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

Abstract

The present invention relates to a process and a chemical plant for separating benzene and 1-methylbenzene from a stream comprising at least one pyrolysis oil which is manufactured from plastic waste and further converting said benzene or 1-methylbenzene into aromatic amines. The aromatic amines are suited as a precursor for di- and poly-isocyanates which are based on benzene or 1-methylbenzene manufactured from plastic waste. Furthermore, polyurethanes, thermoplastic polyurethanes, polyisocyanurates, and polyureas can be manufactured by the process according to the present invention.

Description

[0001] Process for manufacturing aniline and (di)amino derivatives of 1 -methyl benzene from plastic waste and chemical products based on cyclohexanone manufactured from plastic waste

[0002] Technical Area

[0003] The present invention relates to a process for manufacturing aniline and (di)amino derivatives of 1 -methylbenzene and chemical products based on aniline and (di)amino derivatives of 1 -methylbenzene from plastic waste.

[0004] Background of the invention

[0005] Aniline and (di)amino derivatives of 1 -methylbenzene are important intermediate products in the chemical industry from which di- or poly-isocyanate derivatives of benzene and 1-methylbenzene are manufactured. Such isocyanate derivatives of benzene and 1-methylbenzene are then used as building blocks in the manufacture of polyurethanes and thermoplastic polyurethanes (abbreviated PUs and TPUs, respectively, and (T)PUs when referring to both types of polyurethanes), polyisocyanurates (PIR) and polyureas.

[0006] The usual starting materials for the manufacture of aniline is benzene and for (di)amino derivatives of 1- methylbenzene 1-methylbenzene, which are both isolated from fossil sources such as processed crude oil.

[0007] Aniline and (di)amino derivatives of 1-methylbenzene are then manufactured from benzene and 1-methylbenzene by a nitrogenating reaction followed by a hydrogenation reaction if the respective nitrogenated intermediates.

[0008] Future regulations and customers might require a certain percentage of recycled content in aniline, (di)amino derivatives of 1-methylbenzene and chemical products manufactured therefrom. Hence, there is a need for recycling options and recycling feedstock for polymers such as PU that is based on mixed plastic waste (e.g., some PU applications go into very small scale or dispersed applications, such as adhesives and coatings which cannot be collected on a large scale and then recycled in a closed loop).

[0009] The main carbon atom contributor to building blocks of (T)PUs, polyisocyanurates (PIR) and polyureas is the aromatic core molecule, i.e., aniline and / or (di)amino derivatives of 1-methylbenzene and their respective isocyanate derivatives. Accordingly, the aromatic core molecule is also the most important building block that needs to be recycled.

[0010] It is a first objective of the present invention to provide a process for manufacturing aniline and (di)amino derivatives of 1-methylbenzene from plastic waste.

[0011] It is a second objective if the present invention to provide a process for manufacturing of di- and poly-isocyanate derivatives of benzene and 1-methylbenzene such as 1-isocyanato-benzene, 1,1 '-methylenebis(4- isocyanatobenzene) and 2,4-diisocyanato-1-methylbenzene from plastic waste. It is a third objective of the present invention to provide di- and poly-isocyanate derivatives of benzene, such as 1,1 '- methylenebis(4-isocyanatobenzene), and 1 -methylbenzene, such as 2,4-diisocyanato-1-methylbenzene, manufactured from plastic waste for manufacture of (T)PUs, polyisocyanurates and polyureas.

[0012] Summary of the Invention

[0013] These problems are solved by a process for manufacturing aromatic amino compounds from benzene and 1- methylbenzene comprising the steps a) providing 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 whereby nitrobenzene or a nitro-derivative of 1 -methylbenzene is formed, d) hydrogenate the nitrobenzene or nitro-derivative of 1 -methylbenzene formed in step b) in the presence of hydrogen and, optionally, a catalyst, whereby aniline or an amino-derivative of 1 -methylbenzene is formed, characterized in that the at least a portion of the benzene or 1 -methylbenzene provided in step a) is manufactured by the steps a1) providing a liquid stream S1 comprising at least one pyrolysis oil, the liquid stream S1 further comprising C6-C8 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and compounds having C-C double and / or C-C triple bonds, a2) providing a stream S2, the stream S2 comprising hydrogen, a3) evaporating at least a portion of the liquid stream S1 in the presence of the stream S2 and optionally a recycle gas stream S11 in an evaporation unit EU and thereby forming a gaseous stream S3 which comprises stream S2, optionally a recycle gas stream S11 and the evaporated portion of the liquid stream S1 , and a liquid stream S4 which comprises the portion of liquid stream S1 which is not evaporated in the evaporation unit EU, a4) optionally superheating the gaseous stream S3 in a superheater SH and thereby form a superheated stream

[0014] S5, a5) feeding the gaseous stream S3 or, optionally the superheated stream S5 into a first hydrogenation unit HU1 in which at least a portion of the gaseous stream S3 or, optionally the at least a portion of the superheated stream S5 reacts with the hydrogen comprised therein in a hydrogenation reaction whereby a gaseous stream S6 is formed, the gaseous stream S6 comprising C6-C8 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and is depleted in compounds having C-C double and / or C-C triple bonds in respect to gaseous stream S3, a6) heating the gaseous stream S6 in at least one heating device HD and thereby forming a heated gaseous stream S7, a7) subjecting the heated gaseous stream S7 to a second hydrogenation unit HU2 in which a product stream S8 is formed, the product stream S8 comprising C6-C8 aromatic hydrocarbons and being depleted in organic compounds comprising at least one heteroatom and further depleted in compounds having C-C double and / or C-C triple bonds in respect to gaseous stream S3, a8) optionally transferring heat from the product stream S8 to the gaseous stream S3 in the superheater SH and thereby forming a cooled down product stream S8b, a9) continuously or discontinuously feeding a washing water stream S15 to the product stream S8 and thereby forming a stream optionally comprising washing water S8a or optionally continuously or discontinuously feeding a washing water stream S15 to the cooled down product stream S8b and thereby forming a cooled down product stream optionally comprising washing water S8c, a10) optionally transferring heat from the cooled down product stream comprising washing water S8c to the liquid stream S1 , stream S2 comprising H2 and stream S11 in the evaporation unit EU and thereby forming a further cooled down product stream S8d, a11) condensing the product stream optionally comprising washing water S8a or optionally one of the streams selected from the group consisting of the cooled down product stream S8b, the cooled down product stream optionally comprising washing water S8c, and the further cooled down product stream optionally comprising washing water S8d in a condensation unit CU and thereby forming a product stream S9, the product stream S9 comprising a liquid phase and a gas phase, a12) separating the liquid product stream S9 in a separation unit SU into a liquid product stream S10, a recycle gas stream S11 and optionally a waste water stream S17 wherein the recycle gas stream S11 comprises hydrogen and wherein at least a portion of the recycle gas stream S11 is fed into the evaporation unit EU, a13) feeding the refined product stream S10 into a distillation unit DU in which the refined product stream S10 is separated into a stabilized product stream S12 and a gaseous stream S13 and a14) separating benzene and / or 1 -methylbenzene from the stabilized product stream S12 in at least one aromatic hydrocarbon extraction unit AEU.

[0015] These problems are further solved by a chemical plant for separating benzene and 1 -methylbenzene from a feedstock stream comprising at least one pyrolysis oil for manufacturing aromatic amines therefrom, the chemical plant comprising

[0016] (i) an evaporation unit EU,

[0017] (ii) optionally a superheater SH downstream of the evaporation unit EU,

[0018] (iii) a first hydroprocessing unit HU1, the first hydroprocessing unit HU1 comprising at least one inlet and at least one outlet, the first hydroprocessing unit HU1 downstream of the evaporation unit EU or the optional superheater SH and the at least one inlet of the first hydroprocessing unit HU1 fluidically connected to the evaporator or the optional superheater SH,

[0019] (iv) at least one heating unit HD downstream of and fluidically connected to the at least one outlet of the first hydroprocessing unit HU1,

[0020] (v) a second hydroprocessing unit HU2 having at least one inlet and at least one outlet, the second hydroprocessing unit HU2 downstream of the at least one heating unit HD and the at least one outlet of the hydroprocessing unit HU2 fluidically connected to the heating device HD,

[0021] (vi) a condensation unit CU downstream of the second hydroprocessing unit HU2 and fluidically connected to the at least one outlet of the second hydroprocessing unit HU2, (vii) a separation unit SU downstream of and fluidically connected to the condensation unit CU and

[0022] (viii) a distillation unit DU downstream of and fluidically connected to the separation unit SU and an aromatic hydrocarbon extraction unit AEU downstream of the optional distillation unit and fluidically connected to stream S12.

[0023] The process according to the present invention provides the following advantages:

[0024] First, aniline or an amino-derivative of 1 -methylbenzene can be manufactured from plastic waste as feedstock and has therefore a recycle-content of 100 % in case all benzene or 1 -methylbenzene provided in step a) is manufactured by steps a1) to a14).

[0025] Aniline or an amino-derivative of 1 -methylbenzene is formed having a recycle-content of less than 100 % can also be manufactured by the method according to the present invention in case not all benzene or 1 -methylbenzene provided in step a) is manufactured by steps a1) to a14) and instead manufactured e.g., from a fossil feedstock. Accordingly, the process according to the present invention also enables manufacture of aniline or an amino-derivative of 1- methylbenzene with a desired recycle-content of less than 100 %.

[0026] Second, the aniline or an amino-derivative of 1 -methylbenzene manufactured from plastic waste and therefore having a recycle-content can be used as the feedstock for manufacturing di- or poly-isocyanate derivatives of benzene and 1-methylbenzene, such as 1,1 '-methylenebis(4-isocyanatobenzene) (“MDI”) and 2,4-diisocyanato-1- methylbenzene (“TDI”) which, accordingly, also have a recycle-content of up to 100 % in case all aniline or an aminoderivative of 1-methylbenzene is manufactured from benzene or 1-methylbenzene provided in step a) is manufactured by steps a1) to a14). Di- or poly-isocyanate derivatives of benzene and 1-methylbenzene having a recyclecontent of less than 100 % can be manufactured from aniline or an amino-derivative of 1-methylbenzene having a recycle-content of less than 100 %. Accordingly, the process according to the present invention also enables manufacture of di- or poly-isocyanate derivatives of benzene and 1-methylbenzene with a desired recycle-content of less than 100 %.

[0027] Third, the di- or poly-isocyanate derivatives of benzene and 1-methylbenzene manufactured from plastic waste and therefore having a recycle-content can be used as the feedstock for manufacturing (T)PUs, polyisocyanurates and polyurea which, accordingly, have also a recycle-content of up to 100 % in case all di- or poly-isocyanate derivatives of benzene and 1-methylbenzene is manufactured from benzene or 1-methylbenzene provided in step a) is manufactured by steps a1) to a14) and further building blocks for the respective polymerization reaction are have a recycle content of 100 %. (T)PUs, polyisocyanurates and polyurea having a recycle-content of less than 100 % can be manufactured from di- or poly-isocyanate derivatives of benzene and 1-methylbenzene having a recycle-content of less than 100 %. Accordingly, the process according to the present invention also enables manufacture of (T)PUs, polyisocyanurates and polyureas with a desired recycle-content of less than 100 %. Fourth, in case the plastic waste from which (T)PUs, polyisocyanurates and polyurea having a recycle-content is produced comprises (T)PUs, polyisocyanurates and / or polyurea, the process according to the present invention is a closed recycling loop for (T)PUs, polyisocyanurates and / or polyureas.

[0028] Fifth, in manufacture of benzene or 1 -methylbenzene manufactured from plastic waste according to steps a1) to a14) undesired polymerization and fouling is suppressed (see Examples).

[0029] Figure 1 shows a method in which a liquid recycle stream from a second hydroprocessing unit into a first hydroprocessing unit is utilized. Such a recycle stream is employed in the method disclosed in AU 2021 / 222788 A1 and was used therefore as comparative example below.

[0030] Figure 2 shows the process and the chemical plant for separating benzene stream from a feedstock stream comprising at least one pyrolysis oil for the manufacture of cyclohexanone according to the present invention.

[0031] Figure 3 shows the process and the chemical plant for separating benzene stream from a feedstock stream comprising at least one pyrolysis oil for the manufacture of cyclohexanone according to the present invention including an optional superheater SU and optional step a4).

[0032] Figure 4 shows the process and the chemical plant for separating benzene stream from a feedstock stream comprising at least one pyrolysis oil for the manufacture of cyclohexanone according to the present invention including optional steps a4), a8) and a10).

[0033] Detailed description of the invention

[0034] The present invention is further described below with reference to the embodiments, but the present invention is not limited to these embodiments, and any modifications of these embodiments, combinations of these embodiments or substitutions within the basic spirit of the present invention are still within the scope of the present invention as claimed.

[0035] Definitions:

[0036] In the context of the present description and the accompanying claims, the term "about” preferably means a deviation of the thus described value of ±10%. In the context of the present invention, the term “combinations thereof” is inclusive of one or more of the recited elements. In the context of the present invention, the term “mixture thereof” is inclusive of one or more of the recited elements. The term “recycle-content” is defined herein as amount or percentage of recycled materials used in a product or material. It indicates the extent to which recycled materials have 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. “Poly-isocyanate” is defined herein as molecules comprising more than two isocyanate residues. In step a) of the process according to the present invention, benzene or 1-methylbenzene is provided. At least a portion of the benzene or 1-methylbenzene provided in step a) is manufactured by steps a1) to a14). Benzene and 1- methylbenzene manufactured by steps a1) to a14) have a recycle-content of 100 %.

[0037] In step a) of the process according to the present invention, benzene or 1-methylbenzene is provided. At least a portion of the benzene or 1-methylbenzene provided in step a) is manufactured by steps a1) to a14). Benzene and 1- methylbenzene manufactured by steps a1) to a14) have a recycle-content of 100 %.

[0038] In the context of the present invention, the term "pyrolysis” relates to a thermal decomposition or degradation of a feedstock such as plastic waste under inert conditions and results in a gas, a liquid, and a solid char fraction. During the pyrolysis, the feedstock is converted in a pyrolysis unit into a great variety of chemicals including gases such as H2, Ci- to C4-alkanes, C2- to C4-alkenes, ethyne, propyne, 1 -butyne, pyrolysis oil having a boiling temperature of 25 °C to 500 °C and char. In addition, water is formed during the pyrolysis which may be partially dispersed in the pyrolysis oil and may be partially contacted with the pyrolysis oil in a separate phase. The water formed during pyrolysis comprises various organic compounds and / or salts thereof which were also formed during the pyrolysis. The term "pyrolysis” includes slow pyrolysis, fast pyrolysis, flash catalysis and catalytic pyrolysis. These pyrolysis types differ regarding process temperature, heating rate, residence time, feed particle size, etc. resulting in different product quality. The pyrolysis unit may be operated adiabatically, isothermally, nonadiabatically, non-isothermally, or combinations thereof. The pyrolysis reactions of this disclosure may be carried out in a single stage or in multiple stages. For example, the pyrolysis unit can comprise two reactor vessels fluidly connected in series.

[0039] In the context of the present invention, "valued components” means "C6-C8 aromatic hydrocarbons” (benzene, toluene, 1 ,2-xylene, 1 ,3-xylene, 1 ,4-xylene, and ethylbenzene), preferably benzene.

[0040] In the context of the present invention, the term "pyrolysis oil” is understood to mean any oil originating from the pyrolysis of plastic waste. The term "plastic waste” includes rubber waste such as end-of-life tires and feedstocks comprising plastic waste. The pyrolysis oil is obtained and / or obtainable from pyrolysis such plastic waste.

[0041] In the context of the present invention, the term "plastic waste” refers to any plastic material discarded after use, i.e. , the plastic material has reached the end of its useful life and is considered post-consumer waste. The plastic waste can be pure polymeric plastic waste, mixed plastic waste or film waste, including soiling, adhesive materials, fillers, residues etc. The plastic waste may have an oxygen content, a nitrogen content, sulfur content, halogen content and optionally also a heavy metal content. The plastic waste can originate from any plastic material containing source.

[0042] Accordingly, the term "plastic waste” includes industrial and domestic plastic waste and including used tires and agricultural and horticultural plastic material. Typically, plastic waste is a mixture of different plastic materials, including hydrocarbon plastics, e.g., polyolefins such as polyethylene (HDPE, LDPE) and polypropylene, polystyrene, and copolymers thereof, etc., and polymers composed of carbon, hydrogen, and other elements such as chlorine, fluorine, oxygen, nitrogen, sulfur, silicone, etc., for example chlorinated plastics, such as polyvinylchloride (PVC), polyvinylidene chloride (PVDC), etc., nitrogencontaining plastics, such as polyamides (PA), polyurethanes (PU), acrylonitrile butadiene styrene (ABS), etc., oxy- gen-containing plastics such as polyesters, e.g., polyethylene terephthalate (PET), polycarbonate (PC), etc., silicones and / or sulfur bridges crosslinked rubbers.

[0043] Typically, the plastic material comprises additives, such as processing aids, plasticizers, flame retardants, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, antioxidants, etc. These additives may comprise elements other than carbon and hydrogen. For example, bromine is mainly found in connection to flame retardants. Heavy metal compounds may be used as lightfast pigments and / or stabilizers in plastics. Cadmium, zinc, and lead may be present in heat stabilizers and slip agents used in plastics manufacturing. The plastic waste can also contain residues. Residues in the sense of the invention are contaminants adhering to the plastic waste. The additives and residues are usually present in an amount of less than 50 wt.-%, preferably less than 30 wt.-%, more preferably less than 20 wt.-%, even more preferably less than 10 wt.-%, based on the total weight of the dry weight plastic.

[0044] Examples of rubber waste (which is also considered "plastic waste” in the sense of the present invention) include end-of-life tires, rubber waste produced during manufacturing processes and discarded rubber containing products such as latex examining gloves and gaskets. End-of-life tires comprise further ingredients such as textiles and organic and inorganic additives which may be separated from the rubber portion of end-of-life tires prior to pyrolysis. Pyrolysis oils obtained by pyrolysis of (predominantly) end-of-life tires are also known as tire pyrolysis oils (TPO).

[0045] Examples of bio waste which can be comprised in "plastic waste” include green waste, food waste, human waste, manure, sewage, sewage sludge and slaughterhouse waste.

[0046] To obtain the pyrolysis oil according to the present invention, the feedstock is inserted into a pyrolysis reactor using a dosing unit such as a screw or an extruder or a rotary valve or a pneumatic conveyor or a liquid injector. The feedstock is optionally pre-heated in e.g., a heat exchanger prior to insertion into the pyrolysis reactor and / or subjected to a pre-pyrolysis at a temperature in the range of, for example, from about 200 °C to about 360 °C. Next, the feedstock is heated in the pyrolysis reactor to a temperature in the range of from about 350 °C to about 900 °C, more preferably in the range of from 400 °C to about 550 °C, and a pressure in the range of from about 0.5 bar to about 2 bar(abs), more preferably in the range of from 0.9 bar to about 1.5 bar(abs). The pyrolysis reactor is preferably selected from the group comprising fluidized bed reactors, moving bed reactors, entrained flow reactors, screw reactors, extruders, stirred tank reactors and rotary kiln reactor. Preferably, the pyrolysis is performed in the pyrolysis reactor under an inert atmosphere exempt of oxygen or air. Pyrolysis processes as such are known. They are described, e.g., in EP 0713906 A1 and WO 95 / 03375 A1. Suitable pyrolysis oils are also commercially available. The pyrolysis oil is typically a liquid at 15 °C or a wax at said temperature. "Liquid at 15 °C” in the terms of the present invention means that the pyrolysis oil has a density of at most 1 .3 g / ml, e.g., a density in the range from 0.65 to 0.98 g / ml, at 15 °C and 1013 mbar, as determined according to DIN EN ISO 12185.

[0047] The amount of 06-08 aromatic hydrocarbons formed by pyrolysis reaction of the above-described feedstocks can be increased for example in the presence of a suitable catalyst. Another suitable method for increasing the amount of 06-08 aromatic hydrocarbons is disclosed in EP 3744814 A1 : the pyrolysis gas obtained by a pyrolysis reaction of above-described feedstocks is then subjected to a thermo-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, ferrierite, zeolite beta, zeolite Y, zeolite X, mordenite, zeolite A, IM-5, SSZ-20, SSZ-55, MCM-22, TNU-9, metal treated, exchanged or impregnated and combinations of the aforementioned catalysts and post-treatments. Other suitable catalysts comprise sand and alumina. Also, combinations of the aforementioned catalysts can be used for this purpose.

[0048] The amount of C6-C8 aromatic hydrocarbons in a pyrolysis oil can also be increased by reforming a pyrolysis oil or mixture of pyrolysis oils, for example by a catalytic reforming reaction. Such reforming reactions are for example disclosed in https: / / www.e-education.psu.edu / fsc432 / content / catalyic-reforming-processes and can be adapted, if necessary, by the skilled person.

[0049] A pyrolysis oil comprising an increased amount of C6-C8 aromatic hydrocarbons can also be manufactured by a pyrolysis of plastic waste stream comprising polystyrene (Maafa, I.M. Pyrolysis of Polystyrene Waste: A Review. Polymers 2021, 13, 225. https: / / doi.org / 10.3390 / polym13020225).

[0050] The liquid stream S1 preferably comprises at least one pyrolysis oil manufactured by the above-described methods. The liquid stream S1 further comprises C6-C8 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and compounds having C-C double (olefins, dienes) and / or C-C triple bonds. "Further comprises” means here that such components are comprised in the at least one pyrolysis oil and / or another liquid hydrocarbon which is mixed with the at least one pyrolysis oil to form the liquid stream S1.

[0051] The liquid stream S1 , more preferably the at least one pyrolysis oil comprised in the liquid stream S1 comprises C6-C8 aromatic hydrocarbons in an amount of 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.-% based on the total amount of hydrocarbons comprised in the liquid stream S1. Preferably, C6-C8 aromatic hydrocarbons are selected from the group consisting of benzene, toluene, 1 ,2-xylene, 1 ,3-xylene, 1 ,4-xylene and ethylbenzene. The at least one pyrolysis oil comprised in the liquid stream S1 preferably has a bromine number of about 2 g Br2 / 100g to about 150 g E / IOOg (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). Such pyrolysis oils or mixture of pyrolysis oils in the liquid stream S1 are particularly suited for the method and the chemical plant according to the present invention.

[0052] Optionally, the at least one pyrolysis oil is subjected to one or more methods selected from filtration, centrifugation, adsorption, washing, extraction before used as liquid stream S1 or portion thereof in the method according to the present invention and / or as liquid stream S1 or portion thereof for the chemical plant according to the present invention. Such optional pre-treatment methods are for example described in WO 2021 / 224287 A1 , WO 2023 / 061834 A1 , EP 0713906 A1 , and WO 95 / 03375 A1 which are incorporated herein by reference. A skilled person knows how and in which cases to use pre-treatment methods disclosed in said documents and comparable pre-treatment methods disclosed elsewhere.

[0053] A liquid stream S1 comprising at least one pyrolysis oil, the liquid stream S1 further comprising 06-08 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and compounds having 0-0 double and / or 0-0 triple bonds is provided in step a1) of the method according to the present invention. The liquid stream S1 may further comprise at least one further hydrocarbon liquid which comprises C6-C8 aromatic hydrocarbons that is different from a pyrolysis oil obtained by pyrolysis oil of plastic waste. Suitable examples comprise pyrolysis gasoline and coke-oven light oil (CAS number: 65996-78-3). Pyrolysis gasoline is a side product obtained or obtainable from hydrocarbon feedstocks by steam cracking such as steam cracking of naphtha. Pyrolysis gasoline and the manufacture thereof are known in the art. Pyrolysis gasoline comprises C6-C8 aromatic hydrocarbons. Coke-oven light oil can be obtained by extraction from the gas evolved in the high temperature (for example greater than 700°C) destructive distillation of coal. It is primarily composed of benzene, toluene, and xylenes and may contain other minor hydrocarbon constituents.

[0054] A stream S2 comprising H2 is provided in step a2) of the method according to the present invention. The stream S2 can consist essentially of H2 or comprise H2 together with at least one other gas. Preferably the H2 content of the stream S2 is higher than about 50 Vol.-%, more preferably higher than 80 Vol.-% and most preferably higher than about 99 Vol.-%. This minimizes the amount of purge-gas needed to keep the H2 partial pressure high and saves H2. Furthermore, a high H2 partial pressure promotes the catalyst activity and allows low reaction temperatures.

[0055] Such further liquid hydrocarbon feedstock (in case more than one liquid hydrocarbon feedstocks the sum of all liquid hydrocarbon feedstocks) can be comprised in the liquid stream S1 for example in a quantity 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 more with the proviso that at least 2 wt.-% of the liquid stream S1 are comprised of at least one pyrolysis oil manufactured by pyrolysis of plastic waste.

[0056] The advantage of low reaction temperatures is that undesired polymerization of components in stream S3 is suppressed. Furthermore, the stream S2 and stream S11 dilutes reactive components such as compounds having C-C double bonds (e.g., dienes), compounds comprising C-C triple bonds and styrene comprised in the in the liquid stream S1 which further minimizes undesired polymerization of said reactive components in devices and units used in the method according to the present invention, particularly in the evaporation unit EU and / or in the optional superheater SH and / or in the first hydroprocessing unit HU1. In addition to minimizing said undesired polymerization, the dilution also reduces the partial pressure of said reactive components in stream S1 and thereby lowers the dew point of said reactive components in stream S1 . Hence, desired high evaporation rates of the components in stream S1 at a reduced temperature in the evaporation unit EU are achieved compared to undiluted reactive components in stream S1. The dilution during evaporation further suppresses the undesired polymerization of said reactive components in stream S1 .

[0057] Hydrogen (H2) used in the method and system according to the present invention is preferably "green hydrogen” which is generated for example by electrolysis of water using electricity at least partially generated from renewable energy sources (e.g., solar energy, wind energy, tidal energy, and nuclear energy) and / or low-carbon energy sources and / or a methane pyrolysis, preferably a methane pyrolysis using at least partially methane from a renewable source. Methane from a renewable source comprises biomethane.

[0058] Optionally at least a portion of the hydrogen used in the method according to the present invention is hydrogen formed during the pyrolysis reaction and separated from the volatile pyrolysis reaction products.

[0059] Next, in step a3) of the method according to the present invention, the liquid stream S1 and the stream S2 are fed, optionally together with a recycle gas stream S11 into an evaporation unit EU in which at least a portion of the liquid stream S1 is evaporated and leaving the evaporation unit EU, mixed with stream S2 and together with an optional recycle gas stream S11, as gaseous stream S3. Those portions of the liquid stream S1 not evaporated in the evaporation unit EU leave the evaporation unit EU as liquid stream S4.

[0060] Preferably, the liquid stream S1 provided in step a1) and the stream S2 provided in step a2) are mixed before entering the evaporation unit EU and / or mixed inside the evaporation unit EU.

[0061] Preferably, the evaporation of the liquid stream S1 is a mild evaporation, for example not in one stage but in more than one evaporation stages. The desired mild evaporation of the liquid stream S1 can also be achieved by adding a recycle gas stream S11 to the liquid stream S1 prior and / or during evaporation. The desired mild evaporation of the liquid stream S1 is more preferably achieved by evaporating the liquid stream S1 in more than one evaporation stages and adding a recycle gas stream S11 to the liquid stream S1 prior and / or during evaporation.

[0062] The advantage of such a mild evaporation of the liquid stream S1 is a reduced polymerization of components present in the liquid stream S1 such as olefins, dienes and other polymerizable organic compounds such as styrene and organic compounds comprising C-C triple bonds. In case the evaporation conditions are too harsh, undesired fouling in units, tubes and other equipment used for the method according to the present invention occurs. Such undesired fouling is caused by the above-described polymerization.

[0063] The evaporation unit EU comprises at least one evaporator selected from the group comprising pre-evaporators, stage evaporators, and combinations thereof. Such evaporators can be rotary evaporators, circulation evaporators, falling film evaporators, rising film evaporators, climbing film plate evaporators, falling film plate evaporators, multipleeffect evaporators, agitated falling film evaporators, and micro-structured evaporators.

[0064] In one aspect of the present invention, the evaporation unit EU comprises at least one stage evaporator. Preferably, the evaporation unit EU comprising at least one stage evaporator and further comprises at least one pre-evaporator which is upstream of and fluidically connected to the at least one stage evaporator.

[0065] In another aspect the evaporation unit EU comprises at least one pre-evaporator or for example a series of preevaporators in which the liquid stream S1 is heated stepwise and thereby undesired polymerization of compounds having C-C double bonds (e.g., dienes, olefins), compounds comprising C-C triple bonds and styrene comprised in the in the liquid stream S1 is reduced.

[0066] In another aspect of the present invention, the evaporation unit EU comprises at least one falling film evaporator which is particularly suited for the desired mild evaporation of the liquid stream S1.

[0067] Multistage evaporation and other suitable devices are for example described in R. Billet, Ullmann's Encyclopedia of Industrial Chemistry, 2012, Vol. 13, Chapter "Evaporation”, pages 588 to 591 and 597 to 599 which is incorporated herein by reference.

[0068] The temperature for evaporating at least a portion of the liquid stream S1 preferably ranges from about 140 °C to about 220 °C, more preferably from about 160 °C to about 200 °C and most preferably from about 170 °C to about 190 °C.

[0069] At least one evaporator comprised in the evaporation unit EU optionally further comprises at least a second fluidic passage through which another stream than stream S1 , stream S2, stream S3, stream S4 and, optionally, recycle gas stream S11 can flow and thereby transfer heat to the liquid stream S1 and the stream S2 and, optionally, the recycle gas stream S11 which flow to first fluidic passage comprised said at least one evaporator. The first fluidic passage and the at least one second fluidic passage have no fluidic connection between each other. Preferably, the sole reason for the optional presence of at least a second fluidic passage in at least one evaporator of the evaporation unit EU is the heat transfer from a stream which flows to said at least one second fluidic passage to the stream(s) flowing through the first fluidic passage. Heat may be transferred from the stream S8c to the liquid stream S1 and / or an already partially vaporized stream S1 and / or stream S2 and, optionally to the recycle gas stream S11 . Stream S8c will be explained in detail further below.

[0070] Accordingly, at least a portion of the thermal energy required for the evaporation of the liquid stream S1 in step a3) of the method according to the present invention is optionally provided by heat transfer from the stream S8c to the liquid stream S1 and / or an already partially vaporized stream S1 and / or stream S2 and, optionally to the recycle gas stream S11. This embodiment is shown in Figure 3.

[0071] The liquid stream S4 which comprises the portion of liquid stream S1 which is not evaporated in the evaporation unit EU can be for example converted in at least one gasifier and / or by a partial oxidation reaction unit into syngas which comprises a mixture of H2, CO and CO2. Such partial oxidation reactions are known in the art and are for example disclosed in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, Chapter: Gas Production, 2. Processes”, pages 443-455, 2012 which is incorporated herein by reference. The skilled person can select suitable reactors and reaction conditions to convert the liquid stream S4 into syngas by a partial oxidation reaction and / or gasification.

[0072] The liquid stream S4 can also be subjected as a feedstock to an aromatic hydrocarbon separation method whereby the yield of aromatic hydrocarbons which is achieved by the method according to the present invention can be further increased.

[0073] Next, in optional step a4) of the method according to the present invention the gaseous stream S3 is superheated in at least one optional superheater SH and thereby a superheated and / or dry stream S5 is formed. The advantage of applying optional step a4) in the method according to the present invention is as follows: in case the gaseous stream S3 having a temperature lower than the dew point, vapor and liquid phase enters directly the first hydroprocessing unit HU1 which is not desired. Small amounts of liquid can be separated at the bottom of the at least one reactor in the first hydroprocessing unit HU1 if necessary. The first hydroprocessing unit HU1 is optimized for gas phase hydrogenation, hence the gaseous stream S3 is preferably completely vaporized before entering the first hydroprocessing unit HU1 to avoid polymerization and therefore plugging. Due to heat loss on the way from the evaporation unit EU to the first hydroprocessing unit HU1 a liquid phase may be formed by condensation which should preferably not enter the first hydroprocessing unit HU1 because of the reasons explained above.

[0074] Therefore, the gaseous stream S3 is optionally and preferably superheated in at least one optional superheater SH to raise the temperature of the gaseous stream S3 preferably by about 2 °C to about 50 °C, more preferably by about 5 °C to about 40 °C and most preferably by about 10 °C to about 30 °C in respect to the temperature at which the gaseous stream S3 leaves the evaporation unit EU.

[0075] The at least one optional superheater SH more preferably comprises at least one first fluidic passage into which the gaseous stream S3 is fed, superheated, and is leaving the optional superheater SH as superheated stream S5. The superheated stream S5 has a higher temperature than the gaseous stream S3.

[0076] The at least one optional superheater SH is preferably a radiant superheater, a convection superheater, or a separately fired superheater. Preferably, the at least one optional superheater SH is a shell and tube heat exchanger with gaseous stream S3 inside the tubes. In one aspect of the present invention, at least a portion of the thermal energy transferred to the gaseous stream S3 in the at least one optional superheater SH is provided by electrical heating, preferably with electricity from a renewable source such as wind energy, solar energy and / or tidal energy.

[0077] Preferably, the optional superheater SH further comprises at least one heat exchanger such as a shell and tube heat exchanger which comprises at least a first fluidic passage into which the gaseous stream S3 is fed (preferably the tubes), superheated and is leaving the optional superheater SH as superheated stream S5 and at least one second fluidic passage (preferably the shell) through which another stream than the gaseous stream S3 can flow and thereby transfer heat to the gaseous stream S3 which flows through the first fluidic passage. This embodiment is shown in Figure 3.

[0078] The first fluidic passage and the optional at least one second fluidic passage have no fluidic connection between each other. Preferably, heat is transferred from the stream S8 to the gaseous stream S3. Stream S8 will be explained in detail further below.

[0079] More preferably, at least a portion of the thermal energy required for conversion of the gaseous stream S3 into the superheated stream S5 in the at least one optional superheater SH is provided by transferring heat form the stream S8 to the gaseous stream S3.

[0080] Most preferably, up to 100 % of the thermal energy required for conversion of the gaseous stream S3 into the superheated stream S5 in the at least one optional superheater SH is provided by transferring heat form the stream S8 to the gaseous stream S3.

[0081] Stream S8 leaves the at least one optional super heater SH as stream S8b in the aspect of the present invention also shown in Figure 3.

[0082] In method step a5) of the method according to the invention, the gaseous stream S3 (Figure 2) or the superheated stream S5 (in case optional step a4) is applied, Figure 3) is fed into a first hydroprocessing unit HU1 in which compounds comprising C-C double bonds (e.g., dienes) and / or C-C triple bonds present in the gaseous stream S3 or the superheated stream S5 are hydrogenated in a first hydroprocessing unit HU1 . Thereby, C-C single bonds are formed.

[0083] The first hydroprocessing unit HU 1 comprising at least one stage, in which C-C double and / or C-C triple bonds present in the gaseous stream S3 or the superheated stream S5 are hydrogenated whereas the conjugated C-C bonds of the C6-ring in C6-C8 aromatic hydrocarbons present in the gaseous stream S3 or the superheated gaseous stream S5 are preferably not hydrogenated in the first hydroprocessing unit HU1.

[0084] The first hydroprocessing unit HU1 may be any vessel preferably configured to contain a hydroprocessing catalyst. The vessel is preferably configured for gas phase operation. The first hydroprocessing unit HU1 may include one or more beds of the hydroprocessing catalyst, preferably in fixed bed configuration. The first hydroprocessing unit HU1 can be operated adiabatically, isothermally, non-adiabatically, non-isothermally, or combinations thereof. The first hydroprocessing unit HU1 may comprises more than one vessel. Each of such vessels is considered a hydrogenation reactor ("reactor”).

[0085] The gaseous stream S3 or the superheated stream S5 can be contacted with the hydroprocessing catalyst in upward flow, downward flow, radial flow, or combinations thereof.

[0086] Preferably, the first hydroprocessing unit HU1 comprises one single reactor having one single catalyst bed. Thereby, the geometric shape of the first hydroprocessing unit HU1 is minimized, and a cost-efficient reactor design is assured.

[0087] The process temperature depends on catalyst type used and the degree of activity of the catalyst. The process temperature in the first hydroprocessing unit HU1 preferably ranges from about 140 °C to about 250 °C, more preferably from about 150 °C to about 200 °C and most preferably from about 170 °C to about 190 °C. The deactivation of the catalyst can optionally be compensated by raising the process temperature.

[0088] The pressure in the first hydroprocessing unit HU1 preferably ranges from about 1.0 MPa to about 10 MPa abs. in the process. The hydrogen partial pressure in front of the first hydroprocessing unit HU1 preferably ranges from about 5 bar to about 50 bar, more preferably from about 10 bar to about 30 bar and most preferably from about 14 bar to about 20 bar.

[0089] The weight hourly space velocity (WHSV) calculated with reference to the stream S1 preferably ranges from about 0.5 t / (m3Kat / h) to about 5 t / (m3Kat h), more preferably from about 1.0 t / (m3Kat / h) to about 3.0 t / (m3Kat / h) and most preferably from about 1.5 t / (m3Kat / h) to about 2.0 t / (m3Kat / h).

[0090] The amount of hydrogen exhibits a large excess comprised in the first hydroprocessing unit HU1. The process conditions for hydrogen partial pressure, temperature and WHSV as disclosed above ensure a sufficient hydrogenation of the undesired C-C double bonds (e.g. , olefins, dienes) and C-C triple bonds present in the gaseous stream S3 or the superheated stream S5 but insufficient to hydrogenate the desired C6-C8 aromatic hydrocarbons also present in the gaseous stream S3 or the superheated stream S5.

[0091] The hydroprocessing catalyst may be any catalyst used for hydrogenation of C-C double bonds (e.g., olefins, dienes), and C-C triple bonds (e.g., commercially available hydroprocessing catalysts). Suitable hydroprocessing catalysts for this purpose are heterogeneous catalyst selected from the group comprising or consisting of 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, nickelmolybdenum oxides, tungsten-molybdenum oxides, cobalt-molybdenum sulfides, nickel-molybdenum sulfides, tungsten-molybdenum sulfides, molybdenum sulfides. Suitable heterogeneous catalysts further comprise a support, preferably an inorganic support selected from the group comprising or consisting of silica, alumina, silica-aluminas, magnesia, clays, and mixtures thereof. Further suitable hydroprocessing catalysts are for example zeolites comprising one or more metals.

[0092] Most preferably, the at least one heterogeneous catalyst is selected from the group consisting of nickel-molybdenum catalysts and nickel-tungsten catalysts further comprising a support, preferably an inorganic support selected from the group comprising or consisting of silica, alumina, silica-aluminas, magnesia, clays, and mixtures thereof. These catalysts are the most suited ones for the desired hydrotreatment reactions in the first hydroprocessing unit HU 1 (step a5) of the method according to the present invention).

[0093] More than one of the aforementioned hydroprocessing catalysts can be used together in the first hydroprocessing unit HU1.

[0094] In one aspect of the present invention, at least a portion of the catalyst comprises recycled catalysts.

[0095] In the context of the present invention, the at least one catalyst for the first hydroprocessing unit HU1 preferably is in the form of extrudates, pellets, rings, spherical particles or spheres, more preferably spherical particles or extrudates.

[0096] The at least one reactor in the first hydroprocessing unit HU1 comprises the at least one catalyst preferably in form of at least one catalyst bed.

[0097] The height and diameter of the at least one catalyst bed is chosen on reaction kinetics and optimal I iquid / gas flowpattern and pressure drop. The at least one catalyst bed may consist of one or more layers of different solid absorption materials, and one or more different hydrogenation catalysts. The catalyst layers in the at least one catalyst bed may differ from each other by particle size or shape or activity or active sites of material. Inert particles may be used above and below each bed to improve fluid distribution in case more than one catalyst bed is used. In case the at least one hydrogenation reactor in the first hydroprocessing unit HU 1 has at least two stages, the catalyst preferably has different particle size in at least two stages and / or optionally different shape in the at least two stages.

[0098] The particle size means here particle size distribution, which is measured for example by sieve methods, laser diffraction methods or other methods known in the art. A catalyst having a desired particle size and optionally desired shape may be manufactured and used.

[0099] The hydrogenation reaction is an exothermic reaction and therefore each reaction stage may optionally be cooled.

[0100] Preferably, the gaseous stream S3 or the superheated stream S5 enters the at least one reactor of the first hydroprocessing unit HU1 from the bottom section and leaves the at least one reactor of the first hydroprocessing unit HU1 in the top section. Thereby, undesired fouling such as polymerization of reactive compounds (e.g., organic compounds having C-C double and / or triple bonds) is reduced and / or undesired polymerization products formed in the bottom section of the at least one reactor are drawn further down and away from the bottom section of the catalyst bed by gravity. Such undesired polymerization products can then be removed from the bottom section of the reactor without blocking further sections of the at least one catalyst bed in the at least one reactor.

[0101] About 90 % or more, such as 95 % or 99 % of the dienes present in the gaseous stream S3 or the superheated stream S5 are converted in step a5) of the method according to the present invention.

[0102] Next, in step a6) of the method according to the present invention, the temperature of the gaseous stream S6 is increased in a heating device HD to form a heated gaseous stream S7. The temperature increasement is required because the hydrotreatment in the second hydroprocessing unit HU2 requires a higher temperature of the gaseous stream to be hydrotreated than the first hydrotreatment in the first hydroprocessing unit HU1.

[0103] The gaseous stream S6 preferably has a temperature in the range of about 160 °C to about 280 °C, more preferably of about 180 °C to about 230 °C and most preferably of about 200 °C to about 220 °C.

[0104] The heated gaseous stream S7 preferably has a temperature in the range of about 250 °C to about 400 °C, more preferably of about 260 °C to about 380 °C and most preferably of about 280 °C to about 340 °C.

[0105] The at least one heating device HD provides heat to the gaseous stream S6 by direct heating, indirect heating, or a combination thereof (e.g., direct heating with a first heating device HD' and indirect heating with a second heating device HD" or vice versa).

[0106] The at least one heating device HD is preferably selected from the group comprising direct fired heaters, furnaces powered by electrical energy, and heat exchangers. In case the at least one heating device HD comprises a furnace powered by electrical energy, the electricity is preferably provided by a renewable source such as wind energy, solar energy, and tidal energy. Such heating devices HD are more sustainable than e.g., direct fired furnaces and are therefore preferred.

[0107] Direct fired furnaces as heating device HD can be for example provide heat to the gaseous stream by combustion of a gaseous or liquid fuel such as natural gas and an oxidant such as oxygen and / or air.

[0108] Furnaces suitable as heating devices HD may comprise for example at least one radiant section, at least one convection section, at least one radiant coil, at least one burner and an insulation.

[0109] The heating device HD is downstream of and fluidically connected to the at least one outlet of the first hydroprocessing unit HD1.

[0110] Next, in step a7) of the method according to the present invention, the heated gaseous stream S7 is inserted into a second hydroprocessing unit HU2 and converted in the second hydroprocessing unit HU2 to a product stream S8. The product stream S8 is depleted in heteroatoms such as nitrogen, oxygen, halogens (fluorine, chlorine, bromine, iodine), and sulfur in respect to the heated gaseous stream S7 by a hydrotreatment in the second hydroprocessing unit HU2. The heteroatoms leave the second hydroprocessing unit HU2 in form of their respective hydrogenated species as part of the product stream S8. The respective hydrogenated species of heteroatoms comprise NH3, H2O, H(Hal) (HF, HCI, HBr, HI), and H2S. NH3and H(Hal) may form salts of type NH4Hal (NH4F, NH4CI, NH4Br, NH4I) and NH3 and H2S may form the salt NH4SH. Such salts may be formed already in the gas phase in the second hydroprocessing unit HU2 and can then form undesired deposits on metal surfaces by resublimation when stream S8 is cooled down.

[0111] NH4CI, NH4F, NH4Br, NH4I and NH4SH of which at least one may be formed mainly in the second hydroprocessing unit HU2 (a minor portion may also be formed in the first hydroporocessing unit HU1) are preferably removed from the second hydroprocessing unit HU2 by water. More preferably, NH4F, NH4CI, NH4Br, NH4I and / or the respective cations and anions are removed quantitatively with water and NH4SH and / or the respective cation and anion is / are partly removed from the second hydroprocessing unit HU2 with a water stream S15.

[0112] A water stream S15 is fed to the product stream S8. Thereby, a product stream comprising water S8a is formed (aspect of the present invention shown in Figure 2) or a water stream S15 is fed to a product stream S8b and thereby a product stream S8c is formed (aspect of the present invention shown in Figure 3). The addition of a water stream S15 to a product stream S8 or a product stream S8b is further explained below.

[0113] Accordingly, the reactions in the second hydroprocessing unit comprise hydrodenitrogenation, hydrodeoxygenation, hydrodehalogenation and hydrodesulfurization. Furthermore, the reactions comprise hydrodemetallization and, pref- erably, also hydrogenation of the remaining C-C double bonds (olefins and dienes) and C-C triple bonds whereas the conjugated C-C bonds of the C6-ri ng in C6-C8 aromatic hydrocarbons present in heated gaseous stream S7 are preferably not hydrogenated in the second hydroprocessing unit HU2.

[0114] The second hydroprocessing unit HU2 is downstream of and the at least one inlet of the second hydroprocessing unit HU2 is fluidically connected to the heating device HD.

[0115] The second hydroprocessing unit HU2 may be any vessel configured to contain the at least one hydroprocessing catalyst disclosed herein. The vessel is preferably configured for gas phase operation. The second hydroprocessing unit HU2 may include one or more beds of the hydroprocessing catalyst, preferably in fixed bed configuration. The second hydroprocessing unit HU2 can be operated adiabatically, isothermally, non-adiabatically, non-isothermally, or combinations thereof. The second hydroprocessing unit HU2 may comprises more than one vessel. Each of such vessels is considered a hydrogenation reactor.

[0116] The heated gaseous stream S7 can be contacted with the at least one hydroprocessing catalyst in upward flow, downward flow, radial flow, or combinations thereof. Preferably, the heated gaseous stream S7 is contacted with the at least one hydroprocessing catalyst in downward flow.

[0117] Preferably, the heated gaseous stream S7 enters the at least one hydrogenation reactor in the second hydroprocessing unit HU2 from the top section.

[0118] The at least one hydroprocessing catalyst may be any catalyst used for hydrogenation of C-C double bonds (e.g., olefins, dienes) and heteroatom hydrogenation (e.g., commercially available hydroprocessing catalysts). Suitable hydroprocessing catalysts for this purpose are selected from the group comprising or consisting of 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, tungstenmolybdenum sulfides, molybdenum sulfides. Suitable catalysts further comprise a support, preferably an inorganic support selected from the group comprising or consisting of silica, alumina, silica-aluminas, magnesia, clays, and mixtures thereof. Further suitable hydroprocessing catalysts are for example zeolites comprising one or more metals.

[0119] More preferably, the at least one hydroprocessing catalyst is selected from the group consisting of molybdenum catalysts, cobalt-molybdenum catalysts, and cobalt-tungsten catalysts. These catalysts are the most suited ones for the desired hydrotreatment reactions in the second hydroprocessing unit HU2 (step a7) of the method according to the present invention). Most preferably, a cobalt-molybdenum catalyst is used in the at least one hydrogenation reactor in the second hydroprocessing unit HU2, preferably in case the heated gaseous stream S7 enters the at least one hydrogenation reactor in the second hydroprocessing unit HU2 from the top section. More than one of the aforementioned hydroprocessing catalysts can be used together in the second hydroprocessing unit HU2, for example mixed together or as separate catalyst stacks in which each of said stacks comprises one type of catalyst, e.g., in an order stack a (with catalyst A) I stack b (with catalyst B).

[0120] In one aspect of the present invention, at least a portion of the catalyst comprises recycled catalysts.

[0121] The height and diameter of the at least one catalyst bed is chosen on reaction kinetics and optimal gas flow-pattern and pressure drop. The at least one catalyst bed may consist of one or more layers of different solid absorption materials, and one or more layers of the same or different hydrogenation catalysts. The catalyst layers in the at least one catalyst bed may differ from each other by particle size or shape or activity or active sites of material. Inert particles may be used above and below each bed to improve fluid distribution in case more than one catalyst bed is used.

[0122] In the context of the present invention, the at least one hydroprocessing catalyst for the second hydroprocessing unit HU2 preferably is in the form of extrudates, pellets, rings, spherical particles or spheres, more preferably in the form of spherical particles or extrudates.

[0123] In case the at least one hydrogenation reactor (vessel) in the second hydroprocessing unit HU2 has at least two stages, the at least one hydroprocessing catalyst preferably has different particle size in at least two stages and / or optionally different shape in the at least two stages.

[0124] The particle size means here particle size distribution, which is measured for example by sieve methods, laser diffraction methods or other methods known in the art. A catalyst having a desired particle size and optionally desired shape may be manufactured and used.

[0125] The hydrogenation reaction is an exothermic reaction and therefore each reaction stage may optionally be cooled.

[0126] The second hydroprocessing unit HU2 can be operated at various process conditions. For example, the heated gaseous stream S7 is contacted with the at least one hydroprocessing catalyst at a temperature of preferably from about 200 °C to about 400 °C, more preferably from about 250 °C to about 380 °C and most preferably from about 280 °C to about 360 °C.

[0127] The temperature in the second hydroprocessing unit HU2 is attained by using a heated gaseous stream S7 which was further heated using the heating unit HU which is upstream and fluidically connected to the second hydroprocessing unit HU2.

[0128] The pressure in the second hydroprocessing unit HU2 preferably ranges from about 1.0 to about 10 MPa abs. in the process. The hydrogen partial pressure in front of the second hydroprocessing unit HU2 ranges from about 5 bar to about 50 bar more preferably from about 10 bar to about 30 bar and most preferably from about 14 bar to about 20 bar.

[0129] The weight hourly space velocity (WHSV) of the heated gaseous stream S7 preferably ranges from about 0.1 t / (m3Kat / h) to about 5.0 t / (m3Kat ■ h), more preferably from about 0.5 t / (m3Kat / h) to about 1 .0 t / (m3Kat / h).

[0130] More preferably, the product stream S8, or a portion thereof is not recycled (inserted again) into the first hydroprocessing unit HU 1 and / or into the second hydroprocessing unit HU2.

[0131] There is no need to recycle a portion of the product stream S8 or a portion thereof into the first hydroprocessing unit HU 1 because the gaseous stream S6 is stable enough in respect to undesired polymerization and therefore, the gaseous stream S6 can be further heated up in the heating device HD for insertion into the second hydroprocessing unit HU2. This enables to build the first hydroprocessing unit HU1 (liquid recycle stream S3' included) and the second hydroprocessing unit HU2 (recycle-gas included) for "once through capacity” which means that the stream S1 (and the streams obtained thereof by conversion in the individual process units) only flow(s) once through the first hydroprocessing unit HU1 (which it leaves as stream S6) and the second hydroprocessing unit HU2 and then leaves the second hydroprocessing unit HU2, converted, as stream S6.

[0132] The method according to the present invention further comprising the optional step a4) is shown in Figure 3.

[0133] Next, in optional step a8) of the method according to the present invention, the product stream S8 flows to a section of the at least one optional superheater (SH) which is suited for transferring heat from the product stream S8 to the gaseous stream S3 which flows in a fluidically separated sections of the at least one optional superheater (SH) which is suited for transferring heat from the product stream S8 to the gaseous stream S3.

[0134] Thereby, the product stream S8 is converted to the cooled down product stream S8b and the gaseous stream S3 is converted into the superheated gaseous stream S5.

[0135] The method according to the present invention further comprising the optional steps a4), a8) and a10) is shown in Figure 4.

[0136] A washing water stream S15 is preferably feed to the product stream S8 or the product stream S8b. Thereby, NH4CI, NH4F, NH4Br, NH4I and NH4SH of which at least one may be formed in the second hydroprocessing unit HU2 is / are transferred from the product stream S8 into stream S8a (Figures 2 and 3) or stream S8b (Figure 4). Said streams S8a or S8b comprise at least one of NH4CI, NH4F, NH4Br, NH4I and NH4SH and / or the corresponding cations and anions. The portions of streams S8a or S8b comprising at least one of NH4CI, NH4F, N H4Br, NH4I and NH4SH and / or the corresponding cations and anions are later separated from the liquid product stream S9 in the separation unit SU as waste water stream S17 (Figures 2 to 4). The water stream S15 can be added to the product stream S8 or the product stream S8b continuously or discontinuously. In case the water stream S15 is added to the product stream S8 or the product stream S8b discontinuously, stream S15 is for example added in case the characteristics of the heat transfer inside the condensation unit CU and / or the separation unit SU change, which change is indicating the formation of undesired deposits of at least one of NH4CI, NH4F, NH4Br, NH4I and NH4SH inside the second hydroprocessing unit HU2 and / or the condensation unit CU and / or the separation unit SU, and / or said undesired deposits are recognized by another means such as based on a fixed maintenance schedule which is derived on experience by ongoing use of the chemical plant. Furthermore, undesired corrosion on and / or of metal surfaces is reduced when the deposition of the above-described salt thereon is avoided.

[0137] Next, in optional step a9) a washing water stream S15 is fed to the cooled down product stream S8b and thereby a product stream comprising washing water S8c is formed (Figure 4). The washing water of the washing water stream S15 is required to remove the above-mentioned salts which can be formed as side-product(s) in the second hydroprocessing unit HU2. Such salts and / or the corresponding cations and anions can then be comprised in the product stream S8 and product stream S8a or in product stream S8 and the successively cooled down product streams S8b, S8c and S8d from said product streams and can be separated in the at least one separation unit SU (step a12) of the method according to the present invention) from the liquid product stream S9 as a waste water stream S17 in which said salt(s) are comprised.

[0138] Next, in optional step a10) of the method according to the present invention, the cooled down product stream comprising washing water S8c flows to a section of the evaporation unit EU which is suited for transferring heat from the cooled down product stream comprising washing water S8c to the liquid stream S1 (comprising gaseous stream S2 and at least a portion of the optional recycle gas stream S11) which flows to a fluidically separated section of the evaporation unit EU. Thereby, stream S3 is formed (= the evaporated liquid stream S1 comprising the gaseous stream S2 and at least a portion of the optional recycle stream S11). This optional method step is shown in Figure 4.

[0139] Thereby, the cooled down product stream comprising washing water S8c is converted to the further cooled down product stream S8d and the liquid stream S1 comprising gaseous stream S2 and at least a portion of the optional recycle gas stream S11 is converted into the gaseous stream S3.

[0140] Optional step a8) and optional step a10) can be applied in the method according to the present invention or can be both omitted or either step a8) or step a10) can be applied.

[0141] Next, in step a11) of the method according to the present invention, the product stream S8 or optionally, one of the streams selected from the group consisting of the cooled down product stream S8b, the cooled down product stream comprising washing water S8c, and the further cooled down product stream S8d, is condensed in at least one condensation unit CU to a liquid product stream S9. This step is required to enable the separation of a recycle gas stream S11 which comprises hydrogen not converted in the first hydroprocessing unit HU1 and / or the second hydroprocessing unit HU2.

[0142] The condensation unit CU can be for example a device in which the product stream S8 or optionally, one of the streams selected from the group consisting of the cooled down product stream S8b, the cooled down product stream comprising washing water S8c, and the further cooled down product stream S8d is cooled down by directly and / or indirectly contacting said product stream S8 or optionally, one of the streams selected from the group consisting of the cooled down product stream S8b, the cooled down product stream comprising washing water S8c, and the further cooled down product stream S8d with another stream which has a lower temperature than said product stream S8 or optionally, one of the streams selected from the group consisting of the cooled down product stream S8b, the cooled down product stream comprising washing water S8c, and the further cooled down product stream S8d before both streams are brought in contact. Suitable condensation units CU comprise, heat exchangers, with cooling media such as air, cooling water, and other media having a suitable low temperature.

[0143] Most preferably, the at least one condensation unit CU is selected from the group comprising air-cooler and watercooler.

[0144] The at least one condensation unit CU is downstream of and fluidically connected to the at least one outlet of the second hydroprocessing unit HU2 (Figures 2 and 3) or to the at least one evaporation unit EU (Figure 4).

[0145] Next, in step a12) of the method according to the present invention, the product stream S9 is separated into a refined product stream S10 which comprises the desired benzene, a recycle gas stream S11 which comprises hydrogen not converted in the first hydroprocessing unit HU1 and the second hydroprocessing unit HU2, and a waste water stream S17.

[0146] The recycle gas stream S11 is then inserted into the evaporation unit EU and the hydrogen comprised therein is utilized as for hydrogenation reactions in the first hydroprogessing unit HU1 and the second hydroprocessing unit HU2 together with hydrogen comprised in the gaseous stream S2.

[0147] It's beneficial to feed the recycle gas stream S11 back to the evaporation unit EU to save large amounts of hydrogen. Such a use of a recycle-gas stream S11 as described above is also beneficial to evaporate the components of feed stream S1 .

[0148] The "recycle-gas stream S11 to stream ST' ratio is preferably between about 300 Nm3 / t to about 2000 Nm3 / t, more preferably between 600 Nm3 / t to about 1400 Nm3 / t.

[0149] To maintain a high H2 partial pressure in the first hydroprocessing unit HU1 and the second hydroprocessing unit HU2, a purge-gas stream from the recycle gas stream S11 may be used, preferably, when the H2 concentration in stream S2 is lower than 99.9 Vol.-%, to avoid accumulation of inert gaseous components such as N2, CH4, and C2H6 in the recycle gas stream S11 . The purge-gas stream is a portion of the recycle gas stream S11 which is optionally removed from the recycle gas stream S11 to prevent an undesired accumulation (concentration increase) of said inert gaseous components.

[0150] The waste water stream S17 comprises at least one salt selected from the group comprising NH4F, NH4CI, NH4Br, NH4I, and NH4SH which can be formed in the second hydroprocessing unit HU2 as side-product(s).

[0151] The waste water stream S17 is the preferably subjected to a waste water treatment, for example a separation of the dissolved H2S and NH3 in a sour water stripper unit and transferring the waste water then to waste water treatment plant.

[0152] The separation unit SU is downstream of and fluidically connected to the at least one condensation unit CU.

[0153] The separation unit SU can be for example a liquid-liquid-vapor separation unit, preferably using one or more of hydrocyclone, settler tank, centrifuge, more preferably using one or more of settler tank and / or centrifuge.

[0154] Next, in step a13) of the method according to the present invention the refined product stream S10 is subjected to a distillation in a distillation unit DU for separating the refined product stream S10 into a stabilized product stream S12 depleted in high boiling components, a gaseous stream S13 and a stream S14 which comprises high-boiling components.

[0155] The stabilized product stream S12 is suitable for the aromatic hydrocarbon extraction unit AEU and a gaseous stream S13 which comprises gaseous components which are dissolved in the product stream S10. Such gaseous components need to be removed from the refined product stream prior to separation of the individual C6-C8 aromatic hydrocarbons comprised therein.

[0156] The gaseous stream S13 leaves the distillation unit DU as a head product and comprises at least one of the following gases: H2, CH4, C2H6, C3H8, H2S, NH3, HF, HCI, HBr, HI.

[0157] The stabilized product stream S12 comprises the desired benzene and leaves the distillation unit DU as a second product stream.

[0158] The third product stream S14 contains the high boiling components which are not suitable for feeding into the aromatic hydrocarbon extraction unit AEU. The distillation unit DU can be for example at least one distillation column, at least one thin film evaporator or a combination thereof. Preferably, in case the distillation unit DU comprises one distillation column. Said one distillation column can also be a dividing-wall column or a column with liquid or vapor side stream.

[0159] The distillation unit DU is downstream of and fluidically connected to the separation unit SU.

[0160] The distillation unit DU can also comprise two columns, for example a first stripper column and a second column. For example, the gaseous product stream S13 comprising at least one of H2, CH4, C2H6, C3H8, H2S, NH3, HF, HCI, HBr, HI is separated over-head in a first column from the refined product stream S10. Next, the stabilized product stream S12 comprising the desired C6-C8 aromatic hydrocarbons and the third product stream S14.

[0161] In case the distillation unit DU comprises one column, the stabilized product stream S12 preferably leaves said column as a liquid side stream. In case the distillation unit DU comprises two columns, the stabilized product stream S12 preferably leaves the second column over-head.

[0162] The distillation is carried out at a temperature in the range of about 0 °C to about 600 °C, more preferably from about 20 °C to about 400 °C, most preferably from about 80 °C to about 250 °C (the temperature ranges refer to atmospheric pressure of 1.013 bar). The corresponding operating pressure of the at least one distillation column preferably ranges from about 0.1 bar (abs.) to about 20 bar (abs), more preferably from about 0.5 bar to about 16 bar (abs), most preferably from about 1 bar to about 14 bar (abs). The temperature is adjusted accordingly in case the pressure is # 1.013 bar.

[0163] Next, in a step a14) of the process according to the present invention, the stabilized product stream S12 is separated in at least one optional aromatic hydrocarbon extraction unit AEU into a stream S16a which is enriched in benzene, a stream S16b which is enriched in 1-methylbenzene, a stream S16c which is enriched in C8 aromatic hydrocarbons (ethylbenzene, 1 ,2-xylene, 1 ,3-xylene, and 1 ,4-xylene) and a stream S16d which is depleted in the desired C6-C8 aromatic hydrocarbons and is for example suited as a feedstock for a cracking process, preferably steam cracking. The aromatic hydrocarbon extraction unit AEU is shown in Figures 2 to 4.

[0164] The aromatic hydrocarbon extraction unit AEU is downstream of and fluidically connected to the distillation unit DU and thereby enables a flow of the stabilized product stream S12 from of the distillation unit DU into the aromatic hydrocarbon extraction unit AEU.

[0165] The aromatic hydrocarbon extraction unit AEU can be any unit operation suitable to separate the stabilized product stream S12 into a stream S16a which is enriched in benzene, a stream S16b which is enriched in 1-methylbenzene, a stream S16c which is enriched in C8 aromatic hydrocarbons (ethylbenzene, 1 ,2-xylene, 1 ,3-xylene, and 1 ,4-xylene) and a stream S16d which is depleted in the desired C6-C8 aromatic hydrocarbons. For example, the aromatic hydrocarbon extraction unit AEU can comprise at least one selective adsorption unit operation, at least one selective absorption unit operation, at least one extractive distillation unit, at least one solvent extraction followed by distillation and combinations thereof. Preferably, the aromatic hydrocarbon extraction unit AEU comprises at least one extractive distillation unit.

[0166] Suitable optional aromatic hydrocarbon extraction units AEU are commercially available, for example the Morphy- lane® extractive distillation process by Uhde. For example, the stabilized product stream S12 is first split into a C7- fraction and a Cs+ fraction. Next, the C7- fraction is sent to an extractive distillation stage in which a stream S16a comprising benzene and a stream S16b comprising 1 -methylbenzene are separated from the C7--non-aromatics in stream in the stabilized product stream S12. The Cs+ fraction of the stabilized product stream S12 is sent directly to a 1 ,4-xylene loop without the xylenes and ethylbenzene being extracted as stream S16b.

[0167] The stream S16a preferably comprises at least 90 wt.-% benzene, more preferably at least 99.8 wt.-% benzene. This stream is suited to provide benzene in step a) of the process according to the present invention.

[0168] The stream S16b preferably comprises at least 90 wt.-% 1-methylbenzene, more preferably at least 95 wt.-% 1- methylbenzene and most preferably at least 99 wt.-% 1-methylbenzene. This stream is suited to provide 1- methylbenzene in step a) of the process according to the present invention.

[0169] The stream S16c preferably comprises at least 90 wt.-% of xylenes and about 10 wt.-% of nonaromatic Cs+ components, more preferably at least 93 wt.-% of xylene isomers and about 2.5 wt.-% nonaromatic Cs+ components.

[0170] The stream S16d is suited as a feedstock for cracking processes such as (fluid) catalytic cracking, thermal cracking, and steam cracking. The main reaction products from such cracking processes comprise ethylene, propylene, butylene isomers, butadiene, Ce-Cs aromatic hydrocarbons and pyrolysis gasoline. At least a portion of the pyrolysis gasoline can be utilized as a component in liquid stream S1 together with at least one pyrolysis oil.

[0171] Optionally, stream S 16d is utilized as a feedstock for manufacturing syngas by a partial oxidation process and / or a gasification process, said syngas comprising CO and hydrogen). Such processes for manufacturing syngas from a feedstock are for example disclosed in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, Chapter: Gas Production, 2. Processes, pages 443-455, 2012.

[0172] 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 provided in step a) is benzene or 1-methylbenzene manufactured from a non-fossil feedstock.

[0173] 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 provided in step a) is manufactured by steps a1) to a14). Benzene and 1 -methylbenzene can be for example separated from fossil feedstocks such as pyrolysis gasoline and coke-oven light oil. Such fossil feedstocks are described above.

[0174] Preferably, the plastic waste used to manufacture the at least one pyrolysis oil provided in step a1) polyurethanes and / or thermoplastic polyurethanes and / or polyisocyanurates and / or polyureas. In case polyurethanes are manufactured by the process according to the present invention and the plastic waste comprises polyurethanes, a closed recycling loop for polyurethanes is achieved. In case thermoplastic polyurethanes are manufactured by the process according to the present invention and the plastic waste comprises thermoplastic polyurethanes, a closed recycling loop for thermoplastic polyurethanes is achieved. In case polyisocyanurates are manufactured by the process according to the present invention and the plastic waste comprises polyisocyanurates, a closed recycling loop for polyisocyanurates is achieved. In case polyureas are manufactured by the process according to the present invention and the plastic waste comprises polyureas, a closed recycling loop for polyureas is achieved.

[0175] Optionally, the process according to the present invention further comprises a step a15):

[0176] Subjecting the stream S16b and / or the stream S16c to a hydroalkylation unit in at least one optional hydroalkylation unit HAU. In this optional step a15), toluene and / or xylene isomers and / or ethylbenzene are converted into benzene. Accordingly, the benzene yield can be increased by the optional step a15) in the method according to the present invention.

[0177] Hydroalkylation of alkyl-substituted benzene-derivatives into benzene and corresponding hydroalkylation units HAU are known in the art and are for example described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 5, Chapter "Benzene” by H. 0. Folkins, pages 246-251, 2012 and in Industrielle organische Chemie, 3rdEd., K. Weissermel, H.-J. Arpe, pages 351-352, 1988 which are both incorporated by reference herein.

[0178] The optional hydroalkylation step a15) can either be operated as a thermal process (for example at about 550 °C to about 800 °C and a pressure of about 30 bar to about 100 bar) or as a catalytic process (for example at a temperature of about 500 °C to about 650 °C, a pressure of about 30 bar to about 50 bar in the presence of a catalyst such as selected from C^Os and / or MO2O3 on a support such as alumina or at a temperature of about 400 °C to about 480 °C in the presence of a Rh / AhOa (rhodium on an alumina support) catalyst).

[0179] 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 provided in step a) is benzene or 1 -methylbenzene manufactured from a non-fossil feedstock.

[0180] 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 provided in step a) is manufactured by steps a1) to a14). Benzene or 1 -methylbenzene can be for example separated from fossil feedstocks such as pyrolysis gasoline and coke-oven light oil. Such feedstocks are discussed above.

[0181] Preferably, the plastic waste used to manufacture the at least one pyrolysis oil provided in step a1) comprises at least one type of polymers selected from the group consisting of thermoplastic polyurethanes, polyurethanes, poly i- socyanurates and polyureas. Thereby, a closed recycling-loop is achieved by the process according to the present invention.

[0182] In step a) also a mixture of nitric acid and sulfuric acid is provided.

[0183] In step b) of the process according to the present invention, benzene or 1-methylbenzene is contacted with the mixture of nitric acid and sulfuric acid whereby nitrobenzene or a nitro-derivative of 1-methylbenzene is formed, wherein the nitro-derivative of 1-methylbenzene is preferably selected from the group consisting of 2-nitro-1 -methylbenzene, 3-nitro1 -methylbenzene, 4-nitro1 -methylbenzene, 2, 4-dinitro1 -methylbenzene, 2, 6-dinitro1 -methylbenzene and mixtures thereof.

[0184] Benzene or 1-methylbenzene are converted to nitrobenzene or (di)nitro derivatives of 1-methylbenzene by direct nitration in liquid phase using a mixture of nitric acid and sulfuric acid ("nitrating acid”). The nitration reaction can be made by an isothermal reaction at a temperature of about 50 °C to about 100 °C and ambient pressure in a cascade of reactors (stirred cylindrical or tubular) or by an adiabatic reaction in a cascade of stirred reactors or a jet impingement reactor at a temperature in the range of about 90 °C to about 190 °C and ambient pressure or increased pressure such as 1.5 bar, 2 bar or even higher pressure such as 5 bar or 10 bar.

[0185] Further details of the manufacture of nitrobenzene from benzene are for example disclosed in G. Booth, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 24, Chapter "Nitro Compounds, Aromatic”, pages 305 to 309, 2012 and the references cited therein.

[0186] Further details of the manufacture of (di)nitro derivatives of 1-methylbenzene from 1 -methylebenzene are for example disclosed in G. Booth, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 24, Chapter "Nitro Compounds, Aromatic”, pages 309 to 313, 2012 and the references cited therein.

[0187] In step d) of the process according to the present invention, the nitrobenzene or nitro-derivative of 1-methylbenzene formed in step b), preferably the mono-nitro-derivatives of the aforementioned, is hydrogenated in the presence of hydrogen and, optionally, a catalyst, whereby aniline or an amino-derivative of 1-methylbenzene is formed, 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. Aniline is manufactured from benzene via nitrobenzene, (di)amino-derivatives of 1 -methylebenzene are manufactured via (di)nitro-l-methylbenzene derivatives manufactured from 1 -methylbenzene.

[0188] Hydrogen used in step d) can be in principle hydrogen generated from any known source and by any known method.

[0189] Preferably, hydrogen used in step d) is preferably "blue hydrogen” (formed by steam reforming and / or autothermal reforming of natural gas whereby the CO2 formed during said reactions is captured and stored or otherwise used), more preferably "green hydrogen” which is generated for example by electrolysis of water using electricity generated from renewable energy sources (e.g., solar energy, wind energy, tidal energy, and nuclear energy) and / or low-carbon energy sources and / or formed by a methane pyrolysis, preferably a methane pyrolysis using at least partially methane from a renewable source. Methane from a renewable source comprises biomethane. Hydrogen can also be provided as a side product of pyrolysis of plastic waste such as mixed plastic waste and / or end-of-life tires.

[0190] Nitrobenzene or the (di)nitro derivative of 1 -methylbenzene is catalytically hydrogenated to aniline or to a (di)amino derivative of 1 -methylbenzene in vapor phase or liquid phase.

[0191] Fixed-bed or fluidized-bed reactors can be used for the gas-phase hydrogenation of nitrobenzene to aniline and 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 oxide(s) such as alumina or silica) and optionally further comprises elements such as lead, vanadium, phosphorous, chromium as modifiers or promoters. One particular gas-phase process uses a copper catalyst on a silica support promoted with chromium, zinc and barium.

[0192] In case of a catalytic gas-phase hydrogenation, nitrobenzene or a (di)nitro derivative of 1-methylbenzene is preferably hydrogenated in the presence of hydrogen and of at least one catalyst in a fluidized bed, preferably at a temperature of about 250 °C to about 300 °C. The pressure preferably ranges from of about 400 kPa to about 1000 kPa. The product gas stream is then cooled down and aniline or the (di)amino derivative of 1-methylbenzene which is then separated, preferably in a liquid-gas separator, from the product stream.

[0193] Liquid-phase hydrogenation of nitrobenzene to aniline or a (di)nitro derivative of 1-methylbenzene to the respective (di)amino derivative of 1-methylbenzene can be for example operated in a temperature range of about 90 °C to about 200 °C. Preferably, the pressure ranges from about 100 kPa to about 600 kPa. For example, slurry- or fluid- ized-bed reactors 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 such as for example kieselguhr. Further details of the manufacture of aniline from benzene are for example disclosed in T. Kahl, K.-W. Schroder, F. R. Lawrence, W. J. Marshall, H. Hoke, R. Jackh, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 3, Chapter "Aniline”, pages 467 to 470, 2012 and the references cited therein.

[0194] Further details of the manufacture of (di)amino derivatives of 1 -methylbenzene from 1 -methylebenzene by catalytic hydrogenation are for example disclosed in P. F. Vogt, J. J. Gerulis, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 2, Chapter "Amines, Aromatic”, pages 707 to 710, 2012 and the references cited therein.

[0195] In optional step c2), 1,1 '-Methylenebis(4-isocyanatobenzene) and optionally poly-isocyanate derivatives thereof (and likewise, of benzene) is / are manufactured from aniline via the diamine precursor 1 , 1 -methylenebis(4- aminobenzene).

[0196] At least a portion of the aniline provided in in optional step c2) as starting material is manufactured in step d). The remaining aniline is manufactured from benzene not provided by steps a1) to a14). Such remaining aniline can be for example manufactured from benzene manufactured from fossil sources and / or from plastic waste or other feedstocks such as bio-oils by other methods.

[0197] Preferably, at least 2.5 wt.-%, more preferably at least 5.0 wt.-% and most preferably at least 7.5 wt.% of the benzene used for manufacture of aniline provided in optional step c2) is benzene manufactured from a non-fossil feedstock.

[0198] Preferably, at least 2.5 wt.-%, more preferably at least 5.0 wt.-% and most preferably at least 7.5 wt.% of the benzene used for manufacture of aniline provided in optional step c2) is manufactured by steps a1) to a14).

[0199] 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(isocyanatobenzene). The phosgenation of 1,1 '-methylenebis(4-aminobenzene) can be for example made in liquid phase using an aromatic solvent in a batch process or a continuous process. The desired 1,1 '-methylenebis(4-isocyanatobenzene) is then separated from the phosgenation reaction products by a continuous thin-film distillation and / or by crystallization. Both processes are known as "splitting" (or, respectively, the equipment known as "splitters"). In addition to 1,1 '- methylenebis(isocyanatobenzene) also condensation products thereof can be formed thereby which are polyisocyanate derivatives of benzene.

[0200] The residual crude product which comprises or consists of oligomeric 1,1 '-methylenebis(4-isocyanatobenzene) can be for example used for manufacture of rigid polyurethane or polyisocyanurate foams. The residual crude product is for example marketed as polymeric 1,1 '-methylenebis(4-isocyanatobenzene) (“PMDI”, a poly-isocyanate derivatives of benzene) and contains, next to a residual level of monomers, oligomers and polymers of 1,1 '-methylenebis(4- isocyanatobenzene) with a broader distribution of chain lengths. Different PMDI grades vary by viscosity, functionality, and the like. PMDI also has various applications, such as polyisocyanurate rigid insulation foams from high viscous PMDI or such as polyurethane rigid insulation foams, woodbinders (e.g., particle board, OSB, MDF), appliance (fridges, freezers, cold chain in general), pipe insulation, transportation from low viscous PMDI.

[0201] The preparation of such diamine precursors from aniline and their phosgenation to 1 , 1 '-methylenebis(4- isocyanatobenzene) is for example described in C. Six, F. Richter, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 20, Chapter "Isocyanates, Organic”, pages 70 to 76, 2012 and the references cited therein.

[0202] Di- and poly-isocyanate derivatives of benzene, 1-methylbenzene are manufactured from (di)amino derivatives of 1- methylbenzene by phosgenation with phosgene. The phosgenation of (di)amino derivatives of benzene and 1- methylbenzene can be for example made in liquid phase using an aromatic solvent in a batch process or a continuous process. The desired di- and / or poly-isocyanate derivative of benzene and 1-methylbenzene is then for example separated from the phosgenation reaction products by a continuous thin-film distillation and / or by crystallization. Both processes are known as "splitting" (or, respectively, the equipment known as "splitters").

[0203] Optionally, at least a portion of the phosgene used for manufacture of isomers of 1 , 1 '-methylenebis- (isocyanatobenzene) and di- and poly-isocyanate derivatives of benzene and / or 1-methylbenzene is produced from stream S14 by a process comprising the steps a) converting at least a portion of stream S14 by a partial oxidation reaction into a mixture comprising CO and H2, b) separating CO from said mixture and c) converting at least a portion of said CO in a catalytic gas phase reaction with chlorine in the presence of a catalyst into phosgene.

[0204] Phosgene is primarily produced from carbon monoxide and chlorine in a gas phase catalysis, usually over an activated carbon catalyst. Because of the exothermic reaction, the synthesis is carried out in cooled reactors, preferably in tube bundle reactors, the catalyst being filled in the reaction tubes and the cooling in the jacket space being effected by a liquid or boiling coolant medium.

[0205] Phosgene is produced in large-scale in a catalytic gas phase reaction of carbon monoxide and chlorine in the presence of a catalyst, for example, an activated carbon catalyst The reaction is strongly exothermic with a reaction enthalpy AH of -107.6 kJ / mol. To remove the reaction heat the reaction is normally carried out in tube-bundle reactors with catalyst filled inside the tubes (see Ullmann's Encyclopedia of industrial chemistry, Chapter ..Phosgene" 5thEd., Vol. A 19, p 413 ff., VCH Verlagsgesellschaft mbH, Weinheim, 1991). Generally, granular catalyst with a grain size in the range of from 3 to 5 mm is used in pipes with a typical inner diameter between 35 and 70 mm, typically between 39 and 45 mm. In the reaction, carbon monoxide is usually used in excess to ensure that all chlorine is converted, and largely chlorine-free phosgene is produced, since chlorine can lead to undesirable side reactions in the subsequent use of phosgene. The reaction can be carried out without pressure but is usually carried out at an overpressure of 200-600 kPa (2-6 bar). In this pressure range, the formed phosgene can be condensed after the reactor with cooling water or other heat carrier, for example organic heat carrier can be used, so that the condenser can be operated more economically.

[0206] At least a portion of the aniline or (di)amino derivative of 1-methylbenzene provided in in optional step d) as starting material is manufactured in step d). The remaining aniline or (di)amino derivative of 1-methylbenzene is manufactured from benzene or 1-methylbenzene not provided by steps a1) to a14). Such remaining aniline or (di)amino derivative of 1-methylbenzene can be for example manufactured from benzene or 1-methylbenzene manufactured from fossil sources and / or from plastic waste or other feedstocks such as bio-oils by other methods.

[0207] 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 for manufacture of aniline or (di)amino derivative of 1-methylbenzene provided in optional step d) is benzene or 1-methylbenzene manufactured from a non-fossil feedstock.

[0208] 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 for manufacture of aniline or (di)amino derivative of 1-methylbenzene provided in optional step d) is manufactured by steps a1) to a14).

[0209] The manufacture of di- and poly-isocyanate derivatives of benzene and 1-methylbenzene from benzene or 1- methylbenzene including the phosgenation of (di)amino derivatives of benzene and 1-methylbenzene to di- and polyisocyanate derivatives of 1-methylbenzene is for example described in C. Six, F. Richter, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 20, Chapter "Isocyanates, Organic”, pages 70 to 76, 2012 and the references cited therein.

[0210] The amino derivative of benzene is aniline, and most preferably, aniline is converted in optional step c2) into 1,1 - methylenebis(4-aminobenzene) which can be then utilized as starting materials in step d) for manufacture of 1 , 1 '- methylenebis(4-isocyanatobenzene) therefrom.

[0211] The (di)amino derivatives of 1-methylbenzene are 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 derivatives of 1-methylbenzene is 2,4- diamino-1 -methylbenzene.

[0212] The di-isocyanate derivatives of 1-methylbenzene are preferably selected from the group consisting of 2-isocyanato- 1 -methylbenzene, 3-isocyanato-1 -methylbenzene, 4-isocyanato-, 2, 4-diisocyanato-1 -methylbenzene and 2,6- diisocyanato-1 -methylbenzene and mixtures thereof. Most preferably, the (di)isocyanate derivative of 1- methylbenzene is 2, 4-diisocyanato-1 -methylbenzene.

[0213] Polymers derived from isocyanate precursors such as polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates, and polyureas, which for example based on 1,1 '-methylenebis(4-isocyanatobenzene) or 2,4- diisocyanato-1 -methylbenzene, or poly-isocyanates (e.g., oligomers of di-isocyanato derivatives of benzene and 1- methylbenzene) ("building block”), can be for example manufactured in a continuous processes, solvent-based processes or solvent-free process in the presence of at least one further compound ("building block”) selected from the group comprising or consisting of polyesterpolyoles, polyetherpolyoles, polycarbonatepolyoles, polyetheresterpoly- oles, polyacrylatepolyoles, polyesterpolyacrylatepolyoles, diols, polycaprolactane polyols, polytetramethylene glycol, diamines, amino-terminated polyethers and mixtures thereof. Catalysts and additives used to support the desired reactions of the above-mentioned building blocks comprise Lewis-bases, Lewis-acids and insertion catalysts. Optionally, also chemical or physical blowing agents are added in case foams are produced (for example: cyclopentane, pentane, hydrofluoro-olefins (“HFOs”), HCOs, water).

[0214] The manufacture of polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates, and polyureas using 1,1 '-methylenebis(4-isocyanatobenzene) or a (di)isocyanate derivative of 1 -methylbenzene such as 2,4- diisocyanato-1-methylbenzene as a starting material is for example described in G. Brereton et al., Ullmann's Encyclopedia of Industrial Chemistry, Chapter "Polyurethanes”, pages 4 to 27, 2019 and the references cited therein.

[0215] The manufacture of polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates, and polyureas using 1, -methylenebis(4-isocyanatobenzene) or di- and poly-isocyanate derivatives of 1-methylbenzene such as 2, 4-diisocyanato-1 -methylbenzene as a starting material is for example described in T. Ouhadi, S. Abou-Sabet, H.-G. Wussow, L. M. Ryan, L. Plummer, F. E. Baumann, J. Lohmar, H. F. Vermeire, F. L. G. Malet, Ullmann's Encyclopedia of Industrial Chemistry, Chapter "Thermoplastic Elastomers”, pages 13 to 15, 2013 and the references cited therein.

[0216] At least a portion of the di- and / or poly-isocyanate derivatives of benzene and 1-methylbenzene used as building block for the optional synthesis of polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates, and polyureas therefrom are manufactured from benzene or 1-methylbenzene manufactured by steps a1) to a14).

[0217] 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 for manufacture of the di- and / or poly-isocyanate derivatives of benzene and 1- methylbenzene and provided in optional step d) and / or the di- and / or poly-isocyanate derivatives of benzene or 1- methylbenzene used as building block for the synthesis of polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates, and polyureas were manufactured from benzene or 1-methylbenzene which was manufactured from a non-fossil feedstock.

[0218] 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 for manufacture of the di- and / or poly-isocyanate derivatives of benzene and 1- methylbenzene are manufactured by steps a1) to a14). The polyurethanes (PUs), thermoplastic polyurethanes (TPUs), polyisocyanurates, and polyureas comprising di- or multi-isocyanate building blocks which are manufactured from aniline and (di)amino derivatives of 1 -methylbenzene by the process according to the present invention can be used for different applications and markets which comprise: Insulation in appliance applications (such as in refrigerators, freezers, boilers, water heaters, cold storage), diverse applications in the automotive market (such as seating carpet backing, acoustics, steering wheels, panel skins, panel foams, headliner foam, headliner adhesive, coating adhesives, sealants, jounce bumpers, suspension mounts, ABS cables, ESP cables, interior skins), construction market (such as sandwich panels, spray foam, insulated doors, roller profiles, pipe insulation, wood binders, composite binders, laminate insulation boards, canned foam), footwear (casual shoes, safety shoes, sport shoes, synthetic leather, adhesives, soles for sport shoes, soles for safety shoes), furniture, upholstery and mattrasses.

[0219] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The method of any of embodiments 1 to 3", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The method of any of embodiments 1, 2 and 3". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and thus, suitably supports the present invention.

[0220] 1 . Process for manufacturing aromatic amino compounds from benzene and 1 -methylbenzene comprising the steps a) providing 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 whereby nitrobenzene or a nitro-derivative of 1 -methylbenzene is formed, d) hydrogenate the nitrobenzene or nitro-derivative of 1 -methylbenzene formed in step b) in the presence of hydrogen and, optionally, a catalyst, whereby aniline or an amino-derivative of 1 -methylbenzene is formed, characterized in that the at least a portion of the benzene or 1 -methylbenzene provided in step a) is manufactured by the steps a1) providing a liquid stream S1 comprising at least one pyrolysis oil, the liquid stream S1 further comprising C6-C8 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and compounds having C-C double and / or C-C triple bonds, a2) providing a stream S2, the stream S2 comprising hydrogen, a3) evaporating at least a portion of the liquid stream S1 in the presence of the stream S2 and optionally a recycle gas stream S11 in an evaporation unit EU and thereby forming a gaseous stream S3 which comprises stream S2, optionally a recycle gas stream S11 and the evaporated portion of the liquid stream S1 , and a liquid stream S4 which comprises the portion of liquid stream S1 which is not evaporated in the evaporation unit EU, a4) optionally superheating the gaseous stream S3 in a superheater SH and thereby form a superheated stream S5, a5) feeding the gaseous stream S3 or, optionally the superheated stream S5 into a first hydrogenation unit HU1 in which at least a portion of the gaseous stream S3 or, optionally the at least a portion of the superheated stream S5 reacts with the hydrogen comprised therein in a hydrogenation reaction whereby a gaseous stream S6 is formed, the gaseous stream S6 comprising C6-C8 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and is depleted in compounds having C-C double and / or C-C triple bonds in respect to gaseous stream S3, a6) heating the gaseous stream S6 in at least one heating device HD and thereby forming a heated gaseous stream S7, a7) subjecting the heated gaseous stream S7 to a second hydrogenation unit HU2 in which a product stream S8 is formed, the product stream S8 comprising C6-C8 aromatic hydrocarbons and being depleted in organic compounds comprising at least one heteroatom and further depleted in compounds having C-C double and / or C-C triple bonds in respect to gaseous stream S3, a8) optionally transferring heat from the product stream S8 to the gaseous stream S3 in the superheater SH and thereby forming a cooled down product stream S8b, a9) continuously or discontinuously feeding a washing water stream S15 to the product stream S8 and thereby forming a stream optionally comprising washing water S8a or optionally continuously or discontinuously feeding a washing water stream S15 to the cooled down product stream S8b and thereby forming a cooled down product stream optionally comprising washing water S8c, a10) optionally transferring heat from the cooled down product stream comprising washing water S8c to the liquid stream S1, stream S2 comprising H2 and stream S11 in the evaporation unit EU and thereby forming a further cooled down product stream S8d, a11) condensing the product stream optionally comprising washing water S8a or optionally one of the streams selected from the group consisting of the cooled down product stream S8b, the cooled down product stream optionally comprising washing water S8c, and the further cooled down product stream optionally comprising washing water S8d in a condensation unit CU and thereby forming a product stream S9, the product stream S9 comprising a liquid phase and a gas phase, a12) separating the liquid product stream S9 in a separation unit SU into a liquid product stream S10, a recycle gas stream S11 and optionally a waste water stream S17 wherein the recycle gas stream S11 comprises hydrogen and wherein at least a portion of the recycle gas stream S11 is fed into the evaporation unit EU, a13) feeding the refined product stream S10 into a distillation unit DU in which the refined product stream S10 is separated into a stabilized product stream S12 and a gaseous stream S13 and a14) separating benzene and / or 1 -methylbenzene from the stabilized product stream S12 in at least one aromatic hydrocarbon extraction unit AEU. 2. Process according to embodiment 1 wherein the at least one pyrolysis oil is manufactured by a pyrolysis of plastic waste.

[0221] 3. Process according to embodiment 1 or 2 wherein the liquid stream S1 preferably comprises 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.

[0222] 4. Process according to any one of embodiments 1 to 3 wherein the at least one pyrolysis oil in the liquid stream S1 preferably comprises 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.

[0223] 5. Process according to any one of embodiments 1 to 4 wherein the at least one pyrolysis oil in the liquid stream S1 has a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g (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).

[0224] 6. Process according to any one of embodiments 1 to 5 wherein the hydrogen comprised in stream S2 was formed by water electrolysis using electrical energy, said electrical energy preferably generated from renewable sources and / or low-carbon energy sources and / or a methane pyrolysis, preferably a methane pyrolysis using methane from a renewable source.

[0225] 7. Process according to any one of embodiments 1 to 6 wherein the liquid stream S1 , recycle gas stream S11 and the stream S2 are mixed before fed into the evaporation unit EU and / or mixed in the evaporation unit EU.

[0226] 8. Process according to any one of embodiments 1 to 7 wherein the evaporation unit EU comprises at least one device selected from the group comprising stage evaporator, falling film evaporator, pre-evaporator, preferably wherein the evaporation unit EU consists of at least one pre-evaporator and at least one stage evaporator.

[0227] 9. Process according to any one of embodiments 1 to 8 wherein the liquid stream S1 is evaporated with a recycle gas stream S11 which is added to the liquid stream S1 prior and / or during evaporation.

[0228] 10. Process according to any one of embodiments 1 to 9 wherein the liquid stream S4 is converted in at least one gasifier and / or by a partial oxidation reaction unit into syngas.

[0229] 11 . Process according to any one of embodiments 1 to 10 wherein superheater SH is preferably a heat exchanger, more preferably a shell and tube heat exchanger or a spiral heat exchanger. 12. Process according to any one of embodiments 1 to 11 wherein the gaseous stream S3 is superheated in a superheater SH to raise the temperature of the gaseous stream S3 preferably by about 2 °C to about 50 °C, more preferably by about 5 °C to about 40 °C and most preferably by about 10 °C to about 30 °C in respect to the temperature at which the gaseous stream S3 leaves the evaporation unit EU.

[0230] 13. Process according to any one of embodiments 1 to 12 wherein the first hydroprocessing unit HU1 comprises at least one heterogeneous catalyst.

[0231] 14. Process according to any one of embodiments 1 to 13 wherein the at least one heterogeneous catalyst is selected from the group comprising or consisting of nickel-molybdenum catalysts and nickel-tungsten catalysts further comprising a support, preferably an inorganic support selected from the group comprising or consisting of silica, alumina, silica-aluminas, magnesia, clays, and mixtures thereof.

[0232] 15. Process according to any one of embodiments 1 to 14 wherein the process temperature in the first hydroprocessing unit HU1 preferably ranges from about 140 °C to about 250 °C, more preferably from about 140 °C to about 200 °C and most preferably from about 170 °C to about 190 °C.

[0233] 16. Process according to any one of embodiment 1 to 15 wherein the heated gaseous stream S7 preferably has a temperature in the range of about 200 °C to about 400 °C, more preferably of about 240 °C to about 360 °C and most preferably of about 260 °C to about 350 °C.

[0234] 17. Process according to any one of embodiments 1 to 17 wherein the at least one heating device is selected from the group comprising direct fired heaters, furnaces powered by electrical energy, heat exchangers, and combinations thereof.

[0235] 18. Process according to any one of embodiments 1 to 17 wherein the wherein the second hydroprocessing unit HU2 comprises at least one fixed-bed reactor.

[0236] 19. Process according to any one of embodiments 1 to 18 wherein the second hydroprocessing unit HU2 comprises at least one heterogeneous catalyst, preferably, wherein the at least one hetereogeneous cataylst is selected from the group comprising or consisting of molybdenum catalysts, cobalt-molybdenum catalysts, and cobalt-tungsten catalysts.

[0237] 20. Process according to any one of embodiments 1 to 19 wherein the temperature of the hydrogenation reaction in the second hydroprocessing unit HU2 preferably ranges from about 200 °C to about 400 °C, more preferably from about 250 °C to about 380 °C, most preferably from about 280 °C to about 360 °C. 21 . Process according to any one of embodiments 1 to 20 wherein the pressure of the hydrogenation reaction in the second hydroprocessing unit HU2 preferably ranges from about 1 bar to about 200 bar, more preferably from about 10 bar to about 150 bar and most preferably from 15 bar to 60 bar and / or the hydrogen partial pressure in front of hydroprocessing unit HU1 ranges from about 5 bar to about 50 bar, more preferably from about 10 to about 30 bar and most preferably from about 14 bar to about 20 bar.

[0238] 22. Process according to any one of embodiments 1 to 21 wherein the weight hourly space velocity (WHSV) of the heated gaseous stream S7 preferably ranges from about 0.1 t / (m3Kat / h) to about 5.0 t / (m3Kat h), more preferably from about 0.5 t / (m3Kat / h) to about 1.0 t / (m3Kat / h).

[0239] 23. Process according to any one of embodiments 1 to 22 wherein the organic compounds comprising at least one heteroatom in the liquid stream S1 are depleted in the second hydroprocessing unit HU2 by at least 90 %, more preferably by at least 95 %, most preferably at least 99 %.

[0240] 24. Process according to any one of embodiments 1 to 23 wherein the at least one condensation unit CU is selected from the group comprising heat exchangers, with cooling media like air, cooling water, other media with suitable low temperatures.

[0241] 25. Process according to any one of embodiments 1 to 24 wherein the at least one separation unit SU is selected from the group comprising hydrocyclones, settler tanks, centrifuges, and combination thereof, more preferably from settler tanks and / or centrifuges.

[0242] 26. Process according to any one of embodiments 1 to 25 wherein the distillation unit DU preferably comprises one distillation column.

[0243] 27. Process according to any one of embodiments 1 to 26 wherein the distillation in the distillation unit DU is carried out at a temperature in the range of about 0 °C to about 600 °C, more preferably from about 20 °C to about 400 °C, most preferably from about 80 °C to about 250 °C (the temperature ranges referring to atmospheric pressure of 1.013 bar) and preferably a pressure in the range of about 0, 1 bar (abs.) to about 20 bar (abs), more preferably from about 0,5 bar to about 16 bar (abs), most preferably from about 1 bar to about 14 bar (abs).

[0244] 28. Process according to any one of embodiments 1 to 27 wherein the stabilized product stream S12 preferably comprises about 60 wt.-% to about 99 wt.-%, more preferably about 75 wt.-% to about 85 wt.-% of C6-C8 aromatic hydrocarbons which were comprised in liquid stream S1 .

[0245] 29. Process according to any one of embodiments 1 to 28 wherein by separating C6-C8 aromatic hydrocarbons from the stabilized product stream S12 in at least one aromatic hydrocarbon extraction unit AEU, a stream S16a which comprises at least 90 wt.-% benzene, a stream S16b which comprises at least 90 wt.-% 1- methylbenzene, a stream S16c which comprises at least 90 wt.-% C8 aromatic hydrocarbons selected from the group consisting of 1,2-xylene, 1,3 xylene, 1 ,4-xylene, and ethylbenzene, and a stream S16d depleted in C6-C8 aromatic hydrocarbons are obtained. Process according to any one of embodiments 1 to 29 wherein benzene and / or 1 -methylbenzene are separated from the stabilized product stream S12 in step a14) by extractive distillation in at least one optional aromatic hydrocarbon extraction unit AEU. Process according to any one of embodiments 1 to 30 wherein stream S14 is further subjected to a cracking process selected from catalytic cracking, thermal cracking, and steam cracking and / or a partial oxidation process or a gasification process. Process according to any one of embodiments 1 to 31 wherein preferably at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, most preferably 7.5 wt.-% of the benzene or 1 -methylbenzene provided in step a) is manufactured by steps a1) to a14). Process according to any one of embodiments 1 to 32 wherein the nitro-derivative of 1 -methylbenzene formed in step b) is selected from the group consisting of 2-nitro-1 -methylbenzene, 3-nitro-1 -methylbenzene, 4-nitro1- methylbenzene, 2, 4-dinitro-1 -methylbenzene, and 2, 6-dinitro-1 -methylbenzene and mixtures thereof. Process according to any one of embodiments 1 to 33 wherein nitrobenzene or the nitro-derivative of 1- methylbenzeneis 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. Process according to any of one of embodiments 1 to 34 wherein the amino-derivative of 1 -methylbenzene formed in step d) is 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. Process according to any one of embodiments 1 to 35 wherein the hydrogen provided in step d) is manufactured by a process using at least partially energy from a renewable energy source. Process according to any one of embodiments 1 to 36 wherein the hydrogen provided in step d) is manufactured by water electrolysis using at least partially energy from a renewable energy source. Process according to any one of embodiments 1 to 37 wherein the catalyst optionally employed in step d) is a copper and / or palladium catalyst on a support for gas-phase hydrogenation and nickel on a support for liquid-phase hydrogenation. 39. Process according to any one of embodiments 1 to 38 comprising the further step c2) converting aniline into 1, r-methylenebis(4-aminobenzene) by a condensation reaction in the presence of formaldehyde.

[0246] 40. Process according to embodiment 39 wherein preferably at least 2.5 wt.-%, more preferably at least 5.0 wt.- %, most preferably 7.5 wt.-% of the aniline converted in step c2) is manufactured from benzene manufactured by steps a1) to a14).

[0247] 41 . Process according to embodiment 39 or 40 wherein hydrochloric acid used as a catalyst in step c2).

[0248] 42. Process according to any one of embodiments 1 to 41 further comprising the step d) phosgenating aniline or an amino-derivative of 1 -methylbenzene produced in step d), to form a di- or poly-isocyanate-derivative of 1 -methylbenzene, or phosgenating 1,1 '-methylenebis(4-aminobenzene) produced in step c2) with phosgene to form 1,1 '-methylenebis(4-isocyanatobenzene) or a polyisocyanate derivative thereof.

[0249] 43. Process according to embodiment 42 wherein at least a portion of the phosgene is produced from stream S14 by a process comprising the steps a) converting at least a portion of stream S14 by a partial oxidation reaction into a mixture comprising CO and H2, b) separating CO from said mixture and c) converting at least a portion of said CO in a catalytic gas phase reaction with chlorine in the presence of a catalyst into phosgene.

[0250] 44. Process according to embodiment 42 or 43 wherein the amino-derivative of 1 -methylbenzene produced in step d) 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.

[0251] 45. Process according to any one of embodiments 42 to 44 wherein the di- or poly-isocyanate-derivative of 1- methylbenzene is preferably selected from the group consisting of 2-isocyanato-1 -methylbenzene, 3- isocyanato-1 -methylbenzene, 4-isocyanato-1 -methylbenzene, 2,4-diisocyanato-1-methylbenzene and 2,6- diisocyanato-1 -methylbenzene and mixtures thereof and poly-isocyanate derivatives thereof.

[0252] 46. Process according to any one of embodiments 42 to 45 wherein the isocyanates formed in step d) are further converted in the presence of at least one organic compound into a polymer, the polymer selected from the group comprising or consisting of polyurethanes, thermoplastic polyurethanes, polyisocyanurates, and polyureas. 47. Process according to embodiment 46 wherein the at least one organic compound is selected from the group comprising or consisting of polyesterpolyoles, polyetherpolyoles, polycarbonatepolyoles, polyetheresterpoly- oles, polyacrylatepolyoles, polyesterpolyacrylatepolyoles, diols, polycaprolactane polyols, polytetramethylene glycol, diamines, amino-terminated polyethers and mixtures thereof.

[0253] 48. Chemical plant for separating benzene and 1 -methylbenzene from a feedstock stream comprising at least one pyrolysis oil for manufacturing aromatic amines therefrom, the chemical plant comprising

[0254] (i) an evaporation unit EU,

[0255] (II) optionally a superheater SH downstream of the evaporation unit EU,

[0256] (ill) a first hydroprocessing unit HU1, the first hydroprocessing unit HU1 comprising at least one inlet and at least one outlet, the first hydroprocessing unit HU1 downstream of the evaporation unit EU or the optional superheater SH and the at least one inlet of the first hydroprocessing unit HU1 fluidically connected to the evaporator or the optional superheater SH,

[0257] (iv) at least one heating unit HD downstream of and fluidically connected to the at least one outlet of the first hydroprocessing unit HU1,

[0258] (v) a second hydroprocessing unit HU2 having at least one inlet and at least one outlet, the second hydroprocessing unit HU2 downstream of the at least one heating unit HD and the at least one outlet of the hydroprocessing unit HU2 fluidically connected to the heating device HD,

[0259] (vi) a condensation unit CU downstream of the second hydroprocessing unit HU2 and fluidically connected to the at least one outlet of the second hydroprocessing unit HU2,

[0260] (vii) a separation unit SU downstream of and fluidically connected to the condensation unit CU and

[0261] (viii) a distillation unit DU downstream of and fluidically connected to the separation unit SU and an aromatic hydrocarbon extraction unit AEU downstream of the optional distillation unit and fluidically connected to stream S12.

[0262] 49. Use of a chemical plant according to embodiment 48 for a process according to any one of embodiments 1 to 47.

[0263] It is explicitly noted that the above set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and thus, suitably supports, but does not represent the claims of the present invention.

[0264] The invention will be further explained by the following non-limiting examples. Examples

[0265] Methods for separating benzene and 1 -methylbenzene from a feedstock stream comprising a pyrolysis oil for the manufacture of aromatic amines (comparative example and method according to the present invention) were simulated using ASPEN Plus™ V11 simulation software in combination with a kinetic model to calculate the conversion in the first hydroporcessing unit HU1 and the second hydroprocessing HU2.

[0266] Comparative example

[0267] The comparative example is a method and a chemical plant for separating benzene and 1 -methylbenzene from a pyrolysis oil obtained by pyrolysis of plastic waste is shown in Figure 1.

[0268] The process conditions used for the first hydroprocessing unit HU1 are summarized in Table 1 :

[0269] he chosen compositions for the streams S1 , S1' (S1' = S1 +S2 + S3'), S6, S8, S12, S16a, S16b, S16c and S16d are summarized in Table 2:

[0270] The composition of the liquid stream S1 of the hydroprocessing unit HU1 is described in Tab. 2 with a dienic components concentration of 0.8 wt.-% and olefinic components concentration of 3.23 wt.%. The total content of C6-C8 aromatics is 73.13 wt.-%. The composition of the liquid stream S1 is identic to the liquid stream S1 used in the example according to the invention below. The liquid stream S1 is processed in the hydroprocessing unit HU 1 with conditions described in Tab. 1.

[0271] The catalyst in the hydroprocessing unit HU 1 is a Ni-Mo catalyst on an alumina support.

[0272] The pressure at reactor outlet of the first hydroprocessing unit HU 1 is 64 bar (abs.) and the reactor temperature rises from 119 °C (reactor inlet temperature) to 150 °C (reactor outlet temperature) by adiabatic temperature increase. Under these conditions typical trickle-bed flow of the liquid phase over the (solid) catalyst occurs which is desired.

[0273] The ratio "liquid feed S1 : liquid recycle stream S11 " from the hydroprocessing unit HU2 (Figure 1) is 1 : 1. The concentration of dienic components with 0.44 mol.-% is a factor of 2.9 higher than the concentration of dienic components in the example according to the present invention with 0.15 mol.-% (see below) the stream S3.

[0274] The temperature increase of 31 °C (from the reactor inlet to reactor outlet of the first hydroprocessing unit HU1) is comparable with the 30 °C in the example according to the present invention (see below) higher. The much higher dienic components concentration and the flow in liquid regime in comparison to the vapor flow in inventive example (see below) causes a higher polymer formation during processing and so advances plugging which are both undesired.

[0275] The WHSV (weight hourly space velocity) of liquid stream S1 is 0.5 t / (m3Kat *h). The chemical hydrogen consumption in the first hydroprocessing unit HU1 is 23 Nm3 / t. The molar ratio "stream comprising H2 S2 fed to the first hydroprocessing unit HU1 : chemical hydrogen consumption” is 1.08 : 1. The small excess of hydrogen assures the sufficient activity of the catalyst to effect 98 % conversion of the dienic components and 37 % conversion of the olefinic components (stream S3). Under these operation conditions and the catalyst used (Ni-Mo catalyst on an alumina support), no hydrogenation of the aromatic components will occur. The reactor product of hydroprocessing unit HU1 (stream S3 in Fig. 1) is directly fed to the hydroprocessing unit HU2. The process conditions in the second hydroprocessing unit HU2 are summarized in Table 3:

[0276] Table 3 shows the process conditions of the hydroprocessing unit HU2. The pressure at reactor outlet is 63 bar (abs.). The ratio "HU2 internal recycle-gas S6" : feed stream S6” is 392 Nm3 / t and the reactor inlet temperature of the second hydroprocessing unit HU2 is 342 °C. Under these conditions, the feed stream S3 of the hydroprocessing unit HU2 is completely evaporated.

[0277] Caused by the low content of dienic components of < 0.01 wt.-% in the feed stream S6 of the hydroprocessing unit HU2 no undesired polymerization and fouling occurs during total evaporation. The reactor temperature rises from an inlet temperature of 342 °C to an outlet temperature of 355 °C by the exotherm hydrogenation reactions mentioned above. The temperature rise is 13 °C because 69 % of the olefins are already hydrogenated in the hydroprocessing unit HU1 and the 1 : 1 dilution by the "liquid feed S1 : liquid recycle stream S11” from the hydroprocessing unit HU2.

[0278] To limit the undesired hydrogenation of the aromatic rings, such a low exothermic temperature increase of 13 °C is beneficial. The hydrogen partial pressure in the reactor of 39 bar (abs.) is sufficient to assure a sufficient hydrogenation activity but avoid undesired aromatic ring hydrogenation. The catalyst in the second hydroprocessing unit HU2 is a standard Co-Mo catalyst on an alumina support which shows sufficient dienic- and olefinic-hydrogenation, desulfurization, denitration and dehalogenation activity and very low aromatic ring hydrogenation activity but needs higher temperatures than the Co-Mo catalyst on an alumina support in the example according to the present invention below. The loss of aromatic components by aromatic ring hydrogenation is < 0.5 %. The WHSV of the feed stream S3 is 0.7 t / (m3Kat*h).

[0279] The cooled down condensed liquid reaction product S4 leaving the second hydroprocessing unit HU2 is fed with a ratio of 1 : 1 together with the liquid feed stream S1 back to the hydroprocessing unit HU1 to dilute the liquid feed stream S1 bevor entering the first hydroprocessing unit HU1 . The necessity and effect of the dilution is described above for the first hydroprocessing unit HU1 .

[0280] Next step is the distillation in the distillation unit DU to remove the unwanted high boiling components in before feeding the product stream S12 into the aromatic hydrocarbon extraction unit AEU. High boiling components are undesired in the aromatic hydrocarbon extraction unit AEU because they accumulate in the solvent of the aromatic extraction unit AEU and contaminate the solvent. Hence the efficiency of the aromatic hydrocarbon extraction in the aromatic hydrocarbon extraction unit AEU would be affected. The results of the distillation in the distillation unit DU are shown in Table 4 ("fraction over head " = stream S12, "yield of C6-C8 aromatics” = sum of C6-C8 aromatics mass in stream S12 : sum of C6-C8 aromatics mass in stream S8

[0281] * 100):

[0282] In the distillation unit DU, the light boiling fraction with most of the C6-C8 aromatic components goes overhead. These are 78 wt.-% of the stream S4 to the distillation unit DU. The content of C6-C8 aromatic components is thereby raised from 69.5 wt.-% to 83.0 wt.-%. The high boiling components are separated by the bottoms stream S5. The valued product overhead stream S4 is 78 wt.-% of the distillation unit DU feed stream S3 and comprises 93 wt.-% of the C6-C8 aromatic components.

[0283] The stream S12 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 1 -methylbenzene (>99 wt.-%) and a xylene / ethylbenzene mixture (>93 wt.-%) are separated by an extractive distillation process. The remaining stream S8 is depleted in benzene, 1- methylbenzene and xylene / ethylbenzene mixture and comprises the paraffinic components, naphthenic components and the C8+ aromatic hydrocarbons.

[0284] Example (invention)

[0285] The process according to the present invention was simulated in this example following the schematic representation in Figure 2.

[0286] Tab.5 process conditions in the evaporation section EU:

[0287] he chosen compositions for the streams S1 , S3, S4, S6, S8, S12, S13, S16a, S16b, S16c, S16d are summarized in Table 6:

[0288] The composition of the liquid stream S1 fed into the first hydroprocessing unit HU 1 is described in Tab.6 with a dienic components concentration of 0.8 wt.-% and olefinic components concentration of 3.23 wt.-%. The total content of C6-C8 aromatic hydrocarbons is 73.13 wt.-%. The liquid stream S1 is processed in the evaporation section EU. The stream S1 is evaporated in the mixture of the fresh H2 steam S2 and the recycle gas stream S11 of 1240 Nm3 / t stream S1 . The resulting saturated vapor mixture stream S3 have a dew point of 190 °C at 21.9 bar (abs.). 97.8 wt.- % of the feed stream S1 are evaporated.

[0289] In the following super heater SU the saturated vapor phase stream S3 is superheated by 10 °C to a temperature of 200 °C to ensure no liquid entrainment is still existent an no condensation occurs by heat-loss in the chemical plant.

[0290] Tab.7 process conditions in the first hydroprocessing unit HU1 :

[0291] The catalyst in the first hydroprocessing unit HU 1 is a Ni-Mo catalyst on an alumina support which allows the pointed- out reaction conditions in the vapor phase. With 82.48 vol.-% H2 at 21 .8 bar (abs.) the inlet stream H2 partial pressure of the first hydroprocessing unit HU 1 is 18 bar (abs.). This hydrogen partial pressure is sufficient to ensure a high hydrogenation activity and well selectivity of the catalysts in the first and second hydroprocessing units HU 1 and HU2.

[0292] The pressure at the reactor inlet is 21.8 bar (abs.) in the first hydroprocessing unit HU1 and the reactor temperature rises from 200 °C reactor inlet temperature to 230 °C reactor outlet temperature by adiabatic temperature increase.

[0293] The dilution in the inlet stream S1 with fresh H2 stream S2 and recycle gas stream S11 affects a low dienic components concentration of 0.15 mol-% and olefinic components content of 0.67 mol-%. In the comparative example the dienic components molar concentration is 2.9 times higher. The high dilution in the gas phase pressure together with the low dienic components concentration assures the avoidance of undesired polymer formation and fouling during processing.

[0294] The reactor of the hydroprocessing unit HU 1 is operated in up-flow mode. Accordingly, stream S5 enters the at least one reactor of the first hydroprocessing unit HU 1 in the bottom area of said at least one reactor and leaves said at least one reactor as stream S6 in the top section of said at least one reactor. The WHSV (weight hourly space velocity) of the liquid stream S1 is 2.0 t / (m3Kat*h). The chemical hydrogen consumption in the first hydroprocessing unit HU 1 is 21 Nm3 / t. Under these conditions 99 % conversion of the dienic components and 13 % conversion of the olefinic components (stream S3) and no hydrogenation of the aromatic components will occur.

[0295] The stream S3 leaving the first hydrogenation unit HU1 is stable enough (no undesired fouling by polymerization will occur) to be heated up in the heating device HD to 310 °C, which is then the reactor inlet temperature of the second hydroprocessing unit HU2.

[0296] The process conditions of the second hydroprocessing unit HU2 are shown in Table 8:

[0297] Here the remaining small amounts of dienic and olefinic components are hydrogenated in the gas-phase to the corresponding saturated hydrocarbons. The sulfur containing components are hydrogenated to the corresponding saturated hydrocarbons and H2S. The sulfur content in the hydroprocessed product stream S6 is < 0.5 wt.-ppm. The nitrogen containing components are hydrogenated to the corresponding saturated hydrocarbons and NH3. The nitrogen content in the hydroprocessed product stream S6 is < 10 wt.-ppm The halogen-, like chlorine-containing components are hydrogenated to the corresponding saturated hydrocarbons and hydrohalogenic acids such as HCI. The halogens / chlorine content in the hydroprocessed product stream S6 is < 1 wt.-ppm.

[0298] The pressure at reactor inlet is 21.5 bar (abs.). The reactor inlet temperature is 310 °C. Under these conditions, the inlet stream S7 of the second hydroprocessing unit HU2 is complete (as desired) in the vapor phase. Caused by the low content of dienic components of < 0.01 wt.-% in the feed stream S7, no undesired polymerization and fouling occurs during inside the second hydroprocessing unit HU2. The reactor temperature rises from 310 °C inlet temperature to 330 °C outlet temperature by the exotherm hydrogenation reactions. Such a reasonable exothermic temperature increase inside the second hydroprocessing unit HU2 is beneficial to limit the undesired hydrogenation of the C6-C8 aromatic hydrocarbons which is thereby suppressed. The hydrogen partial pressure in the reactor of the second hydroprocessing unit HU2 of 17.7 bar (abs.) is suited to assure a sufficient hydrogenation activity but to avoid the undesired hydrogenation of the C6-C8 aromatic hydrocarbons.

[0299] The catalyst in the second hydroprocessing unit HU2 is a Co-Mo catalyst on an alumina support which shows sufficient dienic- and olefinic-hydrogenation, desulfurization, denitration and dehalogenation activity and the desired very low C6-C8 aromatic hydrocarbons hydrogenation activity. The loss of aromatic components by aromatic ring hydrogenation is < 0.5 %. The WHSV of stream S1 is 0.7 t / (m3Kat*h).

[0300] After leaving the reactor the product stream is successively cooled down, the valued product containing stream S10 is separated from the recycle gas stream S11 .

[0301] The results of the distillation unit DU are shown in Table 9 ("valued product fraction” means stream S12”, yield of C6-C8 aromatics” means the sum of C6-C8 aromatics mass in stream S12 : sum of C6-C8 aromatics mass in stream

[0302] In the following distillation unit DU, the dissolved gases (H2, CH4, C2H6, C3H8, H2S and NH3) are separated as stream S13 from the valued product fraction (stream S12) with most of the C6-C8 aromatic hydrocarbons. The residue stream S14 contents the undesired high boiling aromatic hydrocarbon components for the aromatic hydrocarbon extraction unit AEU. These components would accumulate in the solvent of the aromatic hydrocarbon extraction unit AEU and contaminate the solvent. Hence the efficiency of the aromatic hydrocarbon extraction in the aromatic hydrocarbon extraction unit AEU would be affected.

[0303] These are 77 wt.-% of the total feed to the distillation unit DU stream S10. The content of C6-C8 aromatic hydrocarbons is raised from 69.4 wt.-% to 82.6 wt.% in the distillation unit DU. The high boiling components are separated as bottoms stream S14. The valued product stream S12 is 77 wt.-% of the distillation unit DU feed stream S10 and comprises 92 wt.-% of the C6-C8 aromatic hydrocarbons.

[0304] The stream S12 leaving the second distillation unit DU is the fed to an aromatic hydrocarbon extraction unit AEU which yields pure benzene (>99 wt.-%) in stream S16a, pure 1 -methylbenzene (>99 wt.-%) in stream S16b and a xylene / ethyl benzene mixture (>93 wt.-%) in stream S16c which are separated in the aromatic hydrocarbon extraction unit AEU by an extractive distillation process. The remaining stream S16d is depleted in benzene, 1 -methylbenzene and xylene / ethylbenzene mixture and comprises the paraffinic components, naphthenic components and the C8+ aromatic hydrocarbons.

Claims

Claims1. Process for manufacturing aromatic amino compounds from benzene and 1 -methylbenzene comprising the steps a) providing 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 whereby nitrobenzene or a nitro-derivative of 1 -methylbenzene is formed, d) hydrogenate the nitrobenzene or nitro-derivative of 1 -methylbenzene formed in step b) in the presence of hydrogen and, optionally, a catalyst, whereby aniline or an amino-derivative of 1 -methylbenzene is formed, characterized in that the at least a portion of the benzene or 1 -methylbenzene provided in step a) is manufactured by the steps a1) providing a liquid stream S1 comprising at least one pyrolysis oil, the liquid stream S1 further comprising C6-C8 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and compounds having C-C double and / or C-C triple bonds, a2) providing a stream S2, the stream S2 comprising hydrogen, a3) evaporating at least a portion of the liquid stream S1 in the presence of the stream S2 and optionally a recycle gas stream S11 in an evaporation unit EU and thereby forming a gaseous stream S3 which comprises stream S2, optionally a recycle gas stream S11 and the evaporated portion of the liquid stream S1 , and a liquid stream S4 which comprises the portion of liquid stream S1 which is not evaporated in the evaporation unit EU, a4) optionally superheating the gaseous stream S3 in a superheater SH and thereby form a superheated stream S5, a5) feeding the gaseous stream S3 or, optionally the superheated stream S5 into a first hydrogenation unit HU1 in which at least a portion of the gaseous stream S3 or, optionally the at least a portion of the superheated stream S5 reacts with the hydrogen comprised therein in a hydrogenation reaction whereby a gaseous stream S6 is formed, the gaseous stream S6 comprising C6-C8 aromatic hydrocarbons, organic compounds comprising at least one heteroatom and is depleted in compounds having C-C double and / or C-C triple bonds in respect to gaseous stream S3, a6) heating the gaseous stream S6 in at least one heating device HD and thereby forming a heated gaseous stream S7, a7) subjecting the heated gaseous stream S7 to a second hydrogenation unit HU2 in which a product stream S8 is formed, the product stream S8 comprising C6-C8 aromatic hydrocarbons and being depleted in organic compounds comprising at least one heteroatom and further depleted in compounds having C-C double and / or C-C triple bonds in respect to gaseous stream S3, a8) optionally transferring heat from the product stream S8 to the gaseous stream S3 in the superheater SH and thereby forming a cooled down product stream S8b,a9) continuously or discontinuously feeding a washing water stream S15 to the product stream S8 and thereby forming a stream optionally comprising washing water S8a or optionally continuously or discontinuously feeding a washing water stream S15 to the cooled down product stream S8b and thereby forming a cooled down product stream optionally comprising washing water S8c, a10) optionally transferring heat from the cooled down product stream comprising washing water S8c to the liquid stream S1 , stream S2 comprising H2 and stream S11 in the evaporation unit EU and thereby forming a further cooled down product stream S8d, a11) condensing the product stream optionally comprising washing water S8a or optionally one of the streams selected from the group consisting of the cooled down product stream S8b, the cooled down product stream optionally comprising washing water S8c, and the further cooled down product stream optionally comprising washing water S8d in a condensation unit CU and thereby forming a product stream S9, the product stream S9 comprising a liquid phase and a gas phase, a12) separating the liquid product stream S9 in a separation unit SU into a liquid product stream S10, a recycle gas stream S11 and optionally a waste water stream S17 wherein the recycle gas stream S11 comprises hydrogen and wherein at least a portion of the recycle gas stream S11 is fed into the evaporation unit EU, a13) feeding the refined product stream S10 into a distillation unit DU in which the refined product stream S10 is separated into a stabilized product stream S12 and a gaseous stream S13 and a14) separating benzene and / or 1 -methylbenzene from the stabilized product stream S12 in at least one aromatic hydrocarbon extraction unit AEU.

2. Process according to claim 1 wherein the at least one pyrolysis oil is manufactured by a pyrolysis of plastic waste.

3. Process according to claim 1 or 2 wherein the liquid stream S1 preferably comprises 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.

4. Process according to any one of claims 1 to 3 wherein the at least one pyrolysis oil in the liquid stream S1 has a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g (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).

5. Process according to any one of claims 1 to 4 wherein preferably at least 2.5 wt.-%, more preferably at least 5.0 wt.-%, most preferably 7.5 wt.-% of the benzene or 1-methylbenzene provided in step a) is manufactured by steps a1) to a14).

6. Process according to any one of claims 1 to 5 wherein the nitro-derivative of 1-methylbenzene formed in step b) is selected from the group consisting of 2-nitro-1 -methylbenzene, 3-nitro-1 -methylbenzene, 4-nitro1 - methylbenzene, 2, 4-dinitro-1 -methylbenzene, and 2, 6-dinitro-1 -methylbenzene and mixtures thereof.

7. Process according to any of one of claims 1 to 6 wherein the amino-derivative of 1-methylbenzene formed in step d) is 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. Process according to any one of claims 1 to 7 comprising the further step c2) converting aniline into 1, r-methylenebis(4-aminobenzene) by a condensation reaction in the presence of formaldehyde.

9. Process according to any one of claims 1 to 8 further comprising the step d) phosgenating aniline or an amino-derivative of 1-methylbenzene produced in step d), to form a di- or poly-isocyanate-derivative of 1-methylbenzene, or phosgenating 1,1 '-methylenebis(4-aminobenzene) produced in step c2) with phosgene to form 1,1 '-methylenebis(4-isocyanatobenzene) or a polyisocyanate derivative thereof.

10. Process according to any one of claims 1 to 9 wherein the amino-derivative of 1-methylbenzene produced in step d) 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 . Process according to claim 9 wherein the di- or poly-isocyanate-derivative of 1-methylbenzene is preferably selected from the group consisting of 2-isocyanato-1 -methylbenzene, 3-isocyanato-1 -methylbenzene, 4- isocyanato-1 -methylbenzene, 2, 4-diisocyanato-1 -methylbenzene and 2, 6-diisocyanato-1 -methylbenzene and mixtures thereof and poly-isocyanate derivatives thereof.

12. Process according to any one of claims 9 to 11 wherein the isocyanates formed in step d) are further converted in the presence of at least one organic compound into a polymer, the polymer selected from the group comprising or consisting of polyurethanes, thermoplastic polyurethanes, polyisocyanurates, and polyureas.

13. Process according to claim 12 wherein the at least one organic compound is selected from the group comprising or consisting of polyesterpolyoles, polyetherpolyoles, polycarbonatepolyoles, polyetheresterpolyoles, polyacrylatepolyoles, polyesterpolyacrylatepolyoles, diols, polycaprolactane polyols, polytetramethylene glycol, diamines, amino-terminated polyethers and mixtures thereof.

14. Chemical plant for separating benzene and 1 -methylbenzene from a feedstock stream comprising at least one pyrolysis oil for manufacturing aromatic amines therefrom, the chemical plant comprising(i) an evaporation unit EU,(ii) optionally a superheater SH downstream of the evaporation unit EU,(iii) a first hydroprocessing unit HU1, the first hydroprocessing unit HU1 comprising at least one inlet and at least one outlet, the first hydroprocessing unit HU1 downstream of the evaporation unit EU or the optional superheater SH and the at least one inlet of the first hydroprocessing unit HU1 fluidically connected to the evaporator or the optional superheater SH,(iv) at least one heating unit HD downstream of and fluidically connected to the at least one outlet of the first hydroprocessing unit HU1,(v) a second hydroprocessing unit HU2 having at least one inlet and at least one outlet, the second hydroprocessing unit HU2 downstream of the at least one heating unit HD and the at least one outlet of the hydroprocessing unit HU2 fluidically connected to the heating device HD,(vi) a condensation unit CU downstream of the second hydroprocessing unit HU2 and fluidically connected to the at least one outlet of the second hydroprocessing unit HU2,(vii) a separation unit SU downstream of and fluidically connected to the condensation unit CU and(viii) a distillation unit DU downstream of and fluidically connected to the separation unit SU and an aromatic hydrocarbon extraction unit AEU downstream of the optional distillation unit and fluidically connected to stream S12.

15. Use of a chemical plant according to claim 14 for a process according to any one of claims 1 to 13.

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