Process for hydrotreating feedstocks manufactured from biomass and / or plastic waste

Abstract

The present invention relates to a process for hydrotreating feedstocks manufactured from plastic waste, such pyrolysis oils, using hydrogen having low deuterium content produced with non- fossil resources and energy, to the trackability of the hydrogen used in the hydrotreated feedstocks, and to hydrotreated feedstocks and downstream products thereof with depleted deuterium contents.

Description

[0001] Process for hydrotreating feedstocks manufactured from biomass and / or plastic waste

[0002] Technical Area

[0003] The present invention relates to a process for hydrotreating feedstocks manufactured from plastic waste, such pyrolysis oils, using hydrogen having low deuterium content produced with non-fossil resources and energy, to the trackability of the hydrogen used in the hydrotreated feedstocks, and to hydrotreated feedstocks and downstream products thereof with depleted deuterium contents.

[0004] Background of the invention

[0005] For decades, fossil carbon resources like coal, oil, and gas have been extensively used as the predominant raw materials for energy production and petrochemical processes. This has led to an enormous increase of the carbon dioxide concentration in the atmosphere causing global warming and climate change. In view of the finite availability of fossil resources and the urgency to reduce carbon dioxide emissions, there is a high need to replace fossil carbon resources by renewable and / or recycled carbon resources.

[0006] Thus, the production of hydrocarbons from renewable resources like biomass and from recycled resources like plastic waste has been attracting increasing interest, in particular for the use as fuels and base materials for chemical processes. Such bio-based and recycling-based hydrocarbons exhibit a reduced product carbon footprint and reduce the demand for fossil carbon resources.

[0007] Bio-oils derived from biomass and pyrolysis oils derived from plastic waste may contain large amounts of heteroatoms like oxygen, nitrogen, sulfur, and halogens, which often makes them unsuitable for direct use in many petrochemical processes like steam cracking. Thus, said oils are typically upgraded to improve their characteristics and suitability for further downstream processing. Among the major pathways of such upgrading is the catalytic hydrotreatment of these oils, which includes hydrogenation, decarboxylation, decarbonylation, hydroisomerization, and cracking processes under high temperature and pressure conditions, frequently also including a catalytic isomerization step, resulting in a hydrocarbon mixture. This product mixture may be further separated into gaseous and liquid fractions that may constitute valuable transportation fuels and chemical feedstocks.

[0008] While said product streams may in principle be fully bio- and / or recycling-based regarding their carbon content, it must be borne in mind that large amounts of hydrogen are needed for the hydrotreatment of the oils. To date, the predominant production routes of hydrogen are based on fossil fuels, mainly on steam reforming of natural gas and other light hydrocarbons. However, the petrochemical steam reforming process has its negative impacts regarding its carbon footprint including the consumption of a lot of fossil-based natural resources and energy. Thus, the production of sufficient amounts of hydrogen may represent a challenge where fossil resources and energies should be avoided for sustainability reasons. It is therefore an objective of the present invention to provide environmentally friendly hydrotreated feedstocks made from biomass and / or plastic waste with an environmentally friendly hydrotreatment process and downstream products thereof, that process using as little fossil-based resources and energy as possible. Furthermore, it is an object of the present invention to provide a process for tracking the origin of hydrogen used for hydrotreating a feedstock in the hydrotreated feedstock.

[0009] Summary of the Invention

[0010] In a first aspect, this objective is achieved by a process for hydrotreating feedstocks manufactured from plastic waste, wherein said process comprises the following steps:

[0011] (a) providing hydrogen with a deuterium content 100 ppm, preferably in the range of from 10 to 95 ppm, more preferably in the range of from 10 to < 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, by water electrolysis based on electrical power generated at least in part from nonfossil energy;

[0012] (b) providing at least one feedstock manufactured from plastic waste and optionally blending with at least one feedstock of fossil origin to obtain a blend; and

[0013] (c) reacting hydrogen from step (a) with the at least one feedstock and / or blend from step (b) to form a hydrotreated feedstock.

[0014] In a second aspect, this objective is achieved by a process for tracking the origin of hydrogen used in the preparation of hydrotreated feedstock and / or downstream products thereof, comprising the steps

[0015] (A) providing a test sample of one or more hydrotreated feedstocks and / or one or more downstream products thereof and optionally providing a reference sample of one or more corresponding feedstocks hydrotreated with hydrogen of fossil origin and / or one or more corresponding downstream products;

[0016] (B) determining the deuterium content in said test sample and optionally determining the deuterium content in said reference sample; and

[0017] (C) establishing whether said deuterium content in the test sample does not exceed 100 ppm and / or optionally whether said deuterium content in the test sample is lower than said deuterium content in the reference sample.

[0018] In further aspects, this objective is achieved by providing a hydrotreated feedstock, a fraction thereof, or downstream products thereof like an olefin, an aromatic hydrocarbon, a syngas, a monomer, a polymer, or a polymer product, each with a deuterium content 100 ppm, based on the total hydrogen content, and / or with a deuterium content being lower than the deuterium content in a corresponding feedstock or downstream product thereof obtained via hydrotreatment with hydrogen of fossil origin.

[0019] The processes according to the invention provide an environmental benefit in that the production of hydrotreated feedstocks may consume as little fossil-based energy as possible, ideally no fossil-based energy, and do therefore only add as little as possible, ideally nothing, to CO2 emission Detailed description of the invention

[0020] The process according to the first aspect of the invention provides hydrotreated feedstocks with reduced carbon intensity for chemical or fuel applications. Said reduced carbon footprint is on the one hand due to the use of renewable or recycling-based resources for providing the feedstock to be hydrotreated; on the other hand, the hydrogen needed for the hydrotreatment step is obtained from water electrolysis, preferably powered by renewable energies.

[0021] Said hydrogen is characterized by a deuterium content that is lower than the one of the water from which it is generated; also, it is lower than the deuterium content of hydrogen that is obtained from fossil resources, e.g., via steam reforming. To enable hydrotreatment of bio-oils and pyrolysis oils, the covalent bond of the hydrogen molecule needs to be broken. Since the dissociation energy of protonated hydrogen (H-H) is lower than the one of (partially) deuterated hydrogen (H-D, D-D), it is reasonable to assume that less energy is needed for initiating the hydrotreatment when hydrogen of lower deuterium content is used. Thus, hydrotreatment according to the invention may consume less energy or release more energy, respectively, than hydrotreatment with hydrogen of different origins, e.g., of fossil origin, such that not only the carbon intensity, but also the energy efficiency of the process according to the invention may be advantageous.

[0022] The hydrotreated feedstocks according to the invention may be separated into different fractions that are suitable to be further used in downstream processes of the chemical industry, e.g., a naphtha fraction, or as fuels, e.g., as diesel and / or aviation fuels. As hydrogen of lower deuterium content is used for the hydrotreatment, also the deuterium content of the hydrotreated feedstock according to the invention as well as of any downstream products derived therefrom (e.g., the monomers, polymers, and polymer products described hereinafter) will be lower than the one of analogous feedstocks (and products therefrom) that have been hydrotreated with hydrogen of fossil origin.

[0023] Thus, the process according to the invention allows using the deuterium content in the hydrotreated feedstock as well as in any hydrogen-containing chemical downstream products thereof as tracker for the origin of the hydrogen employed. Hence, the non-fossil origin of hydrogen used in the process according to the present invention can be tracked in the hydrotreated feedstock. This trackability is important to prove the "green” aspect of the hydrotreated feedstock and / or chemicals and products made from said hydrotreated feedstock.

[0024] The present invention is further described below with reference to the embodiments, but the present invention is not limited to these embodiments, and any modifications of these embodiments, combinations of these embodiments or substitutions within the basic spirit of the present invention are still within the scope of the present invention.

[0025] Definitions:

[0026] In the context of the present description and the accompanying claims, the term "about” preferably means a deviation of the thus described value of ±10%. In the context of the present invention, the term “combination 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. “Feedstock of fossil origin” is defined herein as a feedstock derived from sources such as coal, petroleum, and natural gas. The deuterium content of hydrogen and chemical compounds containing hydrogen is given herein in atom-ppm based on the total hydrogen content (i.e. , atoms of deuterium2H in relation to the total sum of atoms of protium1H and deuterium2H).

[0027] In step (a) of the method according to the present invention, hydrogen with a deuterium content 100 ppm, preferably in the range of from 10 to 95 ppm, more preferably in the range of from 10 to 90 ppm, most preferably in the range of from 10 to < 80 ppm, based on the total hydrogen content, by electrolysis of water based on electrical power generated at least in part from non-fossil energy is provided.

[0028] Electrolysis of water is an environmentally friendly method to produce hydrogen because it uses renewable H2O and produces only pure oxygen as by-product. Additionally, water electrolysis utilizes direct current (DC), preferably from sustainable energy resources, for example solar, wind, hydropower, and biomass.

[0029] It is observed that by electrolysis of water, the deuterium atom content of the hydrogen is lower than in the hydrogen generated petrochemically, for example as contained in synthesis gas, in general 100 ppm, preferably in general 90 ppm, for example from 30 to 75 ppm. The deuterium atom content in electrolytically produced hydrogen may be as low as 10 ppm. The deuterium is mainly present in the form of D-H rather than D2.

[0030] Generally, any water source can be used in the water electrolysis in step (a). However, since the hydrogen prepared in step (a) has a deuterium content (i.e., a molar share of deuterium) below 100 ppm, it is preferable to use water having a deuterium content (i.e., a molar share of deuterium) below 160 ppm, based on the total hydrogen content.

[0031] Vienna Standard Mean Ocean Water (VSMOW) is an isotopic water standard defined in 1968 by the International Atomic Energy Agency. Despite the somewhat misleading phrase "ocean water", VSMOW refers to pure water (H2O) and does not include any salt or other substances usually found in seawater. VSMOW serves as a reference standard for comparing hydrogen and oxygen isotope ratios, mostly in water samples. Very pure, distilled VSMOW water is also used for making high accuracy measurement of water's physical properties and for defining laboratory standards since it is considered to be representative of “average ocean water”, in effect representing the water content of Earth.

[0032] The isotopic composition of VSMOW water is specified as ratios of the molar abundance of the rare isotope in question divided by that of its most common isotope and is expressed as parts per million (ppm). The isotopic ratios of VSMOW water are defined as follows:

[0033] 2H / 1H = 155.76 ± 0.1 ppm (a ratio of 1 part per approximately 6420 parts)

[0034] 3H / 1H = 1 .85 ± 0.36 * 10-11ppm (a ratio of 1 part per approximately 541 * 1016parts, ignored for physical properties- related work)

[0035] (see: https: / / en-academic.com / dic.nsf / enwiki / 753132)

[0036] More preferably, the water in step (a) has an average deuterium content of 1 ppm (super light water) to 156 ppm, based on the total hydrogen content, most preferably 2 ppm to 150 ppm, based on the total hydrogen content.

[0037] Processes for the depletion of deuterium in water are known by a person skilled in the art. However, said processes are generally energy consuming electrolysis processes as e.g. described in CN103848399A. In the case that deuterium depleted water is used, it is therefore preferred to employ deuterium depleted water obtained from the following resources:

[0038] A byproduct of "heavy water” (D2O) production (heavy water has applications in organic chemistry, drug development, and nuclear reactors); (deuterium content about 10-120 ppm)

[0039] High mountain water; (deuterium content about 120-150 ppm)

[0040] Surface river and lake water; (deuterium content about 130-150 ppm)

[0041] Any water source with seasonally low deuterium content e.g. water collected at low temperature (cold winter water contains less deuterium than warm summer water); e.g. water obtained in winter time, e.g. from snow or ice; (deuterium content about 120-150 ppm)

[0042] Pole water and antarctic glacier water (deuterium content about 90-150 ppm)

[0043] Low salinity sea water e.g. close to river mouths, desalinated sea water or brackish water and waste water treatment effluent water; (deuterium content about 130-155 ppm)

[0044] One suitable water electrolysis process is alkaline water electrolysis. Hydrogen production by alkaline water electrolysis is a well-established technology up to the megawatt range for a commercial level. In alkaline water electrolysis initially at the cathode side two water molecules of alkaline solution (KOH / NaOH) are reduced to one molecule of hydrogen (H2) and two hydroxyl ions (OH-). The produced H2 emanates from the cathode surface in gaseous form and the hydroxyl ions (OH-) migrate under the influence of the electrical field between anode and cathode through the porous diaphragm to the anode, where they are discharged to half a molecule of oxygen (O2) and one molecule of water (H2O). Alkaline electrolysis operates at lower temperatures such as 30-80°C with alkaline aqueous solution (KOH / NaOH) as the electrolyte, the concentration of the electrolyte being about 20% to 30 %. The diaphragm in the middle of the electrolysis cell separates the cathode and anode and also separates the produced gases from their respective electrodes, avoiding the mixing of the produced gases. However, alkaline electrolysis has negative aspects such as limited current densities (below 400 mA / cm2), low operating pressure and low energy efficiency.

[0045] In one preferred embodiment of the inventive process, hydrogen is provided by polymer electrolyte membrane water electrolysis. Variants of polymer electrolyte membrane water electrolysis are proton exchange membrane water electrolysis (PEMWE) and anion exchange membrane water electrolysis (AEMWE).

[0046] PEM water electrolysis was developed to overcome the drawbacks of alkaline water electrolysis. PEM water electrolysis technology is similar to the PEM fuel cell technology, where solid polysulfonated membranes (Nation®, fumapem®) are used as an electrolyte (proton conductor). These proton exchange membranes have many advantages such as low gas permeability, high proton conductivity (0.1 ± 0.02 S cm-1), low thickness (20-300 pm), and allow high-pressure operation. In terms of sustainability and environmental impact, PEM water electrolysis is one of the most favorable methods for conversion of renewable energy to highly pure hydrogen. PEM water electrolysis has great advantages such as compact design, high current density (above 2 A cm-2), high efficiency, fast response, operation at low temperatures (20-80°C) and production of ultrapure hydrogen. The state-of-the-art electrocatalysts for PEM water electrolysis are highly active noble metals such as Pt / Pd for the hydrogen evolution reaction (HER) at the cathode and I rO2 / RuO2 for the oxygen evolution reaction (OER) at the anode.

[0047] One of the largest advantages of PEM water electrolysis is its ability to operate at high current densities. This can result in reduced operational costs, especially for systems coupled with very dynamic energy sources such as wind and solar power, where sudden spikes in energy output would otherwise result in uncaptured energy. The polymer electrolyte allows the PEM water electrolyzer to operate with a very thin membrane (ca. 100-200 pm) while still allowing high operation pressure, resulting in low ohmic losses, primarily caused by the conduction of protons across the membrane (0.1 S / cm), and a compressed hydrogen output.

[0048] The PEM water electrolyzer utilizes a solid polymer electrolyte (SPE) to conduct protons from the anode to the cathode while insulating the electrodes electrically. Under standard conditions the enthalpy required for the formation of water is 285.9 kJ / mol. One portion of the required energy for a sustained electrolysis reaction is supplied by thermal energy and the remainder is supplied through electrical energy.

[0049] The half reaction taking place on the anode side of a PEM water electrolyzer is commonly referred to as the Oxygen Evolution Reaction (OER). Here the liquid water reactant is supplied to a catalyst where it is oxidized to oxygen, protons, and electrons.

[0050] The half reaction taking place on the cathode side of a PEM water electrolyzer is commonly referred to as the Hydrogen Evolution Reaction (HER). Here the protons that have moved through the membrane are reduced to gaseous hydrogen.

[0051] PEMs can be made from either pure polymer membranes or from composite membranes, where other materials are embedded in a polymer matrix. One of the most common and commercially available PEM materials is the fluoropolymer PFSA, or Nation®, a DuPont product. While Nation® is an ionomer with a perfluorinated backbone like Teflon, there are many other structural motifs used to make ionomers for proton-exchange membranes. Many use polyaromatic polymers, while others use partially fluorinated polymers.

[0052] An overview of hydrogen production by PEM water electrolysis is given in S. Kumar and V. Himabindu, Material Science for Energy Technologies 2 (2019), pp. 4442-4454.

[0053] An overview of hydrogen production by anion exchange membrane water electrolysis is given in H. A. Miller et al., Sustainable Energy Fuels, 2020, 4, pp. 2114-2133.

[0054] K. Harada et al., International Journal of Hydrogen Energy 45 (2020), pp. 31389-31395 report a deuterium depletion by a factor from 2 to 3 in polymer electrolyte membrane water electrolysis The separation factor p

[0055] P = ([H] / [D])gas / ([H] / [D]),iquidwhere "gas” is the evolved gas and "liquid” is water before the electrolysis was found to be between 2 and 3 at current densities of from 1 .0 to 2.0 A cm-2, corresponding to a stoichiometric number A of between 4 and 9 at the given water mass flow in the anode. The stoichiometric number A is defined as follows:

[0056] A = V x p / (J / 2F x 60 x MH2o) where V (mL min-1) is the water mass flow in the anode, F is the Faraday constant, J is electrolysis current (A), p is the density of water (g mb1) and MH2o (g moH) is the molar weight of water. A stoichiometric number A of 10 means that 10 times the amount of fresh water than can be theoretically consumed by electrolysis at the given electrolysis current is supplied to the anode.

[0057] H. Sato et al., International Journal of Hydrogen Energy 46 (2021), pp. 33689-33695, report for anion exchange membrane water electrolysis that deuterium concentration in the evolving hydrogen gas is diluted by approximately 1 / 5 against the feed water, at A = 4.

[0058] Hence, deuterium in the evolving hydrogen gas can easily be depleted by a factor of from 2 to 5 with regard to feed water in polymer electrolyte membrane water electrolysis. Depending on the electrolysis conditions (water flow, current density), even higher depletion factors are possible. Since the average deuterium content of water is about 150 ppm, based on the total hydrogen content, hydrogen provided in step (a) of the inventive process may have a deuterium content of from 30 to 75 ppm, based on the total hydrogen content, or even lower.

[0059] The electrical power is generated at least in part from non-fossil, renewable resources.

[0060] The term “at least in part” means that part of the electrical power can still be produced from fossil fuels, preferably from natural gas, since combustion of natural gas causes much lower carbon dioxide emission per Megajoule of electrical energy produced than combustion of coal. However, the portion of electrical energy produced from fossil fuels should be as low as possible, preferably 50%, more preferably 30%, most preferably 20%, further most preferably 10%. In one embodiment, the electrical power is generated exclusively from non-fossil resources.

[0061] Various methods for certification and tracking of the “energy source mix” have been set up based on local legislations. Certificates such as “Non-Fossil Certificate Contracts” are common practice for tracking the ratio of non- fossil energy used in industrial processes and related products (https: / / www.ekoenerqv.ora / ecolabel / criteria / trackinq / )

[0062] Preferably, the electrical power is generated at least in part from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydroelectricity (tidal power, wave power, hydroelectric dams, in-river-hydrokinetics), geothermal energy, ambient or industrial heat captured by heat pumps, bioenergy (biofuel, biomass), the renewable part of waste energy sources or nuclear energy (fission).

[0063] In a further embodiment, the electrical power is generated at least in part from renewable resources, preferably from wind power, solar energy (thermal, photovoltaic and concentrated solar power), hydroelectricity (tidal power, wave power, hydroelectric dams, in-river-hydrokinetics), geothermal energy, ambient heat captured by heat pumps, bioenergy (biofuel, biomass), or the renewable part of waste.

[0064] The types of electrical power resources mentioned above are generally known by a person skilled in the art

[0065] In step (b) of the method according to the present invention, a feedstock manufactured from biomass and / or plastic waste is provided.

[0066] The feedstock is preferably manufactured from biomass, plastic waste, or a combination thereof which are referred herein to as “sources” of the feedstock provided in step (b). The feedstock comprises one or more bio-oils and / or one or more pyrolysis oils and / or mixtures thereof. Pyrolysis oils are for example manufactured by a pyrolysis reaction from sources such as plastic waste.

[0067] A first type of feedstock suited for the process according to the present invention are bio-oils which are manufactured from biomass as the source:

[0068] Biomass is biological material derived from living, or recently living organisms. The biomass used for the manufacture of bio-oils may be any material of plant or animal origin that is in principle suitable to be converted at least into bio-oils. In particular, the term biomass comprises plants or parts thereof like crops, wood, or residues thereof, marine organisms like algae, and bio waste such as organic food waste, e.g. , animal fat from meat industry waste, fish fat from fish processing waste, or used cooking oil. The bio-oils can also be manufactured from more than one of the above-mentioned sources.

[0069] According to one embodiment of the present invention, the biomass is of plant or animal origin or a mixture thereof, preferably it is of plant origin.

[0070] Preferably, said biomass of plant origin comprises or is derived from algae, oil crops, oil palms, soybeans, rapeseed, mustard, flax, cottonseed, sunflower, corn, hemp, field pennycress, pongamia, jatropha, mahua, camelina, salicornia, carinata, eucalyptus, lignocellulose, wood, forestry residues, agricultural residues, crop residues, residues from vegetable oil production, green waste, food waste, and used vegetable cooking oil, more preferably it comprises or is derived from algae, oil crops, oil palms, soybeans, rapeseed, pongamia, jatropha, camelina, and carinata.

[0071] According to another embodiment of the present invention, the biomass is of animal origin, preferably it comprises or is derived from animal fat, livestock-related products like tallow, fish fat, or food waste.

[0072] The biomass is converted to a feedstock for the process according to the present invention. Such conversion may comprise both mechanical and physical operations, like harvesting and collecting as well as crushing, cracking, cutting, shredding, grinding, chipping, milling, extrusion, irradiation, squeezing, pressing, filtering, sieving, adsorption, and thermal treatments such as drying and torrefaction, and chemical processes, like extraction, distillation, thermochemical conversions like pyrolysis or hydrothermal liquefaction, hydrolysis, saponification, neutralization, or ketonization. Also, the mechanical, physical, and / or chemical separation of the products and by-products of said operations and processes, in particular the separation of gaseous, liquid, and solid fractions, forms part of the biomass processing to provide the feedstock according to step (b). In essence, said processing comprises the removal of all by-products from the biomass conversion product stream that are not suitable or are detrimental for further use as a feedstock for subsequent hydrotreatment in step (c). The right choice of suitable process steps and operating conditions is mainly dependent on the biomass to be processed; the one skilled in the art will be familiar with such considerations.

[0073] The product stream obtained by said biomass processing comprises, preferably consists of bio-oil. Bio-oil designates a liquid compound mixture mainly comprising highly oxygenated compounds (e.g., glycerides, esters, carboxylic acids, phenols, alcohols, ketones, aldehydes, furans, and sugars) and water, while its exact composition depends on the biomass feedstocks and the processing steps applied. The term bio-oil includes in particular vegetable oils like rapeseed oil, sunflower oil, soybean oil, corn oil, and palm oil, waste cooking oil, tall oil, animal fats, and oils obtained by thermochemical conversion of biomass, e.g., biomass-derived pyrolysis or hydrothermal liquefaction oils.

[0074] It is to be understood that the manufacture of the feedstock from biomass may also comprise purification steps, e.g., to remove any by-products, contaminants, or impurities that may be detrimental for the further use of the biomass- derived feedstock in step (c).

[0075] Thus, according to one embodiment of the present invention, the processing of biomass in the manufacture of the feedstock provided in step (b) comprises mechanical and physical operations and chemical processes, optionally also the separation of the obtained products and any by-products.

[0076] According to another embodiment of the present invention, the processing of biomass in the manufacture of the feedstock provided in step (b) comprises extraction, pyrolysis, and / or hydrothermal liquefaction of the biomass.

[0077] According to another embodiment of the present invention, the processing of biomass in the manufacture of the feedstock provided in step (b) yields a product stream comprising, preferably consisting of, bio-oil.

[0078] According to another embodiment of the present invention, the processing of biomass in the manufacture of the feedstock provided in step (b) comprises purification steps applied to the product stream prior to providing the feedstock in step (b)

[0079] A second type of feedstocks which is particularly preferred, and which can be provided in step (b) and is suited for the process according to the present invention are pyrolysis oils manufactured from plastic waste as the source:

[0080] In the context of the present invention, the term “plastic waste” refers to any plastic material discarded after use, i.e., the plastic material has reached the end of its useful life and is considered post-consumer waste. The plastic waste can be pure polymeric plastic waste, mixed plastic waste or film waste, optionally including soiling, adhesive materials, fillers, residues etc. The plastic waste may have an oxygen content, a nitrogen content, sulfur content, halogen content and optionally also a heavy metal content. The plastic waste can originate from any plastic material containing source.

[0081] Accordingly, the term “plastic waste” includes industrial and domestic plastic waste and including used tires and agricultural and horticultural plastic material.

[0082] 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.

[0083] 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.

[0084] Examples of rubber waste (which is also considered “plastic waste” in the sense of the present invention) include end-of-life tires, rubber waste produced during manufacturing processes and discarded rubber containing products such as latex examining gloves and gaskets. End-of-life tires comprise further ingredients such as textiles and organic and inorganic additives which may be separated from the rubber portion of end-of-life tires prior to pyrolysis. Pyrolysis oils obtained by pyrolysis of (predominantly) end-of-life tires are also known as tire pyrolysis oils (TPO).

[0085] In the context of the present invention, the term “pyrolysis” relates to a thermal decomposition or degradation of a source such as plastic waste under inert conditions and results in a gas, a liquid, and a solid char fraction (Note: The remarks on pyrolysis of plastic waste to obtain pyrolysis oils apply equally to the pyrolysis of biomass to obtain biooils, as defined herein.). During the pyrolysis, the source is converted in a pyrolysis unit into a great variety of chemicals including gases such as H2, Ci-4-alkanes, 02-4-alkenes, ethyne, propyne, 1 -butyne, a pyrolysis oil having a boiling temperature of about 25 °C to about 500 °C and char. In addition, water is formed during the pyrolysis which may be partially dispersed in the pyrolysis oil and may be partially contacted with the pyrolysis oil in a separate phase. The water formed during pyrolysis comprises various organic compounds and / or salts thereof which were also formed during the pyrolysis.

[0086] The term “pyrolysis” includes slow pyrolysis, fast pyrolysis, flash catalysis and catalytic pyrolysis. These pyrolysis types differ regarding process temperature, heating rate, residence time, feed particle size, etc. resulting in different product quality. The pyrolysis unit may be operated adiabatically, isothermally, nonadiabatically, non-isothermally, or combinations thereof. The pyrolysis reactions of this disclosure may be carried out in a single stage or in multiple stages. For example, the pyrolysis unit can comprise two reactor vessels fluidly connected in series.

[0087] To manufacture the pyrolysis oil suitable as a feedstock according to the present invention, the plastic waste 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 plastic waste 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.

[0088] Next, the plastic waste is heated in the pyrolysis reactor to a temperature in the range of from about 350 °C to about 900 °C, more preferably in the range of from 400 °C to about 550 °C, and a pressure in the range of from about 0.5 bar to about 2 bar(abs), more preferably in the range of from 0.9 bar to about 1.5 bar(abs).

[0089] 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 , WO 95 / 03375 A1 and Jorg Woidasky, Ullmanns Encyclopedia of Industrial Chemistry, chapter 5.2.1 "Pyrolysis”, pages 15-17, 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim (DOI: 10.1002 / 14356007. a21_057.pub2). Suitable pyrolysis oils made from plastic waste 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

[0090] The at least one pyrolysis oil manufactured from plastic waste preferably has a bromine number of about

[0091] 2 g Br2 / 100g to about 150 g Br2 / 100g (determined by ASTM 1159) and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-% (determined by ASTM D 5134) and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-% (determined by ASTM D 5134). Such pyrolysis oils manufactured from plastic waste are particularly suited for the process according to the present invention.

[0092] The feedstock provided in step (b), preferably pyrolysis oils made from plastic waste, can be optionally mixed (“blended”) with feedstocks of fossil origin. Mixed feedstocks of this type are referred herein to as “blends”. Blending of feedstocks is not uncommon to improve their characteristics, e.g., to optimize their physical or chemical properties for the intended use. In such a case, a “blend” comprising a feedstock provided in step (b) is reacted in step (c) with the hydrogen from step (a) to form a hydrotreated “blend”.

[0093] Said optional feedstocks of fossil origin can be comprised in the blend for example in a quantity of about 0 wt.-%, 5 wt.-%, 10 wt.-%, 15 wt.-%, 20 wt.-%, 25 wt.-%, 30 wt.-%, 35 wt.-%, 40 wt.-%, 45 wt.-%, 50 wt.-%, 55 wt.-%, 60 wt.- %, 65 wt.-%, 70 wt.-%, 75 wt.-%, 80 wt.-% or more with the proviso that at least 2 wt.-% of the blend are comprised of at least one feedstock manufactured from biomass and / or at least one feedstock manufactured from plastic waste.

[0094] Said optional feedstocks of fossil origin are preferably selected from the group comprising, preferably consisting of, crude oil fractions, heavy crude oil, vacuum gas oil, residues from atmospheric and vacuum distillation units, coal tar, bitumen, shale oil, and natural gas liquids.

[0095] Next, in step (c) of the method according to the present invention, the hydrogen from step (a) is reacted with a feedstock and / or blend from step (b) in the presence of at least one catalyst, preferably at least one heterogeneous catalyst, preferably at high temperatures and pressures to form a hydrotreated feedstock. For instance, temperatures from 100°C to 600°C and pressures from 5 bar to 200 bar may be applied.

[0096] Said reaction (herein referred to as “catalytic hydrotreatment") is a well-established upgrading technology, e.g., for processing feedstocks such as bio-oils or, preferably, pyrolysis oils and comprises different chemical transformations using hydrogen. More specifically, catalytic hydrotreatment comprises the processes of hydrodeoxygenation, hydrodenitrogenation, hydrodehalogenation, hydrodesulfurization, hydrodemetallation, hydrocracking, hydroisomerization, and hydrogenation (e.g., of C-C double bonds, C-C triple bonds, conjugated C-C double bonds). Thus, the resulting hydrotreated feedstock is depleted, in comparison to the feedstock provided in step (b), in at least one respect of the group comprising amount of C-C double bonds, amount of C-C triple bonds, amount of dienes, amount of aromatics, amount of heteroatoms like oxygen, nitrogen, halogens, sulfur, and metals, amount of organic compounds comprising at least one heteroatom, the heteroatoms preferably selected from the group comprising nitrogen, oxygen, halogens, and sulfur, and / or mass fraction of alkanes or alkyl residues having n carbon atoms with 10 < n < 30.

[0097] Hydrotreatment of feedstocks and / or blends provided in step (b) may be required to obtain a more valuable feedstock for successive processing in e.g., cracking processes such as a steam cracking process for producing olefins (in particular ethylene, propylene, and C4 olefins) and aromatic hydrocarbons (in particular benzene, toluene, xylenes, and ethylbenzene) from said feedstock, or a partial oxidation reaction and / or gasification processes for producing syngas (a gaseous product stream comprising H2, CO and CO2) from said feedstock. Such steam cracking processes are known in the art and for example disclosed in H. Zimmermann, R. Walzl, Ullmann's Encyclopedia of Industrial Chemistry, Vol. 13 “Ethylene”, pp. 469-494, 2012. Such partial oxidation reactions are known in the art and are for example disclosed in WO 2022 / 200532 A1 and Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, Chapter: Gas Production, 2. Processes”, pages 443-455, 2012.

[0098] Chemicals, chemical materials, and related products manufactured from the hydrotreated feedstocks obtained by step (c) in successive processing are referred herein to as “downstream intermediates”, “downstream products”, “chemical material”, “monomer”, “polymer”, or “polymer product”.

[0099] Each of the aforementioned successive processes has certain specifications in respect to amount of C-C double bonds, amount of C-C triple bonds, amount of dienes, amount of aromatics, amount of heteroatoms like oxygen, nitrogen, halogens, sulfur, and metals, amount of organic compounds comprising at least one heteroatom, the heteroatoms preferably selected from the group comprising nitrogen, oxygen, halogens, sulfur, and the final boiling point. The final boiling point is affected by the chain length of hydrocarbons present in said feedstock.

[0100] Other reasons for a hydrotreatment of such feedstocks comprise preventing fouling in further process steps, increasing the physical and chemical (storage) stability of such feedstocks, and providing feedstocks which are within required specifications for successive unit operations. Such specifications may comprise final boiling point, chemical composition, concentration limits for heteroatoms such as nitrogen, oxygen, or sulfur, viscosity, miscibility, and the like.

[0101] The desired chemical reactions during a hydrotreatment of such feedstocks according to the present invention comprise hydrogenation of C-C double and C-C triple bonds, hydrogenation of conjugated C-C double bonds in dienes and aromatics, removal of heteroatoms such as for example nitrogen, oxygen, halogens, and sulfur in organic compounds comprising said heteroatoms, hydrodemetallization for removal of metal atom impurities in such feedstocks, hydroisomerization, and hydrocracking reactions in which longer chain hydrocarbons are cracked to smaller chain hydrocarbons to reduce the final boiling point of such feedstocks.

[0102] Hydrotreatment methods for plastic waste derived pyrolysis oils as feedstock are for example disclosed in WO 2023 / 073059 A1, WO 2017 / 083018 A1, FR 3 103 822 A1, and US 2019 / 062646 A1 which are incorporated by reference herein. The methods, catalysts and process parameters can also be used for the method according to the present invention or used by the operator as a starting point for further optimization in respect to a given feedstock composition and / or a given set of specifications (e.g., concentration of olefins, dienes, sulfur compounds) to be reached by the hydrotreatment.

[0103] Hydrocracking is used to break long-chain hydrocarbons into shorter hydrocarbons. Catalytic hydrocracking is typically carried out over bifunctional catalysts in a hydrogen atmosphere at pressures between 40 bar and 200 bar and temperatures between 300 °C and 600 °C. If the process takes place at medium pressure between 40 bar to 80 bar, it is referred to as mild hydrocracking (MHC). The bifunctional catalysts contain a de- / hydrogenation and an acid functionality, e.g., nickel, molybdenum or noble metals on alumina, zeolites, or other aluminosilicates.

[0104] Hydrocracking methods suitable for step (c) in the process according to the present invention are for example disclosed in WO 2019 / 229072 A1 , EP 2770040 A2 and US 2013 / 0116491 A1.

[0105] Alkanes or alkyl residues having a length n with 10 < n < 30 present in the at least one feedstock and / or blend provided in step (b) are at least partially converted, in case step (c) comprises a hydrocracking reaction, into alkanes or alkyl residues having a chain length m with m < n wherein 1 < m 18, preferably 2 m 16, more preferably 2 m s 12, most preferably 3 < m < 9.

[0106] The hydrotreatment of feedstocks selected from bio-oils, pyrolysis oils manufactured from plastic waste, and mixtures thereof as well as of blends as described herein comprise thermal reactions, catalytic reactions and combinations thereof. A common feature of hydrotreatment is that it requires hydrogen as a reactant. Preferably, the hydrotreatment is conducted in the presence of at least one heterogeneous catalyst.

[0107] Such hydrotreatment reactions can be single-phase reactions or multi-phase reactions (e.g., one or more liquid feedstock reacts with gaseous hydrogen; one or more liquid feedstock reacts with gaseous hydrogen in the presence of at least one heterogeneous catalyst; one or more gaseous feedstock reacts with gaseous hydrogen; one or more gaseous feedstock reacts with gaseous hydrogen in the presence of at least one heterogeneous catalyst and so on).

[0108] Accordingly, different types of reactors can be used for such hydrotreatment reactions, depending for example on the number of phases which must be brought to a reaction. Examples for suitable reactors in case one or more liquid feedstock reacts with gaseous hydrogen in the presence of at least one (solid) heterogeneous catalyst comprise trickle-bed reactors. Examples for suitable reactors in case one or more gaseous feedstock reacts with gaseous hydrogen in the presence of at least one (solid) heterogeneous catalyst comprise fixed bed reactors.

[0109] A hydrotreatment can be conducted in a single stage (reactor) or in successive stages (successive reactors) in which case different process conditions, reactor types and catalysts may be employed to achieve an improved result compared to a single stage hydrotreatment.

[0110] Heterogeneous catalysts employed in hydrotreatment reactions of such feedstocks comprise solid catalyst; said solid catalysts typically comprise at least one active metal and a support. The at least one active metal is preferably selected from nickel, cobalt, molybdenum, tungsten, palladium, rhodium, and the like. Combinations of said active metals such as for example nickel-molybdenum, cobalt-molybdenum and the like can also be used

[0111] The support in such heterogeneous catalysts is preferably selected from the group comprising alumina, silica, silica- aluminas, silica-alumina phosphates, magnesium oxide, clays, carbon, and mixtures thereof. The supports may also comprise support-dopands such as zirconium dioxide, cerium dioxide, titanium dioxide, and mixtures thereof. “Silica- aluminas” also comprise zeolites.

[0112] The temperature, pressure residence time, reactor type, catalyst type and other parameters depend for example on the type of feedstock (composition) used for the hydrotreatment reaction and the type of the desired hydrotreatment reaction (kind of feedstock components to be depleted). The one of skill the art will be familiar with such considerations and will find sufficient guidance in the prior art to select suitable process parameters.

[0113] Optionally, the process according to the first aspect of the invention may be followed by further steps to convert the hydrotreated feedstock into downstream intermediates and products, e.g., fuel blends, olefins, aromatic hydrocarbons, and syngas. In particular, the process may comprise the following steps

[0114] (d) separating the hydrotreated feedstock into at least one fuel fraction and into at least one further fraction and / or separating the hydrotreated feedstock into at least one naphtha fraction and into at least one further fraction;

[0115] (e1) blending the at least one naphtha fraction obtained in step (d) with at least one fuel, e.g., with gasoline, to obtain a fuel blend; and / or

[0116] (e2) subjecting the at least one naphtha fraction obtained in step (d) to steam cracking, in particular to obtain olefins, in particular ethylene, propylene, and C4 olefins, and aromatic hydrocarbons, in particular benzene, toluene, xylenes, and ethylbenzene; and / or

[0117] (e3) subjecting at least one fraction obtained in step (d) to partial oxidation reaction and / or to gasification processes to obtain syngas.

[0118] The one of skill in the art will find no difficulty to carry out these well-established process steps. For instance, separation according to step (d) may be performed by distillation. A suitable distillation unit may comprise at least one distillation column, at least one thin film evaporator or a combination thereof. Preferably, the distillation unit comprises or consists of one distillation column. The distillation may be carried out at a temperature in the range of about 0 °C to about 600 °C, more preferably from about 20 °C to about 400 °C, most preferably from about 80 °C to about 250 °C (the temperature ranges refer to atmospheric pressure of 1 .013 bar). The corresponding operating pressure of the at least one distillation column preferably ranges from about 0.001 bar to about 4 bar (abs), more preferably from about 0.001 bar to about 2.0 bar (abs), most preferably from about 0 9 bar to about 1 .8 bar (abs). The temperature is adjusted accordingly in case the pressure is A 1.013 bar. Optionally, the distillation unit comprises at least one thin-film evaporator. In thin-film evaporators, the medium to be evaporated or the solution to be concentrated by evaporation, respectively, is applied to the evaporator area as a thin film. Thereby, a short contact time with the heating surface is feasible and thermally unstable liquids and substances, respectively, can be evaporated in such thin-film evaporators. Furthermore, thin-film evaporators can be used for separation tasks if the product accumulating as a residue has poor flow properties and / or is prone to agglutinations. Thin-film evaporation processes are based on the principle of simple distillation according to which the separating capacity of said type of evaporator is limited. Suitable thin-film evaporators are available in various designs, for example as fallingfilm evaporators or as rotary evaporators. Further process steps may follow to yield further downstream intermediates and products (e.g., the monomers, polymers, and polymer products described hereinafter) from said olefins, aromatic hydrocarbons, and / or syngas.

[0119] Thus, the invention further relates to a process as described hereinbefore, further comprising the step:

[0120] (f) converting the hydrotreated feedstock obtainable by or obtained by the process as described herein or a chemical material obtainable by or obtained by the process as described herein to obtain a monomer, polymer, or polymer product.

[0121] The converting step(s) to obtain the chemical material, monomer, polymer, or polymer product from the hydrotreated feedstock may comprise one or more synthesis steps and can be performed by conventional synthesis and techniques well known to a person skilled in the art. In particular, step (f) may comprise the processes described in steps (d), (e2), and / or (e3). Independent of the person skilled in the art to assess novelty and inventive step of the independent claim(s), the person skilled in the art to perform the converting step(s) is preferably from the technical field(s) pyrolysis, gasification, remonomerization, depolymerization, synthesis, production of monomers, polymers and polymer compounds, and / or its further processing (e.g. extrusion, injection molding). Examples of the step(s) of the conversion is / 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, 4thedition, CreateSpace Independent Publishing Platform, 2011, ISBN: 978-1466407824, EP0989146 (A1 ), EP1460094 (A1), WC2006034800 (A1 ), EP1529792 (A1 ), WC2006042674 (A1), EP0364854 (A2), US5506275 (A), EP0897402 (A1), WC2015082316 (A1), WC2021021855 (A1), WC2021126938 (A1), WC2021021902 (A1), WC2021092311 (A1), WC2008155271 (A1), WO2013139827 (A1), each of which is incorporated herein by reference.

[0122] In a preferred embodiment, the monomer is a di- or polyol; preferably butanediol; 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.

[0123] In a preferred embodiment, the polymer is and / or the polymer product comprises polyamide (PA); preferably PA 6 or 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 (PTFE), 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 co-terephthalate (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 copolymer or mixture thereof.

[0124] In a preferred embodiment, the polymer and / or the polymer product is / are or is / are 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, housing part for heat exchanger, coolant cooler, charge air cooler, thermostat, water pump, radiator, fastening part, part of battery system for electromobility, dashboard, steering column switch, seat, headrest, center console, transmission component, door module, 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, cushion, or coating; a cloth; preferably shirt, trousers, pullover, boot, shoe, shoe sole, tight or jacket; an electrical part; preferably electrical or electronic passive or active component, 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, microswitch, microbutton, 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 hook (snap-in), or spring tongue; a consumer, agricultural product 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, insulation, detergent, dishwasher tabs or powder, shampoo, body wash, shower gel, soap, fertilizer, fungicide, or pesticide; a packaging for the food industry; preferably mono- or multi-layer blown film, cast film (mono- or multi-layer), biaxially stretched film, or laminating film; or a part of a construction; preferably a rotor blade, insulating material, frame, housing, wall, coating, or separating wall.

[0125] In a preferred embodiment, the content of the hydrotreated feedstock in the product stream comprising olefins, aromatic hydrocarbons, syngas, monomer, polymer 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 hydrotreated feedstock in the product stream comprising olefins, aromatic hydrocarbons, syngas, monomer, polymer 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 wherein 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.

[0126] The process according to the second aspect of the present invention can be used to track the origin of the hydrogen provided in step (a), consumed as a reactant in step (c) to form a hydrotreated feedstock and downstream products manufactured from said hydrotreated feedstock. At least a portion of the hydrogen provided in step (a) is chemically added to the hydrotreated feedstock which results from step (c) and to downstream products manufactured from said hydrotreated feedstock in successive processing (e.g., by formation of C-D and C-H bonds). Accordingly, when analyzing the deuterium content in the hydrotreated feedstock and / or the downstream products, the non-fossil origin of the hydrogen provided in step (a) and reacted in step (c) can be tracked. In particular, a deuterium content of < 100 ppm in a test sample (hydrogen, hydrotreated feedstocks, e.g., as obtained in step (c), and / or downstream products obtained from said hydrotreated feedstocks) is considered indicative of water electrolysis being the hydrogen origin. Alternatively, comparative determinations of the deuterium content in a test sample and in a corresponding reference sample (produced with hydrogen of fossil origin) may be indicative of water electrolysis being the origin of hydrogen in the test sample if the deuterium content in the test sample is lower than in the reference sample.

[0127] Hence, the deuterium content in hydrogen, hydrotreated feedstock, e.g., as obtained in step (c), and downstream products obtained from said hydrotreated feedstocks can be used for tracking the origin of preparation of hydrogen, hydrotreated feedstock, e.g., as obtained in step (c), and downstream products based on hydrogen.

[0128] Tracking of the origin of hydrogen is required for establishing in a reliable way that a process for hydrotreating a feedstock uses as little fossil-based energy as possible.

[0129] The inventive process for tracking the origin of hydrogen, hydrotreated feedstocks, and downstream products mentioned above may be employed as a single tracking method or in combination with further tracking methods.

[0130] The one of skill in the art will be familiar with test methods and procedures to determine the deuterium content in hydrogen, hydrotreated feedstocks, and downstream products.

[0131] In particular, a method suitable for determining the deuterium content in the hydrotreated feedstock comprises the steps: i) combusting a sample of the hydrotreated feedstock and thereby forming a combustion gas comprising water; ii) separating the water from the combustion gas formed in step i); and ill) determining the deuterium content in the water separated from the combustion gas in step ii).

[0132] An analogous method will be suitable to determine the deuterium content in downstream products manufactured from the hydrotreated feedstock described herein. For instance, the following method descriptions are suited for determination of the molar share of deuterium based on the total hydrogen content (deuterium content) of gas and liquid samples. The isotopic H / D-share analysis is based on mass spectrometry or NMR spectroscopy. Three different methods can be used: method A for gas samples, method B for liquid samples, and method C can be used for any sample soluble in suitable solvents for NMR spectroscopy.

[0133] For the determination of the “D content in gas and liquid samples” it is of crucial importance not to contaminate the samples e.g., with ambient humidity or other ambient components containing hydrogen or deuterium. Therefore gastight materials and sealings must be used with clean sample containers to avoid any cross-contamination. Therefore, before filling and sealing a sample container it must be flushed at least 20 times the sample container volume with the gas or liquid stream to be analyzed. The same is valid for the experimental setup of the gas sampler and mass spectrometer Utmost care must be taken to avoid cross-contamination e.g., via condensation of humidity. The analytical setup from sampling to mass spectrometry is validated with known reference samples.

[0134] Method A) Gas samples

[0135] Total deuterium from HD and D2 in hydrogen gas samples can be determined via ultra-high resolution quadrupole mass spectrometry using a Hiden DLS-20 (Hiden Analytical Ltd., Warrington, Cheshire, UK) analyzer setup. The general method setup is described in C.C. Klepper, T.M. Biewer, U. Kruezi, S. Vartanian, D. Douai, D.L. Hillis, C. Marcus, Extending helium partial pressure measurement technology to JET DTE2 and ITER; Rev. Sci. Instrum., 87 (11) (2016); doi: 10.1063 / 1.4963713. For the hydrogen gas samples, the threshold ionization mass spectrometry mode (TIMS) can be used as described in S. Davies, J. A. Rees, D.L. Seymour; Threshold ionisation mass spectrometry (TIMS); A complementary quantitative technique to conventional mass resolved mass spectrometry; Vacuum, 101 (2014), pp. 416-422; doi: 10.1016 / j. vacuum.2013.06.004. Sensitivity is + / -1 ppm.

[0136] Method B) Liquid samples

[0137] Analysis of liquid samples can be executed via isotope ratio monitoring gas chromatography / mass spectrometry (IRMS). Therefore, a DELTA V PLUS CF-IRMS mass spectrometer can be used. This mass spectrometer with magnetic sector with continuous flux DELTA V PLUS CF-IRMS can be used to measure the isotopic ratio of2H / 1H.

[0138] Measurement of D / H in a continuous He-flow mode needs the complete removal of low energy 4 He+ions from the HD+ ion beam at m / z 3). The method is described in RAPID COMMUNICATIONS IN MASS SPECTROMETRY Rapid Commun. Mass Spectrom. 13, 1226-1230 (1999), W.A. Brandt et al. Sensitivity is within +1-3 ppm.

[0139] Method C) Analysis of isotope ratios in starting materials and products

[0140] Analysis of isotope ratios in starting materials and products can be furthermore executed via SNIF-NMR related methods (“site-specific natural isotope fractionation studied by nuclear magnetic resonance'') using high resolution2H-NMR (Bruker Avance NEO 600 MHz NMR Spectrometer and Bruker Avance III HD 700 MHz NMR Spectrometer both equipped with TCI probes).

[0141] Principles of this technology are described in Gerard J. Martin, Serge Akoka, and Maryvonne L. Martin; SNIF-NMR Part 1 : Principles; in Graham A. Webb (ed.), Modern Magnetic Resonance, Springer (2008) pp 1651-1658 as well as Maryvonne Martin, Benli Zhang, and Gerard J. Martin; SNIF-NMR Part 2: Isotope Ratios as Tracers of Chemical and Biochemical Mechanistic Pathways; in Graham A. Webb (ed.), Modern Magnetic Resonance, Springer (2008) pp 1659-1667 and Gerard J. Martin, Maryvonne L. Martin and Gerald Remaud; SNIF-NMR Part 3: From Mechanistic Affiliation to Origin Inference; in Graham A. Webb (ed.), Modern Magnetic Resonance, Springer (2008) pp 1669— 1680.

[0142] In further aspects, the invention relates to the products obtained by carrying out the processes described herein, in particular to hydrotreated feedstocks as well as to any fractions and downstream products obtainable thereof like fuel blends, olefins, aromatic hydrocarbons, syngas, monomers, polymers, or polymer products, all of which are characterized by a deuterium content < 100 ppm, based on the total hydrogen content, and / or by a deuterium content being lower than the deuterium content in a corresponding feedstock, fraction thereof, or downstream product thereof obtained via hydrotreatment with hydrogen of fossil origin.

[0143] The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The method of any of embodiments 1 to 3”, every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to “The method of any of embodiments 1 , 2 and 3”. Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred embodiments of the present invention, and thus, suitably supports the claims of the present invention.

[0144] 1. A process for hydrotreating feedstocks manufactured from biomass and / or plastic waste, wherein said process comprises the following steps:

[0145] (a) providing hydrogen with a deuterium content 100 ppm, based on the total hydrogen content, by water electrolysis based on electrical power generated at least in part from non-fossil energy;

[0146] (b) providing at least one feedstock manufactured from plastic waste and optionally blending with at least one feedstock of fossil origin to obtain a blend; and

[0147] (c) reacting hydrogen from step (a) with the at least one feedstock and / or blend from step (b) to form a hydrotreated feedstock.

[0148] 2. The process according to embodiment 1, wherein in step (a) the electrical power is generated at least in part from renewable resources, preferably from wind power, solar energy, hydroelectricity, geothermal energy, ambient heat captured by heat pumps, bioenergy, or the renewable part of waste. The process according to embodiment 1, wherein in step (a) the electrical power is generated at least in part from wind power, solar energy, hydroelectricity, geothermal energy, ambient or industrial heat captured by heat pumps, bioenergy, the renewable part of waste energy sources or nuclear energy (fission), preferably from wind power, solar energy, biomass, hydropower, and geothermal energy. The process according to any one of embodiments 1 to 3, wherein in step (a) the portion of electrical power generated from fossil fuels does not exceed 50%, preferably does not exceed 30%, more preferably does not exceed 20%, most preferably does not exceed 10%. The process according to any one of embodiments 1 to 4, wherein in step (a) the electrical power is generated exclusively from non-fossil resources. The process according to any one of embodiments 1 to 5, wherein in step (a) water having a deuterium content below 160 ppm, based on the total hydrogen content, is used for water electrolysis. The process according to any one of embodiments 1 to 6, wherein in step (a) hydrogen is provided by polymer electrolyte membrane water electrolysis or alkaline water electrolysis, preferably by proton exchange membrane water electrolysis (PEMWE) or anion exchange membrane water electrolysis (AEMWE). The process according to any one of embodiments 1 to 7, wherein in step (a) the deuterium content in the hydrogen provided in step (a) is in the range of from 10 to 95 ppm, preferably in the range of from 10 to 90 ppm, more preferably in the range of from 20 to 80 ppm, and most preferably in the range of from 30 to 75 ppm, based on the total hydrogen content. The process according to any one of embodiments 1 to 8, wherein in step (b) the at least one feedstock manufactured from plastic waste is selected from the group comprising, preferably consisting of, one or more pyrolysis oils. The process according to embodiment 9, wherein in step (b) the one or more pyrolysis oils originate from plastic waste selected the group comprising, preferably consisting of, industrial and domestic plastic waste, used tires, agricultural and horticultural plastic material, pure polymeric plastic waste, mixed plastic waste or film waste, optionally including biomass, soiling, adhesive materials, fillers, and residues.

[0149] 11. The process according to embodiment 9 or 10, wherein in step (b) the one or more pyrolysis oils originate from plastic waste selected from the group comprising, preferably consisting of, polyethylene, polypropylene, polystyrene, and copolymers thereof, 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.

[0150] 12. The process according to any one of embodiments 9 to 11, wherein in step (b) the one or more pyrolysis oils have a bromine number of about 2 g Brs / WO g to about 150 g Br2 / 100 g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-%, as determined by ASTM D 5134, and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-%, as determined by ASTM D 5134.

[0151] 13. The process according to any one of embodiments 1 to 12, wherein in step (b) the at least one feedstock of fossil origin is selected from the group comprising, preferably consisting of, crude oil fractions, heavy crude oil, vacuum gas oil, residues from atmospheric and vacuum distillation units, coal tar, bitumen, shale oil, and natural gas liquids.

[0152] 14. The process according to any one of embodiments 1 to 13, wherein in step (b) the blend comprises the at least one feedstock of fossil origin in a quantity of about 0 wt.-%, 5 wt.-%, 10 wt.- %, 15 wt.-%, 20 wt.-%, 25 wt.-%, 30 wt.-%, 35 wt.-%, 40 wt.-%, 45 wt.-%, 50 wt.-%, 55 wt.-%, 60 wt.-%, 65 wt.-%, 70 wt.-%, 75 wt.-%, 80 wt.-% or more and wherein the blend comprises at least 2 wt.-% of at least one feedstock manufactured from plastic waste.

[0153] 15. The process according to any one of embodiments 1 to 14, wherein step (c) comprises one or more reactions selected from the group consisting of hydrodeoxygenation, hydrodenitrogenation, hydrodehalogenation, hydrodesulfurization, hydrodemetallation, hydrocracking, hydroisomerization, and hydrogenation. 16. The process according to any one of embodiments 1 to 15, wherein step (c) is carried out in the presence of at least one catalyst, preferably at least one heterogeneous catalyst selected from the group comprising, preferably consisting of, nickel, cobalt, molybdenum, tungsten, palladium, rhodium, nickel-molybdenum, cobalt-molybdenum, noble metals on alumina, zeolites, or other aluminosilicates.

[0154] 17. The process according to any one of embodiments 1 to 16, wherein step (c) is carried out at high temperatures, in particular from 100 °C to 600 °C, and / or high pressures, in particular from 5 bar to 200 bar.

[0155] 18. The process according to any one of embodiments 1 to 17, wherein the hydrotreated feedstock obtained in step (c) is depleted, in comparison to the feedstock provided in step (b), in at least one respect of the group comprising amount of C-C double bonds, amount of C-C triple bonds, amount of dienes, amount of aromatics, amount of heteroatoms, the heteroatoms preferably selected from the group comprising nitrogen, oxygen, halogens, sulfur, and metals, amount of organic compounds comprising at least one heteroatom, the heteroatoms preferably selected from the group comprising nitrogen, oxygen, halogens, and sulfur, and / or mass fraction of alkanes or alkyl residues having n carbon atoms with 10 < n < 30

[0156] 19. The process according to any one of embodiments 1 to 18, the process further comprising step (d)

[0157] (d) separating the hydrotreated feedstock into at least one fuel fraction and into at least one further fraction and / or separating the hydrotreated feedstock into at least one naphtha fraction and into at least one further fraction.

[0158] 20. A process for obtaining a fuel blend, comprising the steps (a), (b), (c), and (d) of the process for hydrotreating feedstocks according to embodiment 19, and further comprising step (e1)

[0159] (e1) blending the at least one naphtha fraction obtained in step (d) with at least one fuel, e.g., with gasoline, to obtain a fuel blend.

[0160] 21. A process for obtaining olefins and aromatic hydrocarbons, comprising the steps (a), (b), (c), and (d) of the process for hydrotreating feedstocks according to embodiment 19, and further comprising step (e2) (e2) subjecting the at least one naphtha fraction obtained in step (d) to steam cracking, in particular to obtain olefins and aromatic hydrocarbons. A process for obtaining syngas, comprising the steps (a), (b), (c), and (d) of the process for hydrotreating feedstocks according to embodiment 19, and further comprising step (e3)

[0161] (e3) subjecting at least one fraction obtained in step (d) to partial oxidation reaction and / or to gasification processes to obtain syngas. A process for obtaining a monomer, a polymer, or a polymer product, comprising the steps (a), (b), and (c) of the process for hydrotreating feedstocks according to any one of embodiments 1 to 18, optionally further comprising one or more of steps (d), (e2), and (e3) according to any one of embodiments 19, 21 , and 22, and further comprising step (f)

[0162] (f) converting the hydrotreated feedstock of step (c), at least one fraction of step (d), the olefins and / or aromatic hydrocarbons of step (e2), and / or the syngas of step (e3) or a chemical material obtainable by or obtained by any one of embodiments 1 to 25 to obtain a monomer, polymer, or polymer product. A process for tracking the origin of hydrogen used in the preparation of hydrotreated feedstock and / or downstream products thereof, comprising the steps

[0163] (A) providing a test sample of one or more hydrotreated feedstocks and / or one or more downstream products thereof and optionally providing a reference sample of one or more corresponding feedstocks hydrotreated with hydrogen of fossil origin and / or one or more corresponding downstream products;

[0164] (B) determining the deuterium content in said test sample and optionally determining the deuterium content in said reference sample; and

[0165] (C ) establishing whether said deuterium content in the test sample does not exceed 100 ppm and / or optionally whether said deuterium content in the test sample is lower than said deuterium content in the reference sample. A hydrotreated feedstock or a fraction thereof with a deuterium content 100 ppm, based on the total hydrogen content, and / or with a deuterium content being lower than the deuterium content in a corresponding feedstock hydrotreated with hydrogen of fossil origin. A downstream product of a hydrotreated feedstock with a deuterium content 100 ppm, based on the total hydrogen content, and / or with a deuterium content being lower than the deuterium content in a corresponding downstream product of a feedstock hydrotreated with hydrogen of fossil origin. 27. An olefin or an aromatic hydrocarbon obtained from a hydrotreated feedstock and having a deuterium content < 100 ppm, based on the total hydrogen content, and / or having a deuterium content being lower than the deuterium content in a corresponding olefin or aromatic hydrocarbon obtained from a feedstock hydrotreated with hydrogen of fossil origin.

[0166] 28. A syngas obtained from a hydrotreated feedstock and having a deuterium content 100 ppm, based on the total hydrogen content, and / or having a deuterium content being lower than the deuterium content in a corresponding syngas obtained from a feedstock hydrotreated with hydrogen of fossil origin. 29. A monomer, a polymer, or a polymer product obtained from a hydrotreated feedstock and having a deuterium content 100 ppm, based on the total hydrogen content, and / or having a deuterium content being lower than the deuterium content in a corresponding monomer, polymer, or polymer product obtained from a feedstock hydrotreated with hydrogen of fossil origin.

Claims

Claims1. A process for hydrotreating feedstocks manufactured from plastic waste, wherein said process comprises the following steps:(a) providing hydrogen with a deuterium content 100 ppm, based on the total hydrogen content, by water electrolysis based on electrical power generated at least in part from non-fossil energy;(b) providing at least one feedstock manufactured from plastic waste and optionally blending with at least one feedstock of fossil origin to obtain a blend; and(c) reacting hydrogen from step (a) with the at least one feedstock and / or blend from step (b) to form a hydrotreated feedstock.2 The process according to claim 1, wherein in step (a) the electrical power is generated at least in part from wind power, solar energy, hydroelectricity, geothermal energy, ambient or industrial heat captured by heat pumps, bioenergy, the renewable part of waste energy sources or nuclear energy, preferably from wind power, solar energy, biomass, hydropower, and geothermal energy.3 The process according to any one of claims 1 to 2, wherein in step (b) the at least one feedstock manufactured from plastic waste is selected from the group comprising, preferably consisting of, one or more pyrolysis oils.

4. The process according to claims 3, wherein in step (b) the one or more pyrolysis oils originate from plastic waste selected the group comprising, preferably consisting of, industrial and domestic plastic waste, used tires, agricultural and horticultural plastic material, pure polymeric plastic waste, mixed plastic waste or film waste, optionally including soiling, adhesive materials, fillers, and residues.5 The process according to claim 3 or 4 wherein in step (b) the one or more pyrolysis oils have a bromine number of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-%, as determined by ASTM D 5134, and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-%, as determined by ASTM D 51346. The process according to any one of claims 1 to 5, wherein in step (b) the at least one feedstock of fossil origin is selected from the group comprising, preferably consisting of, crude oil fractions, heavy crude oil, vacuum gas oil, residues from atmospheric and vacuum distillation units, coal tar, bitumen, shale oil, and natural gas liquids.

7. The process according to any one of claims 1 to 6, wherein in step (b) the blend comprises the at least one feedstock of fossil origin in a quantity of about 0 wt.-%, 5 wt -%, 10 wt.- %, 15 wt.-%, 20 wt.-%, 25 wt.-%, 30 wt.-%, 35 wt.-%, 40 wt.-%, 45 wt.-%, 50 wt.-%, 55 wt -%, 60 wt.-%, 65 wt.-%, 70 wt.-%, 75 wt.-%, 80 wt.-% or more and wherein the blend comprises at least 2 wt.-% of at least one feedstock manufactured from at least one feedstock manufactured from plastic waste.

8. The process according to any one of claims 1 to 7, wherein step (c) comprises one or more reactions selected from the group consisting of hydrodeoxygenation, hydrodenitrogenation, hydrodehalogenation, hydrodesulfurization, hydrodemetallation, hydrocracking, hydroisomerization, and hydrogenation.

9. The process according to any one of claims 1 to 8, the process further comprising step (d)(d) separating the hydrotreated feedstock into at least one fuel fraction and into at least one further fraction and / or separating the hydrotreated feedstock into at least one naphtha fraction and into at least one further fraction.

10. A process for obtaining olefins and aromatic hydrocarbons, comprising the steps (a), (b), (c), and (d) of the process for hydrotreating feedstocks according to claim 6, and further comprising step (e2)(e2) subjecting the at least one naphtha fraction obtained in step (d) to steam cracking, in particular to obtain olefins and aromatic hydrocarbons11. A process for obtaining syngas, comprising the steps (a), (b), (c), and (d) of the process for hydrotreating feedstocks according to claim 6, and further comprising step (e3)(e3) subjecting at least one fraction obtained in step (d) to partial oxidation reaction and / or to gasification processes to obtain syngas.

12. A process for obtaining a monomer, a polymer, or a polymer product, comprising the steps (a), (b), and (c) of the process for hydrotreating feedstocks according to any one of claims 1 to 8, optionally further comprising one or more of steps (d), (e2), and (e3) according to any one of claims 9, 10, and 11, and further comprising step (f)(f) converting the hydrotreated feedstock of step (c), at least one fraction of step (d), the olefins and / or aromatic hydrocarbons of step (e2), and / or the syngas of step (e3) or a chemical material obtainable by or obtained by any one of claims 1 to 11 to obtain a monomer, polymer, or polymer product13. A process for tracking the origin of hydrogen used in the preparation of hydrotreated feedstock and / or downstream products thereof, comprising the steps[A] providing a test sample of one or more hydrotreated feedstocks and / or one or more downstream products thereof and optionally providing a reference sample of one or more corresponding feedstocks hydrotreated with hydrogen of fossil origin and / or one or more corresponding downstream products;[B] determining the deuterium content in said test sample and optionally determining the deuterium content in said reference sample; and[C] establishing whether said deuterium content in the test sample does not exceed 100 ppm and / or optionally whether said deuterium content in the test sample is lower than said deuterium content in the reference sample.

14. A hydrotreated feedstock or a fraction thereof with a deuterium content 100 ppm, based on the total hydrogen content, and / or with a deuterium content being lower than the deuterium content in a corresponding feedstock hydrotreated with hydrogen of fossil origin.

15. A downstream product of a hydrotreated feedstock with a deuterium content < 100 ppm, based on the total hydrogen content, and / or with a deuterium content being lower than the deuterium content in a corresponding downstream product of a feedstock hydrotreated with hydrogen of fossil origin.