Process for increasing yield of low boiling fractions from pyrolysis oil and cracker feedstocks

Abstract

The present invention relates to a process for increasing the yield of a low boiling fraction from a pyrolysis oil, wherein the pyrolysis oil or a high boiling fraction obtained therefrom is heat-treated to produce an additional low boiling fraction. A high boiling residue is also obtained by the heat treatment. The heat treatment is preferably performed in an inert atmosphere at a temperature in the range of about 350 DEG C to about 500 DEG C. The further low boiling fraction is then separated from the high boiling residue. The further low boiling fraction obtained is suitable as a feedstock for cracking to produce (light) olefins and aromatics. The high boiling residue can be further used for partial oxidation, pyrolysis or incineration.

Description

TECHNICAL FIELD

[0001] The present invention relates to a method for increasing the yield of a low boiling fraction from a pyrolysis oil produced by a pyrolysis reaction of a feedstock. BACKGROUND

[0002] Pyrolysis oils made from feedstocks such as plastic waste are used as a source of base chemicals such as light olefins, aromatic compounds and synthesis gas. Light olefins and aromatic compounds can be produced by a cracking process such as steam cracking having an initial boiling point of about 60 °C and a final boiling point of up to about 360 °C, which low boiling fractions are obtained from pyrolysis oils as cracker feedstock for said cracking. The pyrolysis low boiling fraction yield depends on various variables such as the type of feedstock used for the pyrolysis reaction, the pyrolysis reaction parameters and the upgrading of the pyrolysis oil. The low boiling fraction contains for example C6 - C 21 hydrocarbons and is obtained for example with a yield of only 35 wt.-% based on the total weight of the pyrolysis oil, which generally limits the use of such cracker feedstock compared to fossil based cracker feedstock such as naphtha.

[0003] It is therefore an object of the present invention to increase the yield of a low boiling fraction obtained from pyrolysis oils which are suitable as feedstock for the production of olefins and aromatic compounds by cracking. SUMMARY

[0004] This problem is solved by a method for increasing the yield of a low boiling fraction from a pyrolysis oil, the method comprising the steps of:

[0005] (i) providing a pyrolysis oil produced by a pyrolysis reaction of a feedstock, wherein the pyrolysis oil comprises a mixture of a first low boiling fraction LBF1 and a high boiling fraction HBF,

[0006] (ii) subjecting the mixture of the first low boiling fraction LBF1 and the high boiling fraction HBF to a thermal treatment, whereby by said thermal treatment the first low boiling fraction LBF1, a second low boiling fraction LBF2 and a high boiling residue HBR

[0007] or

[0008] subjecting the high boiling fraction HBF to a thermal treatment after separating the first low boiling fraction LBF1 and the high boiling fraction HBF, whereby by said thermal treatment a second low boiling fraction LBF2' and a high boiling residue HBR' are obtained,

[0009] wherein the mixture of the first low boiling fraction LBF1 and the high boiling fraction HBF or the high boiling fraction HBF after separation of the first low boiling fraction LBF1 from the high boiling fraction HBF is heat treated in an inert atmosphere at a temperature in the range of about 350 °C to about 500 °C for about 1 min to about 240 min,

[0010] (iii) separating the first low boiling fraction LBF1 and the second low boiling fraction LBF2 from the high boiling residue HBR

[0011] or

[0012] separating the second low boiling fraction LBF2' from the high boiling residue HBR'.

[0013] The method according to the present application increases the yield of a low boiling fraction from pyrolysis oil. The low boiling fraction can then be used as a cracker feedstock from which olefins and aromatics can be produced by a cracking process. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 A method for increasing the yield of a low boiling fraction from pyrolysis oil according to a first embodiment of the present application is shown.

[0015] Figure 2 A method for increasing the yield of a low boiling fraction from pyrolysis oil according to a second embodiment of the present application is shown.

[0016] Figure 3 Results of SIMDIST measurements performed in Example 2 are shown.

[0017] Figure 4 Results of SIMDIST measurements performed in Example 4 are shown. DETAILED DESCRIPTION

[0018] The present application is further described below with reference to the examples and the accompanying drawings.

[0019] Definitions:

[0020] In the context of the present specification and the appended claims, the term "about" is construed as being accurate to the method used to measure it.

[0021] In the context of the present application, the term "combinations thereof includes one or more of the recited elements.

[0022] In the context of the present application, the term "mixtures thereof includes one or more of the recited elements.

[0023] In the context of the present invention, the term "pyrolysis" relates to the thermal decomposition or degradation of a feedstock, such as plastic waste, under inert conditions and produces a gaseous, liquid and solid char fraction. During pyrolysis, the feedstock is converted into a variety of chemicals, including gases, such as H2, C1 - C4-alkanes, C2 - C4-alkenes, acetylene, propyne, 1 -butyne, pyrolysis oil having a boiling temperature of about 25 °C to about 500 °C, and char. The term "pyrolysis" includes slow pyrolysis, fast pyrolysis, flash catalytic, and catalytic pyrolysis. These pyrolysis types differ in process temperature, heating rate, residence time, feedstock particle size, etc., resulting in different product qualities.

[0024] In the context of the present invention, the term "pyrolysis oil" is to be understood to mean any oil derived from the pyrolysis of a feedstock, such as plastic waste. Pyrolysis oil is obtained and / or obtainable from the pyrolysis of a feedstock, such as plastic waste, rubber waste, biological waste, and mixtures thereof. "Pyrolysis oil" comprises a mixture of low boiling point fractions and high boiling point fractions.

[0025] The term "pyrolysis gas" is to be understood in the context of the present invention to mean any gas derived from the pyrolysis of a feedstock. Pyrolysis gas is obtained and / or obtainable from the pyrolysis of a feedstock, such as plastic waste, mixed plastic waste, rubber waste, biological waste, and mixtures thereof.

[0026] The term "pyrolysis product" comprises "pyrolysis oil", "pyrolysis gas", and mixtures thereof.

[0027] "Initial boiling point" and "final boiling point" are determined at atmospheric pressure (1 atm, 1.013 bar) by the methods described in chapters 10 and 11 of ASTM D86-23.

[0028] In the context of the present invention, the term "plastic waste" also refers to any plastic material that is discarded after use, i.e. the plastic material has reached the end of its useful life and is considered waste after consumption. The plastic waste can be pure polymeric plastic waste, mixed plastic waste, or film waste, including dirt, adhesive material, fillers, residues, etc. The plastic waste can have a nitrogen content, a sulfur content, a halogen content, and optionally also a heavy metal content. The plastic waste can originate from any source of plastic-containing material.

[0029] The term "plastic waste" thus includes industrial and household plastic waste and includes waste tires as well as agricultural and horticultural plastic material. The term "plastic waste" also includes waste oil-based hydrocarbon material, such as waste motor oil, machine oil, grease, wax, etc.

[0030] Typically, the plastic waste is a mixture of different plastic materials, including hydrocarbon plastics, such as polyolefins like 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., such as chlorinated plastics, such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), etc., nitrogen-containing plastics, such as polyamides (PA), polyurethanes (PU), acrylonitrile-butadiene-styrene (ABS), etc., oxygen-containing plastics, such as polyesters (e.g. polyethylene terephthalate (PET), polycarbonate (PC), etc.), silicones and / or sulfur-bridge cross-linked rubbers. PET plastic waste is typically sorted out before pyrolysis, as PET has a profitable resale value. Thus, the plastic waste to be pyrolyzed typically contains less than about 10 wt.-%, preferably less than about 5 wt.-%, and most preferably essentially no PET plastic waste, based on the dry weight of the plastic materials.

[0031] Typically, the plastic materials contain additives, such as processing aids, plasticizers, flame retardants, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, antioxidants, etc. These additives can contain elements other than carbon and hydrogen. For example, the presence of bromine is mainly related to flame retardants. Heavy metal compounds can be used as light-resistant pigments and / or stabilizers in plastics. Cadmium, zinc and lead can be present in heat stabilizers and slip agents used in plastic manufacturing. The plastic waste can also contain residues. In the sense of the present invention, residues are contaminants adhering to the plastic waste. The additives and residues are typically 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 plastic.

[0032] Examples of rubber waste include scrap tires, rubber waste generated during manufacturing processes and discarded rubber-containing products such as latex examination gloves. Scrap tires contain additional components such as textiles and organic and inorganic additives, which can be separated from the rubber fraction of the scrap tires before pyrolysis.

[0033] Examples of biological waste include green waste, food waste, human excreta, manure, sewage, sewage sludge and slaughterhouse waste.

[0034] To obtain the pyrolysis oil according to the present application, the feedstock is added to the pyrolysis reactor using a metering unit, such as e.g. a screw or an extruder or a rotary valve or a pneumatic conveyor or a liquid injector. Optionally, the feedstock is preheated in e.g. a heat exchanger and / or subjected to a pre-pyrolysis at a temperature in the range of e.g. about 200 °C to about 360 °C before being added to the pyrolysis reactor. Subsequently, the feedstock is heated in the pyrolysis reactor to a temperature in the range of about 350 °C to about 900 °C, more preferably in the range of about 400 °C to about 550 °C and to a pressure in the range of about 0.5 bar to about 2 bar (abs), more preferably in the range of about 0.9 bar to about 1.5 bar (abs). The pyrolysis reactor is preferably selected from the group comprising a fluidized bed reactor, a moving bed reactor, an entrained flow reactor, a screw reactor, an extruder, a stirred tank reactor and a rotary kiln reactor. Preferably, the pyrolysis is carried out in the pyrolysis reactor under an inert atmosphere without oxygen or air.

[0035] Pyrolysis processes are known per se. They are described, for example, in EP 0713906 A1 and WO 95 / 03375 A1. Suitable pyrolysis oils are also commercially available. Pyrolysis oils are typically liquid at 15 °C or waxes at said temperature. "Liquid at 15 °C" means in the present application that the pyrolysis oil has a density of at most 1.3 g / ml at 15 °C and 1013 mbar, for example a density in the range of 0.65 to 0.98 g / ml, as determined according to DIN EN ISO 12185.

[0036] In the context of the present application, the short notation "cracking" includes steam cracking as well as catalytic cracking such as catalytic hydrocracking and fluidized catalytic cracking (FCC). In an analogous manner, the short notation "cracker" includes cracking reactors such as steam crackers, thermal crackers (i.e. thermal cracking in the absence of steam and catalyst) as well as catalytic cracking reactors such as catalytic hydrocracking reactors and fluidized catalytic cracking reactors.

[0037] Figure 1 A first embodiment of the process according to the present application is shown in Figure 1.

[0038] A pyrolysis oil (1) is provided. The pyrolysis oil (1) is manufactured by a pyrolysis reaction from a feedstock as described above, such as plastic waste, mixed plastic waste, rubber waste, textiles, biological waste, and mixtures thereof.

[0039] The pyrolysis oil (1) preferably has a heating value (measured according to DIN 51900) in the range of about 35 kJ / g to about 46 kJ / g and / or a bromine value (measured according to ASTM 1159) in the range of about 2 g Br2 / 100 g to about 160 g Br2 / 100 g.

[0040] The pyrolysis oil (1 ) obtained by the above pyrolysis reaction of the feedstock comprises a mixture of a first low-boiling fraction LBF1 and a high-boiling fraction HBF. The first low-boiling fraction LBF1 preferably has an initial boiling point of up to about 60 °C and a final boiling point of up to about 360 °C and / or comprises C6 - C 21 alkanes.

[0041] The high-boiling residue HBR preferably has a final boiling point of higher than 360 °C, preferably a final boiling point of up to about 700 °C and / or comprises C >21 alkanes, such as C 22 and C 22+ alkanes.

[0042] The pyrolysis oil (1 ) is then added to the apparatus (2) for thermal treatment of the pyrolysis oil (1 ) and subjected to thermal treatment (step (ii)).

[0043] The apparatus (2) for thermal treatment is preferably selected from the group consisting of an apparatus for thermal treatment in an inert atmosphere and an apparatus for thermal dehalogenation of the pyrolysis oil (1 ). The apparatus for thermal treatment in an inert atmosphere can be, for example, a heated section of a vessel or reactor or distillation column. The apparatus for thermal dehalogenation of the pyrolysis oil (1 ) can be, for example, a vessel or reactor or adsorber bed. An "inert atmosphere" (or "inert conditions") is defined herein as the apparatus for thermal treatment in an inert atmosphere comprising an inert gas or mixture of inert gases (such as nitrogen and / or argon) instead of air to suppress or prevent uncontrolled oxidation of organic matter inside the apparatus for thermal treatment in an inert atmosphere and / or hydrogen atmosphere.

[0044] The pyrolysis oil (1) comprising the mixture of the first low boiling fraction LBF1 and the high boiling fraction HBF is preferably heat treated in step (ii) in an inert atmosphere at a temperature in the range of about 350 °C to about 500 °C, more preferably in the range of about 380 °C to about 500 °C. The pyrolysis oil (1) comprising the mixture of the first low boiling fraction LBF1 and the high boiling fraction HBF is preferably heat treated in step (ii) in an inert atmosphere for about 1 min to about 240 min, more preferably for about 5 min to about 180 min and most preferably for about 10 min to about 120 min in an inert atmosphere. More preferably, the pyrolysis oil (1) comprising the mixture of the first low boiling fraction LBF1 and the high boiling fraction HBF is heat treated in an inert atmosphere at a temperature in the range of about 350 °C to about 500 °C for about 1 min to about 240 min. Most preferably, the high boiling fraction HBF is heat treated in step (ii) in an inert atmosphere at a temperature in the range of about 380 °C to about 500 °C for about 1 min to about 240 min. The heat treatment can be applied at atmospheric pressure (1.013 bar) or under reduced pressure or under elevated pressure.

[0045] The temperature ranges given above apply for the treatment at the specific temperature. In case the pyrolysis oil (1) is heated slowly to the final treatment temperature, the total time the pyrolysis oil (1) is subjected to such temperature ranges in total can be longer.

[0046] The pyrolysis oil (1) is converted by the heat treatment in step (ii) to a heat treated pyrolysis oil (3) which is then separated in step (iii) of the process according to the present application in the device (4) for separation. The heat treated pyrolysis oil (3) comprises a mixture of the first low boiling fraction LBF1, a second low boiling fraction LBF2 and a high boiling residue HBR, wherein the second low boiling fraction LBF2 comprises further low boiling hydrocarbons which are formed from the high boiling fraction HBF by the heat treatment of step (ii).

[0047] Thus, the yield of one or more low boiling fractions obtained from the pyrolysis oil is increased by the first embodiment of the process according to the present application. The combined low boiling fractions (6) comprising the first low boiling fraction LBF1 and the second low boiling fraction LBF2 are separated in the device (4) for separation from the high boiling residue HBR (5).

[0048] The second low boiling fraction LBF2 preferably has an initial boiling point of up to about 60 °C and a final boiling point of up to about 360 °C and / or comprises C6 - C 21 alkanes.

[0049] The combined low boiling fraction (6) comprising a first low boiling fraction LBF1 and a second low boiling fraction LBF2 preferably has a boiling point range of an initial boiling point of about 60 °C up to a final boiling point of about 360 °C and / or comprises C6 - C 21 alkanes.

[0050] The apparatus (4) for separation in step (iii) can be, for example, at least one distillation column, at least one thin-film evaporator or a combination thereof.

[0051] Optionally, the heat-treated pyrolysis oil (3) is subjected to distillation at elevated temperature to obtain a high boiling residue HBR (5) as a bottom product and a combined low boiling fraction (6) comprising a first low boiling fraction LBF1 and a second low boiling fraction LBF2 as a gaseous overhead product, which is condensed as a liquid product. Optionally, the high boiling residue HBR (5) is then subjected to at least one further distillation in at least one further distillation column to increase the yield of the combined low boiling fraction (6).

[0052] Preferably, the separation in step (iii) is carried out in a distillation column, wherein the heat-treated pyrolysis oil (3) is depleted into a high boiling residue HBR (5) obtained from the bottom of the distillation column and a combined low boiling fraction (6) comprising a first low boiling fraction LBF1 and a second low boiling fraction LBF2 obtained from the top of the at least one distillation column, for example in a condenser.

[0053] Preferably, the distillation in step (iii) is carried out at a temperature in the range of about 0 °C to about 600 °C, more preferably about 20 °C to about 400 °C, most preferably about 50 °C to about 360 °C (temperature range applies for 1.013 bar of atmospheric pressure). The respective operating pressure of the at least one distillation column preferably ranges from about 0.001 bar to about 4 bar (abs), more preferably from about 0.001 bar to about 0.98 bar (abs), most preferably from about 0.01 bar to about 0.05 bar (abs). In case of pressure ≠ 1.013 bar, the temperature is adjusted accordingly.

[0054] Preferably, the combined low boiling fraction (6) is obtained in one distillation column or a series of distillation columns, wherein a first distillation column is operated at a pressure of ≥ 0.98 bar (abs) to recover low boiling components, which otherwise can be difficult to recover at lower pressure. Optionally, a second distillation column is operated under reduced pressure ("vacuum distillation") to increase the yield of the desired combined low boiling fraction (6).

[0055] More preferably, the combination of temperature and pressure within the at least one distillation column is selected to obtain a combined low boiling fraction (6) having a final boiling point of ≤ 360 °C.

[0056] The amount of the combined low boiling fraction (6) comprising the first low boiling fraction LBF1 and the second low boiling fraction LBF2 obtained from step (iii) is greater than the amount of the first low boiling fraction LBF1 in the pyrolysis oil (1) obtained from the pyrolysis reaction of the feedstock.

[0057] Optionally, the combined low boiling fraction (6) comprising the first low boiling fraction LBF1 and the second low boiling fraction LBF2 is then converted into olefins and aromatic compounds in a cracking process in a cracker in step (iv)a.

[0058] The cracking process is preferably selected from the group comprising steam cracking, catalytic cracking and thermal cracking. Catalytic cracking comprises catalytic hydrocracking and fluid catalytic cracking. Thermal cracking comprises thermal cracking in the absence of steam and catalyst.

[0059] The combined low boiling fraction (6) comprising the first low boiling fraction LBF1 and the second low boiling fraction LBF2 is preferably converted into olefins and aromatic compounds in a steam cracker by steam cracking (step (iv)a). The combined low boiling fraction (6) is diluted with steam and heated briefly in the absence of oxygen in at least one steam-cracker furnace, which is part of the steam cracker. The temperature inside the at least one steam-cracker furnace is for example about 850 °C.

[0060] The olefins obtained by said cracking, preferably by steam-cracking, in optional step (iv)a comprise ethylene, propylene, butylenes, and butadiene. The aromatic compounds obtained by said thermal cracking, preferably by steam-cracking, in optional step (iv)a comprise benzene, toluene and xylene isomers.

[0061] Optionally, the high boiling residue HBR (5) is then subjected to further utilization in step (iv)b as feedstock, which utilization is selected from the group comprising partial oxidation, pyrolysis and incineration.

[0062] The partial oxidation in step (iv)b can be a thermal partial oxidation and / or a catalytic partial oxidation of the high boiling residue HBR (5) with an oxidizing agent such as air and / or oxygen. Preferably, during the partial oxidation, the molar ratio

[0063] The oxygen : oxygen required for complete oxidation of the high boiling residue HBR (5) ranges from 0.3 to < 1.

[0064] Among the partial oxidations, the thermal partial oxidation is preferred in case the sulfur content in the high boiling residue HBR (5) exceeds for example 50 ppm or exceeds 400 ppm.

[0065] Pyrolysis can be a pyrolysis reaction in a pyrolysis reactor as described in detail above. Therefore, in this further utilization in step (iv)b, the high-boiling-point residue HBR (5) is converted into pyrolysis oil, which can then optionally undergo the method according to the invention. The reaction conditions and reactor described above can also be used for the optional pyrolysis in step (iv)b. The high-boiling-point residue HBR (5) can be mixed with other suitable raw materials (e.g., plastic waste, mixed plastic waste, rubber waste, biological waste, and mixtures thereof) for the optional pyrolysis reaction in step (iv)b.

[0066] High-boiling-point residues (HBR) (5) can also be incinerated (“complete oxidation”) to obtain, for example, thermal energy.

[0067] Figure 2 A second embodiment of the method according to the present invention is shown in the figure.

[0068] Pyrolysis oil (11) is provided. Pyrolysis oil (11) is manufactured by a pyrolysis reaction from raw materials such as plastic waste, mixed plastic waste, rubber waste, biological waste, and mixtures thereof, as described above.

[0069] The pyrolysis oil (11) preferably has a calorific value of about 35 kJ / g to about 46 kJ / g (measured according to DIN 51900) and / or a bromine value of about 2 g Br2 / 100 g to about 160 g Br2 / 100 g (measured according to ASTM 1159).

[0070] The pyrolysis oil (11) obtained by the above-mentioned pyrolysis reaction of the raw materials comprises a mixture of the first low-boiling fraction LBF1 (14) and the high-boiling fraction HBF (13).

[0071] The first low-boiling fraction LBF1 preferably has an initial boiling point as low as about 60°C and a final boiling point as high as about 360°C and / or contains C6–C6. 21 Alkanes.

[0072] High-boiling-point residues (HBRs) preferably have a final boiling point above 360°C, more preferably above 360°C and up to about 700°C, and / or contain C. >21 Alkanes, such as C 22 and C 22+ Alkanes.

[0073] The first low-boiling fraction LBF1 (14) and the high-boiling fraction HBF (13) in the pyrolysis oil (11) are separated in a separation device (12).

[0074] The device (12) for separation can be, for example, at least one distillation column, at least one thin-film evaporator, or a combination thereof.

[0075] Preferably, the pyrolysis oil (11) is distilled at an elevated temperature to obtain a high-boiling fraction HBF (13) as the bottom product and a first low-boiling fraction LBF1 (14) as the gaseous top product, which is then condensed as a liquid product. Optionally, the high-boiling fraction HBF (13) is then subjected to at least one additional distillation / separation step in at least one additional distillation column to increase the yield of the desired first low-boiling fraction LBF1 (14).

[0076] Preferably, the separation in step (iii) is carried out in a distillation column, wherein the pyrolysis oil (11) is depleted into a high-boiling fraction HBF (13) obtained from the bottom of the distillation column and a first low-boiling fraction LBF1 (14) obtained from the top of at least one distillation column in, for example, a condenser.

[0077] Preferably, the distillation in step (iii) is carried out at a temperature ranging from about 0°C to about 600°C, more preferably from about 20°C to about 400°C, and most preferably from about 50°C to about 360°C (the temperature range applies to an atmospheric pressure of 1.013 bar). The corresponding operating pressure of at least one distillation column is preferably from about 0.001 bar to about 4 bar (absolute pressure), more preferably from about 0.001 bar to about 0.98 bar (absolute pressure), and most preferably from about 0.01 bar to about 0.05 bar (absolute pressure). When the pressure is ≠ 1.013 bar, the temperature is adjusted accordingly.

[0078] Preferably, the first low-boiling fraction LBF1 (14) is obtained in a distillation column or a series of distillation columns, wherein the first distillation column is operated at a pressure of ≥ 0.98 bar (absolute pressure) to recover the low-boiling components, which may otherwise be difficult to recover at lower pressures.

[0079] More preferably, a combination of temperature and pressure within at least one distillation column is selected to obtain a first low-boiling fraction LBF1 (14) having a final boiling point of ≤ 360°C.

[0080] The first low-boiling fraction LBF1 (14) is then preferably fed into a cracker and subjected thereto to a cracking process selected from the group consisting of steam cracking, catalytic cracking, and thermal cracking. Catalytic cracking includes catalytic hydrogenation cracking and fluidized bed catalytic cracking. Thermal cracking includes thermal cracking in the absence of steam and catalyst.

[0081] The high-boiling fraction HBR (13), which is separated as a bottom product in the separation apparatus (12), preferably in at least one distillation column, is then subjected to the heat treatment in step (ii) in the heat treatment apparatus (15).

[0082] The apparatus (15) for heat treatment is preferably selected from the group consisting of apparatus for heat treatment in an inert atmosphere and apparatus for thermal dehalogenation. The apparatus (15) for heat treatment in an inert atmosphere may be, for example, a vessel, a reactor, or at least one distillation column, preferably a heating section of at least one distillation column. The apparatus for thermal dehalogenation of the high-boiling fraction HBF (13) may be, for example, a vessel, a reactor, or an adsorber bed.

[0083] Preferably, the high-boiling-point fraction HBF (13) is heat-treated in step (ii) in an inert atmosphere at a temperature ranging from about 350°C to about 500°C, more preferably from about 380°C to about 500°C. Preferably, the high-boiling-point fraction HBF (13) is heat-treated in step (ii) in an inert atmosphere for about 1 min to about 240 min, more preferably for about 5 min to about 180 min, and most preferably for about 10 min to about 120 min. More preferably, the high-boiling-point fraction HBF (13) is heat-treated in step (ii) in an inert atmosphere at a temperature ranging from about 350°C to about 500°C for about 1 min to about 240 min. Most preferably, the high-boiling-point fraction HBF (13) is heat-treated in step (ii) in an inert atmosphere at a temperature ranging from about 380°C to about 500°C for about 1 min to about 240 min. Heat treatment can be applied at atmospheric pressure (1.013 bar) or under reduced or increased pressure.

[0084] The temperature ranges given above apply to processing at specific temperatures. In cases where, for example, the high-boiling-point fraction HBF (13) is slowly heated to the final processing temperature, the total time for the high-boiling-point fraction HBF (13) to be subjected to such a temperature range can be longer.

[0085] The high-boiling fraction HBF (13) is converted into the high-boiling residue HBR' (16) and the second low-boiling fraction LBF2' (17) by heat treatment in step (ii).

[0086] Next, the high-boiling-point residue HBR´ (16) and the second low-boiling-point fraction LBF2´ (17) are separated in the separation apparatus (15) in step (iii) of the method according to the invention.

[0087] The second low-boiling fraction LBF2' contains additional low-boiling hydrocarbons formed from the high-boiling fraction HBF by heat treatment in step (ii). The total amount of the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2' is preferably greater than the amount of the first low-boiling fraction LBF1. Therefore, the yield of one or more low-boiling fractions obtained from pyrolysis oil is increased by the second embodiment of the method according to the invention.

[0088] The second low-boiling fraction LBF2' preferably has an initial boiling point as low as about 60°C and a final boiling point as high as about 360°C, and / or contains C6 – C 21 Alkanes.

[0089] The high-boiling-point residue HBR´(16) preferably has a final boiling point above 360°C, more preferably above 360°C and up to about 700°C, and / or contains C >21 Alkanes, such as C 22 and C 22+ Alkanes.

[0090] The separation device (15) in step (iii) can be, for example, at least one distillation column and / or a thin-film evaporator. Optionally, if the heat treatment device (15) in step (ii) is at least one distillation column, preferably a heating section of at least one distillation column, the separation device (15) in step (iii) is also at least one distillation column. Optionally, in this aspect of the second embodiment of the invention, the same distillation column is used in steps (ii) and (iii).

[0091] The high-boiling fraction HBF (13) is then distilled at an elevated temperature to obtain a high-boiling residue HBR' (16) as the bottom product and a second low-boiling fraction LBF2' (17) as the gaseous top product, which is then condensed as a liquid product. Optionally, the high-boiling residue HBR' (16) is then subjected to at least one additional distillation / separation step in at least one additional distillation column to increase the yield of the desired low-boiling fraction.

[0092] Preferably, the separation in step (iii) is carried out in a distillation column, wherein the high-boiling fraction HBF (13) is depleted into a high-boiling residue HBR' (16) obtained from the bottom of the distillation column and a second low-boiling fraction LBF2' (17) obtained from the top of at least one distillation column in, for example, a condenser.

[0093] Preferably, the distillation in step (iii) is carried out at a temperature ranging from about 0°C to about 600°C, more preferably from about 20°C to about 400°C, and most preferably from about 50°C to about 360°C (the temperature range applies to an atmospheric pressure of 1.013 bar). The corresponding operating pressure of at least one distillation column is preferably from about 0.001 bar to about 4 bar (absolute pressure), more preferably from about 0.001 bar to about 0.98 bar (absolute pressure), and most preferably from about 0.01 bar to about 0.05 bar (absolute pressure). When the pressure is ≠ 1.013 bar, the temperature is adjusted accordingly.

[0094] Preferably, the second low-boiling fraction LBF2´(17) ​​is obtained in a distillation column or a series of distillation columns, wherein the first distillation column is operated at a pressure of ≥ 0.98 bar (absolute pressure) to recover the low-boiling components, which may otherwise be difficult to recover at lower pressures.

[0095] More preferably, a combination of temperature and pressure within at least one distillation column is selected to obtain a second low-boiling fraction LBF2´ (17) with a final boiling point of ≤ 360°C.

[0096] Optionally, the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2' are then mixed to form a combined low-boiling fraction LBF1+2'.

[0097] The combined low-boiling fraction LBF1+2' preferably has an initial boiling point as low as about 50°C and a final boiling point as high as about 360°C and / or contains C5 – C64. 20 hydrocarbon.

[0098] Optionally, the first low-boiling fraction LBF1 or the second low-boiling fraction LBF2' or the combined low-boiling fraction LBF1+2' is then converted into olefins and aromatic compounds in a cracker via the cracking process in step (vi)a.

[0099] The cracking process is preferably selected from the group consisting of steam cracking, catalytic cracking, and thermal cracking. Catalytic cracking includes catalytic hydrogenation cracking and fluidized bed catalytic cracking. Thermal cracking includes thermal cracking in the absence of steam and catalyst.

[0100] Preferably, the combined low-boiling fraction LBF1+2', comprising the first low-boiling fraction LBF1 (14) and the second low-boiling fraction LBF2' (17), is converted into olefins and aromatic compounds by steam cracking (step (vi)a) in a steam cracker. The combined low-boiling fraction is diluted with steam and briefly heated in the absence of oxygen in at least one steam-cracker furnace (which is part of a steam cracker). The temperature inside the at least one steam-cracker furnace is, for example, about 850°C.

[0101] The olefins obtained by the cracking in optional step (vi)a, preferably by steam cracking, include ethylene, propylene, butene, and butadiene. The aromatic compounds obtained by the thermal cracking in optional step (vi)a, preferably by steam cracking, include benzene, toluene, and xylene isomers.

[0102] Optionally, the high-boiling-point residue HBR´(16) is then further utilized as a feedstock in step (iv)b, the utilization being selected from the group consisting of partial oxidation, pyrolysis and incineration.

[0103] The partial oxidation in step (iv)b can be a thermal partial oxidation and / or catalytic partial oxidation of the high-boiling-point residue HBR´(16) using air and / or oxygen as the oxidant. Preferably, during partial oxidation, the molar ratio is...

[0104] Oxygen: The range of oxygen required for complete oxidation of the high-boiling-point residue HBR (5) is 0.3 to < 1.

[0105] In partial oxidation, thermal partial oxidation is preferred when the sulfur content in the high-boiling-point residue HBR´(16) exceeds, for example, 50 ppm or 400 ppm.

[0106] Pyrolysis can be a pyrolysis reaction in a pyrolysis reactor as described in detail above. Therefore, in this further utilization in step (iv)b, the high-boiling-point residue HBR'(16) is converted into pyrolysis oil, which can then optionally undergo the method according to the invention. The reaction conditions and reactor described above can also be used for the optional pyrolysis in step (iv)b. The high-boiling-point residue HBR'(16) can be mixed with other suitable raw materials (e.g., plastic waste, rubber waste, biological waste, and mixtures thereof) for the optional pyrolysis reaction in step (iv)b.

[0107] High-boiling-point residues HBR´(16) can also be subjected to incineration (“complete oxidation”) to obtain, for example, thermal energy.

[0108] The method according to the invention for increasing the yield of low-boiling fractions from pyrolysis oil may optionally include the following additional steps:

[0109] The following items, or chemical materials, which are obtainable or acquireable by the method according to the invention, are converted: the low-boiling fraction LBF1, the low-boiling fraction LBF2, the second low-boiling fraction LBF2', the high-boiling residue HBR, the high-boiling residue HBR', or any combination thereof; preferably the second low-boiling fraction LBF2' and / or the first low-boiling fraction LBF1 are converted, more preferably after combining the second low-boiling fraction LBF2' and the first low-boiling fraction LBF1; to obtain a monomer, polymer, or polymer product.

[0110] Preferably, the monomer is a diol or polyol; butanediol is preferred; aldehyde; formaldehyde is preferred; diisocyanate or polyisocyanate; methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) is preferred; amide; caprolactam is preferred; olefin; styrene, ethylene and norbornene are preferred; alkyne; (di) ester; methyl methacrylate is preferred; monoacid or diacid; adipic acid or terephthalic acid is preferred; diamine; hexamethylene diamine, nonadiamine is preferred; or sulfone; 4,4'-dichlorodiphenyl sulfone is preferred.

[0111] Preferably, the polymer and / or polymer product comprises polyamide (PA); preferably PA 6 and PA 66; a polyisocyanate addition polymer; preferably polyurethane (PU), thermoplastic polyurethane (TPU), polyurea or polyisocyanurate (PIR); low-density polyethylene (LDPE), high-density polyethylene (HDPE), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl acetate (PVA), polystyrene (PS), polyacrylonitrile-butadiene-styrene (ABS), polystyrene-acrylonitrile (SAN), polyacrylate-styrene-acrylonitrile (ASA), polytetrafluoroethylene (Teflon), poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), polybutadiene (BR, PBD), poly(cis-1,4-isoprene), poly(trans-1,4-) Isoprene, polyoxymethylene (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate (PBAT), polyester (PES), polyethersulfone (PESU), polyhydroxyalkanoate (PHA), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), polyhydroxyoctanoate (PHO), polylactic acid (PLA), polysulfone (PSU), polyphenylene sulfone (PPSU), polycarbonate (PC), polyetheretherketone (PEEK), poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); or copolymers or mixtures thereof.

[0112] Preferably, the polymer and / or polymer product is one or more of the following:

[0113] - Automotive parts, preferably cylinder head covers, engine hoods, turbocharger housings, turbocharger baffles, intake pipes, intake manifolds, connectors, gears, fan wheels, coolant tanks, heat exchanger housings or housing parts, coolant coolers, turbocharger coolers, thermostats, water pumps, radiators, fasteners or parts for electric vehicle battery systems, dashboards, steering column switches, seats, headrests, center consoles, transmission components, door modules, A, B, C or D pillar covers for automotive exteriors, spoilers, door handles, exterior mirrors, windshield wipers, windshield wiper protective housings, decorative grilles, cover strips, roof rails, window frames, sunroof frames, antenna panels, headlights and taillights, engine hoods, cylinder head covers, intake manifolds, airbags or buffer pads;

[0114] - Fabric, preferably shirts, trousers, sweaters, boots, shoes, shoe soles, bodysuits or jackets;

[0115] - Electrical components, preferably electrical or electronic passive or active components, printed circuit boards, printed circuit boards, housing components, foil, wire, switches, plugs, sockets, distributors, relays, resistors, capacitors, inductors, spools, lamps, diodes, LEDs, transistors, connectors, voltage regulators, integrated circuits (ICs), processors, controllers, memory, sensors, connectors, microswitches, micro buttons, semiconductors, reflector housings for light-emitting diodes (LEDs), fasteners, gaskets, bolts, strips, slide-in guides, screws, nuts, membrane hinges, spring hooks (snap-in type) or spring tongues;

[0116] - Consumer goods and / or pharmaceutical products, preferably tennis strings, climbing ropes, bristles, brushes, artificial turf, 3D printed filaments, lawnmowers, zippers, hook and loop fasteners, paper machine fabrics, extrusion coatings, fishing lines, fishing nets, offshore lines and ropes, vials, syringes, ampoules, bottles, sliding elements, spindle nuts, chain conveyors, sliding bearings, rollers, wheels, gears, ring gears, screws and spring dampers, hoses, pipes, cable sheaths, sockets, switches, cable ties, fan wheels, carpets, cosmetic boxes or bottles, mattresses, cushions or insulating materials; or

[0117] Packaging for the food industry; preferably single or multi-layer blown film, cast film (single or multi-layer), biaxial stretch film, or laminated film.

[0118] Preferably, the content of pyrolysis oil in the monomer, polymer, and / or polymer product is 1% by weight or more, preferably 2% by weight or more, more preferably 5% by weight or more, more preferably 15% by weight or more, more preferably 30% by weight or more, more preferably 40% by weight or more, more preferably 60% by weight or more, more preferably 80% by weight or more, more preferably 90% by weight or more, more preferably 95% by weight or more; and / or

[0119] The content of pyrolysis oil in the monomer, polymer and / or polymer product is 100% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, more preferably 50% by weight or less, more preferably 25% by weight or less, more preferably 10% by weight or less; and more preferably, this content is determined based on identity preservation and / or segregation and / or quality balance and / or book and claims custody model, preferably based on quality balance, preferably based on the International Sustainability and Carbon Certification (ISCC) standard.

[0120] The conversion steps to obtain monomers, polymers, or polymer products may include one or more synthetic steps and may be performed by conventional synthesis and techniques well known to those skilled in the art. Regardless of whether the conversion steps are performed by those skilled in the art who evaluate the novelty and inventive step of the independent claim, those skilled in the art who perform the conversion steps are from the technical fields of pyrolysis, vaporization, remonomerization, depolymerization, and / or synthesis and / or production of monomers, polymers, and polymer compounds, and their further processing (e.g., extrusion, injection molding). Examples of conversion steps are described in the following titles: “Industrial Organic Chemistry”, Volume 3, Wiley-VCH, 1997; ISBN: 978-3-527-28838-0; “Kunststoffhandbuch”, Volume 11, Subvolume 17, Carl Hanser Verlag, especially Volume 6, “Polyamide”, 1st edition, 1966; Volume 7, “Polyurethane”, 3rd edition, 1993; and Volume 8, “Polyester”, 1st edition, 1973; “Industrial Organic Chemistry”, Volume 3, Wiley-VCH, 1997; ISBN: 978-3-527-28838-0; "Injection Molding Reference Guide", 4th Edition, CreateSpace Independent Publishing Platform, 2011, ISBN: 978-1466407824; EP0989146 (A1), EP 1460094 (A1), WO 2006034800 (A1), EP1529792 (A1), WO 2006042674 (A1), EP 0364854 (A2), US 5506275 (A), EP 0897402 (A1), WO 2015082316 (A1), WO2021021855 (A1), WO 2021126938 (A1), WO 2021021902 (A1), WO 2021092311 (A1), WO2008155271 (A1), WO 2013139827 (A1).

[0121] A combined low-boiling-point fraction comprising a) one of a first low-boiling-point fraction LBF1 and a second low-boiling-point fraction LBF2, b) a second low-boiling-point fraction LBF2', and c) a combined low-boiling-point fraction LBF1'+2' can be used as a cracker feedstock, i.e., a feedstock suitable for producing olefins and aromatic compounds via a thermal cracking process, wherein the cracking process is preferably selected from the group consisting of steam cracking, catalytic cracking, and thermal cracking. Catalytic cracking includes catalytic hydrogenation cracking and fluidized bed catalytic cracking. Thermal cracking includes thermal cracking in the absence of steam and catalyst. The cracker feedstock, or a portion thereof, is produced using a method according to the invention for increasing the yield of low-boiling-point fractions from pyrolysis oil.

[0122] The cracker feedstock comprising one of a) a first low-boiling fraction LBF1 and a second low-boiling fraction LBF2, b) a second low-boiling fraction LBF2', and c) a combined low-boiling fraction LBF1'+2', optionally further comprises petroleum naphtha and / or bio-naphtha, such as 1 wt.-% to 99 wt.-% petroleum naphtha and / or bio-naphtha, or 10 wt.-% petroleum naphtha and / or bio-naphtha, or 20 wt.-% petroleum naphtha and / or bio-naphtha, or 30 wt.-% petroleum naphtha and / or bio-naphtha, or 40 wt.-% petroleum naphtha and / or bio-naphtha, or 50 wt.-% petroleum naphtha and / or bio-naphtha, or 60 wt.-% petroleum naphtha and / or bio-naphtha, or 70 wt.-% petroleum naphtha and / or bio-naphtha. wt.-% petroleum naphtha and / or bio-naphtha or 80 wt.-% petroleum naphtha and / or bio-naphtha or 90 wt.-% petroleum naphtha and / or bio-naphtha.

[0123] Petroleum naphtha is obtained from the refining of fossil sources such as crude oil, and contains hydrocarbons and preferably has a boiling point range of from an initial boiling point as low as about 30°C to a final boiling point as high as about 220°C, more preferably having an initial boiling point as low as about 120°C and a final boiling point as high as about 220°C. Petroleum naphtha can also be produced, for example, from other feedstocks such as coal tar, shale sediments, and tar sands.

[0124] Bio-naphtha can be obtained, for example, through the hydrogenation of renewable resources (such as oils and / or fats).

[0125] The cracker feedstock comprising one of a) a first low-boiling point fraction LBF1 and a second low-boiling point fraction LBF2, b) a second low-boiling point fraction LBF2', and c) a combined low-boiling point fraction LBF1'+2' may optionally further comprise at least one other pyrolysis oil and / or fraction thereof, such as 1 wt.-% to 99 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 10 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 20 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 30 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 40 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 50 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 60 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 70 wt.-% of at least one other pyrolysis oil and / or fraction thereof, or 80 wt.-% of at least one other pyrolysis oil and / or fraction thereof. wt.-% of at least one other pyrolysis oil and / or its fraction or 90 wt.-% of at least one other pyrolysis oil and / or its fraction.

[0126] Other pyrolysis oils refer to pyrolysis oils other than those provided in step (i), for example, as produced in another batch and / or from another raw material and / or under other pyrolysis reaction conditions.

[0127] Therefore, the pyrolysis feedstock may further include at least one of petroleum naphtha, bio-naphtha, other pyrolysis oils, and low-boiling fractions of other pyrolysis oils.

[0128] The combined low-boiling fractions comprising the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2, the second low-boiling fraction LBF2', the combined low-boiling fractions LBF1'+2', olefins and aromatic compounds produced therefrom by a cracking process, the high-boiling residue HBR, the high-boiling residue HBR', and products or fractions thereof produced therefrom by partial oxidation, pyrolysis and separation of aromatic compounds are recycled products.

[0129] The weight or fraction of each of the recycled products attributable to the pyrolysis oil provided in step (i) or the raw material for producing the pyrolysis oil provided in step (i) is determined by mass balance.

[0130] Optionally, the weight or fraction of the recycled products attributable to the pyrolysis oil provided in step (i) or the raw material for manufacturing the pyrolysis oil provided in step (i) is determined by mass balance, and one or more recycled products are certified as recycled in accordance with the International Sustainability and Carbon Certification (ISCC) standards.

[0131] The present invention will be further explained through the following non-limiting examples. Example

[0132] Example 1

[0133] Pyrolysis oil obtained from scrap tires via a pyrolysis reaction is provided. The pyrolysis oil is then separated into a high-boiling fraction HBF and a first low-boiling fraction LBF1 in a thin-film evaporator at 200°C and 30 mbar. The first low-boiling fraction LBF1 obtained in this separation step has a final boiling point of 310°C. The high-boiling fraction HBF has a final boiling point > 500°C. The final boiling point is determined by the method described in ASTM-D86 and is therefore applicable to a pressure of 1 atm (1.013 bar).

[0134] Example 2

[0135] The high-boiling-point fraction HBF obtained in Example 1 is then subjected to heat treatment in the heating section of the distillation unit (step (ii)). For practical reasons, the heat treatment according to step (ii) is carried out in two separate steps (referred to as "first heat treatment" and "second heat treatment" respectively).

[0136] First, during step (ii), the high-boiling-point fraction HBF is heated from ambient temperature to 400°C over 1.1 h (“first part of heat treatment”). A first portion of the second low-boiling-point fraction LBF2” is obtained and separated from the high-boiling-point fraction HBF. Next, the remaining portion of the high-boiling-point fraction HBF is heated from 400°C to 480°C over 1.2 h (“second part of heat treatment”), and a second portion of the low-boiling-point fraction LBF2” and the high-boiling-point residue HBR” are obtained, and the second portion of the low-boiling-point fraction LBF2” is separated from the high-boiling-point residue HBR”.

[0137] The equipment used for heat treatment (step (ii)) in Example 2 does not have a cooling trap. Therefore, the volatile portion of the second low-boiling fraction LBF2' formed during the "first part of heat treatment" and "second part of heat treatment" is not collected during heat treatment. Their yield is calculated by subtracting the weight of the first portion of the second low-boiling fraction LBF2', the second portion of the second low-boiling fraction LBF2', and the weight of the high-boiling residue HBR' from the initial weight of the high-boiling fraction HBF used in Example 2.

[0138] The total weight of the low-boiling-point fraction LBF2' is the sum of the weights of the first portion of the second low-boiling-point fraction LBF2', the second portion of the second low-boiling-point fraction LBF2', and the volatile portion of the second low-boiling-point fraction LBF2'.

[0139] The first part of the heat treatment (step (ii)) begins with 150.9 g of the high-boiling-point fraction HBF. The first part of the heat treatment (step (ii)) produces a first portion of 12.3 g of the second low-boiling-point fraction LBF2', and the second part of the heat treatment produces a second portion of 8.8 g of the second low-boiling-point fraction LBF2'. The yield of the volatile portion of the second low-boiling-point fraction LBF2' is then calculated to be 11.6 g as described above. Therefore, according to the heat treatment in step (ii), 32.7 g of the second low-boiling-point fraction LBF2' is produced from 150.0 g of the high-boiling-point fraction HBF. The yield of the desired low-boiling-point fraction obtained by the method according to the invention is 21.7%.

[0140] The high-boiling fraction HBF, the first portion of the second low-boiling fraction LBF2', and the second portion of the second low-boiling fraction LBF2' were subjected to SIMDIST (simulated distillation) measurements according to EN 15199-1-3 (better suited for samples with a final boiling point above 500°C, for the high-boiling fraction HBF) and ASTM D7213 (better suited for samples with a final boiling point below 500°C, for the first portion of the second low-boiling fraction LBF2' and the second portion of the second low-boiling fraction LBF2'), respectively. Both standards were based on retention time calibration of the boiling point using alkane standards. Measurements were performed using an Agilent dual-tower gas chromatograph with a PAC SIMDIST UPTO C120 system. The results of these measurements are shown in... Figure 3 middle.

[0141] The solid line represents the high-boiling fraction HBF with an initial boiling point of 242.5°C. The dashed line represents the first portion of the second low-boiling fraction LBF2', of which 17.6% of the first portion (corresponding to 12.3 g of the first portion of the second low-boiling fraction LBF2') has a final boiling point below 242.5°C. The dotted line represents the second portion of the second low-boiling fraction LBF2', of which 15.7% of the second portion (corresponding to 8.8 g of the second portion of the second low-boiling fraction LBF2') has a final boiling point below 242.5°C.

[0142] Example 3

[0143] A pyrolysis oil obtained from a mixture of waste plastics via a pyrolysis reaction is provided. The pyrolysis oil is then separated into a high-boiling fraction HBF and a first low-boiling fraction LBF1 in a thin-film evaporator at 200°C and 30 mbar. The first low-boiling fraction LBF1 obtained in this separation step has a final boiling point of 310°C. The high-boiling fraction HBF has a final boiling point > 500°C. The final boiling point is determined by the method described in ASTM-D86 and is therefore applicable to a pressure of 1 atm.

[0144] Example 4

[0145] The high-boiling-point fraction HBF obtained in Example 3 is then subjected to heat treatment in the heating section of the distillation unit (step (ii)). For practical reasons, the heat treatment according to step (ii) is carried out in two separate steps (referred to as "first heat treatment" and "second heat treatment" respectively).

[0146] First, during step (ii), the high-boiling-point residue HBF is heated from ambient temperature to 400°C over 1.3 h (“First Part of Heat Treatment”). A first portion of the second low-boiling-point fraction LBF2” is obtained and separated from the high-boiling-point residue HBF. Next, the remaining portion of the high-boiling-point fraction HBF is heated from 400°C to 480°C over 2.4 h (“Second Part of Heat Treatment”), and a second portion of the low-boiling-point fraction LBF2” and the high-boiling-point residue HBR” are obtained, and the second portion of the low-boiling-point fraction LBF2” is separated from the high-boiling-point residue. The volatile portion of the second low-boiling-point fraction LBF2” formed during “First Part of Heat Treatment” and “Second Part of Heat Treatment” is collected in a cooling trap.

[0147] The first part of the heat treatment begins with 260 g of the high-boiling-point fraction HBF. In the cooling trap, the first part of the heat treatment produces 21.0 g of the first portion of the second low-boiling-point fraction LBF2', and the second part of the heat treatment produces 14.5 g of the second portion of the second low-boiling-point fraction LBF2' and 9.7 g of the volatile portion of the second low-boiling-point fraction LBF2'. Therefore, according to step (ii), the heat treatment yields 45.2 g of the second low-boiling-point fraction LBF2' from 260.0 g of the high-boiling-point fraction HBF. The yield of the desired low-boiling-point fraction obtained by the method according to the invention is equal to 17.4%.

[0148] For the SIMDIST measurement, the same equipment and measurement parameters as described in Example 2 were applied, and the results are shown below. Figure 4The solid line represents the high-boiling fraction HBF with an initial boiling point of 230°C. The dashed line (short dashed line) represents the first portion of the second low-boiling fraction LBF2', of which 23.3% of the first portion (corresponding to 21.0 g of the first portion of the second low-boiling fraction LBF2') has a final boiling point below 230°C. The dotted line represents the second portion of the second low-boiling fraction LBF2', of which 16.7% of the second portion (corresponding to 14.5 g of the second portion of the second low-boiling fraction LBF2') has a final boiling point below 230°C. The dashed line (long dashed line) represents the volatile portion of the second low-boiling fraction LBF2', of which 96.7% of the volatile portion (corresponding to 9.7 g of the volatile portion of the second low-boiling fraction LBF2') has a final boiling point below 233°C.

Claims

1. A method for increasing the yield of low-boiling-point fractions from pyrolysis oil, the method comprising the following steps: (i) Providing a pyrolysis oil produced by the pyrolysis reaction of a feedstock, wherein the pyrolysis oil comprises a mixture of a first low-boiling fraction LBF1 and a high-boiling fraction HBF. (ii) subjecting a mixture of the first low-boiling fraction LBF1 and the high-boiling fraction HBF to heat treatment, thereby obtaining the first low-boiling fraction LBF1, the second low-boiling fraction LBF2, and the high-boiling residue HBR by said heat treatment. or After separating the first low-boiling fraction LBF1 and the high-boiling fraction HBF, the high-boiling fraction HBF is subjected to heat treatment, thereby obtaining a second low-boiling fraction LBF2' and a high-boiling residue HBR' through the heat treatment. The mixture of the first low-boiling fraction LBF1 and the high-boiling fraction HBF, or after separating the first low-boiling fraction LBF1 from the high-boiling fraction HBF, is heat-treated in an inert atmosphere at a temperature ranging from about 350°C to about 500°C for about 1 min to about 240 min. (iii) Separate the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2 from the high-boiling residue HBR. or The second low-boiling fraction LBF2´ was separated from the high-boiling residue HBR´.

2. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to claim 1, wherein, The raw material is selected from the group including: plastic waste, mixed plastic waste, rubber waste, biological waste, and mixtures thereof.

3. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 and 2, wherein, The heat treatment in step (ii) is selected from the group consisting of: heat treatment in an inert atmosphere and thermal dehalogenation.

4. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 to 3, wherein, In step (ii), the amount of the second low-boiling fraction LBF2 or the second low-boiling fraction LBF2' increases, and in step (ii), the amount of the high-boiling fraction HBF decreases.

5. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 to 4, wherein, Step (iii) is a distillation process, provided that the heat treatment in step (ii) is a heat treatment in an inert atmosphere or a thermal dehalogenation process.

6. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 to 5, wherein, Step (iii) is a separation process using at least one distillation column, provided that the first heat treatment in step (ii) is a distillation process using at least one distillation column, and wherein the at least one distillation column used in step (ii) and the at least one distillation column used in step (iii) are optionally the same.

7. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 to 6, the method further comprising one or more of the following steps: (iv)a The low-boiling fraction LBF1 and the low-boiling fraction LBF2 are converted into olefins and aromatic compounds by thermal cracking process, or optionally, after the second low-boiling fraction LBF2' and the first low-boiling fraction LBF1 are combined. and / or (iv)b subjecting the high-boiling-point residue HBR or the high-boiling-point residue HBR´ to further utilization.

8. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to claim 7, wherein, The pyrolysis process is selected from the group consisting of steam pyrolysis, catalytic pyrolysis, and thermal pyrolysis.

9. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 7 and 8, wherein, The further utilization is selected from the group consisting of partial oxidation, pyrolysis and incineration.

10. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 to 9, wherein, The first low-boiling fraction LBF1 has a boiling point range from an initial boiling point as low as about 60°C to a final boiling point as high as about 360°C and / or contains C6–C6. 21 Alkanes, and / or the second low-boiling fraction LBF2 having an initial boiling point as low as about 60°C and a final boiling point as high as about 360°C and / or containing C6–C6+. 21 Alkanes, and / or the second low-boiling fraction LBF2' having an initial boiling point as low as about 60°C and a final boiling point as high as about 360°C and / or containing C6–C6+. 21 Alkanes.

11. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 to 10, wherein, The pyrolysis oil provided in step (i) has a calorific value of about 35 kJ / g to about 46 kJ / g (measured according to DIN 51900) and / or a bromine value of about 2 g Br2 / 100 g to about 160 g Br2 / 100 g (measured according to ASTM 1159).

12. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 1 to 11, the method comprising the additional step of: The following items, or chemical materials, that are obtainable or acquireable by the method according to any one of claims 1 to 13, are converted: the low-boiling fraction LBF1, the low-boiling fraction LBF2, the second low-boiling fraction LBF2', the high-boiling residue HBR, the high-boiling residue HBR', or any combination thereof; preferably the second low-boiling fraction LBF2' and / or the first low-boiling fraction LBF1 are converted, more preferably after combining the second low-boiling fraction LBF2' and the first low-boiling fraction LBF1; to obtain a monomer, polymer, or polymer product.

13. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to claim 12, wherein, The monomer is a diol or polyol; preferably butanediol; an aldehyde; preferably formaldehyde; a diisocyanate or polyisocyanate; preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI); an amide; preferably caprolactam; an olefin; preferably styrene, ethylene and norbornene; an alkyne; a (di) ester; preferably methyl methacrylate; a monoacid or diacid; preferably adipic acid or terephthalic acid; a diamine; preferably hexamethylenediamine, nonadiamine; or a sulfone; preferably 4,4'-dichlorodiphenyl sulfone.

14. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 12 to 13, wherein, The polymer and / or the polymer product contains polyamide (PA); preferably PA 6 and PA 66; a polyisocyanate addition polymer; preferably polyurethane (PU), thermoplastic polyurethane (TPU), polyurea or polyisocyanurate (PIR); low-density polyethylene (LDPE), high-density polyethylene (HDPE), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl acetate (PVA), polystyrene (PS), polyacrylonitrile-butadiene-styrene (ABS), polystyrene-acrylonitrile (SAN), polyacrylate-styrene-acrylonitrile (ASA), polytetrafluoroethylene (Teflon), poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), polybutadiene (BR, PBD), poly(cis-1,4-isoprene), poly(trans-1,4-) Isoprene, polyoxymethylene (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate (PBAT), polyester (PES), polyethersulfone (PESU), polyhydroxyalkanoate (PHA), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), polyhydroxyoctanoate (PHO), polylactic acid (PLA), polysulfone (PSU), polyphenylene sulfone (PPSU), polycarbonate (PC), polyetheretherketone (PEEK), poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); or copolymers or mixtures thereof.

15. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 12 to 14, wherein, The polymer and / or the polymer product is one or more of the following: - Automotive parts, preferably cylinder head covers, engine hoods, turbocharger housings, turbocharger baffles, intake pipes, intake manifolds, connectors, gears, fan wheels, coolant tanks, heat exchanger housings or housing parts, coolant coolers, turbocharger coolers, thermostats, water pumps, radiators, fasteners or parts for electric vehicle battery systems, dashboards, steering column switches, seats, headrests, center consoles, transmission components, door modules, A, B, C or D pillar covers for automotive exteriors, spoilers, door handles, exterior mirrors, windshield wipers, windshield wiper protective housings, decorative grilles, cover strips, roof rails, window frames, sunroof frames, antenna panels, headlights and taillights, engine hoods, cylinder head covers, intake manifolds, airbags or buffer pads; - Fabric, preferably shirts, trousers, sweaters, boots, shoes, shoe soles, bodysuits or jackets; - Electrical components, preferably electrical or electronic passive or active components, printed circuit boards, printed circuit boards, housing components, foil, wire, switches, plugs, sockets, distributors, relays, resistors, capacitors, inductors, spools, lamps, diodes, LEDs, transistors, connectors, voltage regulators, integrated circuits (ICs), processors, controllers, memory, sensors, connectors, microswitches, micro buttons, semiconductors, reflector housings for light-emitting diodes (LEDs), fasteners, gaskets, bolts, strips, slide-in guides, screws, nuts, membrane hinges, spring hooks (snap-in type) or spring tongues; - Consumer goods and / or pharmaceutical products, preferably tennis strings, climbing ropes, bristles, brushes, artificial turf, 3D printed filaments, lawnmowers, zippers, hook and loop fasteners, paper machine fabrics, extrusion coatings, fishing lines, fishing nets, offshore lines and ropes, vials, syringes, ampoules, bottles, sliding elements, spindle nuts, chain conveyors, sliding bearings, rollers, wheels, gears, ring gears, screws and spring dampers, hoses, pipes, cable sheaths, sockets, switches, cable ties, fan wheels, carpets, cosmetic boxes or bottles, mattresses, cushions or insulating materials; or Packaging for the food industry; preferably single or multi-layer blown film, cast film (single or multi-layer), biaxial stretch film, or laminated film.

16. The method for increasing the yield of low-boiling fractions from pyrolysis oil according to any one of claims 12 to 15, wherein, The content of the pyrolysis oil in the monomer, polymer, and / or polymer product is 1% by weight or more, preferably 2% by weight or more, more preferably 5% by weight or more, more preferably 15% by weight or more, more preferably 30% by weight or more, more preferably 40% by weight or more, more preferably 60% by weight or more, more preferably 80% by weight or more, more preferably 90% by weight or more, more preferably 95% by weight or more; and / or The content of the pyrolysis oil in the monomer, polymer, and / or polymer product is 100% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, more preferably 50% by weight or less, more preferably 25% by weight or less, and more preferably 10% by weight or less; and Preferably, the content is determined based on an identity preservation and / or segregation and / or quality balance and / or book and claims custody model, preferably based on quality balance, and preferably based on the International Sustainability and Carbon Certification (ISCC) standard.

17. A pyrolysis feedstock selected from the group consisting of a combined low-boiling fraction comprising the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2, the second low-boiling fraction LBF2' and the combined low-boiling fraction LBF1'+2', the pyrolysis feedstock being produced by a method according to any one of claims 1 to 11 for increasing the yield of low-boiling fractions from pyrolysis oil.

18. The pyrolysis feedstock according to claim 17, further comprising at least one of petroleum naphtha, bio-naphtha, other pyrolysis oils, and low-boiling fractions of other pyrolysis oils.

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