step a1) of the method according to the invention, a liquid stream S1 comprising at least one pyrolysis oil is provided, the liquid stream S1 further comprising C6-C8 aromatic hydrocarbons, an organic compound comprising at least one heteroatom, and a compound having a C-C double bond and / or a C-C triple bond. Figure 2 and 3 Steps a1) through a6) are shown. Liquid stream S1 may further comprise at least one additional liquid hydrocarbon feedstock containing C6-C8 aromatics different from those obtained from pyrolysis oil derived from plastic waste. Suitable examples of such additional liquid hydrocarbon feedstocks include pyrolysis gasoline and coke oven light oil (CAS No.: 65996-78-3). Pyrolysis gasoline is obtained from hydrocarbon feedstocks via steam cracking, such as steam cracking of naphtha, or is a byproduct that can be obtained. Pyrolysis gasoline and its production are known in the art. Pyrolysis gasoline comprises C6-C8 aromatics. Coke oven light oil can be obtained by extraction from gases escaping from the destructive distillation of coal at high temperatures (e.g., greater than 700°C). It consists primarily of benzene, toluene, and xylene and may contain other minor hydrocarbon components.

[0067] This additional liquid hydrocarbon feedstock (the sum of all liquid hydrocarbon feedstocks in the case of more than one liquid hydrocarbon feedstock) may, for example, be included in liquid stream S1 in an amount of 0 wt.-%, 5 wt.-%, 10 wt.-%, 15 wt.-%, 20 wt.-%, 25 wt.-%, 30 wt.-%, 35 wt.-%, 40 wt.-%, 45 wt.-%, 50 wt.-%, 55 wt.-%, 60 wt.-%, 65 wt.-%, 70 wt.-%, 75 wt.-%, 80 wt.-% or greater, provided that at least 2 wt.-% of liquid stream S1 consists of at least one pyrolysis oil produced by the pyrolysis of plastic waste.

[0068] In step a2) of the method according to the invention, a stream S2 containing H2 is provided. Stream S2 may consist substantially of H2 or contain H2 along with at least one other gas. Preferably, the H2 content of stream S2 is greater than about 50% by volume, more preferably greater than about 80% by volume, and most preferably greater than about 95% by volume. This minimizes the amount of purge gas required to maintain a high H2 partial pressure and conserves H2. A high H2 partial pressure promotes catalyst activity and allows for a low reaction temperature. The advantage of a low reaction temperature is that undesirable polymerization of the components in stream S2 is suppressed. Such polymerization leads to undesirable scaling during processing.

[0069] The hydrogen (H2) used in the methods and systems according to the invention is preferably “green hydrogen” generated, for example, through water electrolysis and / or methane pyrolysis using electricity generated from renewable energy sources (e.g., solar, wind, tidal, and nuclear) and / or low-carbon energy sources, preferably at least partially from methane pyrolysis from renewable sources. Methane from renewable sources includes biomethane.

[0070] Optionally, at least a portion of the hydrogen used in the method according to the invention is hydrogen formed during the pyrolysis reaction and separated from the volatile pyrolysis reaction products.

[0071] In step a3) of the method according to the invention, a compound having C-C double bonds and / or C-C triple bonds present in liquid stream S1 is hydrogenated in the first hydrogenation treatment unit HU1 in the presence of stream S2. This forms a liquid stream S3 exiting the first hydrogenation treatment unit HU1. Optionally and preferably, a portion of liquid stream S3 is separated from liquid stream S3 and fed into the first hydrogenation treatment unit HU1 as liquid recycle S3' together with liquid stream S1 and stream S2.

[0072] The first hydrogenation treatment unit HU1 includes at least one stage in which CC double bonds and / or CC triple bonds present in the liquid stream S1 are hydrogenated. The first hydrogenation treatment unit HU1 is preferably a three-phase reactor, more preferably a three-phase reactor having a fixed catalyst bed. The three-phase reactor is most preferably operated in a trickle flow mode or a pulse flow mode. The fixed catalyst bed preferably contains at least one catalyst used in at least one stage of the first hydrogenation treatment unit HU1. The first hydrogenation treatment unit HU1 may also contain two or more such reactors, or a single reactor may contain one or more beds, each containing one or more catalysts.

[0073] Preferably, the first hydrogenation treatment unit HU1 comprises a single reactor with a single catalyst bed. This minimizes the geometry of the first hydrogenation treatment unit HU1 and ensures a cost-effective reactor design.

[0074] The at least one hydrogenation reactor of the first hydrogenation treatment unit HU1 is preferably designed to operate in a trickle or pulse flow mode, wherein the gas phase (gas flow S2 containing H2) is continuous or semi-continuous, and the liquid phase (liquid flow S1) flows along the surface of the solid, mainly along the surface of the at least one catalyst, thereby efficiently wetting them.

[0075] The process temperature in the at least one hydrogenation reactor of the first hydrogenation treatment unit HU1 depends on the type and activity of the catalyst used. The process temperature preferably ranges from about 60°C to about 250°C, more preferably from about 60°C to about 200°C, and most preferably from about 80°C to about 120°C. Catalyst deactivation can optionally be compensated for by increasing the process temperature.

[0076] In the at least one hydrogenation reactor of the first hydrogenation treatment unit HU1, the hydrogen pressure is preferably in the range of about 1.0 to about 10 MPa (absolute value).

[0077] The weight time space velocity (WHSV) of the liquid flow S1, excluding the optional liquid recirculation flow S3', is preferably in the range of about 0.1 t / (m²). 3 Kat. •h) to approximately 5 t / (m 3 Kat. •h), more preferably about 0.5 t / (m 3 Kat. •h) to approximately 1.0 t / (m 3 Kat. •h).

[0078] The selected process conditions allow the liquid stream S1 to be maintained in the liquid phase during step a3). The amount of hydrogen contained in the first hydrogenation treatment unit HU1 is sufficient to hydrogenate the undesirable C-C double bonds (olefins, dienes) and C-C triple bonds present in the liquid stream S1, but insufficient to hydrogenate the desired C6-C8 aromatic hydrocarbons also present in the liquid stream S1 by cyclohydrogenation.

[0079] The optional liquid recirculation flow S3' dilutes the liquid flow S1, further reducing unwanted scaling caused by polymerization within the first hydrogenation treatment unit HU1. Furthermore, when the optional liquid recirculation flow S3' dilutes the liquid flow S1, the temperature inside the first hydrogenation treatment unit HU1 can be better controlled.

[0080] The ratio “liquid recirculation flow S3´ : liquid flow S1” preferably ranges between about 2 : 1 and about 20 : 1, more preferably between about 8 : 1 and about 15 : 1.

[0081] Preferably, the liquid stream S1 and the optional recirculated liquid stream S3' are mixed before entering the at least one reactor of the first hydrogenation treatment unit HU1.

[0082] Preferably, a suitable catalyst for the first hydrogenation treatment unit HU1 comprises at least one catalytically active metal selected from elements of groups 8 to 12 of the periodic table, more preferably selected from the group consisting of nickel, palladium, platinum, and rhodium, and most preferably palladium. When palladium is the catalytically active metal, the catalyst comprises palladium in an amount (calculated as elemental palladium) ranging from about 0.01 wt.-% to about 5 wt.-%, more preferably from about 0.1 wt.-% to about 1 wt.-%, and most preferably from 0.15 wt.-% to 0.8 wt.-% based on the total weight of the catalyst.

[0083] Suitable catalysts further comprise a support, preferably an inorganic support, such as silica, alumina, silica-alumina, silica-alumina phosphate, magnesium oxide, clay, carbon, and mixtures thereof. The support may also comprise a support-dopant, such as zirconium dioxide, cerium dioxide, titanium dioxide, and mixtures thereof. "Silica-alumina" also includes zeolite.

[0084] Preferably, the catalyst for the first hydrogenation treatment unit HU1 further comprises a promoter, more preferably one or more elements of Groups 10 and 11 of the periodic table, preferably one or more of copper, gold, silver and platinum, more preferably one or more of silver and platinum, and most preferably silver.

[0085] Preferably, the at least one catalytically active element is from Groups 8 to 12 of the periodic table, more preferably comprising or consisting of the group consisting of nickel, palladium, platinum, and rhodium, and most preferably the atomic ratio of palladium to the promoter is in the range of 0.1:1 to 10:1, more preferably 2:1 to 7:1, and more preferably 2.5:1 to 6:1.

[0086] Most preferably, the catalyst for the first hydrogenation treatment unit HU1 comprises palladium supported on a support material, preferably as defined above, wherein the support material is more preferably alumina or carbon, most preferably alumina.

[0087] In the context of this invention, the at least one catalyst used in the first hydrogenation treatment unit HU1 is preferably in the form of an extrusion, granules, rings, spherical particles or spheres, more preferably earth-shaped particles or extrusions.

[0088] Particle size here refers to particle size distribution, which is measured, for example, by sieving, laser diffraction, or other methods known in the art. Catalysts with desired particle size and optionally desired shape can be manufactured and used.

[0089] The catalyst used in the first hydrogenation unit HU1 (most preferably containing palladium or composed of palladium) is preferably activated at about 50°C to about 130°C under a hydrogen gas flow (e.g., GHSV = 1000 / h) for, for example, about 6 h to about 24 h, such as about 12 h, preferably under atmospheric conditions. When the catalyst is reduced in a larger reactor, the hydrogen gas can be diluted with nitrogen to avoid excessively high temperatures.

[0090] The height and diameter of the at least one catalyst bed are selected based on reaction kinetics, optimal liquid / gas flow patterns, and pressure drop. The at least one catalyst bed may consist of one or more layers of different solid absorbent materials, and / or one or more hydrogenation catalysts. The catalyst layers in the at least one catalyst bed may differ from each other in terms of particle size, shape, activity, or active sites. When using more than one catalyst bed, inert particles may be used above and below each bed to improve fluid distribution.

[0091] In the case where the at least one hydrogenation reactor in the first hydrogenation treatment unit HU1 has at least two stages, the catalyst preferably has different particle sizes in the at least two stages and / or optionally different shapes in the at least two stages.

[0092] Hydrogenation is an exothermic reaction and therefore each stage of the reaction can be optionally cooled.

[0093] Preferably, at least a portion of the liquid stream S3 is fed into the first hydrotreating unit HU1 as a recirculation stream S3' for at least a second time. In this case, the first hydrotreating unit HU1 preferably also includes a recirculation unit in which a desired portion of the optional recirculation stream S3' can be separated from the liquid stream S3. Before entering the first hydrotreating unit HU1, the liquid stream S1 is diluted with the optional recirculation stream S3', and thereby, undesirable scaling caused by the polymerization of compounds (olefins, dienes) with C / C double bonds and compounds with C / C triple bonds present in the liquid stream S1 is reduced.

[0094] The reactor inlet temperature of the first hydrotreating unit HU1 is optionally and preferably adjusted by mixing the warm liquid recirculation stream S3' and the cooled liquid recirculation stream S3' from the outlet of the at least one reactor of the first hydrotreating unit HU1 with the liquid stream S1 to adjust the desired reactor inlet temperature. This optional and preferred design avoids contact with the heat exchange surface, and thus avoids undesirable fouling on the heat exchanger surface, which would also lead to reduced heat transfer inside the heat exchanger, which is avoided by the optional and preferred design. If the outlet stream of the at least one reactor of the first hydrotreating unit HU1 is not warm enough, the polymerization stabilization stream S3 is heated by the heat exchanger to adjust the necessary temperature.

[0095] About 90% or more, preferably more than 95% and most preferably 99% of the diene present in the liquid stream S1 is converted in step a3) of the method according to the invention.

[0096] To maintain a high H2 partial pressure in the first hydrogenation treatment unit HU1, the first hydrogenation treatment unit HU1 is preferably operated with an exhaust gas stream S2'. More preferably, the H2 concentration in stream S2 is below 99.9% by volume to avoid the accumulation of inert gas components such as N2, CH4, and C2H6 in stream S2. The ratio of "H2 content in fresh H2 feed stream S2 : chemical H2 consumption caused by hydrogenation reaction in the first hydrogenation treatment unit HU1" is preferably in the range of about 1:1 to about 5:1, more preferably about 1:1 to about 3:1, and most preferably about 1:1 to about 2:1.

[0097] The total pressure at the outlet of the at least one reactor in the first hydrogenation treatment unit HU1 is preferably in the range of about 5 bar (absolute value) to about 60 bar (absolute value), more preferably about 10 bar (absolute value) to about 40 bar (absolute value), and most preferably about 20 bar (absolute value) to about 40 bar (absolute value).

[0098] Next, in step a4) of the method according to the invention, at least a portion of the liquid stream S3 is distilled at high temperature in a distillation unit DU to separate at least a portion or the remainder of the liquid stream S3 into a stream S4 rich in valuable components (mononuclear aromatic components: benzene, toluene, ethylbenzene, and xylene, i.e., C6-C8 aromatic hydrocarbons) and a liquid stream S5 having a higher boiling point range than stream S4. "The remainder of liquid stream S3" means the portion of stream S3 remaining after stream S3' is optionally separated from it in step (iii). Stream S4 also refers to a "light stream" and stream S5 refers to a "heavy stream". Stream S4 contains at least a portion of C6-C8 aromatic hydrocarbons and an organic compound containing at least one heteroatom contained in liquid stream S3. Stream S4 preferably has a final boiling point of about 100°C to about 220°C, more preferably about 120°C to about 190°C, and most preferably about 150°C to about 170°C.

[0099] Liquid stream S5 preferably has the same final boiling point as liquid stream S1. Liquid stream S5 can then be converted into syngas, primarily a mixture of H2 and CO, for example, in at least one vaporizer and / or partial oxidation reaction unit. Such partial oxidation reactions are known in the art and are disclosed, for example, in WO 2022 / 200532 A1, which is incorporated herein by reference. Those skilled in the art can select suitable reactors and reaction conditions to convert liquid stream S5 into syngas via partial oxidation and / or vaporization.

[0100] The final boiling points of streams S1, S3, S4, S5 and S6 are preferably measured by the methods described in ASTM D86 and ASTM D7169, and for very high boiling point liquids, also by ASTM D7182.

[0101] The distillation unit DU includes at least one distillation column, at least one thin-film evaporator, or a combination thereof. The distillation unit DU is downstream of and fluidly connected to the first hydrogenation treatment unit HU1. Preferably, the distillation unit DU includes or is composed of a distillation column.

[0102] Distillation is carried out at a temperature ranging from about 0°C to about 600°C, more preferably from about 20°C to about 400°C, and most preferably from about 80°C to about 250°C (the temperature range relates to an atmospheric pressure of 1.013 bar). The corresponding operating pressure of the at least one distillation column preferably ranges from about 0.001 bar to about 4 bar (absolute value), more preferably from about 0.001 bar to about 2.0 bar (absolute value), and most preferably from about 0.9 bar to about 1.8 bar (absolute value). When the pressure is ≠ 1.013 bar, the temperature is adjusted accordingly.

[0103] Optionally, the distillation unit DU includes at least one thin-film evaporator. In the thin-film evaporator, the medium to be evaporated or the solution to be concentrated by evaporation is applied as a thin film to the evaporator region. Thus, short contact times with the heated surface are feasible, and thermally unstable liquids and substances can be evaporated separately in such thin-film evaporators. Furthermore, if the product accumulating as residue has poor flow characteristics and / or is prone to aggregation, the thin-film evaporator can be used for separation tasks. The thin-film evaporation process is based on the principle of simple distillation, according to which the separation capacity of evaporators of this type is limited. Suitable thin-film evaporators are available in various designs, such as falling film evaporators or rotary evaporators.

[0104] Next, during step a5) of the method according to the invention, the stream S4 containing valuable components is converted in the second hydrogenation treatment unit HU2 into a purified stream S6 and a gas stream S6' containing valuable components. By hydrogenating the gas stream S4' containing hydrogen (H2) in the second hydrogenation treatment unit HU2, the purified stream S6 containing valuable components is depleted of heteroatoms such as nitrogen, oxygen, halogens (fluorine, chlorine, bromine, iodine), and sulfur relative to the stream S4. Optionally, the waste gas stream S2' can be fed into the second hydrogenation treatment unit HU2. In this case, the stream S4' balances the hydrogen demand of the second hydrogenation treatment unit HU2. Heteroatoms exit the second hydrogenation treatment unit HU2 as gas stream S6' in the form of their corresponding hydrides.

[0105] The corresponding hydrides of heteroatoms include NH3, H2O, H(Hal) (HF, HCl, HBr, HI), and H2S. NH3 and H(Hal) can form salts of the NH4Hal type (NH4F, NH4Cl, NH4Br, NH4I), and NH3 and H2S can form the salt NH4SH. Such salts may have already formed in the gas phase in the second hydrogenation unit HU2, and can then form undesirable deposits on the metal surface by resublimation when stream S6 cools.

[0106] NH4Cl, NH4F, NH4Br, NH4I, and NH4SH (at least one of which can be formed primarily in the second hydrogenation treatment unit HU2 (and a small portion may also be formed in the first hydrogenation treatment unit HU1)) are preferably removed from the second hydrogenation treatment unit HU2 by water. More preferably, NH4F, NH4Cl, NH4Br, NH4I, and / or the corresponding cations and anions are quantitatively removed by water, and NH4SH and / or the corresponding cations and anions are partially removed from the second hydrogenation treatment unit HU2 by a water stream. Figure 2 and 3 (Not shown in the image).

[0107] Therefore, the reactions in the second hydrogenation treatment unit HU2 include hydrodenitrogenation, hydrodeoxygenation, hydrodehalogenation, and hydrodesulfurization. Furthermore, the reactions include hydrodemetallization, and preferably, hydrogenation of the remaining C-C double bonds (olefins and dienes) and C-C triple bonds, while the conjugated C-C bonds in the C6-C8 aromatics present in the gas stream S4 are substantially not hydrogenated by the cyclohydrogenation in the second hydrogenation treatment unit HU2.

[0108] The second hydrogenation unit HU2 is downstream of the distillation unit DU and is fluidly connected to the distillation unit DU.

[0109] The second hydrotreating unit HU2 can be any vessel configured to contain the hydrotreating catalyst disclosed herein. The vessel is preferably configured for gas-phase operation. The second hydrotreating unit HU2 may include beds of one or more hydrotreating catalysts, preferably in a fixed-bed configuration. The second hydrotreating unit HU2 can operate adiabatically, isothermally, non-adiabatically, non-isothermally, or a combination thereof. The second hydrotreating unit HU2 may contain more than one vessel. Each of such vessels is considered a hydrogenation reactor.

[0110] The stream S4 containing valuable components can be contacted with the hydrotreating catalyst in an upward, downward, radial, or combination thereof, with or without the staged addition of gas stream S4, gas stream S2', or combinations thereof.

[0111] Preferably, heteroatoms containing halogens (such as chlorine), nitrogen, oxygen, and sulfur are removed from the stream S4 containing valuable components in the second hydrogenation treatment unit HU2. These heteroatoms are separated from organic residues, such as HF, HCl, HBr, NH3, H2O, and H2S, by hydrogenation treatment conditions, and the separated heteroatoms are replaced by hydrogen atoms in the organic residues. Furthermore, the remaining olefins and / or dienes in the stream S4 containing valuable components that were not converted to saturated hydrocarbons in the first hydrogenation unit HU1 are converted to saturated hydrocarbons in the second hydrogenation treatment unit HU2.

[0112] The hydrotreating catalyst can be any catalyst used for the hydrogenation of olefins, dienes, and heteroatom hydrogenation (e.g., commercially available hydrotreating catalysts). For this purpose, suitable hydrotreating catalysts include molybdenum catalysts (Mo catalysts), cobalt-molybdenum catalysts (Co-Mo catalysts), nickel-molybdenum catalysts (Ni-Mo catalysts), tungsten-molybdenum catalysts (W-Mo catalysts), cobalt-molybdenum oxides, nickel-molybdenum oxides, tungsten-molybdenum oxides, cobalt-molybdenum sulfides, nickel-molybdenum sulfides, tungsten-molybdenum sulfides, and molybdenum sulfides. Suitable catalysts further include a support, preferably an inorganic support, such as silica, alumina, silica-alumina, magnesium oxide, clay, and mixtures thereof. Other suitable hydrotreating catalysts are, for example, zeolites containing one or more metals. More than one of the aforementioned hydrotreating catalysts can be used together in the second hydrotreating unit HU2.

[0113] The height and diameter of the at least one catalyst bed are selected based on reaction kinetics, optimal liquid / gas flow patterns, and pressure drop. The at least one catalyst bed may consist of one or more layers of different solid absorbent materials, and / or one or more hydrogenation catalysts. The catalyst layers in the at least one catalyst bed may differ from each other in terms of particle size, shape, activity, or active sites. When using more than one catalyst bed, inert particles may be used above and below each bed to improve fluid distribution.

[0114] In the context of this invention, the catalyst for the second hydrogenation unit HU2 is preferably in the form of an extrusion, granules, rings, spherical particles or spheres, more preferably earth-shaped particles or extrusions.

[0115] In the case where the at least one hydrogenation reactor (vessel) in the second hydrogenation treatment unit HU2 has at least two stages, the catalyst preferably has different particle sizes in the at least two stages and / or optionally different shapes in the at least two stages.

[0116] Particle size here refers to particle size distribution, which is measured, for example, by sieving, laser diffraction, or other methods known in the art. Catalysts with desired particle size and optionally desired shape can be manufactured and used.

[0117] Hydrogenation is an exothermic reaction and therefore each stage of the reaction can be optionally cooled.

[0118] The second hydrotreating unit HU2 can operate under various process conditions. For example, the stream S4 containing valuable components is preferably contacted with the hydrotreating catalyst at a temperature preferably from about 200°C to about 400°C, more preferably from about 240°C to about 380°C, and most preferably from about 260°C to about 360°C in the presence of a gas stream S4' containing hydrogen and / or an optional internal recirculated gas stream S6''. Optionally, the gas stream S4' further comprises at least a portion of the stream S2'. The presence of the gas stream S4' is preferred to balance the amount of hydrogen consumed or otherwise lost in the second hydrotreating unit HU2. The aspect of the invention further comprising the optional internal recirculated gas stream S6'' is... Figure 3 As shown in the image.

[0119] The temperature in the second hydrogenation treatment unit HU2 can be obtained by using a preheated stream S4 containing valuable components and / or by using at least one heat exchanger to thermally integrate the stream S4 containing valuable components with the purified stream S6 containing valuable components.

[0120] The pressure during hydrogenation in the second hydrogenation unit HU2 is preferably in the range of about 1 bar to about 200 bar, more preferably about 10 bar to about 150 bar, and most preferably 20 bar to 60 bar.

[0121] The weight time space velocity (WHSV) of the stream S4 containing valuable components is preferably in the range of about 0.1 t / (m²). 3 Kat. •h) to approximately 5 t / (m 3 Kat. •h), more preferably about 0.5 t / (m 3 Kat. •h) to approximately 1.0 t / (m 3 Kat. •h).

[0122] In another aspect of the invention, the second hydrogenation treatment unit HU2 operates with the optional recirculated gas stream S6'' added. This means that hydrogen not consumed by the hydrogenation reaction within the second hydrogenation treatment unit HU2 is separated from streams S6 and S6', and then fed back into the second hydrogenation treatment unit HU2 as recirculated gas stream S6''. The remaining non-hydrogen portion of the exhaust gas stream S2'' and the volatile compounds formed by the hydrogenation reaction with stream S6 leave the second hydrogenation treatment unit HU2 as stream S6''. This aspect... Figure 3 As shown in the image.

[0123] The optional addition of recirculating gas stream S6'', as described above, also benefits the evaporation of stream S4 and its retention in the gas phase. Furthermore, the optional recirculating gas stream S6'' dilutes stream S4. This limits the adiabatic temperature rise caused by the hydrogenation reaction and achieves a high H2 partial pressure, which is beneficial for the hydrogenation activity of the catalyst.

[0124] The ratio “recirculated gas stream S6´´ : stream S4 containing valuable products” is preferably at about 300 Nm 3 / t to approximately 2000 Nm 3 / t, more preferably 500 Nm 3 / t to approximately 800 Nm 3 Between / t.

[0125] More preferably, the stream S6 or a portion thereof is not recycled (re-inserted) into the first hydrogenation treatment unit HU1.

[0126] There is no need to recycle a portion of stream S6 into the first hydrotreating unit HU1 because stream S4 is sufficiently stable relative to undesirable polymerization, and therefore, stream S4 can be vaporized and heated for insertion into the second hydrotreating unit HU2. This enables the establishment of the first hydrotreating unit HU1 (including optional liquid recirculated stream S3') and the second hydrotreating unit HU2 (including recirculated gas) for "one-pass capacity," meaning that liquid stream S1 (and its stream produced by conversion in a separate process unit) passes through the first hydrotreating unit HU1 only once (it exits as stream S3), the distillation unit DU (then enters stream S5 into HU2), and then exits the second hydrotreating unit HU2 as stream S6 (converted).

[0127] Next, in step a6) of the method according to the invention, the purified stream S6 containing valuable components is separated in at least one aromatic hydrocarbon extraction unit AEU into a benzene-rich stream S7´, a toluene-rich stream S7´´, a C8 aromatic hydrocarbon-rich stream S7´´´ (ethylbenzene, 1,2-xylene, 1,3-xylene, 1,4-xylene) stream S7´´´ and a stream S8 depleted of desired C6-C8 aromatic hydrocarbons.

[0128] The at least one aromatic hydrocarbon extraction unit AEU is downstream of and fluidly connected to the second hydrogenation treatment unit HU2, thereby enabling a stream S6 containing valuable components to flow from the outlet of the second hydrogenation treatment unit HU2 into the at least one aromatic hydrocarbon extraction unit AEU.

[0129] The at least one aromatic hydrocarbon extraction unit AEU can be any unit operation suitable for separating a stream S6 containing valuable components into a benzene-rich stream S7', a toluene-rich stream S7'', and a C8 aromatic hydrocarbon-rich stream S7'''. For example, the at least one aromatic hydrocarbon extraction unit AEU can include at least one selective adsorption unit operation, at least one selective absorption unit operation, at least one extractive distillation unit operation, at least one solvent extraction followed by distillation, and combinations thereof.

[0130] Suitable aromatic hydrocarbon extraction units (AEUs) are commercially available, such as Uhde's Morphylane® extractive distillation process. For example, the S6 stream is first split into C... 7- Classification and C 8+ Grade division. Next, C... 7- The fractions are sent to the extractive distillation stage, where the benzene-containing stream S7' and the toluene-containing stream S7'' are mixed with C from stream S6. 7- - Separation of non-aromatic compounds. The C from stream S6... 8+ The fraction is fed directly to the 1,4-xylene circuit without extracting xylene and ethylbenzene.

[0131] Stream S7' preferably contains at least 90 wt.% benzene, more preferably at least 95 wt.% benzene, and most preferably at least 99 wt.% benzene. Stream S7' is suitable for providing benzene in step a) of the method according to the invention.

[0132] Stream S7'' preferably contains at least 90 wt.% 1-methylbenzene, more preferably at least 95 wt.% 1-methylbenzene, and most preferably at least 99 wt.% methylbenzene. Stream S7'' is suitable for providing 1-methylbenzene in step a) of the method according to the invention.

[0133] Stream S8 is suitable as a feedstock for cracking processes such as (fluid) catalytic cracking, thermal cracking, and steam cracking. The main reaction products from such cracking processes include ethylene, propylene, butene isomers, butadiene, and pyrolysis gasoline. At least a portion of the pyrolysis gasoline can be used as a co-feedstock in stream S1, together with pyrolysis oil obtained from the pyrolysis of plastic waste. This pyrolysis gasoline contains C6-C8 aromatic hydrocarbons.

[0134] The individual units and their connections in a chemical plant for producing aromatic amino compounds from a liquid stream containing at least one pyrolysis oil of benzene and 1-methylbenzene Figure 2 It is shown in the following description:

[0135] A chemical apparatus for producing aromatic amino compounds from benzene and 1-methylbenzene from a liquid stream containing at least one pyrolysis oil comprises: at least one first hydrotreating unit HU1, the at least one first hydrotreating unit HU1 having at least one inlet and at least one outlet; optionally downstream of and fluidly connected to the inlet and outlet of the first hydrotreating unit HU1; at least one distillation unit DU downstream of and fluidly connected to the outlet of the first hydrotreating unit HU1, the at least one distillation unit having a bottom outlet BO and a top outlet HO; a second hydrotreating unit HU2 downstream of and fluidly connected to the top outlet HO of the at least one distillation unit DU; and at least one aromatic hydrocarbon extraction unit AEU downstream of and fluidly connected to the second hydrotreating unit HU2. A heavy stream (stream S5) exits the distillation unit DU through the bottom outlet BO, and a light stream (stream S4) exits the distillation unit DU through the top outlet HO.

[0136] Liquid stream S1 (containing C6-C8 aromatic hydrocarbons, organic compounds containing at least one heteroatom, and compounds having C-C double bonds and / or C-C triple bonds) of pyrolysis oil or a mixture thereof is converted by stream S2 in the first hydrotreating unit HU1. The remainder of stream S2 leaves the first hydrotreating unit HU1 as stream S2'. Liquid stream S1 is converted into stream S3 in the first hydrotreating unit HU1. Optionally, a portion of stream S3 is recycled as stream S3', which is mixed with stream S1 and inserted into the first hydrotreating unit HU1.

[0137] Stream S3 is separated into stream S4 (“light stream”) and stream S5 (“heavy stream”) in the distillation unit DU.

[0138] Optionally, the gas stream S4' further includes at least a portion of the waste gas stream S2'. The gas stream S4' is required to balance the amount of hydrogen consumed or otherwise lost in the second hydrogenation treatment unit HU2.

[0139] In the second hydrogenation treatment unit HU2, stream S4 is converted into stream S6 together with gas stream S4' and optionally additionally with waste gas stream S2'. In this case, gas stream S4' balances the hydrogen demand of the second hydrogenation treatment unit HU2. The remaining non-hydrogen portion of waste gas stream S2'' and the volatile compounds formed by the hydrogenation reaction with stream S6 leave the second hydrogenation treatment unit HU2 as stream S6'.

[0140] Stream S6 enters the aromatic hydrocarbon extraction unit AEU, where stream S6 is separated into streams S7', S7'', S7''', and S8. Stream S7' contains benzene and is suitable for providing benzene in step a) of the method according to the invention.

[0141] The specifications of all units and flows are described above in the “Method” section of method steps a1) to a6) and are preferably the same in the case of the method according to the invention and the chemical equipment according to the invention.

[0142] The benzene or 1-methylbenzene provided in step a) preferably comprises at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, and most preferably at least 7.5 wt.% of benzene or 1-methylbenzene manufactured from non-fossil raw materials.

[0143] The benzene or 1-methylbenzene provided in step a) is preferably at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, and most preferably at least 7.5 wt.% produced by steps a1) to a6).

[0144] Benzene and 1-methylbenzene can be separated, for example, from fossil feedstocks such as pyrolytic gasoline and coke oven light oil as described above.

[0145] Preferably, the plastic waste used to manufacture the at least one pyrolysis oil provided in step a1) comprises at least one type of polymer selected from the group consisting of thermoplastic polyurethane, polyurethane, polyisocyanurate, and polyurea. Thus, a closed recycling loop is achieved by the method according to the invention.

[0146] In step a), a mixture of nitric acid and sulfuric acid is also provided.

[0147] In step b) of the method according to the invention, benzene or 1-methylbenzene is contacted with a mixture of nitric acid and sulfuric acid, thereby forming nitrobenzene or a nitro derivative of 1-methylbenzene, wherein the nitro derivative of 1-methylbenzene is preferably selected from the group consisting of: 2-nitro-1-methylbenzene, 3-nitro-1-methylbenzene, 4-nitro-1-methylbenzene, 2,4-dinitro-1-methylbenzene, 2,6-dinitro-1-methylbenzene and mixtures thereof.

[0148] Benzene or 1-methylbenzene can be converted to nitrobenzene or (di)nitro derivatives of 1-methylbenzene by direct nitration in the liquid phase using a mixture of nitric acid and sulfuric acid (“nitrifying acid”). The nitration reaction can be carried out isothermally at a temperature of about 50°C to about 100°C and ambient pressure in a reactor cascade (stirred cylindrical or tubular) or adiabaticly at a temperature of about 90°C to about 190°C and ambient pressure, or at increased pressures such as 1.5 bar, 2 bar, or even higher pressures such as 5 bar or 10 bar, in a stirred reactor cascade or jet impingement reactor.

[0149] In step c1) of the method according to the invention, the nitrobenzene or nitro derivative of 1-methylbenzene formed in step b), preferably the mononitro derivative described above, is hydrogenated in the presence of hydrogen and optionally a catalyst, thereby forming aniline or an amino derivative of 1-methylbenzene, wherein the amino derivative of 1-methylbenzene is preferably selected from the group consisting of: 2-amino-1-methylbenzene, 3-amino-1-methylbenzene, 4-amino-1-methylbenzene, 2,4-amino-1-methylbenzene, 2,6-amino-1-methylbenzene and mixtures thereof.

[0150] Aniline is produced from benzene via nitrobenzene, and (di)amino derivatives of 1-methylbenzene are produced via (di)nitro-1-methylbenzene derivatives produced from 1-methylbenzene.

[0151] The hydrogen used in step c1) can, in principle, be hydrogen from any known source and generated by any known method.

[0152] Preferably, the hydrogen used in step c1) is preferably "blue hydrogen" (formed by steam reforming and / or autothermal reforming of natural gas, thereby capturing and storing or otherwise using the CO2 formed during the reaction), more preferably "green hydrogen," which is generated, for example, by water electrolysis using renewable energy sources (e.g., solar, wind, tidal, and nuclear) and / or low-carbon energy sources, and / or by methane pyrolysis, preferably using at least partially methane from renewable sources. Methane from renewable sources includes biomethane. Hydrogen can also be provided as a byproduct of the pyrolysis of plastic waste (such as mixed plastic waste and / or end-of-life tires).

[0153] Catalytic hydrogenation of nitrobenzene or (di)nitro derivatives of 1-methylbenzene in the vapor or liquid phase to aniline or (di)amino derivatives of 1-methylbenzene.

[0154] Fixed-bed or fluidized-bed reactors can be used for the gas-phase hydrogenation of nitrobenzene to aniline and the gas-phase hydrogenation of (di)nitro derivatives of 1-methylbenzene to (di)amino derivatives of 1-methylbenzene in the presence of at least one catalyst. The at least one catalyst is preferably a copper and / or palladium catalyst on a support (e.g., activated carbon or oxides such as alumina or silica), and optionally further comprises elements such as lead, vanadium, phosphorus, and chromium as modifiers or promoters. One particular gas-phase method uses a copper catalyst on a silica support promoted by chromium, zinc, and barium.

[0155] In the case of catalytic gas-phase hydrogenation, nitrobenzene or the (di)nitro derivative of 1-methylbenzene is preferably hydrogenated in a fluidized bed in the presence of hydrogen and at least one catalyst, preferably at a temperature of about 250°C to about 300°C. The pressure is preferably in the range of about 400 kPa to about 1000 kPa. The product gas stream is then cooled, and then preferably the aniline or the (di)amino derivative of 1-methylbenzene is separated from the product stream in a liquid-gas separator.

[0156] The liquid-phase hydrogenation of nitrobenzene to aniline or the (di)nitro derivative of 1-methylbenzene to the corresponding (di)amino derivative of 1-methylbenzene can be operated, for example, in a temperature range of about 90°C to about 200°C. Preferably, the pressure range is from about 100 kPa to about 600 kPa. For example, a slurry bed reactor or a fluidized bed reactor can be used for the liquid-phase hydrogenation of nitrobenzene in the presence of hydrogen and at least one catalyst. Suitable catalysts comprise nickel on a support (e.g., like diatomaceous earth).

[0157] Further details regarding the production of aniline from benzene are disclosed, for example, in G. Booth, Ullmann's Encyclopedia of Industrial Chemistry, Volume 24, Chapter “Nitro Compounds, Aromatic,” pp. 305–309, 2012, and the references cited therein, as well as in T. Kahl, K.-W. Schröder, FR Lawrence, WJ Marshall, H. Höke, R. Jäckh, Ullmann's Encyclopedia of Industrial Chemistry, Volume 3, Chapter “Aniline,” pp. 467–470, 2012, and the references cited therein.

[0158] Further details regarding the production of (di)amino derivatives of 1-methylbenzene from 1-methylbenzene by catalytic hydrogenation are disclosed, for example, in G. Booth, Ullmann's Encyclopedia of Industrial Chemistry, Volume 24, Chapter “Nitro Compounds, Aromatic,” pp. 309–313, 2012, and the references cited therein, as well as in PF Vogt, JJ Gerulis, Ullmann's Encyclopedia of Industrial Chemistry, Volume 2, Chapter “Amines, Aromatic,” pp. 707–710, 2012, and the references cited therein.

[0159] In optional step c2), 1,1'-methylenebis(4-isocyanophenyl) is produced from aniline via the diamine precursor 1,1'-methylenebis(4-aminophenyl).

[0160] At least a portion of the aniline provided as a starting material in optional step c2) is manufactured in step c1). The remaining aniline is manufactured from benzene not provided in steps a1) to a6). This remaining aniline may be manufactured, for example, from benzene produced from fossil sources and / or from plastic waste or other raw materials such as bio-oil by other methods.

[0161] Preferably, at least 2.5 wt.-% of the benzene used to manufacture aniline provided in optional step c2) is benzene manufactured from non-fossil feedstock, more preferably at least 5.0 wt.-% and most preferably at least 7.5 wt.-%.

[0162] Preferably, at least 2.5 wt.-% of the benzene used to manufacture aniline provided in optional step c2) is produced by steps a1) to a6). More preferably at least 5.0 wt.-% and most preferably at least 7.5 wt.%

[0163] First, two equivalents of aniline are condensed with formaldehyde, preferably in the presence of hydrochloric acid as a catalyst, to form the diamine precursor 1,1'-methylenebis(4-aminobenzene). Next, 1,1'-methylenebis(4-aminobenzene) is phosgenated with phosgene to form different isomers of 1,1'-methylenebis(isocyanophenylene). The phosgenation of 1,1'-methylenebis(4-aminobenzene) can be carried out in the liquid phase, for example, using an aromatic solvent in a batch or continuous process. The desired 1,1'-methylenebis(4-isocyanophenylene) is then separated from the phosgenation reaction products by continuous thin-film distillation and / or by crystallization. Both methods are referred to as "split" (or, correspondingly, as a device called a "splitter"). In addition to 1,1'-methylenebis(isocyanophenylene), its condensation products, which are polyisocyanate derivatives of benzene, can also be formed.

[0164] Residual crude products containing oligomeric 1,1'-methylenebis(4-isocyanatobenzene) or composed thereof can be used, for example, to manufacture rigid polyurethane or polyisocyanurate foams. The residual crude products are sold, for example, as polymerized 1,1'-methylenebis(4-isocyanatobenzene) (“PMDI”, a polyisocyanate derivative of benzene), and contain oligomers and polymers with a wider chain length distribution of 1,1'-methylenebis(4-isocyanatobenzene) in addition to residual levels of monomers. Different PMDI grades vary with viscosity, functionality, etc. PMDI also has various applications, such as polyisocyanurate rigid insulating foams or rigid insulating foams like polyurethane from high-viscosity PMDI, wood adhesives (e.g., particleboard, OSB, MDF), appliances (refrigerators, freezers, general cold chain), pipe insulation materials, and transportation vehicles from low-viscosity PMDI.

[0165] The preparation of such diamine precursors from aniline and their phosgenation to 1,1'-methylenebis(4-isocyanophenyl) is described, for example, in C. Six, F. Richter, Ullmann's Encyclopedia of Industrial Chemistry, Volume 20, Chapter "Isocyanates, Organic", pp. 70-76, 2012 and the references cited therein.

[0166] Diisocyanates and polyisocyanate derivatives of benzene and 1-methylbenzene are produced from (di)amino derivatives of 1-methylbenzene by phosgenation with phosgene. The phosgenation of benzene and (di)amino derivatives of 1-methylbenzene can be carried out in the liquid phase, for example, in a batch or continuous process using aromatic solvents. The desired diisocyanates and / or polyisocyanate derivatives of benzene and 1-methylbenzene are then separated from the phosgenation reaction products, for example, by continuous thin-film distillation and / or by crystallization. Both methods are referred to as "split" (or, correspondingly, by a "splitter").

[0167] Optionally, at least a portion of phosgene used to produce isomers of 1,1'-methylenebis-(isocyanatobenzene) and diisocyanates and polyisocyanate derivatives of benzene and / or 1-methylbenzene is produced by stream S5 by a method comprising the following steps: a) converting at least a portion of stream S5 into a mixture comprising CO and H2 by a partial oxidation reaction, b) separating CO from the mixture, and c) converting at least a portion of the CO into phosgene in a catalytic gas-phase reaction with chlorine in the presence of a catalyst.

[0168] Phosgene is primarily produced by the gas-phase catalysis of carbon monoxide and chlorine, typically over an activated carbon catalyst. Due to the exothermic reaction, synthesis takes place in a cooled reactor, preferably a tube-buffered reactor, with the catalyst packed in the reaction tubes and cooling of the jacket space achieved by a liquid or boiling coolant medium.

[0169] Phosgene is produced on a large scale in the catalytic gas-phase reaction of carbon monoxide and chlorine in the presence of a catalyst (e.g., activated carbon catalyst). The reaction is strongly exothermic, with an enthalpy ΔH of -107.6 kJ / mol. To remove the heat of reaction, the reaction is typically carried out in a tube-bundle reactor, where the catalyst is packed inside the tubes (see Ullmann's Encyclopedia of Industrial Chemistry, Chapter "Phosgene," 5th edition, Vol. A19, p. 413 and subsequent pages, VCH Verlagsgesellschaft mbH, Weinheim, 1991). Typically, particulate catalysts with particle sizes in the range of 3 to 5 mm are used in tubes with typical inner diameters between 35 and 70 mm, and typically between 39 and 45 mm. In the reaction, carbon monoxide is usually used in excess to ensure that all chlorine is converted and to produce phosgene that is largely free of chlorine, as chlorine can cause undesirable side reactions when phosgene is subsequently used. The reaction can proceed without pressure, but is typically carried out under overpressure of 200–600 kPa (2–6 bar). Within this pressure range, the phosgene formed can be condensed after the reactor using cooling water or other heat transfer fluids, such as organic heat transfer fluids, allowing the condenser to operate more economically.

[0170] At least a portion of the aniline or 1-methylbenzene (diamino) derivative provided as a starting material in optional step d) is produced in step c1). The remaining aniline or 1-methylbenzene (diamino) derivative is produced from benzene or 1-methylbenzene not provided in steps a1) to a6). Such remaining aniline or 1-methylbenzene (diamino) derivative can be produced, for example, from benzene or 1-methylbenzene produced from fossil sources and / or from plastic waste or other raw materials such as bio-oil by other methods.

[0171] Preferably, at least 2.5 wt.-% of the benzene or 1-methylbenzene provided in optional step d) for the manufacture of aniline or a (di)amino derivative of 1-methylbenzene, more preferably at least 5.0 wt.-% and most preferably at least 7.5 wt.% is benzene or 1-methylbenzene manufactured from non-fossil feedstock.

[0172] Preferably, at least 2.5 wt.-% of benzene or 1-methylbenzene for the manufacture of aniline or a (di)amino derivative of 1-methylbenzene, as provided in optional step d), more preferably at least 5.0 wt.-% and most preferably at least 7.5 wt.% is produced by steps a1) to a6).

[0173] The production of diisocyanates and polyisocyanate derivatives of benzene and 1-methylbenzene from benzene or 1-methylbenzene, including diisocyanates and polyisocyanate derivatives of benzene and 1-methylbenzene by phosgenation of (di)amino derivatives of benzene and 1-methylbenzene to 1-methylbenzene, are described, for example, in C. Six, F. Richter, Ullmann's Encyclopedia of Industrial Chemistry, Volume 20, Chapter “Isocyanates, Organic”, pp. 70-76, 2012 and the references cited therein.

[0174] The amino derivative of benzene is aniline, and most preferably, aniline is converted to 1,1'-methylenebis(4-aminobenzene) in optional step c2), which can then be used as a starting material in step d) for the production of 1,1'-methylenebis(4-isocyanobenzene).

[0175] The (di)amino derivative of 1-methylbenzene is preferably selected from the group consisting of 2-amino-1-methylbenzene, 3-amino-1-methylbenzene, 4-amino-1-methylbenzene, 2,4-diamino-1-methylbenzene, 2,6-diamino-1-methylbenzene, and mixtures thereof. Most preferably, the (di)amino derivative of 1-methylbenzene is 2,4-diamino-1-methylbenzene.

[0176] The diisocyanate derivative of 1-methylbenzene is preferably selected from the group consisting of 2-isocyano-1-methylbenzene, 3-isocyano-1-methylbenzene, 4-isocyano-, 2,4-diisocyano-1-methylbenzene, and 2,6-diisocyano-1-methylbenzene and mixtures thereof. Most preferably, the (di)isocyanate derivative of 1-methylbenzene is 2,4-diisocyano-1-methylbenzene.

[0177] Polymers derived from isocyanate precursors, such as polyurethane (PU), thermoplastic polyurethane (TPU), polyisocyanurate, and polyurea, which are based, for example, on 1,1'-methylenebis(4-isocyanatobenzene) or 2,4-diisocyanato-1-methylbenzene, or polyisocyanates (e.g., oligomers of diisocyanate derivatives of benzene and 1-methylbenzene) (“building units”), can be manufactured, for example, by a continuous process, a solvent-based process, or a solvent-free process, in the presence of at least one additional compound selected from the group consisting of: polyester polyols, polyether polyols, polycarbonate polyols, polyether ester polyols, polyacrylate polyols, polyester polyacrylate polyols, diols, polycaprolactone polyols, polytetramethylene glycol, diamines, amino-terminated polyethers, and mixtures thereof. Catalysts and additives used to support the desired reaction of the aforementioned building units comprise Lewis bases, Lewis acids, and insertion catalysts. Optionally, in the case of foam generation, chemical or physical foaming agents (e.g., cyclopentane, pentane, hydrofluoroolefins (“HFOs”), HCOs, water) may also be added.

[0178] Polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanates, and polyureas are manufactured using (di)isocyanate derivatives of 1,1'-methylenebis(4-isocyanatobenzene) or 1-methylbenzene (such as 2,4-diisocyanato-1-methylbenzene) as starting materials, for example, as described in G. Brereton et al., Ullmann's Encyclopedia of Industrial Chemistry, chapter “Polyurethanes”, pp. 4–27, 2019, and the references cited therein.

[0179] Polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanates, and polyureas are manufactured using diisocyanates and polyisocyanate derivatives of 1,1'-methylenebis(4-isocyanophenyl) or 1-methylbenzene (such as 2,4-diisocyano-1-methylbenzene) as starting materials, for example, as described in T. Ouhadi, S. Abou-Sabet, H.-G. Wussow, LM Ryan, L. Plummer, FE Baumann, J. Lohmar, HF Vermeire, FLG Malet, Ullmann's Encyclopedia of Industrial Chemistry, Chapter "Thermoplastic Elastomers", pp. 13-15, 2013, and the references cited therein.

[0180] At least a portion of the benzene and 1-methylbenzene diisocyanates and / or polyisocyanate derivatives used as building blocks for the optional synthesis of polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates and polyureas made therefrom are made from benzene or 1-methylbenzene produced by steps a1) to a6).

[0181] Preferably, at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, and most preferably at least 7.5 wt.% of the benzene or 1-methylbenzene used to manufacture benzene and 1-methylbenzene diisocyanates and / or polyisocyanate derivatives and provided in optional step d) and / or used as building blocks for the synthesis of polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates and polyureas are made from benzene or 1-methylbenzene produced from non-fossil feedstocks.

[0182] Preferably, at least 2.5 wt.-% of benzene or 1-methylbenzene used to manufacture diisocyanates and / or polyisocyanate derivatives of benzene and 1-methylbenzene, more preferably at least 5.0 wt.-% and most preferably at least 7.5 wt.% are produced by steps a1) to a6).

[0183] Polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanates, and polyureas comprising diisocyanate or polyisocyanate building blocks, manufactured by the method according to the invention from aniline and a (di)amino derivative of 1-methylbenzene, can be used in various applications and markets, and contain:

[0184] Insulation materials for appliance applications (such as refrigerators, freezers, boilers, water heaters, and cold storage); various applications in the automotive market (such as seat and carpet backings, audio systems, steering wheels, panel coverings, panel foam, headliner foam, headliner adhesives, paint adhesives, sealants, shock absorbers, suspension mounts, ABS cables, ESP cables, and interior skins); the construction market (such as sandwich panels, spray foam, insulated doors, roll profiles, pipe insulation materials, wood adhesives, composite adhesives, laminated insulation boards, and canned foam); footwear (casual shoes, safety shoes, athletic shoes, synthetic leather, adhesives, athletic shoe soles, and safety shoe soles); furniture, interior decoration, and mattresses.

[0185] The invention is further illustrated by the following set of embodiments and by combinations of embodiments derived from the dependent relationships and reverse references shown. In particular, it should be noted that in each instance in which a series of embodiments is mentioned, for example in the context of the term "method as described in any one of Embodiments 1 to 3," each embodiment in this series is intended to clearly disclose to a person skilled in the art that the wording of the term should be understood by a person skilled in the art to be synonymous with "method as described in any one of Embodiments 1, 2, and 3." Furthermore, it should be clearly noted that the following set of embodiments represents a suitable structural portion of the general description of preferred aspects of the invention and, therefore, appropriately supports the claims of the invention.

[0186] 1. A method for producing an aromatic amino compound from benzene and 1-methylbenzene, the method comprising the following steps:

[0187] a) Provide benzene or 1-methylbenzene and a mixture of nitric acid and sulfuric acid,

[0188] b) Contacting benzene or 1-methylbenzene with the mixture of nitric acid and sulfuric acid, thereby forming nitrobenzene or a nitro derivative of 1-methylbenzene.

[0189] c1) Hydrogenating the nitrobenzene or nitro derivative of 1-methylbenzene formed in step b) in the presence of hydrogen and optionally a catalyst, thereby forming aniline or an amino derivative of 1-methylbenzene.

[0190] Characterized in that at least a portion of the benzene or 1-methylbenzene provided in step a) is manufactured by the following manner

[0191] a1) Provides a liquid stream S1 comprising at least one pyrolysis oil, the liquid stream S1 further comprising C6-C8 aromatic hydrocarbons, an organic compound comprising at least one heteroatom, and a compound having a C-C double bond and / or a C-C triple bond.

[0192] a2) Provides a stream S2, which contains H2.

[0193] a3) The liquid stream S1 and the liquid stream S2 are fed into the hydrogenation unit HU1, in which at least a portion of the components of the liquid stream S1 reacts with the liquid stream S2 in a hydrogenation reaction to form a liquid stream S3, wherein the liquid stream S3 is depleted relative to the liquid stream S1 of compounds having C-C double bonds and / or C-C triple bonds, and

[0194] Optionally, at least a portion of the liquid recirculation stream S3' is fed into the hydrogenation unit HU1, and the liquid recirculation stream S3' is separated from the liquid stream S3. Preferably, the mass ratio of "liquid recirculation stream S3' : liquid stream S3" preferably ranges from about 1 : 1 to about 30 : 1, more preferably from about 5 : 1 to about 20 : 1, and most preferably from about 10 : 1 to about 15 : 1.

[0195] a4) subjecting at least a portion or the remainder of the liquid stream S3 to a distillation unit DU, in which at least a portion or the remainder of the liquid stream S3 is separated into a stream S4 containing valuable products and a liquid stream S5, wherein the stream S4 containing valuable products comprises C6-C8 aromatic hydrocarbons and organic compounds containing at least one heteroatom.

[0196] a5) The stream S4 containing the valuable product is subjected to a hydrogenation unit HU2, in which the stream S4 is converted into a stream S6, wherein the stream S6 contains C6-C8 aromatic hydrocarbons and is relatively lean compared to stream S4, containing at least one heteroatom and / or C / C double bond of an organic compound, and

[0197] a6) Separate benzene and / or 1-methylbenzene from stream S6 in the aromatic hydrocarbon extraction unit AEU.

[0198] 2. The method according to Example 1, wherein the benzene or 1-methylbenzene provided in step a) is preferably at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, and most preferably 7.5 wt.-% produced by steps a1) to a6).

[0199] 3. The method according to Example 1 or 2, wherein the at least one pyrolysis oil is produced by pyrolysis of plastic waste.

[0200] 4. The method according to any one of Examples 1 to 3, wherein the liquid stream S1 preferably contains at least 15 wt.% of C6-C8 aromatic hydrocarbons, more preferably at least 50 wt.% of C6-C8 aromatic hydrocarbons, and most preferably at least 80 wt.% of C6-C8 aromatic hydrocarbons.

[0201] 5. The method according to any one of Examples 1 to 4, wherein the at least one pyrolysis oil in the liquid stream S1 has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (determined by ASTM 1159) and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-% (determined by ASTM D 5134) and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-% (determined by ASTM D 5134) and / or a styrene content of about 0.02 wt.-% to about 29.5 wt.-% (determined by ASTM D 5134) and / or a toluene content of about 4.3 wt.-% to about 71.5 wt.-% (determined by ASTM D 5134).

[0202] 6. The method according to any one of Examples 1 to 5, wherein the first hydrogenation treatment unit HU1 comprises at least one three-phase reactor, preferably at least one three-phase reactor having at least one fixed catalyst bed.

[0203] 7. The method according to any one of Examples 1 to 6, wherein the first hydrogenation treatment unit HU1 comprises at least one heterogeneous catalyst, the at least one heterogeneous catalyst comprising at least one catalytically active metal selected from elements of Groups 8 to 12 of the periodic table, more preferably the at least one catalytically active metal selected from the group consisting of or composed of the following: nickel, palladium, platinum, rhodium, and most preferably the catalytically active metal is palladium.

[0204] 8. The method according to any one of Examples 1 to 7, wherein the ratio “H2 in fresh H2 feed stream S2 : chemical H2 consumption caused by hydrogenation reaction in the first hydrogenation treatment unit HU1” preferably ranges from about 1:1 to about 5:1, more preferably from about 1:1 to about 3:1 and most preferably from about 1:1 to about 2:1.

[0205] 9. The method according to any one of Examples 1 to 8, wherein the total pressure at the outlet of the at least one reactor in the first hydrogenation treatment unit HU1 is preferably in the range of about 5 bar (absolute value) to about 60 bar (absolute value), more preferably about 10 bar (absolute value) to about 40 bar (absolute value) and most preferably about 20 bar (absolute value) to about 40 bar (absolute value).

[0206] 10. The method according to any one of Examples 1 to 9, wherein the mass ratio of “liquid recirculation flow S3´ : liquid flow S3” preferably ranges from about 1 : 1 to about 30 : 1, more preferably from about 5 : 1 to about 20 : 1 and most preferably from about 10 : 1 to about 15 : 1.

[0207] 11. The method according to any one of Examples 1 to 10, wherein the second hydrogenation treatment unit HU2 comprises at least one fixed-bed reactor.

[0208] 12. The method according to any one of Examples 1 to 11, wherein the first hydrogenation treatment unit HU1 comprises at least one heterogeneous catalyst, the at least one heterogeneous catalyst comprising at least one catalytically active metal selected from the group consisting of or composed of nickel, palladium, platinum and rhodium.

[0209] 13. The method according to any one of Examples 1 to 12, wherein the second hydrogenation treatment unit HU2 comprises at least one heterogeneous catalyst selected from or consisting of the group consisting of: Co-Mo catalyst, Ni-Mo catalyst, Ni-W catalyst, Co-W catalyst and Mo catalyst.

[0210] 14. The method according to any one of Examples 1 to 13, wherein C6-C8 aromatic hydrocarbons are separated from stream S6 by extractive distillation in at least one aromatic hydrocarbon extraction unit AEU.

[0211] 15. The method according to any one of Examples 1 to 14, wherein the stream S5 is converted into syngas in at least one gasifier and / or partial oxidation reaction unit and / or wherein the stream S8 is further subjected to a cracking process selected from catalytic cracking, thermal cracking and steam cracking.

[0212] 16. The method according to any one of Examples 1 to 15, wherein the nitro derivative of 1-methylbenzene formed in step b) is preferably selected from the group consisting of 2-nitro-1-methylbenzene, 3-nitro-1-methylbenzene, 4-nitro-1-methylbenzene, 2,4-dinitro-1-methylbenzene and 2,6-dinitro-1-methylbenzene and mixtures thereof.

[0213] 17. The method according to any one of Examples 1 to 16, wherein the nitrobenzene or nitro derivative of 1-methylbenzene is formed by an isothermal reaction at a temperature of about 50°C to about 100°C or by an adiabatic reaction at a temperature in the range of about 90°C to about 190°C.

[0214] 18. The method according to any one of Examples 1 to 17, wherein the amino derivative of 1-methylbenzene formed in step c1) is preferably selected from the group consisting of 2-amino-1-methylbenzene, 3-amino-1-methylbenzene, 4-amino-1-methylbenzene, 2,4-amino-1-methylbenzene, 2,6-amino-1-methylbenzene and mixtures thereof.

[0215] 19. The method according to any one of Examples 1 to 18, wherein the hydrogen provided in step c1) is produced by a method that uses energy from renewable energy sources in at least part of the form.

[0216] 20. The method according to any one of Examples 1 to 19, wherein the hydrogen provided in step c1) is produced by water electrolysis using at least part of energy from renewable energy sources.

[0217] 21. The method according to any one of Examples 1 to 20, wherein, optionally, the catalyst used in step c1) is a copper and / or palladium catalyst on a support for gas-phase hydrogenation and a nickel catalyst on a support for liquid-phase hydrogenation.

[0218] 22. The method according to any one of Examples 1 to 21, further comprising the following additional steps.

[0219] c2) In the presence of formaldehyde, aniline is converted into 1,1'-methylenebis(4-aminobenzene) by a condensation reaction.

[0220] 23. The method according to Example 22, wherein the aniline converted in step c2) preferably at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, and most preferably 7.5 wt.-% is produced from benzene produced by steps a1) to a6).

[0221] 24. The method according to Example 22 or 23, wherein hydrochloric acid is used as a catalyst in step c2).

[0222] 25. The method according to any one of Examples 22 to 24, further comprising the following steps:

[0223] d) Phosgenetically phos ...

[0224] 26. The method according to Example 25, wherein at least a portion of the phosgene is generated from stream S5 by means of the following steps: a) converting at least a portion of stream S5 into a mixture comprising CO and H2 by a partial oxidation reaction, b) separating CO from the mixture, and c) converting at least a portion of the CO into phosgene in a catalytic gas-phase reaction with chlorine in the presence of a catalyst.

[0225] 27. The method according to Example 25 or 26, wherein the amino derivative of 1-methylbenzene produced in step c1) is preferably selected from the group consisting of 2-amino-1-methylbenzene, 3-amino-1-methylbenzene, 4-amino-1-methylbenzene, 2,4-diamino-1-methylbenzene, 2,6-diamino-1-methylbenzene and mixtures thereof.

[0226] 28. The method according to any one of Examples 25 to 27, wherein the diisocyanate or polyisocyanate derivative of the 1-methylbenzene is preferably selected from the group consisting of: 2-isocyano-1-methylbenzene, 3-isocyano-1-methylbenzene, 4-isocyano-1-methylbenzene, 2,4-diisocyano-1-methylbenzene and 2,6-diisocyano-1-methylbenzene and mixtures thereof and their polyisocyanate derivatives.

[0227] 29. The method according to any one of Examples 25 to 28, wherein the isocyanate formed in step d) is further converted into a polymer in the presence of at least one organic compound selected from the group consisting of or composed of polyurethane, thermoplastic polyurethane, polyisocyanurate and polyurea.

[0228] 30. The method according to any one of Examples 29, wherein the at least one organic compound is selected from the group consisting of or composed of: polyester polyols, polyether polyols, polycarbonate polyols, polyether ester polyols, polyacrylate polyols, polyester polyacrylate polyols, diols, polycaprolactone polyols, polytetramethylene glycol, diamines, amino-terminated polyethers, and mixtures thereof.

[0229] 31. A chemical apparatus for producing aromatic amino compounds from benzene and 1-methylbenzene from a liquid stream comprising at least one pyrolysis oil, the chemical apparatus comprising

[0230] (i) at least one first hydrogenation processing unit HU1, the at least one first hydrogenation processing unit HU1

[0231] (ii) It contains at least one inlet and at least one outlet.

[0232] (iii) Optionally, a recirculation unit is located downstream of and fluidly connected to the inlet and outlet of the first hydrogenation treatment unit HU1.

[0233] (iv) A distillation unit DU, which is downstream of and fluidly connected to the outlet of the first hydrogenation treatment unit HU1, has a bottom outlet BO and a top outlet HO, wherein a heavy stream (stream S5) exits the distillation unit DU through the bottom outlet BO, and wherein a light stream (stream S4) exits the distillation unit DU through the top outlet HO.

[0234] (v) A second hydrogenation treatment unit HU2, which is downstream of and fluidly connected to the top outlet HO of the distillation unit DU.

[0235] (vi) At least one aromatic hydrocarbon extraction unit AEU, which is downstream of and fluidly connected to the second hydrogenation treatment unit HU2.

[0236] 32. Use of the chemical equipment according to Example 31 for the method according to any one of Examples 1 to 30.

[0237] It should be clearly noted that the above set of embodiments represents appropriate structural portions of a general description of preferred aspects of the invention, and therefore appropriately supports but does not represent the claims of the invention.

[0238] The present invention will be further explained through the following non-limiting examples. Example

[0239] The present invention will be further explained through the following non-limiting examples.

[0240] Using ASPEN Plus TM The V11 simulation software is combined with a kinetic model to simulate the method steps for separating benzene from pyrolysis oil (comparative examples and method steps a1 to a6 according to the invention) to calculate the conversion rates in the first hydrotreating unit HU1 and the second hydrotreating unit HU2.

[0241] Comparison Examples

[0242] A comparative example is a method and chemical apparatus for producing benzene (stream S7') from a liquid stream S1 containing pyrolysis oil obtained from the pyrolysis of plastic waste taught in AU 2021 / 222788 A1, and in Figure 1 It is shown schematically in the diagram.

[0243] The process conditions for the first hydrogenation treatment unit HU1 are summarized in Table 1:

[0244]

[0245]

[0246] The composition of liquid stream S1 in hydrotreating unit HU1 is described in Table 2, wherein the diene component concentration is 0.8 wt.-% and the olefin component concentration is 3.23 wt.%. The total content of C6-C8 aromatic compounds is 73.13 wt.-%. The composition of liquid stream S1 is the same as that used in the following examples according to the invention. Liquid stream S1 is treated in hydrotreating unit HU1 under the conditions described in Table 1.

[0247] The catalyst in the hydrotreating unit HU1 is a Ni-Mo catalyst on an alumina support taught in AU 2021 / 222788 A1.

[0248] The pressure at the reactor outlet of the first hydrogenation unit HU1 is 64 bar (absolute value), and the reactor temperature is increased from 119°C (reactor inlet temperature) to 150°C (reactor outlet temperature) through adiabatic temperature rise. Under these conditions, typical trickle bed flow of the liquid phase over the (solid) catalyst occurs, which is desirable.

[0249] From the hydrogenation treatment unit HU2 ( Figure 1 The ratio of "liquid feed S1 : liquid recirculation flow S3'" is 1 : 1. Therefore, the concentration of diene components in the reactor inlet flow S1', having 0.4 wt.% is 5.7 times the concentration of diene components in the example according to the invention (see below). The much higher temperature increase (from reactor inlet to reactor outlet of the first hydrogenation treatment unit HU1) compared to 5°C in the example according to the invention (see below), along with the much higher diene component concentration, leads to higher polymer formation during treatment and thus promotes blockage, both of which are undesirable.

[0250] The WHSV (weight hourly space velocity) of liquid flow S1 is 0.5 t / (m²). 3 Kat. h). The chemical hydrogen consumption in the hydrogenation unit HU1 is 23 Nm. 3 / t. The molar ratio of "feed to hydrotreating unit HU1 containing H2 stream S2 : chemical hydrogen consumption" is 1.08 : 1. A small excess of hydrogen ensures sufficient catalyst activity to achieve 99% conversion of diene components and 68% conversion of olefin components (stream S3). Under these operating conditions and with the catalyst used (Ni-Mo catalyst on alumina support), no hydrogenation of aromatic components will occur. The reactor products of hydrotreating unit HU1 ( Figure 1 The feed (S3) is directly fed into the hydrotreating unit HU2.

[0251] The process conditions in the second hydrogenation unit HU2 are summarized in Table 3:

[0252]

[0253] Table 3 shows the process conditions for the hydrotreating unit HU2. The pressure at the reactor outlet is 63 bar (absolute). The ratio of "HU2 internal recirculated gas S4'' : feed stream S3" is 392 Nm. 3 / t, and the reactor inlet temperature of the second hydrotreating unit HU2 is 342°C. Under these conditions, the feed stream S3 of the hydrotreating unit HU2 is completely evaporated.

[0254] Due to the feed stream S3 of the hydrotreating unit HU2 < A low diene content of 0.01 wt.% does not result in undesirable polymerization and scaling during complete evaporation. Through the exothermic hydrogenation reaction mentioned above, the reactor temperature is increased from an inlet temperature of 342°C to an outlet temperature of 355°C. The temperature increase is 13°C because 69% of the olefins have already been hydrogenated in the hydrogenation treatment unit HU1.

[0255] To limit undesirable hydrogenation of aromatic rings, this low exothermic temperature increase of 13°C is beneficial. A hydrogen partial pressure of 39 bar (absolute value) in the reactor is sufficient to ensure adequate hydrogenation activity while avoiding undesirable aromatic ring hydrogenation. The catalyst in the hydrotreating unit HU2 is a standard Co-Mo catalyst on an alumina support, which exhibits sufficient activity for diene and olefin hydrogenation, desulfurization, denitrification, and dehalogenation, as well as very low aromatic ring hydrogenation activity, but requires a higher temperature than the Co-Mo catalyst on an alumina support described in the example below according to the invention. The loss of aromatic components through aromatic ring hydrogenation is <0.5%. The WHSV of the feed stream S3 is 0.7 t / (m³). 3 Kat. h).

[0256] The cooled condensate reaction product S4 leaving the second hydrotreating unit HU2 is fed back to the hydrotreating unit HU1 at a 1:1 ratio along with the liquid feed stream S1 to dilute the liquid feed stream S1 before it enters the first hydrotreating unit HU1. The necessity and effect of dilution in the hydrotreating unit HU1 have been described above.

[0257] The next step is distillation in the distillation unit DU to remove unwanted high-boiling components before the aromatic hydrocarbon extraction unit AEU. High-boiling components are undesirable in the aromatic hydrocarbon extraction unit AEU because they accumulate in the solvent and contaminate it. Therefore, the efficiency of aromatic hydrocarbon extraction in the aromatic hydrocarbon extraction unit AEU will be affected.

[0258] The distillation results in distillation unit DU are shown in Table 4.

[0259]

[0260] In distillation unit DU, the light boiling fraction, containing the majority of C6-C8 aromatic components, enters the overhead distillate. This constitutes 78 wt.-% of the feed stream S4 to distillation unit DU, thus increasing the C6-C8 aromatic component content from 69.5 wt.-% to 83.0 wt.-%. The high-boiling components are separated by the bottom stream S5. The valuable product overhead distillate S4 is 78% of the feed stream S3 to distillation unit DU and contains 93 wt.-% C6-C8 aromatic components.

[0261] The feed stream S6 from the head section of the distillation unit DU is then fed into the aromatic hydrocarbon extraction unit AEU. Here, pure benzene (> 99 wt.-%), pure toluene (> 99 wt.-%), and the xylene / ethylbenzene mixture (> 93 wt.-%) are separated by an extractive distillation process. The remaining stream S8 is lean for C6-C8 aromatic components and contains paraffinic components, cycloalkanes, and C8+ aromatic hydrocarbons.

[0262] Example (of this invention)

[0263] According to the method steps a1) to a6) of the present invention, in this example, they are performed as follows: Figure 3 The schematic simulation in the diagram (flow S7' is suitable for providing benzene in method step a).

[0264] Table 5. Process conditions in the first hydrogenation treatment unit HU1:

[0265]

[0266]

[0267] The composition of the liquid stream S1 fed into the first hydrotreating unit HU1 is described in Table 6, wherein the diene component concentration is 0.8 wt.-% and the olefin component concentration is 3.23 wt.%. The total content of C6-C8 aromatic compounds is 73.13 wt.-%. Liquid stream S1 is treated in the first hydrotreating unit HU1 under the conditions described in Table 5. The catalyst in the first hydrotreating unit HU1 is a palladium catalyst contained on an alumina support, which allows for very mild reaction conditions (e.g., lower temperatures). The pressure at the reactor outlet in the first hydrotreating unit HU1 is 30 bar (absolute), and the reactor temperature is increased from a reactor inlet temperature of 80°C to a reactor outlet temperature of 85°C by adiabatic temperature increase. Under these conditions, typical trickle bed flow of the liquid phase over the catalyst occurs. The ratio "liquid feed S1 : liquid recirculation flow S3'" results in a very low diene concentration of 0.07 wt.% and an olefin content of 0.97 wt.% in the reactor inlet flow S1'. The low temperature and mild temperature increase of only 6°C, combined with the high pressure and low diene concentration, ensure that undesirable polymer formation and fouling are avoided during treatment.

[0268] The WHSV (weight hourly space velocity) of liquid flow S1 is 0.5 t / (m²). 3 Kat. h). The chemical hydrogen consumption in the first hydrogenation unit HU1 is 28 Nm. 3 The molar ratio of "hydrogen-containing stream S2 fed to the first hydrogenation unit HU1 : chemical hydrogen consumption" is 1.2 : 1. A small excess of hydrogen ensures sufficient catalyst activity to achieve 99% conversion of diene components and 76% conversion of olefin components (stream S3). Under these operating conditions, no hydrogenation of aromatic components will occur. Stream S3 leaving the first hydrogenation unit HU1 is sufficiently stable and no undesirable scaling caused by polymerization occurs in the distillation unit DU.

[0269] The distillation results in distillation unit DU are shown in Table 7:

[0270]

[0271] For liquid stream S1, it is necessary to separate high-boiling-point substances from stream S3 to ensure that stream S3 is completely evaporated in the second hydrogenation treatment unit HU2.

[0272] In distillation unit DU, the light boiling fraction, containing the majority of C6-C8 aromatics, enters the overhead distillate. This constitutes 78 wt.-% of the total feed to distillation unit DU stream S4. The C6-C8 aromatic content increases from 69.0 wt.-% to 82.5 wt.%. High-boiling components are separated by the bottom stream S5. The valuable product overhead distillate S4 is 78 wt.-% of the feed stream S3 from distillation unit DU and contains 93 wt.-% C6-C8 aromatics.

[0273] The valuable overhead distillate stream S4 from distillation unit DU is further processed in the second hydrotreating unit HU2. Here, the remaining trace amounts of dienes and alkenes are hydrogenated in the gas phase to the corresponding saturated hydrocarbons. Sulfur-containing components are hydrogenated to the corresponding saturated hydrocarbons and H₂S. The sulfur content in the hydrotreating product stream S6 is < 0.5 wt.-ppm. Nitrogen-containing components are hydrogenated to the corresponding saturated hydrocarbons and NH₃. The nitrogen content in the hydrotreating product stream S6 is < 10 wt.-ppm. Halogen-containing components (such as chlorine-containing components) are hydrogenated to the corresponding saturated hydrocarbons and hydrohalic acids (such as HCl). The halogen / chlorine content in the hydrotreating product stream S6 is < 1 wt.-ppm.

[0274] The process conditions for the second hydrogenation unit HU2 are shown in Table 8:

[0275]

[0276] Table 8 shows the process conditions for the second hydrogenation unit HU2. The pressure at the reactor outlet is 51 bar (absolute value). The ratio of "recirculated gas flow S6'' : feed flow S4" is 577 Nm. 3 / t, and the reactor inlet temperature is 267°C. Under these conditions, the inlet stream S4 of the second hydrogenation treatment unit HU2 is completely evaporated. Due to the feed stream S4 <With a low diene content of 0.01 wt.%, no undesirable polymerization or scaling occurs within the second hydrotreating unit HU2. Through the exothermic hydrogenation reaction within the second hydrotreating unit HU2 mentioned above, the reactor temperature increases from an inlet temperature of 267°C to an outlet temperature of 281°C. This temperature increase is advantageously limited to a low 14°C because 76% of the olefins have already been hydrogenated in the first hydrotreating unit HU1. This low exothermic temperature increase within the second hydrotreating unit HU2 is beneficial in limiting undesirable hydrogenation of C6-C8 aromatics. The hydrogen partial pressure of 36 bar in the reactor of the second hydrotreating unit HU2 is suitable for ensuring sufficient hydrogenation activity while avoiding undesirable hydrogenation of C6-C8 aromatics. The catalyst in the second hydrotreating unit HU2 is a Co-Mo catalyst on an alumina support, which exhibits sufficient activity for diene and olefin hydrogenation, desulfurization, denitrification, and dehalogenation, as well as the desired very low activity for C6-C8 aromatic hydrogenation. The loss of aromatic components through aromatic ring hydrogenation is <0.5%. The WHSV of stream S4 is 0.7 t / (m 3 Kat. h).

[0277] Stream S6, exiting the second hydrogenation unit HU2, is fed to the aromatics extraction unit AEU, which produces pure benzene (>99 wt.-%), pure toluene (>99 wt.-%), and a xylene / ethylbenzene mixture (>93 wt.-%), which are separated in the aromatics extraction unit AEU by an extractive distillation process. The remaining stream S8 is lean for C6-C8 aromatics and contains paraffinic components, cycloalkanes, and C8+ aromatics. Stream S7' is then suitable for providing benzene in step a) of the method according to the invention.

Claims

1. A method for producing an aromatic amino compound from benzene and 1-methylbenzene, the method comprising the following steps: a) Provide benzene or 1-methylbenzene and a mixture of nitric acid and sulfuric acid, b) Contacting benzene or 1-methylbenzene with the mixture of nitric acid and sulfuric acid, thereby forming nitrobenzene or a nitro derivative of 1-methylbenzene. c1) Hydrogenating the nitrobenzene or nitro derivative of 1-methylbenzene formed in step b) in the presence of hydrogen and optionally a catalyst, thereby forming aniline or an amino derivative of 1-methylbenzene. Its features are, At least a portion of the benzene or 1-methylbenzene provided in step a) is manufactured by the following manner a1) Provides a liquid stream S1 comprising at least one pyrolysis oil, the liquid stream S1 further comprising C6-C8 aromatic hydrocarbons, an organic compound comprising at least one heteroatom, and a compound having a C-C double bond and / or a C-C triple bond. a2) Provides a stream S2, which contains H2. a3) The liquid stream S1 and the liquid stream S2 are fed into the hydrogenation unit HU1, in which at least a portion of the components of the liquid stream S1 reacts with the liquid stream S2 in a hydrogenation reaction to form a liquid stream S3, wherein the liquid stream S3 is depleted relative to the liquid stream S1 of compounds having C-C double bonds and / or C-C triple bonds, and Optionally, at least a portion of the liquid recirculation stream S3' is fed into the hydrogenation unit HU1, the liquid recirculation stream S3' being separated from the liquid stream S3, preferably wherein the mass ratio of "liquid recirculation stream S3' : liquid stream S3" preferably ranges from about 1 : 1 to about 30 : 1, more preferably from about 5 : 1 to about 20 : 1, and most preferably from about 10 : 1 to about 15 :

1. a4) subjecting at least a portion or the remainder of the liquid stream S3 to a distillation unit DU, in which at least a portion or the remainder of the liquid stream S3 is separated into a stream S4 containing valuable products and a liquid stream S5, wherein the stream S4 containing valuable products comprises C6-C8 aromatic hydrocarbons and organic compounds containing at least one heteroatom. a5) The stream S4 containing the valuable product is subjected to a hydrogenation unit HU2, in which the stream S4 is converted into a stream S6, wherein the stream S6 contains C6-C8 aromatic hydrocarbons and is relatively lean compared to stream S4, containing at least one heteroatom and / or C / C double bond of an organic compound, and a6) Separate benzene and / or 1-methylbenzene from stream S6 in the aromatic hydrocarbon extraction unit AEU.

2. The method according to claim 1, wherein, The benzene or 1-methylbenzene provided in step a) is preferably at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, and most preferably 7.5 wt.-% produced by steps a1) to a6).

3. The method according to claim 1 or 2, wherein, This at least one pyrolysis oil is produced by the pyrolysis of plastic waste.

4. The method according to any one of claims 1 to 3, wherein, The liquid stream S1 preferably contains at least 15 wt.% C6-C8 aromatic hydrocarbons, more preferably at least 50 wt.% C6-C8 aromatic hydrocarbons, and most preferably at least 80 wt.% C6-C8 aromatic hydrocarbons.

5. The method according to any one of claims 1 to 4, wherein, The at least one pyrolysis oil in the liquid stream S1 has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (as determined by ASTM 1159) and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-% (as determined by ASTM D 5134) and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-% (as determined by ASTM D 5134) and / or a styrene content of about 0.02 wt.-% to about 29.5 wt.-% (as determined by ASTM D 5134) and / or a toluene content of about 4.3 wt.-% to about 71.5 wt.-% (as determined by ASTM D 5134).

6. The method according to any one of claims 1 to 5, wherein, The nitro derivative of 1-methylbenzene formed in step b) is preferably selected from the group consisting of 2-nitro-1-methylbenzene, 3-nitro-1-methylbenzene, 4-nitro-1-methylbenzene, 2,4-dinitro-1-methylbenzene and 2,6-dinitro-1-methylbenzene and mixtures thereof.

7. The method according to any one of claims 1 to 6, wherein, The amino derivative of 1-methylbenzene formed in step c1) is preferably selected from the group consisting of 2-amino-1-methylbenzene, 3-amino-1-methylbenzene, 4-amino-1-methylbenzene, 2,4-amino-1-methylbenzene, 2,6-amino-1-methylbenzene and mixtures thereof.

8. The method according to any one of claims 1 to 7, further comprising the following additional steps. c2) In the presence of formaldehyde, aniline is converted into 1,1'-methylenebis(4-aminobenzene) by a condensation reaction.

9. The method according to any one of claims 7 or 8, further comprising the following steps: d) Phosgenetically phos ...

10. The method according to claim 9, wherein, The amino derivative of 1-methylbenzene produced in step c1) is preferably selected from the group consisting of: 2-amino-1-methylbenzene, 3-amino-1-methylbenzene, 4-amino-1-methylbenzene, 2,4-diamino-1-methylbenzene, 2,6-diamino-1-methylbenzene and mixtures thereof.

11. The method according to claim 9 or 10, wherein, The diisocyanate or polyisocyanate derivative of 1-methylbenzene is preferably selected from the group consisting of: 2-isocyano-1-methylbenzene, 3-isocyano-1-methylbenzene, 4-isocyano-1-methylbenzene, 2,4-diisocyano-1-methylbenzene and 2,6-diisocyano-1-methylbenzene and mixtures thereof, as well as their polyisocyanate derivatives.

12. The method according to any one of claims 9 to 11, wherein, The isocyanate formed in step d) is further converted into a polymer in the presence of at least one organic compound, the polymer being selected from or consisting of the group consisting of polyurethane, thermoplastic polyurethane, polyisocyanurate and polyurea.

13. The method according to claim 12, wherein, The at least one organic compound is selected from the group consisting of or composed of the following: polyester polyols, polyether polyols, polycarbonate polyols, polyether ester polyols, polyacrylate-polyols, polyester-polyacrylate polyols, diols, polycaprolactone polyols, polytetramethylene glycol, diamines, amino-terminated polyethers, and mixtures thereof.

14. A chemical apparatus for producing aromatic amino compounds from benzene and 1-methylbenzene from a liquid stream comprising at least one pyrolysis oil, the chemical apparatus comprising (i) at least one first hydrogenation processing unit HU1, the at least one first hydrogenation processing unit HU1 (ii) It contains at least one inlet and at least one outlet. (iii) Optionally, a recirculation unit is located downstream of and fluidly connected to the inlet and outlet of the first hydrogenation treatment unit HU1. (iv) A distillation unit DU, which is downstream of and fluidly connected to the outlet of the first hydrogenation treatment unit HU1, has a bottom outlet BO and a top outlet HO, wherein a heavy stream (stream S5) exits the distillation unit DU through the bottom outlet BO, and wherein a light stream (stream S4) exits the distillation unit DU through the top outlet HO. (v) A second hydrogenation treatment unit HU2, which is downstream of and fluidly connected to the top outlet HO of the distillation unit DU. (vi) At least one aromatic hydrocarbon extraction unit AEU, which is downstream of and fluidly connected to the second hydrogenation treatment unit HU2.

15. Use of the chemical equipment according to claim 14 for the method according to any one of claims 1 to 13.

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