EP4713415A1

EP4713415A1 - Method for increasing the low-boiling fraction yield from pyrolysis oils and cracker feedstock

Info

Publication number: EP4713415A1
Application number: EP24726552.3A
Authority: EP
Inventors: Gisela Hieber; Armin Lange De Oliveira; Steffen Mueller; Oliver PILARSKI; Daniel KOEPKE; Monica Haag; Mathias Feyen; Michael Schreiber; Andreas Melzer; Hina QAMMAR; Juergen Jose VARGAS SCHMITZ
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-05-16
Filing date: 2024-05-07
Publication date: 2026-03-25
Also published as: KR20260009929A; WO2024235732A1; CN121335964A

Abstract

The present invention concerns a method for increasing the low-boiling fraction yield from pyrolysis oils in which the pyrolysis oil or a high-boiling fraction obtained thereof is thermally treated to yield an additional low-boiling fraction. A high-boiling residue is also obtained by the thermal treatment. The thermal treatment is preferably conducted at a temperature the range of about 350 °C to about 500 °C in an inert atmosphere. The additional low-boiling fraction is then separated from the high-boiling residue. The additional low-boiling fraction gained is suitable as a feedstock for cracking to produce (light) olefins and aromatics. The high-boiling residue can be further utilized to a partial oxidation, pyrolysis, or incineration.

Description

METHOD FOR INCREASING THE LOW-BOILING FRACTION YIELD FROM PYROLYSIS OILS AND CRACKER FEEDSTOCK

Technical area

The present invention relates to a method for increasing the low-boiling fraction yield from pyrolysis oils produced by a pyrolysis reaction of a feedstock.

Background of the invention

Pyrolysis oil made from feedstocks such as plastic waste is utilized as a source for base chemicals such as light olefins, aromatics, and syngas. Light olefins and aromatics can be made by cracking processes such as steam cracking of low-boiling fractions 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 a cracker feedstock for said cracking. The low- boiling fraction yield of a pyrolysis depends on various variables such as the type of feedstocks used for the pyrolysis reaction, the pyrolysis reaction parameters, and the upgrading of the pyrolysis oil. The low-boiling fraction comprises for example Ce - C21 alkanes and is obtained for example with a yield of only 35 wt.-% based on the overall weight of the pyrolysis oil which is often limiting the use of such cracker feedstocks in comparison with fossil-based cracker feedstocks such as naphtha.

Accordingly, it is the objective of the present invention to increase the yield of the low-boiling fraction obtained from pyrolysis oils which are suitable as a feedstock for the manufacture of olefins and aromatics by cracking.

Summary of the invention

This problem is solved by a method for increasing the low-boiling fraction yield from pyrolysis oils comprising the steps

(i) providing a pyrolysis oil manufactured 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,

(ii) subjecting to a thermal treatment: the mixture of the first low-boiling fraction LBF1 and the high-boiling fraction HBF whereby the first low-boiling fraction LBF1 , a second low-boiling fraction LBF2 and a high-boiling residue HBR are obtained by said thermal treatment or the high-boiling fraction HBF, after separation of the first low-boiling fraction LBF1 and the high-boiling fraction HBF, whereby a second low-boiling fraction LBF2' and a high-boiling residue HBR' are obtained by said thermal treatment, wherein the mixture of the first low-boiling fraction LBF1 and the high-boiling fraction HBF or the high-boiling fraction HBF after separating the first low-boiling fraction LBF1 from said high-boiling fraction HBF is thermally treated at a temperature in the range of about 350 °C to about 500 °C in an inert atmosphere for about 1 min to about 240 min, (iii) separating the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2 from the high-boiling residue HBR or separating the second low-boiling fraction LBF2' from the high-boiling residue HBR'.

The method according to the present invention increases the yield of low-boiling fractions from pyrolysis oil. The low- boiling fractions can then be used as cracker feedstock from which olefins and aromatics can be produced by a cracking process.

Figures

Figure 1 shows a method for increasing the yield of low-boiling fraction from pyrolysis oils according to a first embodiment of the present invention.

Figure 2 shows a method for increasing the yield of low-boiling fraction from pyrolysis oils according to a second embodiment of the present invention.

Figure 3 shows the results of SIMDIST measurements made in Example 2. Figure 4 shows the results of SIMDIST measurements made in Example 4.

Detailed description of the invention

The present invention is further described below with reference to the embodiments and figures.

Definitions:

In the context of the present description and the accompanying claims, the term "about” is interpreted as being as accurate as the method used to measure it.

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.

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 into a great variety of chemicals including gases such as H2, Ci - C4- alkanes, C2 - C4-alkenes, ethyne, 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 catalysis and catalytic pyrolysis. These pyrolysis types differ regarding process temperature, heating rate, residence time, feed particle size, etc. resulting in different product quality. In the context of the present invention, the term "pyrolysis oil” is understood to mean any oil originating from the pyrolysis of feedstocks such as plastic waste. The pyrolysis oil is obtained and/or obtainable from pyrolysis of feedstocks such as plastic waste, rubber waste, bio waste and mixtures thereof. A "pyrolysis oil” comprises a mixture of a low-boiling fraction and a high-boiling fraction.

The term "pyrolysis gas” is in the context of the present invention is understood to mean any gas originating from the pyrolysis of a feedstock. The pyrolysis gas is obtained and/or obtainable from pyrolysis of feedstocks such as plastic waste, mixed plastic waste, rubber waste, bio waste and mixtures thereof.

The term "pyrolysis product” comprises "pyrolysis oil”, "pyrolysis gas” and mixtures thereof.

The "initial boiling point” and the "final boiling point” are determined by the method described in ASTM D86-23, chapter 10 and 11, at atmospheric pressure (1 atm, 1.013 bar).

In the context of the present invention, the term "plastic waste” also 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 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.

Accordingly, the term "plastic waste” includes industrial and domestic plastic waste and including used tires and agricultural and horticultural plastic material. The term "plastic waste” also includes used petroleum-based hydrocarbon material such as used motor oil, machine oil, greases, waxes, etc.

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., oxygen-containing plastics such as polyesters, e.g., polyethylene terephthalate (PET), polycarbonate (PC), etc.), silicones and/or sulfur bridges crosslinked rubbers. PET plastic waste is often sorted out before pyrolysis since PET has a profitable resale value. Accordingly, the plastic waste to be pyrolyzed often contains less than about 10 wt.-%, preferably less than about 5 wt.-% and most preferably substantially no PET based plastic waste on the dry weight of the plastic material.

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.

Examples of rubber waste include end-of-life tires, rubber waste produced during manufacturing processes and discarded rubber containing products such as latex examining gloves. 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.

Examples of bio waste include green waste, food waste, human waste, manure, sewage, sewage sludge and slaughterhouse waste.

To obtain the pyrolysis oil according to the present invention, the feedstock is inserted into a pyrolysis reactor using a dosing unit such as for example 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 about 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 about 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.

In the context of the present invention, the abbreviated notation "cracking” includes steam cracking and catalytic cracking such as catalytic hydrocracking and fluidized catalytic cracking (FOO). In a similar manner, the abbreviated notation "cracker” includes a cracking reactor such as steam cracker, thermal cracker (i.e., thermal cracking in absence of steam and a catalyst) and a catalytic cracking reactor, such as a catalytic hydrocracking reactor and a fluidized catalytic cracking reactor. A first embodiment of the method according to the present invention is shown in Figure 1.

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

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

The pyrolysis oil (1) obtained by the above-described pyrolysis reaction of a 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 down to about 60 °C and a final boiling point of up to about 360 °C and/or comprises Ce - C_2i alkanes.

The high-boiling residue HBR preferably has a final boiling point of more than 360 °C, preferably a final boiling point of up to about 700 °C and/or comprises C>₂1 alkanes such as C₂₂ and C₂₂₊ alkanes.

The pyrolysis oil (1) is then inserted into a means for thermal treatment (2) of the pyrolysis oil (1) and subjected to a thermal treatment (step (II)).

The means for thermal treatment (2) is preferably selected from the group consisting of means for a thermal treatment in an inert atmosphere and means for thermal dehalogenation of the pyrolysis oil (1). The means for a thermal treatment in an inert atmosphere can be for example a vessel or a reactor or the heating section of a distillation column. The means for a thermal dehalogenation of the pyrolysis oil (1) can be for example a vessel or a reactor or an adsorber bed. "Inert atmosphere” (or "inert conditions”) is defined herein that the means for thermal treatment in an inert atmosphere comprises an inert gas or mixtures of inert gases such as nitrogen and/or argon instead of air to suppress or prevent an uncontrolled oxidation of the organic matter inside the means for thermal treatment in an inert atmosphere and/or a hydrogen atmosphere.

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

The temperature ranges given above refer to the treatment at a particular temperature. The overall time during which a pyrolysis oil (1) is subjected to such a temperature range in total may be longer in case e.g., the pyrolysis oil (1) is heated slowly to the final treatment temperature.

The pyrolysis oil (1) is converted by the thermal treatment in step (ii) into a heat-treated pyrolysis oil (3) which is then separated in a means for separation (4) in step (iii) of the method according to the present invention. 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 additional low-boiling hydrocarbons which are formed from the high-boiling fraction HBF by the thermal treatment of step (ii).

Accordingly, the yield of low-boiling fraction(s) obtained from the pyrolysis oil is increased by the first embodiment of the method according to the present invention. The combined low-boiling fraction (6) comprising the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2 is separated in the means for separation (4) from the high- boiling residue HBR (5).

The second low-boiling fraction LBF2 preferably has an initial boiling point of down to about 60 °C and a final boiling point of up to about 360 °C and/or comprises Ce - C21 alkanes.

The combined low-boiling fraction (6) comprising the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2 preferably has a boiling point range with an initial boiling point of about 60 °C to a final boiling point of up to about 360 °C and/or comprises Ce - C21 alkanes.

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

The heat-treated pyrolysis oil (3) is optionally subjected to a distillation at an elevated temperature to obtain the high- boiling residue HBR (5) as bottom product and the combined low-boiling fraction (6) comprising the first low-boiling fraction LBF1 and the 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).

Preferably, the separation in step (iii) is performed in a distillation column wherein the heat-treated pyrolysis oil (3) depletes into the high-boiling residue HBR (5) which is obtained from the bottom of the distillation column and the combined low-boiling fraction (6) comprising the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2 which is obtained from the top of the at least one distillation column in e.g., a condenser.

Preferably, the distillation in step (ill) 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 50 °C to about 360 °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 0.001 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). The temperature is adjusted accordingly in case the pressure is # 1.013 bar.

Preferably, the combined low-boiling fraction (6) is obtained in one distillation column or in a series of distillation columns, wherein the first distillation column is operated at a pressure > 0.98 bar (abs) to recover low boiling components which might otherwise be difficult to recover from lower pressures. Optionally, a second distillation column is operated with a reduced pressure ("vacuum distillation”) to increase the yield of the desired combined low- boiling fraction (6).

The combination of temperature and pressure inside the at least one distillation column is more preferably selected to obtain a combined low-boiling fraction (6) having a final boiling point of < 360 °C.

The amount of combined low-boiling fraction (6) comprising the first low-boiling fraction LBF1 and the second low- boiling fraction LBF2 obtained from step (ill) is larger than the amount of the first low-boiling fraction LBF1 in the pyrolysis oil (1) which is obtained from a pyrolysis reaction of a feedstock.

Optionally, the combined low-boiling fraction (6) comprising the first low-boiling fraction LBF1 and the second low- boiling fraction LBF2 is then converted in a cracker into olefins and aromatics by a cracking process in step (iv)a.

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 absence of steam and a catalyst.

The combined low-boiling fraction (6) comprising the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2 is preferably converted in a steam cracker into olefins and aromatics by steam-cracking (step (iv)a). The combined low-boiling fraction (6) is diluted with steam and briefly heated in at least one steam-cracker furnace (which is part of the steam cracker) in the absence of oxygen. The temperature inside the at least one steam-cracker furnace is for example around 850 °C. Olefins obtained by said cracking in optional step (iv)a, preferably by steam-cracking, comprise ethylene, propylene, butylene, and butadiene. Aromatics obtained by said thermal cracking in optional step (iv)a, preferably by steamcracking, comprise benzene, toluene, and xylene isomers.

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

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 oxidant such as air and/or oxygen. Preferably during the partial oxidation, the molar ratio oxygen : oxygen required for a total oxidation of the high-boiling residue HBR (5) ranges from 0.3 to < 1.

Among partial oxidation, thermal partial oxidation is preferred in case the sulfur content in the high-boiling residue HBR (5) is for example more than 50 ppm or more than 400 ppm.

The pyrolysis can be a pyrolysis reaction in a pyrolysis reactor as described in detail above. Accordingly, in this further utilization in step (iv)b, the high-boiling residue HBR (5) is converted into a pyrolysis oil which can optionally be subjected to the method according to the present invention afterwards. The reaction conditions and reactors described above can also be used for an optional pyrolysis in step (iv)b. The high-boiling residue HBR (5) can be mixed with other suitable feedstocks such as plastic waste, mixed plastic waste, rubber waste, bio waste and mixtures thereof for the optional pyrolysis reaction in step (iv)b.

The high-boiling residue HBR (5) can also be subjected to an incineration ("total oxidation”) to obtain for example thermal energy.

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

A pyrolysis oil (11) is provided. The pyrolysis oil (11) is manufactured by a pyrolysis reaction from feedstocks such as plastic waste, mixed plastic waste, rubber waste, bio waste, and mixtures thereof as described above.

The pyrolysis oil (11) preferably has a heating value (measured according to DIN 51900) of about 35 kJ/g to about 46 kJ/g and/or a bromine number (measured according to ASTM 1159) of about 2 g Br₂/100g to about 160 g Br₂/100g. The pyrolysis oil (11) obtained by the above-described pyrolysis reaction of a feedstock comprises a mixture of a first low-boiling fraction LBF1 (14) and a high-boiling fraction HBF (13).

The first low-boiling fraction LBF1 preferably has an initial boiling point of down to about 60 °C and a final boiling point of up to about 360 °C and/or comprises Ce - C21 alkanes.

The high-boiling residue HBR preferably has a final boiling point of more than 360 °C, preferably of more than 360 °C and up to about 700 °C, and/or comprises C>21 alkanes such as C22 and C22+ alkanes.

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

The means for separation (12) can be for example at least one distillation column, at least one thin film evaporator or a combination thereof.

The pyrolysis oil (11) is preferably subjected to a distillation at an elevated temperature to obtain the high-boiling fraction HBF (13) as bottom product and the first low-boiling fraction LBF1 (14) as a gaseous overhead product which is then condensed as a liquid product. Optionally, the high-boiling fraction HBF (13) is then subjected to at least one further distil lation/separation step in at least one further distillation column to increase the yield of the desired first low-boiling fraction LBF1 (14).

Preferably, the separation in step (ill) is performed in a distillation column wherein the pyrolysis oil (11) depletes into the high-boiling fraction HBF (13) which is obtained from the bottom of the distillation column and the first low-boiling fraction LBF1 (14) which is obtained from the top of the at least one distillation column in e.g., a condenser.

Preferably, the first low-boiling fraction LBF1 (14) is obtained in one distillation column or in a series of distillation columns, wherein the first distillation column is operated at a pressure > 0.98 bar (abs) to recover low boiling components which might otherwise be difficult to recover from lower pressures. The combination of temperature and pressure inside the at least one distillation column is more preferably selected to obtain a first low-boiling fraction LBF1 (14) having a final boiling point of < 360 °C.

The first low-boiling fraction LBF1 (14) is then preferably fed into a cracker and subjected therein to a cracking process 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 absence of steam and a catalyst.

The high-boiling fraction HBR (13) separated as bottom product in the means for separation (12), preferably in at least one distillation column, is then subjected to a thermal treatment in step (II) in a means for thermal treatment

(15).

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

The high-boiling fraction HBF (13) is preferably thermally treated 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 in an inert atmosphere in step (II). The high-boiling fraction HBF (13) is preferably thermally treated for about 1 min to about 240 min in an inert atmosphere, more preferably for about 5 min to about 180 min in an inert atmosphere and most preferably from about 10 min to about 120 min in an inert atmosphere in step (II). More preferably, the high-boiling fraction HBF (13) is thermally treated at a temperature in the range of about 350 °C to about 500 °C in an inert atmosphere for about 1 min to about 240 min in step (II). Most preferably, the high-boiling fraction HBF (13) is thermally treated at a temperature in the range of about 380 °C to about 500 °C in an inert atmosphere for about 1 min to about 240 min in step (II). The thermal treatment can be applied at atmospheric pressure (1.013 bar) or reduced pressure or increased pressure.

The temperature ranges given above refer to the treatment at a particular temperature. The overall time during which the high-boiling fraction HBF (13) is subjected to such a temperature range in total may be longer in case e.g., the high-boiling fraction HBF (13) is heated slowly to the final treatment temperature.

The high-boiling fraction HBF (13) is converted by the thermal treatment in step (II) into a high-boiling residue HBR'

(16) and a second low-boiling fraction LBF2' (17).

Next, the high-boiling residue HBR' (16) and the second low-boiling fraction LBF2' (17) are then separated in a means for separation (15) in step (ill) of the method according to the present invention. The second low-boiling fraction LBF2' comprises additional low boiling hydrocarbons which are formed from the high-boiling fraction HBF by the thermal treatment of step (II). The overall amount of first low-boiling fraction LBF1 and second low-boiling fraction LBF2' is preferably larger than the amount of first low-boiling fraction LBF1. Accordingly, the yield of low-boiling fraction(s) obtained from the pyrolysis oil is increased by the second embodiment of the method according to the present invention.

The second low-boiling fraction LBF2' preferably has an initial boiling point of down to about 60 °C and a final boiling point of up to about 360 °C, and/or comprises Ce - C21 alkanes.

The high-boiling residue HBR' (16) preferably has a final boiling point of more than 360 °C, preferably of more than 360 °C and up to about 700 °C, and/or comprises C>21 alkanes such as C22 and C22+ alkanes.

The means for separation (15) in step (iii) can be for example at least one distillation column and/or a thin film evaporator. Optionally, the means for separation (15) in step (iii) is at least one distillation column also in case the means for thermal treatment (15) in step (ii) is at least one distillation column, preferably the heating section of at least one distillation column. Optionally, the same distillation column is used in step (ii) and in step (iii) in this aspect of the second embodiment of the present invention.

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

Preferably, the separation in step (iii) is performed in a distillation column wherein the high-boiling fraction HBF (13) depletes into the high-boiling residue HBR' (16) which is obtained from the bottom of the distillation column and the second low-boiling fraction LBF2' (17) which is obtained from the top of the at least one distillation column in e.g., a condenser.

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 from about 20 °C to about 400 °C, most preferably from about 50 °C to about 360 °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 0.001 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). The temperature is adjusted accordingly in case the pressure is A 1.013 bar. Preferably, the second low-boiling fraction LBF2' (17) is obtained in one distillation column or in a series of distillation columns, wherein the first distillation column is operated at a pressure > 0.98 bar (abs) to recover low boiling components which might otherwise be difficult to recover from lower pressures.

The combination of temperature and pressure inside the at least one distillation column is more preferably selected to obtain a second low-boiling fraction LBF2' (17) having a final boiling point of < 360 °C.

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'.

The combined low-boiling fraction LBF1+2' preferably has an initial boiling point of down to about 50 °C and a final boiling point of up to about 360 °C and/or comprises C5 - C20 hydrocarbons.

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 in a cracker into olefins and aromatics by a cracking process in step (vi)a.

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

Olefins obtained by said cracking in optional step (vi)a, preferably by steam-cracking, comprise ethylene, propylene, butylene, and butadiene. Aromatics obtained by said thermal cracking in optional step (vi)a, preferably by steamcracking, comprise benzene, toluene, and xylene isomers.

Optionally, the high-boiling residue HBR' (16) is then subjected to a further utilization in step (iv)b as a feedstock, the utilization selected from the group comprising partial oxidation, pyrolysis, and incineration.

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' (16) with air and/or oxygen as oxidant. Preferably during the partial oxidation, the molar ratio oxygen: oxygen required for a total oxidation of the high-boiling residue HBR (5) ranges from 0.3 to < 1.

Among partial oxidation, thermal partial oxidation is preferred in case the sulfur content in the high-boiling residue HBR' (16) is for example more than 50 ppm or more than 400 ppm.

The pyrolysis can be a pyrolysis reaction in a pyrolysis reactor as described in detail above. Accordingly, in this further utilization in step (iv)b, the high-boiling residue HBR' (16) is converted into a pyrolysis oil which can optionally be subjected to the method according to the present invention afterwards. The reaction conditions and reactors described above can also be used for an optional pyrolysis in step (iv)b. The high-boiling residue HBR' (16) can be mixed with other suitable feedstocks such as plastic waste, rubber waste, bio waste and mixtures thereof for the optional pyrolysis reaction in step (iv)b.

The high-boiling residue HBR' (16) can also be subjected to an incineration ("total oxidation”) to obtain for example thermal energy.

The method for increasing the low-boiling fraction yield from pyrolysis oils according to the present invention optionally comprises the further step: converting 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, more preferably after combining the second low- boiling fraction LBF2' and the first low-boiling fraction LBF1; obtainable or obtained by the method according to the present invention or a chemical material obtainable by or obtained by the method according to the present invention to obtain a monomer, polymer or polymer product.

Preferably, the monomer is a di- or polyol; preferably butandiol; aldehyde; preferably formaldehyde; di- or polyisocyanate; preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylenediisocyanate (HDI) or isophoronediisocyanate (IPDI); amide; preferably caprolactam; alkene; preferably styrene, ethene and norbornene; alkyne, (di)ester; preferably methyl methacrylate; mono or diacid; preferably adipic acid or terephthalic acid; diamine; preferably hexamethylenediamine, nonanediamine, or sulfones; preferably 4,4’-dichlorodiphenyl sulfone.

Preferably, the polymer is and/or the polymer product comprises polyamide (PA); preferably PA 6 and PA 66; polyisocyanate polyaddition product; 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), poly acrylonitrile butadiene styrene (ABS), poly styrene acrylonitrile (SAN), poly acrylate 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 coterephthalate (PBAT), polyester (PES), polyether sulfone (PESO), 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), polyether ether ketone (PEEK), poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); or copolymers or mixtures thereof.

Preferably, the polymer and/or the polymer product is/are or is/are a part of:

- a part of a car, preferably cylinder head cover, engine cover, housing for charge air cooler, charge air cooler flap, intake pipe, intake manifold, connector, gear wheel, fan wheel, cooling water box, housing or housing part for heat exchanger, coolant cooler, charge air cooler, thermostat, water pump, radiator, fastening part or part of battery system for electromobility, dashboard, steering column switch, seat, headrest, center console, transmission component, door module, car exterior for A, B, C or D pillar cover, spoiler, door handle, exterior mirror, windscreen wiper, windscreen wiper protection housing, decorative grill, cover strip, roof rail, window frame, sunroof frame, antenna panel, headlight and taillight, engine cover, cylinder head cover, intake manifold, airbag, or cushion;

- a cloth, preferably shirt, trousers, pullover, boot, shoe, shoe sole, tight or jacket;

- an electrical part, preferably electrical or electronic passive or active component, printed circuit board, printed circuit board, housing component, foil, line, switch, plug, socket, distributor, relay, resistor, capacitor, inductor, bobbin, lamp, diode, LED, transistor, connector, regulator, integrated circuit (IC), processor, controller, memory, sensor, connectors, microswitches, microbuttons, semiconductor, reflector housing for light-emitting diodes (LED), fastener for electrical or electronic component, spacer, bolt, strip, slide-in guide, screw, nut, film hinge, snap hooks (snap-in) or spring tongue;

- a consumer and/or pharmaceutical product, preferably tennis string, climbing rope, bristle, brush, artificial grass, 3D printing filament, grass trimmer, zipper, hook and loop fastener, paper machine clothing, extrusion coating, fishing line, fishing net, offshore line and rope, vial, syringe, ampoule, bottle, sliding element, spindle nut, chain conveyor, plain bearing, roller, wheel, gear, roller, ring gear, screw and spring dampers, hose, pipeline, cable sheathing, socket, switch, cable tie, fan wheel, carpet, box or bottle for cosmetics, mattress, cushion or insulation; or

- packaging for the food industry; preferably mono- or multi-layer blown film, cast film (mono- or multi-layer), biaxially stretched film, or laminating film.

Preferably, the content of the pyrolysis oil in the monomer, polymer and/or polymer product is 1 weight-% or more, preferably 2 weight-% or more, more preferably 5 weight-% or more, more preferably 15 weight-% or more, more preferably 30 weight-% or more, more preferably 40 weight-% or more, more preferably 60 weight-% or more, more preferably 80 weight-% or more, more preferably 90 weight-% or more, more preferably 95 weight-% or more; and/or the content of the pyrolysis oil in the monomer, polymer and/or polymer product is 100 weight-% or less, preferably 95 weight-% or less, more preferably 90 weight-% or less, more preferably 50 weight-% or less, more preferably 25 weight-% or less, more preferably 10 weight-% or less; and more preferably the content is determined based on identity preservation and/or segregation and/or mass balance and/or book and claim chain of custody models, preferably based on mass balance, preferably the International Sustainability and Carbon Certification (ISCC) standard.

The converting steps to obtain the monomer, polymer or polymer product may comprise one or more synthesis steps and can be performed by conventional synthesis and technics well known to a person skilled in the art. Independent of the person skilled in the art to assess novelty and inventive step of the independent claims, the person skilled in the art to perform the converting step is from the technical field(s) pyrolysis, gasification, remonomerization, depolymerization and/or synthesis and/or production of monomers, polymers and polymer compounds, and its further processing (e.g. extrusion, injection molding). Examples of the steps of the conversion are described in "Industrial Organic Chemistry”, 3. volume, Wiley-VCH, 1997; ISBN: 978-3-527-28838-0; „Kunststoffhandbuch", 11 volumes in 17 sub-volumes, Carl Hanser Verlag, especially volume 6, ..Polyamide", 1. edition, 1966; volume 7, ..Polyurethane", 3. edition, 1993; and volume 8, "Polyester”, 1. edition 1973, "Industrial Organic Chemistry”, 3. volume, 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), EP1460094 (A1), W02006034800 (A1), EP1529792 (A1 ), W02006042674 (A1), EP0364854 (A2), US5506275 (A), EP0897402 (A1), WO2015082316 (A1), WO2021021855 (A1), WO2021126938 (A1), W02021021902 (A1), WO2021092311 (A1), W02008155271 (A1), WO2013139827 (A1).

The combined low-boiling fraction comprising one of a) the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2, b) the second low-boiling fraction LBF2', and c) the combined low-boiling fraction LBF1 '+2' can be used as a cracker feedstock, i.e., a feedstock suitable to be used for producing olefins and aromatics by a thermal cracking process wherein 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 absence of steam and a catalyst. Said cracker feedstock or a portion thereof is produced with the method for increasing the low-boiling fraction yield from pyrolysis oils according to the present invention.

Said cracker feedstock comprising one of the combined low-boiling fraction comprising a) the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2, b) the second low-boiling fraction LBF2', and c) the 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 or 80 wt.-% petroleum naphtha and/or bionaphtha or 90 wt.-% petroleum naphtha and/or bio-naphtha.

Petroleum naphtha is obtained from refining of fossil sources such as crude oil and comprises hydrocarbons and preferably having a boiling point range with an initial boiling point of down to about 30 °C and a final boiling point of up to about 220 °C, more preferably having an initial boiling point of down to about 120 °C and a final boiling point of up to about 220 °C. Petroleum naphtha can for example also be produced from other feed stocks such as coal tar, shale deposits, and tar sands.

Bio-naphtha can be for example obtained by hydrotreatment of renewable sources such as oils and/or fats.

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

Other pyrolysis oil means a pyrolysis oil which was for example manufactured as another batch and/or from another feedstock and/or with other pyrolysis reaction conditions other than the pyrolysis oil provided in step (I).

Accordingly, the cracker feedstock can further comprise at least one of petroleum naphtha, bio-naphtha, other pyrolysis oil, and low-boiling fraction of other pyrolysis oil.

The combined low-boiling fraction comprising the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2, the second low-boiling fraction LBF2', the combined low-boiling fraction LBF1 '+2', the olefins and aromatics made thereof by a cracking process, the high-boiling residue HBR, the high-boiling residue HBR' and the products made thereof by partial oxidation, pyrolysis, and separation of aromatics, or a fraction thereof, are circular products.

The weight or the fraction of each of said circular products attributable to the pyrolysis oil provided in step (I) or the feedstock from which the pyrolysis oil provided in step (I) was manufactured, is determined by mass balance.

Optionally, the circular product(s) is(are) certified as Circular in accordance with International Sustainability and Carbon Certification (ISCC) standards, based upon the weight or fraction of circular product attributable to the pyrolysis oil provided in step (i) or the feedstock from which the pyrolysis oil provided in step (I) was manufactured, is determined by mass balance.

The invention will be further explained by the following non-limiting examples.

Example 1

A pyrolysis oil obtained from end-of-life tires by a pyrolysis reaction was provided. Next, the pyrolysis oil was separated into a high-boiling fraction HBF and the 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 had a final boiling point of 310 °C. The high-boiling fraction HBF had a final boiling point of > 500 °C. The final boiling points were determined by the method described in ASTM-D86 and, accordingly, refer to a pressure of 1 atm (1.013 bar).

Example 2

The high-boiling fraction HBF obtained in example 1 was then subjected to a thermal treatment (step (ii)) in the heating section of a distillation unit. For practical reasons, the thermal treatment according to step (ii) was conducted in two separate steps (denoted "first thermal treatment” and "second thermal treatment”, respectively).

The high-boiling fraction HBF was first heated to a temperature of 400 °C during step (ii) from ambient temperature within 1 .1 h ("first part of thermal treatment”). A first portion of the second low-boiling fraction LBF2' was obtained and separated from the high-boiling fraction HBF. Next, the remaining part of the high-boiling fraction HBF was heated from 400 °C to 480 °C within 1 .2 h ("second part of thermal treatment”) and a second portion of the second portion of the low-boiling fraction LBF2' and a high-boiling residue HBR' were obtained and the second portion of the low-boiling fraction LBF2' was separated from the high-boiling residue HBR'.

The equipment used in example 2 for the thermal treatment (step (ii)) had no cooling trap. Accordingly, the volatile portions of the second low-boiling fraction LBF2' formed during the "first part of thermal treatment” and the "second part of thermal treatment” were not collected during the thermal treatment. Their yield was calculated from the initial weight of high-boiling fraction HBF used in example 2, reduced by 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 high-boiling residue HBR'.

The overall weight of low-boiling fraction LBF2' is the sum of the weights of the first portion of the second low-boiling fraction LBF2', the second portion of the second low-boiling fraction LBF2' and said volatile portion of the second low-boiling fraction LBF2'.

The first part of the thermal treatment (step (ii)) started with 150.9 g of high-boiling fraction HBF. The first part of the thermal treatment (step (ii)) yielded 12.3 g of first portion of the second low-boiling fraction LBF2', the second part of the thermal treatment yielded 8.8 g of second portion of the second low-boiling fraction LBF2'. A yield of 11 .6 g volatile portion of the second low-boiling fraction LBF2' was then calculated as described above. Accordingly, the thermal treatment according to step (ii) yielded 32.7 g of the second low-boiling fraction LBF2' from 150.0 g of the high-boiling fraction HBF. This is a 21.7 % yield of desired low-boiling fraction gained by the method according to the present invention.

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 separately subjected to SIMDIST (simulated distillation) measurements according to EN 15199-1-3 (better suited for samples having a final boiling point above 500 °C) for the high-boiling fraction HBF and ASTM D7213 (better suited for samples having 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'. Both norms are based on a retention time calibration of boiling points using alkane standards. The measurements were made with a SIMDIS UPTO C120 system by PAG using dual tower gas chromatographs by Agilent. The results of these measurements are shown in Figure 3.

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

Example 3

A pyrolysis oil obtained from mixed waste plastic by a pyrolysis reaction was provided. Next, the pyrolysis oil was separated into a high-boiling fraction HBF and the 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 had a final boiling point of 310 °C. The high-boiling fraction HBF had a final boiling point of > 500 °C. The final boiling points were determined by the method described in ASTM-D86 and, accordingly, refer to a pressure of 1 atm.

Example 4

The high-boiling fraction HBF obtained in example 3 was then subjected to a thermal treatment (step (ii)) in the heating section of a distillation unit. For practical reasons, the thermal treatment according to step (ii) was conducted in two separate steps (denoted "first thermal treatment” and "second thermal treatment”, respectively).

The high-boiling residue HBF was first heated to a temperature of 400 °C during step (ii) from ambient temperature within 1 .3 h ("first part of thermal treatment”). A first portion of the second low-boiling fraction LBF2' was obtained and separated from the high-boiling residue HBF. Next, the remaining part of the high-boiling fraction HBF was heated from 400 °C to 480 °C within 2.4 h ("second part of thermal treatment”) and a second portion of the second portion of the low-boiling fraction LBF2' and a high-boiling residue HBR' were obtained and the second portion of the low-boiling fraction LBF2' was separated from the high-boiling residue. The volatile portions of the second low-boiling fraction LBF2' formed during the "first part of thermal treatment” and "second part of thermal treatment” were collected in a cooling trap.

The first part of the thermal treatment started with 260 g of high-boiling fraction HBF. The first part of the thermal treatment yielded 21 .0 g of first portion of the second low-boiling fraction LBF2', the second part of the thermal treatment yielded 14.5 g of second portion of the second low-boiling fraction LBF2' and 9.7 g of volatile portion of the second low-boiling fraction LBF2' in the cooling trap. Accordingly, the thermal treatment according to step (II) yielded 45.2 g of the second low-boiling fraction LBF2' from 260.0 g of the high-boiling fraction HBF. This equals with a 17.4 % yield of desired low-boiling fraction gained by the method according to the present invention.

The same equipment and measurement parameters were applied for the SI MD 1ST measurements as described for example 2, the results are shown in Figure 4. The solid line represents the high-boiling fraction HBF having an initial boiling point of 230 °C. The dashed line (short dashes) represents the first portion of the second low-boiling fraction LBF2' from which 23.3 % (corresponding to 21 .0 g of 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' from which 16.7 % (corresponding to 14.5 g of second portion of the second low-boiling fraction LBF2') has a final boiling point below 230 °C. The dashed line (long dashes) represents the volatile portion of the second low-boiling fraction LBF2' from which 96.7 % (corresponding to 9.7 g of volatile portion of the second low-boiling fraction LBF2' has a final boiling point below 233 °C.

Claims

1. Method for increasing the low-boiling fraction yield from pyrolysis oils comprising the steps

(ii) subjecting to a thermal treatment: the mixture of the first low-boiling fraction LBF1 and the high-boiling fraction HBF whereby the first low- boiling fraction LBF1 , a second low-boiling fraction LBF2 and a high-boiling residue HBR are obtained by said thermal treatment or the high-boiling fraction HBF, after separation of the first low-boiling fraction LBF1 and the high-boiling fraction HBF, whereby a second low-boiling fraction LBF2' and a high-boiling residue HBR' are obtained by said thermal treatment, wherein the mixture of the first low-boiling fraction LBF1 and the high-boiling fraction HBF or the high-boiling fraction HBF after separating the first low-boiling fraction LBF1 from said high-boiling fraction HBF is thermally treated at a temperature in the range of about 350 °C to about 500 °C in an inert atmosphere for about 1 min to about 240 min,

(ill) separating the first low-boiling fraction LBF1 and the second low-boiling fraction LBF2 from the high- boiling residue HBR or separating the second low-boiling fraction LBF2' from the high-boiling residue HBR'.

2. Method for increasing the low-boiling fraction yield from pyrolysis oils according to claim 1 wherein the feedstock is selected from the group comprising plastic waste, mixed plastic waste, rubber waste, bio waste, and mixtures thereof.

3. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 1 and 2 wherein the thermal treatment of step (ii) is selected from the group consisting of thermal treatment in an inert atmosphere and thermal dehalogenation.

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

5. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 1 to 4 wherein the step (ill) is a distillation process with the proviso that the thermal treatment in step (ii) is a thermal treatment in an inert atmosphere or a thermal dehalogenation process.

6. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 1 to 5 wherein step (ill) is a separation process using at least one distillation column with the proviso that the first thermal 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 (ill) are optionally the same.

7. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 1 to 6 further comprising the step(s)

(iv)a converting the low-boiling fraction LBF1 and the low-boiling fraction LBF2 or the second low-boiling fraction LBF2', optionally after combining the second low-boiling fraction LBF2' and the first low-boiling fraction LBF1 , into olefins and aromatics by a thermal cracking process. and/or

(iv)b subjecting the high-boiling residue HBR or the high boiling residue HBR' to a further utilization.

8. Method for increasing the low-boiling fraction yield from pyrolysis oils according to claim 7 wherein the cracking process is selected from the group comprising steam cracking, catalytic cracking, and thermal cracking.

9. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 7 and 8 wherein the further utilization is selected from the group comprising partial oxidation, pyrolysis, and incineration.

10. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 1 to 9 wherein the first low-boiling fraction LBF1 has a boiling point range with an initial boiling point of down to about 60 °C and a final boiling point of up to about 360 °C and/or comprises Ce - C21 alkanes, and/or the second low-boiling fraction LBF2 has an initial boiling point of down to about 60 °C and a final boiling point of up to about 360 °C and/or comprises Ce - C21 alkanes, and/or the second low-boiling fraction LBF2' has an initial boiling point of down to about 60 °C and a final boiling point of up to about 360 °C and/or comprises Ce - C21 alkanes.

11. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 1 to 10 wherein the pyrolysis oil provided in step (I) has a heating value (measured according to DIN 51900) of about 35 kJ/g to about 46 kJ/g and/or a bromine number (measured according to ASTM 1159) of about 2 g Br2/100g to about 160 g Br2/100g.

12. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 1 to 11, comprising the further step: converting 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, more preferably after combining the second low- boiling fraction LBF2' and the first low-boiling fraction LBF1 ; obtainable or obtained by the method according to any one of claims 1 to 13 or a chemical material obtainable by or obtained by the method according to any one of claims 1 to 13 to obtain a monomer, polymer or polymer product.

13. Method for increasing the low-boiling fraction yield from pyrolysis oils according to claim 12, wherein the monomer is a di- or polyol; preferably butandiol; aldehyde; preferably formaldehyde; di- or polyisocyanate; preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylenediisocyanate (HDI) or isophoronediisocyanate (IPDI); amide; preferably caprolactam; alkene; preferably styrene, ethene and norbornene; alkyne, (di)ester; preferably methyl methacrylate; mono or diacid; preferably adipic acid or terephthalic acid; diamine; preferably hexamethylenediamine, nonanediamine, or sulfones; preferably 4,4'-dichlorodiphenyl sulfone.

14. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 12 to 13, wherein the polymer is and/or the polymer product comprises polyamide (PA); preferably PA 6 and PA 66; polyisocyanate polyaddition product; 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), poly acrylonitrile butadiene styrene (ABS), poly styrene acrylonitrile (SAN), poly acrylate 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 coterephthalate (PBAT), polyester (PES), polyether sulfone (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), polyether ether ketone (PEEK), poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); or copolymers or mixtures thereof.

15. Method for increasing the low-boiling fraction yield from pyrolysis oils according to any one of claims 12 to 14, wherein the polymer and/or the polymer product is/are or is/are a part of:

- a cloth, preferably shirt, trousers, pullover, boot, shoe, shoe sole, tight or jacket; - an electrical part, preferably electrical or electronic passive or active component, printed circuit board, printed circuit board, housing component, foil, line, switch, plug, socket, distributor, relay, resistor, capacitor, inductor, bobbin, lamp, diode, LED, transistor, connector, regulator, integrated circuit (IC), processor, controller, memory, sensor, connectors, microswitches, microbuttons, semiconductor, reflector housing for light-emitting diodes (LED), fastener for electrical or electronic component, spacer, bolt, strip, slide-in guide, screw, nut, film hinge, snap hooks (snap-in) or spring tongue;

16. Method for increasing the low-boiling fraction yield from pyrolysis oils 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 weight-% or more, preferably 2 weight-% or more, more preferably 5 weight-% or more, more preferably 15 weight-% or more, more preferably 30 weight-% or more, more preferably 40 weight-% or more, more preferably 60 weight-% or more, more preferably 80 weight-% or more, more preferably 90 weight-% or more, more preferably 95 weight- % or more; and/or wherein the content of the pyrolysis oil in the monomer, polymer and/or polymer product is 100 weight-% or less, preferably 95 weight-% or less, more preferably 90 weight-% or less, more preferably 50 weight-% or less, more preferably 25 weight-% or less, more preferably 10 weight-% or less; and preferably wherein the content is determined based on identity preservation and/or segregation and/or mass balance and/or book and claim chain of custody models, preferably based on mass balance, preferably the International Sustainability and Carbon Certification (ISCC) standard.

17. Cracker feedstock selected from the group consisting of the 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 cracker feedstock produced with the method for increasing the low- boiling fraction yield from pyrolysis oils according to any one of claims 1 to 11 .

18. Cracker feedstock according to claim 17 further comprising at least one of petroleum naphtha, bio-naphtha, other pyrolysis oil, and low-boiling fraction of other pyrolysis oil.