Process for manufacture of synthesis gas from end-of-life tires

Abstract

The present invention relates to a process for manufacturing synthesis gas from end-of-life tires which comprises reducing the size and sorting if said end-of-life tires into sorted fragments. The sorted fragments are then subjected to a gasification reaction in at least one plasma gasifier comprising at least three plasma torches. Thereby, the sorted fragments of end-of-life tires are converted into synthesis gas whereby less CO2 is produced in comparison to state- of-the-art processes for treatments of end-of-life tires. Said synthesis gas is then preferably used as a feedstock for manufacturing synthetic fuels such as methane, methanol, Fischer-Tropsch hydrocarbons (and upgraded products made thereof).

Description

[0001] 240746W001

[0002] 1

[0003] Process for manufacture of synthesis gas from end-of-life tires

[0004] Technical area of the invention

[0005] The present invention relates to a process for manufacture of synthesis gas from waste streams comprising rubber such as end-of-life tires by gasification.

[0006] Background of the invention

[0007] End-of-life tires are widely produced and usually disposed in landfills, incinerated or pyrolyzed for production of thermal energy or fuels. Thereby undesired CO2 is formed. Accordingly, the demand of more sustainable utilizations of end-of-life tires is growing.

[0008] WO 2013 / 184074 A1 relates to a system and method for converting waste tires in a plasma thermal processor into syngas and carbon black. The plasma thermal processor consists of a plasma torch and an RF induction coil and further comprises a chamber and an LF induction coil.

[0009] WO 2023 / 132784 A1 relates to a method for tire recycling using a plasma jet which is generated by a hybrid plasma torch comprising an arc plasma torch and a radio frequency (RF) plasma torch.

[0010] WO 2006 / 128285 A1 relates to a carbonaceous feedstock gasification system comprising a gasification reaction vessel (or converter) having one or more plasma heat sources such as plasma torches.

[0011] US 2016 / 045841 A1 relates to eco-friendly systems, methods and processes for completely self-sustained, closed loop, emission-free processing of multiple source feedstock(s).

[0012] It is the objective of the present invention to provide a process for converting end-of-life tires into synthesis gas and chemical products.

[0013] It is a further objective of the present invention to provide process for converting end-of-life tires into synthesis gas in which undesired fouling is suppressed.

[0014] It is a further objective of the present invention to provide a process for converting end-of-life tires into an essentially CC free synthesis gas which is suited for conversion into chemical products.

[0015] It is a further objective to provide a process for converting end-of-life tires into synthesis gas and chemical products having a reduced product carbon footprint and / or reduced CO2emissions compared to state-of-the-art processes. 240746W001

[0016] 2

[0017] It is a further objective to provide a provide a synthesis gas composition produced from end-of-life tires which is suited for conversion by a further process selected from the group comprising methanization, methanol synthesis and Fischer-Tropsch synthesis.

[0018] It is a further objective to provide a process for converting end-of-life tires into synthetic fuels.

[0019] Summary of the invention

[0020] These problems are solved by a process for manufacturing synthesis gas from end-of-life tires, said process comprising the steps

[0021] (i) providing a first feedstock F1 wherein said first feedstock F1 comprises sorted fragments of end-of-life tires, said sorted fragments of end-of-life tires formed by sorting from a non-sorted end-of-life tires, wherein said non-sorted end-of-life tires comprise a tread and a carcass, and further comprise metal fragments, non-metallic inorganic fillers, rubber and at least one polymer P selected from the group consisting of polyamides, polyesters and mixtures thereof, wherein said non-sorted end-of-life tires are presorted to form the sorted fragments of end-of-life tires, preferably in this order, by a) optionally separating the tread from the carcass of the non-sorted end-of-life tires, b) reducing the size of non-sorted end-of-life tires and / or the size of the carcass separated in optional step a) from the tread, and thereby produce fragments of non-sorted end-of-life tires and / or fragments of the carcass, and c) separating at least a portion of said metal fragments, and optionally separating at least a portion of said non-metallic inorganic fillers and / or at least a portion of the at least one polymer P from the fragments formed in step b), and thereby form sorted fragments of end-of-life tires and / or sorted fragments of carcasses, whereby said sorted fragments of end-of-life tires and / or sorted fragments of carcasses is / are depleted in metal fragments and optionally also depleted in non-metallic inorganic fillers and / or in at least a portion of polymer P, and whereby optionally step b) and / or step c) is / are repeated at least once,

[0022] (ii) preferably providing at least one further feedstock F2,

[0023] (iii) converting said first feedstock F1 provided in step (i), preferably together with at least one further feedstock F2 provided in step (ii), in at least one plasma gasifier PG into a gas stream GS1 , said gas stream GS1 comprising synthesis gas wherein said synthesis gas comprises H2, CO and CO2and wherein said at least one plasma gasifier PG comprises at least three plasma torches, said at least three plasma torches operated with electricity,

[0024] (iv) removing at least a portion of the CO2comprised in the gas stream GS1 in a synthesis gas upgrading unit SUU and thereby forming a gas stream GS2 which is depleted in CO2, and

[0025] (v) optionally using at least a portion of the said CO2removed from the gas stream GS2 in step (iv) as a further feedstock F2 in step (iii). 240746W001

[0026] 3

[0027] These problems are further solved by a use of plasma gasification in at least one plasma gasifier PG to convert a sorted fragments of end-of-life tires, said sorted fragments of end-of-life tires formed by sorting from non-sorted end- of-life tires, wherein said non-sorted end-of-life tires comprises a tread and a carcass, and further comprise metal fragments and non-metallic inorganic fillers, rubber and at least one polymer P selected from the group consisting of polyamides, polyesters and mixtures thereof, wherein said non-sorted end-of-life tires is presorted to form the sorted end-of-life tires and wherein said at least one plasma gasifier PG comprises at least three plasma torches.

[0028] The process and use according to the present invention suppress undesired fouling caused by deposition of tar in the at least one plasma gasifier PG, particularly in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG.

[0029] Said synthesis gas can then be further converted into synthetic fuels such as methane, methanol, Fischer-Tropsch hydrocarbons and upgraded fuels made from methanol and Fischer-Tropsch hydrocarbons. The molar ratio H2: CO of the synthesis gas produced by the process according to the present invention is more suited, particularly because it is essentially free of CO2, than that of synthesis gas produced by processes comprising no plasma-gasifier, particularly no fixed bed plasma gasifier.

[0030] Further aspects of the present invention will become apparent to the person skilled in the art directly from the foregoing and following description and the examples.

[0031] Detailed description of the invention

[0032] Definitions:

[0033] In the context of the present description and the accompanying claims, the term “about” preferably means a deviation of the thus described value of ±10 %. In the context of the present invention, the term “combinations thereof” is inclusive of one or more of the recited elements. In the context of the present invention, the term “mixture thereof” is inclusive of one or more of the recited elements.

[0034] “End-of-life-tires” (ELT) also known as scrap tires or waste tires, refer to tires that have reached the end of their usable life and are no longer suitable for their original purpose. These tires are usually worn out, damaged, or have tread depths that are below the legal limit for safe use on roads. End-of-life tires are considered waste materials and pose environmental and health risks if not managed properly.

[0035] “Refuse-derived fuel” (RDF) is defined herein as a fuel produced form various types of waste such as municipal solid waste (MSW), industrial waste or commercial waste. RDF consists largely of combustible components of such waste, as non-recydable plastics (not including PVC), paper cardboard, labels, and other corrugated materials. These fractions are separated by different processing steps, such as screening, air classification, ballistic separation, separation of ferrous and non-ferrous materials, glass, stones, and other foreign materials and shredding into a uniform grain size, or also pelletized to produce a homogeneous material which can be used as a feedstock for 240746W001

[0036] 4 gasification processes (Y. Yang et al., Gasification of refuse-derived fuel from municipal solid waste for energy production: a review, Environmental Chemistry Letters (2021) 19, 2127-2140 (https: / / doi.org / 10.1007 / s10311-020- 01177-5).

[0037] “Synthetic fuels” are defined herein as fuels produced from end-of-life tires via gasification of said end-of-life tires and the resulting synthesis gas.

[0038] “Jet fuel”, also known as aviation turbine fuel (ATF) is defined herein as a type of aviation fuel designed for use in aircraft powered by gas-turbine engines which comprises a mixture of hydrocarbons. Jet fuel types comprise Jet A, Jet A-1 , Jet B, and TS-1. The boiling point of jet fuel ranges between about 175 to about 270 °C.

[0039] The term “downstream of” is defined herein in respect to a succession of unit operations as located next to on the side which is in the flow direction of fluids passing said succession of unit operations.

[0040] The term “fluidically connected to” in respect to two or more units is defined herein that a fluid such as a particulate solid, liquids, gases, and mixtures thereof can flow from one of such unit to the other such unit and flow through and / or along such an analytical unit. Two units “fluidically connected to” each other are for example connected by one or more pipes which each other or by screw conveyors or by extruders or by solids pumps.

[0041] The process according to the present invention is described in detail below.

[0042] In step i) of the process according to the present invention, a first feedstock F1 is provided. Said first feedstock F1 consists of sorted fragments of end-of-life tires which are formed from presorting of non-sorted end-of-life tires, preferably in this order, by a) optionally separating the tread from the carcass of the non-sorted end-of-life tires, b) reducing the size of non-sorted end-of-life tires and / or the size of the carcass separated in optional step a) from the tread, and thereby produce fragments of non-sorted end-of-life tires and / or fragments of the carcass, and c) separating at least a portion of said metal fragments, and optionally separating at least a portion of said non-metallic inorganic fillers and / or at least a portion of the at least one polymer P from the fragments formed in step b), and thereby form sorted fragments of end-of-life tires and / or sorted fragments of carcasses, whereby said sorted fragments of end-of-life tires and / or sorted fragments of carcasses is / are depleted in metal fragments and optionally also depleted in non-metallic inorganic fillers and / or in at least a portion of the at least one polymer P, and whereby optionally step b) and / or step c) is / are repeated at least once. 240746W001

[0043] 5

[0044] The rubber part of end-of-life tires may comprise natural and synthetic rubber. Non-metallic inorganic fillers are for example carbon black particles, silica particles and / or zinc oxide particles which are comprised in the rubber part of tires as fillers. Another important component of end-of-life tires are metal fragments, preferably steel belts, which are placed beneath the rubber tread to provide strength and stability to the tire. The carcass (sidewall) of the tire is made of rubber and reinforced with fabric made of or comprising at least one polymer P selected from the group consisting of polyamides, polyesters and mixtures thereof to help protect the tire from damage and provide a smooth ride.

[0045] End-of-life tires for passenger cars may have the following composition: 47 wt.-% natural and synthetic rubbers, 14 wt.-% steel, 5.5 wt.-% of at least one polymer selected from the group consisting of polyamides, polyesters and mixtures thereof, 22.5 wt.-% carbon black and silica, 2.5 wt.-% vulcanizing agents, and 8.5 wt.-% additives (antioxidants, antiozonants, curing system).

[0046] End-of-life tires for trucks and busses may have the following composition: 45 wt.-% natural and synthetic rubbers, 23.5 wt.-% steel, 1 wt.-% of at least one polymer selected from the group consisting of polyamides, polyesters and mixtures thereof, 21 wt.-% carbon black and silica, 3 wt.-% vulcanizing agents, and 6.5 wt.-% additives (antioxidants, antiozonants, curing system).

[0047] Said compositions may also differ for certain types of end-of-life tires which can still be utilized as first feedstock F1 in the process according to the present invention.

[0048] The sorted fragments obtained from step (i) c) (feedstock F1), also denoted “rubber crumbs”, “granulated rubber” and “ground tire rubber (GTR)”, mainly comprise rubber, non-metallic inorganic fillers (such as carbon black, silica) and additives (antioxidants, antiozonants, curing system). Most of the at least one polymer P selected from the group consisting of polyamides, polyesters and mixtures thereof is preferably separated therefrom during step (i) as “fluff” and only residual amounts are then comprised in feedstock F1.

[0049] The sorted fragments obtained in step (i) c) (feedstock F1) are preferably dry and not lumpy and more preferably free flowing.

[0050] The sorted fragments of end-of-life tires and / or sorted fragments of carcasses obtained in step (i) c) (feedstock F1) preferably comprise:

[0051] 14 to 42 wt.-% natural rubber

[0052] 18 to 26 wt.-% synthetic rubber up to 5 wt.-% reclaimed rubber

[0053] 28 to 44 wt.-% non-metallic inorganic fillers (mainly carbon black and silica) up to 1 wt.-% vulcanizing agents up to 7 wt.-% additives (antioxidants, antiozonants, curing system). 240746W001

[0054] 6

[0055] A particular feedstock F1 has the following compositions which is only to be understood as one particular composition among manyfold compositions suited as feedstock F1 in the process according to the present invention. This particular composition for a feedstock F1 was also used in the examples further below:

[0056] 85.9 wt.-% carbon (sum of carbon composed in rubber and carbon of carbon black)

[0057] 8 wt.-% hydrogen

[0058] 0.4 wt.-% nitrogen

[0059] 1 wt.-% sulfur

[0060] 2.3 wt.-% oxygen

[0061] 2.4 wt.-% ash (i.e., non-metallic inorganic fillers other than carbon black)

[0062] 66.5 wt.-% volatiles

[0063] 30.3 wt.-% fixed carbon

[0064] 0.8 wt.-% moisture

[0065] 40 MJ / kg gross calorific value

[0066] In one aspect of the present invention, the carcass and the tread of unsorted end-of-life tires are separated from each other in optional step a) in step (i).

[0067] The shredded material is then passed through screens and separators that separate the different components based on their size, weight, and density. The carcass and tread can have different characteristics that allow them to be effectively separated during this process. For example, the steel belts in the carcass can be separated using magnets and / or by a bead extractor, while the rubber tread can be separated through a combination of screens, air classifiers, and gravity separators. The carcass separated by this method is then subjected to step b) in step (i).

[0068] Another method suitable for separating the carcass and tread in optional step a) of step (i) is through manual or automated cutting. In this approach, the end-of-life tire is cut into sections or strips using specialized cutting machines. The separated carcass is the suited for step b) in step (i).

[0069] Another method suitable for separating the carcass and the tread in optional step a) of step (i) is by degrading the tread. In this aspect of the present invention, the carcass and the tread can be further comminuted. Preferably, the carcass may then be subjected to steps b) and c) of step (i) whereby rubber crumbs (granulated rubber) are formed which are depleted in metal fragments and optionally also depleted in the at least one polymer P.

[0070] Preferably, the tread and carcass of the non-sorted end-of-life tires are separated on optional step a) by a method selected from the group comprising or more preferably consisting of mechanical shredding, manual cutting, automated cutting, degrading, and combinations thereof.

[0071] The unsorted end-of-life tires and / or the carcass separated in optional step a) from the tread of end-of-live tires are reduced in size in step b) to obtain the preferred fragment size of at least 90 wt.-% of the fragments of end-of-life tires 240746W001

[0072] 7 and / or sorted fragments of carcasses formed in step b) are smaller than 5 cm, preferably at least 95 wt.-% smaller than 5 cm and more preferably at least 95 wt.-% are smaller than 3 cm.

[0073] The method employed in step b) is selected from the group comprising or consisting of shredding, grinding, milling, sieving, classifying and combinations thereof. Step b) may further comprise optical and / or manual separation to remove fragments too large for step c). Such methods are known to the skilled person and can be adapted to a given non-sorted end-of-life tires provided in step (i) and / or carcasses separated in optional step a). Such fragments too large are optionally subjected to the size reduction in step b) for a second or further time until the requirements for suitable size as defined in the previous paragraph are obtained.

[0074] Step b) in step (i) comprises breaking down the non-sorted end-of-life tires or fragments of the carcass into smaller pieces preferably using a shredder or a granulator. A first method suitable for separating the carcass and tread in optional step a) in step (i) is mechanical shredding. In this process, the end-of-life tire is shredded into smaller pieces using specialized shredding equipment. Various methods are known in the art and can be applied to step b) in step (i): mechanical granulation, preferably at a temperature below 40 °C (EP 404525 B1), shredding using a shredding mill (PL 241204 B1), mechanical shredding at ambient temperature to obtain rubber granules (EP 3741798 A1), shredding and hammering, optionally followed by granulation (CN 2310978 A), shredding with hook-type knives at the surface of rotating rolls (US 5120767 A), shredding using a rasper (US 6527208 B1).

[0075] After size reduction in step b), the metal fragments such as ferrous and non-ferrous metal fragments, preferably ferrous metal fragments, are be separated from the fragments of non-sorted end-of-life tires or fragments of the carcass in step c).

[0076] Step c) comprises at least separating metal fragments from said fragments of non-sorted end-of-life tires or fragments of the carcass. Metal fragments comprise or preferably consist of ferrous metal fragments.

[0077] Preferably, step c) is selected from the group comprising or preferably consisting of magnetic separation, density separation, manual sorting and combinations thereof.

[0078] The ferrous metal fragments are preferably removed by magnetic separators. The magnetic separators utilize the magnetic properties of ferrous metals to attract and separate them from non-magnetic materials, preferably rubber, polymer P, and non-metallic inorganic fillers. The fragments of non-sorted end-of-life tires or fragments of the carcass obtained in step b) are fed onto a conveyor belt or a vibrating feeder, and as the fragments of non-sorted end-of-life tires or fragments of the carcass move along the conveyor belt or vibrating feeder, a powerful magnetic field is generated by the magnetic separator (e.g., the magnetic field is created by passing an electric current through a coil, which produces a magnetic force). When the fragments of non-sorted end-of-life tires or fragments of the carcass pass through the magnetic field, the ferrous metals, being magnetic, are attracted to the magnetic separator. Once the ferrous metals are attracted to the magnetic separator, they can be separated from the rest of the fragments of 240746W001

[0079] 8 non-sorted end-of-life tires or fragments of the carcass and collected separately. This can be done using a separate chute or conveyor belt to direct the separated ferrous metals to a designated collection area. This magnetic separation procedure can be repeated if necessary.

[0080] Optionally, said non-metallic inorganic fillers may also be separated in step c), preferably by density separation from the fragments of end-of-life tires obtained from step b) or fragments of carcasses optionally obtained from step b). Suitable methods for density separation are cyclone separation, jigging, air separation, or sink-float separation.

[0081] The cyclone separation is usually a method used to separate materials based on their density and size using a device called a cyclone. A cyclone typically consists of a cylindrical body with a conical base and an inlet and outlet at the top. The inlet may be tangentially connected to the body, which creates a swirling motion inside the cyclone. As the material spins inside the cyclone, centrifugal force can be generated which may cause the denser and larger particles to move towards the outer wall of the cyclone, while the lighter and smaller particles tend to stay closer to the center.

[0082] The jigging separation is a method usually used to separate materials based on their density using a device called a jig, which typically consists of a rectangular or circular container with a screen or mesh on the bottom. The container can be mounted on a frame with a mechanism that causes it to move up and down. The jig can be filled with water, and a pulsating flow of water is introduced from the bottom of the container. The pulsation may cause the material to move up and down in the container. The denser particles may tend to settle faster and move towards the bottom of the container, while the lighter particles tend to stay near the top.

[0083] The air separation is often based a stream of air, e.g., in an air classifier structure which typically consists of a vertical chamber with an inlet at the bottom and an outlet at the top. The chamber may contain a series of vanes or blades that create a centrifugal force that separates the materials. A stream of air is usually introduced from the bottom of the chamber and the air flow causes the material to move upwards and separates it based on its density. The denser particles often tend to move towards the outer wall of the chamber, while the lighter particles tend to stay closer to the center. The separated materials can be collected at different points of the air classifier.

[0084] The sink-float separation is usually based on the principle that materials with different densities will behave differently when placed in a fluid medium: Dense materials often sink while less dense materials float. The fluid medium can be a heavy liquid, such as water or a specialized solution, or a finely ground powdered material. The liquid is usually chosen to have a density that is between the densities of the materials to be separated.

[0085] Preferably, the density separation is a method selected from the group comprising or more preferably consisting of cyclone separation, jigging, air separation, sink-float separation and combinations thereof. 240746W001

[0086] 9

[0087] The fragments of end-of-life tires obtained from step b) and the fragments of carcasses optionally obtained from step b) comprise rubber and preferably at least one more polymer P selected from polyamides, polyesters and mixtures thereof. More preferably, the at least one more polymer is selected from the group consisting of polyamide 6 (PA6), polyamide 6.6 (PA6.6), polyethylene terephthalate (PET) and mixtures thereof. Depending on the method(s) applied in step b), the at least one polymer P forms “tire fluff” during size reduction in step b) and can be optionally separated from the rubber fragments in step c) by e.g., vibrating screens and removal therefrom using vacuums, or other fabric separators.

[0088] Optionally, rubber and the at least one more polymer P selected from polyamides, polyesters and mixtures thereof are not separated in step c) from each other to keep the sorting process as simple as possible. Also, the at least one polymer P is suited for gasification in step (iii). Accordingly, the mixture of rubber and at least one more polymer P selected from polyamides, polyesters and mixtures thereof comprised in the sorted fragments of end-of-life tires and / or the sorted fragments of carcasses from which metal fragments, and optionally at least a portion of the non- metallic inorganic fillers and / or at least a portion of the at least one polymer P were separated in step c) is converted in step (iii) in at least one plasma gasifier PG into a gas stream GS1.

[0089] The sorted fragments of end-of-life tires obtained from step c) preferably comprise about 14 to about 42 wt.-% natural rubber, about 18 to about 26 wt.-% synthetic rubber, up to about 5 wt.-% reclaimed rubber, about 28 to about 44 wt.- % non-metallic inorganic fillers. The sorted fragments of end-of-life tires obtained from step c) preferably have a calorific value of about 25 to about 45 MJ / kg. Said values can be determined by standardized methods known by the skilled person.

[0090] The non-sorted end-of-life tires and / or sorted fragments of end-of-life tires are optionally dried before step (iii) for example with hot air.

[0091] Optionally, a further feedstock F2 is provided in step (ii) and subjected to the gasification process in step (iii) wherein said gasification process comprises at least one plasma gasifier PG and whereby said further feedstock F2 is inserted into the at least one plasma gasifier PG “together” with the first feedstock F1 provided in step (i). The meaning of “together” depends on the kind of optional further feedstock F2 and the type of plasma gasifier PG employed in step (iii) and is explained in detail below.

[0092] Preferably, the optional further feedstock F2 provided in step (ii) is selected from the group comprising or consisting of biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from end-of-life tires, pyrolysis oils made from biomass, heating oils, vacuum residues, preferably vacuum distillation residues, crude oil residues, heavy crude oils, extra heavy crude oils, tar sand bitumen, visbreaker bottom residues, deasphalter bottom residues, 05 asphalthene fraction, high viscous residues, fuel oils, pyrolysis gasolines, tire pyrolysis oils (TPO), waste oils, used oils, municipal solid waste (MSW), coal, tar oils, natural gas, CO2, waste streams from tire production, pre-sorted automotive shredder residue (ASR), and mixtures thereof. 240746W001

[0093] 10

[0094] The term “biomass” includes but is not limited to wood, wood pellets, wood chips, straw, lignocellulosic biomass, energy crops, algae, bio-based oils, and bio-based fats (preferably hydrated).

[0095] Biomass is preferably torrefied or converted by pyrolysis into a pyrolysis oil before used in step (iii) as a further feedstock F2. Municipal solid waste (MSW) is optionally pre-treated by methods such as drying, shredding, sorting, inert removal and preferably used in step (iii) in form of refuse-derived fuel (RDF). Torrefied biomass is preferably pre-heated to a temperature such as 200 °C before fed into said at least one plasma gasifier PG as a further feedstock F2 in step (iii).

[0096] “Waste streams from tire production” comprise rubber parts and vulcanization residues formed during production of tires.

[0097] The at least one further feedstock F2 optionally provided in step (ii) is preferably selected from the group comprising or preferably consisting of biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from end-of-life tires, pyrolysis oils made from biomass, municipal solid waste (MSW), coal, CO2, and mixtures thereof.

[0098] The optional at least one further feedstock F2 is preferably pre-treated before step (ii) by a method selected from the group comprising or consisting of sorting, sieving, milling, grinding, pyrolysis, torrefaction, metal sorting and combinations thereof.

[0099] The weight ratio “first feedstock F1 : further feedstock F2” preferably ranges from 10 : 1 to 1 : 10, more preferably from 1 : 2 to 1 : 10 and most preferably from 1 : 5 to 1 : 10.

[0100] Liquid further feedstocks F2 such as bio-based oils and pyrolysis oils are preferably pre-heated and / or pressurized to > 1 bar(abs.), more preferably to > 2 bar(abs.) and most preferably to about 4 bar(abs.) before fed into the at least one plasma gasifier PG. Suitable means for pre-heating and / or pressurizing liquid feedstocks for feeding into said at least one plasma gasifier PG are known in the art, comprise for example flaps and locks but also annual gaps, pressure nozzles and pressure atomizers, and can be adapted to a given further feedstock F2 by the skilled person.

[0101] An overview of plasma gasifiers PG is for example provided in James G. Speight, Handbook of Gasification Technology, Scrivener Publishing and Wiley, 2020, chapter 8.4.2, pages 259 to 262.

[0102] The at least one plasma gasifier PG has at least one inlet through which the first feedstock F1 is fed into said at least one plasma gasifier PG and at least one outlet through which the synthesis gas is purged from said at least one plasma gasifier PG. Preferably, the at least one plasma gasifier PG has more than one inlet. Thereby, at least one 240746W001

[0103] 11 further feedstock F2 can be fed into the at least one plasma gasifier PG through a separate inlet. The term “inlet” comprises openings in the at least one plasma gasifier PG such as flaps and locks but also annual gaps as part of a burner such as in twin fluid atomizers, pressure nozzles and pressure atomizers. The plasma is formed by at least three plasma torches in the at least one plasma gasifier PG. Plasma gasifiers PG are preferred for first feedstocks F1 because said feedstock type which has a lower calorific value than e.g., refuse-derived fuel (RDF) and fossil-based feedstocks such as coal are converted more efficiently in such plasma gasifiers PG. Furthermore, less CO2 is produced from gasification of first feedstocks F1 in plasma gasifiers PG, particularly if steam is used as plasma source PS.

[0104] Plasma gasification is a high-temperature waste treatment process that uses plasma, a gas composed of highly charged particles, to break down organic matter into a gas. In this process, the first feedstock F1 and optionally at least one further feedstock F2 are / is fed into the plasma gasifier PG, preferably, the first feedstock F1 and at least oner further feedstock F2 are fed into the plasma gasifier PG, where they / it are / is exposed to at least three plasma torches, which ionizes the first feedstock F1 and the optional at least one further feedstock F2 and creates a plasma.

[0105] Preferably at least one plasma torch is installed in the part of the at least one plasma gasifier PG where the first feedstock F1 and / or the optional at least one further feedstock F2 are / is fed onto said at least one plasma gasifier PG and two plasma torches, preferably at least two plasma torches, are installed in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG. Most preferably, said two plasma torches, preferably at least two plasma torches, are installed in an arrangement which forces the synthesis gas to pass said two plasma torches, preferably at least two plasma torches, in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG.

[0106] The at least first plasma torch ensures rapid gasification and initial cracking of the first feedstock F1 and / or the optional at least one further feedstock F2, while the two plasma torches, preferably at least two plasma torches, preferably installed in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG maintain a high temperature in said part, preventing cold spots and, accordingly, incomplete conversion. Such incomplete conversion results in undesired formation and / or accumulation of tars. Said undesired tars cause fouling, particularly in said downstream section of the at least one plasma gasifier PG. Hence, the assembly and distribution of at least three plasma torches in the at least one plasma gasifier PG suppresses undesired fouling, particularly in the downstream section of said at least one plasma gasifier PG.

[0107] Furthermore, the configuration comprising at least three plasma torches provides better thermal distribution inside the at least one plasma gasifier PG than, e.g., a single plasma torch and an RF induction coil, or an LF induction coil, or a hybrid plasma torch comprising an arc plasma torch and a radio frequency (RF) plasma torch. The at least one first plasma torch ensures rapid gasification and initial cracking of feedstock, while the two, preferably at least two, “downstream section” plasma torches maintain high temperatures in said “downstream section”, preventing cold spots, incomplete conversion, and formation of tars which then result in undesired fouling. In contrast, a single 240746W001

[0108] 12 plasma torch systems or other means for plasma generation as described above often create a strong temperature gradient, leading to uneven gasification / cracking and thereby undesired fouling.

[0109] The process according to the present invention which utilizes at least three plasma torches in the at least one plasma gasifier PG enables higher and more stable temperatures near the outlet zone (“downstream section”) reduce the formation of heavy hydrocarbons and tars. This results in a cleaner syngas with higher H2 / C0 ratio having lower impurities and suppresses undesired fouling. The at least three plasma torches in the at least one plasma gasifier PG may also be used to fine-tune plasma energy input to maintain optimal conditions for said first feedstock F1 provided in step (i), optionally together with at least one further feedstock F2 provided in step (ii), improving process flexibility and syngas calorific value.

[0110] Tar cracking requires sustained high temperatures (>1000 °C). Placing at least two torches near said in the part of the plasma gasifier PG where the synthesis gas leaves the plasma gasifier PG (“downstream section”) ensures that any residual tars are cracked before leaving the reactor and thereby suppressing undesired fouling, particularly in the downstream section of the at least one plasma gasifier PG.

[0111] Conventional single-plasma torch plasma gasifier designs (and other configurations described in the literature) often rely on secondary reformers or quench systems to handle tars, adding complexity and cost. Furthermore, tars may cause, particularly in the means connecting the plasma gasifier and such secondary reformer to undesired fouling, because said means has a lower temperature (incomplete thermal insulation) which is beneficial for deposition of tars whereby fouling is enabled. Said means is for example a pipe such as a pipe made from steel.

[0112] The high temperatures inside the plasma gasifier PG, which can reach up to about 10000 K, cause the first feedstock F1 and the optional at least one further feedstock F2 to vaporize and break down into the constituent components, including hydrogen, carbon monoxide, and methane.

[0113] The at least one plasma gasifier PG is preferably a fixed-bed plasma gasifier PG or a fluidized bed plasma gasifier PG. Most preferably, the at least one plasma gasifier PG is a fixed-bed plasma gasifier. Fixed-bed plasma gasifiers PG are better suited to first feedstocks F1 because the non-metallic inorganic fillers comprised therein cause less plugging and related undesired effects than in other types of plasma gasifiers PG compared to fluidized- bed plasma gasifiers PG.

[0114] Preferably, the electricity used for operating the at least one plasma torch of the at least one plasma gasifier PG is generated from a renewable source, whereby the product carbon footprint (PCF) of the synthesis gas comprised in gas stream GS1 is reduced. More preferably, the electricity used for operating the at least three plasma torches of the at least one plasma gasifier PG is generated from at least one source selected from the group consisting of solar energy, wind energy, tidal energy, nuclear energy, geothermal energy, and combinations thereof. Most preferably, the at least one plasma gasifier PG comprises three plasma torches. 240746W001

[0115] 13

[0116] The plasma in the at least one plasma gasifier PG is preferably generated from at least one plasma source PS selected from the group comprising or consisting of steam, oxygen, CO2, air, and combinations thereof. Steam as plasma source PS is most preferred in case a synthesis gas having a molar ratio H2 : CO > 1 is desired, particularly for further processes FP.

[0117] The at least one plasma source is co-fed into the at least one plasma gasifier PG in step (iii). Most preferably, steam is co-fed into the at least one plasma gasifier PG in step (iii). The weight ratio “(first feedstock F1 and optional further feedstock F2 combined) : steam” preferably ranges from 1 : 1 to 10 : 1 , more preferably from 2 : 1 to 10 : 1 and most preferably from 5 : 1 to 10 : 1 or higher.

[0118] Preferably, the ratio “electrical power applied to the plasma torches : mass of gas stream GS1 produced” preferably ranges from 0.1 to 15 kW / h : kg, more preferably from 0.5 to 10 kW / h : kg and most preferably from 1 to 8 kW / h : kg. Such a ratio is preferred to maintain the desired process conditions inside the at least one plasma gasifier PG when using a first feedstock F1.

[0119] The first feedstock F1 and the optional at least one further feedstock F2 is / are preferably compressed up to 4 bar(abs.) before fed into the at least one plasma gasifier PG.

[0120] The temperature of the gas leaving the plasma gasifier PG is preferably in the range of 1100 to 1400 °C, most preferably around 1300 °C. The pressure of the synthesis gas leaving the plasma gasifier PG is preferably at least 0.7 bar(abs.) and more preferably at least 1 bar(abs.). The residence time of the reactants inside the plasma gasifier PG is at least 2 to 3 s. The plasma is preferably generated from a gas selected from the group comprising CO2, steam, O2, air and mixtures thereof. More preferably, the plasma is generated from a CO2, steam or a mixture of CO2 and steam.

[0121] The first feedstock F1 is preferably fed into the plasma gasifier PG through an opening separate of the opening through which the optional further feedstock F2 is fed. Steam is preferably fed to the plasma gasifier through still another opening.

[0122] A gas stream GS1 then leaves the at least one plasma gasifier PG. Said gas stream GS1 comprises CO and H2(“synthesis gas”) and byproducts of the gasification reaction such as CO2, CH4 and ash. The synthesis gas formed in step (iii) preferably comprises < 15 Vol.-% CO2, more preferably < 10 Vol.-% CO2 and most preferably < 8 Vol.-% CO2.

[0123] The process comprises a further step (iv) in which at least a portion of the CO2, impurities and other undesired components are removed from the gas stream GS1 formed in step (iii) in a synthesis gas upgrading unit SUU. Thereby, a gas stream GS2 depleted in CO2 and having a first molar ratio H2 : CO is obtained. 240746W001

[0124] 14

[0125] The synthesis gas upgrading unit SUU comprises a unit for removing at least a portion of CO2 from the gas stream GS1 in step (iv) by a method selected from the group comprising or consisting of absorption, adsorption, membrane separation, cryogenic separation, and combinations thereof. Most preferably, said unit is a washing unit such as an “amine wash” or a “methanol” wash which uses one or more amine compounds such as alkanolamines or methanol to absorb CO2. Such units are known in the art and can be adapted for removal of at least a portion of the CO2 from a gaseous stream GS1 by the skilled person.

[0126] Removal of at least a portion of CO2 comprised in gas stream GS1 has various benefits, particularly in the downstream utilization of synthesis gas: for example, CO2 may cause undesired hot spots in a methanization reactor due to the more exothermic methanization reaction of CO2 compared to CO. Further, CO2 lowers the desired ratio R = CO+CC : (H2-CO2) in the synthesis gas which should be about 2 for methanol synthesis. Excess CO2 lowers this ratio R, making such synthesis gas unsuitable without adjustment. Removing C02helps achieve the correct ratio for efficient conversion and high methanol yield. Furthermore, C02does not participate in Fischer-Tropsch reactions. Accordingly, CO2dilutes the reactive components, reducing reactor productivity of a Fischer-Tropsch process which is highly undesirable.

[0127] Typical impurities in the gas stream GS1 comprise chlorides, sulfur-containing organic compounds such as sulfur dioxide, trace heavy metals (e.g., as respective salts), tars / condensable hydrocarbons and particulate residues. Various chemical and / or physical methods for removal of such impurities from said gas stream GS1 such as filtration, scrubbing, condensation and ab- / adsorption are known and can be chosen and adapted according to the type and respective concentration of the impurities in said gas stream GS1 and the tolerance to such impurities in a further process FP1 . Some selected methods for removal of impurities from said gas stream GS1 will be discussed in more detail. One or more of said methods can also be implemented into the synthesis gas upgrading unit SUU. However, this selection of methods is not limiting the scope of the present invention.

[0128] Other gaseous substances such as HOI and H2S are formed and / or separated from the gas stream GS1 in the synthesis gas upgrading unit SUU. The impurities are removed from the gas stream GS1 and a gas stream GS2 having a first molar ratio H2: CO is obtained.

[0129] Particulate impurities can be removed from the gas stream GS1 by a cyclone and / or filters, chlorides by wet scrubbing, trace heavy metals, catalytic hydrolysis for converting sulfur-containing organic compounds to H2S and acid gas removal for extracting sulfur-containing gases such as H2S. Bulky and (fine) particles such as dust in the gas stream GS1 may also be removed with a quench in a soot water washing unit.

[0130] Fine particles can be optionally removed from the raw synthesis gas directly with filters after the gas stream GS1 leaves the at least one plasma gasifier PG. Hence, the removal of fine particles from the gas stream GS1 can be part of the at least one plasma gasifier PG and / or part of the synthesis gas upgrading unit SUP which is fluidically connected to the at least one plasma gasifier PG. 240746W001

[0131] 15

[0132] CO and / or H2 are optionally separated from the gas stream GS1 . CO can be separated from the gas stream GS1 in a synthesis gas separation unit which is, optionally, downstream of and fluidically connected to the at least one gasifier G. CO can be separated from gas stream GS1 by cryogenic separation methods, commonly referred to as a “cold box” which makes use of the different boiling points of CO and H2. H2 can be separated using ^-selective membranes thorough which H2 permeates and is thereby separated from the GS1 stream.

[0133] The gas stream GS1 has a first molar ratio H2 : CO. Optionally, the gas stream GS1 is then preferably subjected to a water-gas shift reaction in a water-gas shift unit. Thereby, the H2 content in the gas stream GS1 is increased by reacting a portion of the CO of the gas stream GS1 with water to form additional H2 and CO2 and thereby gas stream GS2 having a second molar ratio H2 : CO is formed and leaves the water-gas shift unit. The H2 content in said gas stream GS2 leaving the water-gas shift unit and having a second molar ratio H2 : CO is higher than in said gas stream GS1 leaving the at least one gasifier having a first molar ratio H2 : CO. The hydrogen content in gas stream GS1 can for example also be increased by adding hydrogen provided by another source such as hydrogen formed by electrolysis of water, preferably using electrical energy from a renewable source such as solar and / or wind energy. Thereby, the product carbon footprint (PCF) of the synthesis gas formed by the process according to the present invention may be even further reduced.

[0134] The water-gas shift reaction will operate with a variety of catalysts (such as copper-zinc-aluminum catalysts and chromium or copper promoted iron-based catalysts) in the temperature range between about 200 and about 480 °C.

[0135] The gas stream GS2 is optionally compressed to a pressure in the range 1 .5 to 4 bar(abs.).

[0136] Optionally, at least of the portion of said CO2 separated from the gas stream GS1 in step (iv) in the synthesis gas upgrading unit SUU is co-fed together with the first feedstock F1 and the optional further feedstock F2 into the at least plasma gasifier PG and thereby converted into synthesis gas (optional step (v)). The ratio CO2 : feedstocks F1 and F2 combined” fed into the at least one plasma gasifier ranges from 0 to 2, preferably from 0 to 1 .5 and more preferably from 0 to 1. Thereby, undesired CO2 formed during a gasification process of a first feedstock F1 and an optional further feedstock F2 can be utilized as an additional feedstock for the manufacturing of synthesis gas.

[0137] Further CO2from other sources such as other chemical processes can optionally also be co-fed with the first feedstock F1 and the optional further feedstock F2 into the at least plasma gasifier PG and thereby converted into synthesis gas. Thereby, undesired CO2 from other sources can be utilized as an additional feedstock for the manufacturing of synthesis gas.

[0138] Preferably, the gas stream GS2 is then subjected to a further process FP1 in optional step (vi), said further process FP1 selected from the group comprising methanization, methanol synthesis and Fischer-Tropsch synthesis, whereby at least one first product stream PS1 is formed. Methane formed by methanization from gas stream GS2 is a 240746W001

[0139] 16 synthetic fuel (gas). Methanol formed from gas stream GS2 is a liquid synthetic fuel and can be further converted into other synthetic fuels by processes described further below. Products (“Fischer-Tropsch liquids”) made by Fischer- Tropsch synthesis from gas stream GS2 can be used as synthetic fuels or further converted into more advanced synthetic fuels. The gas stream GS2 can also be used directly as a fuel (gas). Accordingly, methane, methanol and hydrocarbons formed therefrom, and products made by Fischer-Tropsch synthesis and successive upgrading processes such as isomerization are considered “synthetic fuels” herein. Said optional further processes FP1 (optional step (vi)) are briefly described below:

[0140] Optionally, the gas stream gas stream GS2 can be converted into methane by a methanation reaction. The methanation reaction is described by chemical reaction schemes (1) and (2):

[0141] CO + 3H2^ CH4+ H2O (1)

[0142] CO2+ 4H2^ CH4+ 2H2O (2)

[0143] The methanation reaction and suitable methanation units are for example described in S. Rbnsch, J. Schneider, S. Matthischke, M. Schluter, M. Gbtz, J. Lefebvre, P. Prabhakaran, S. Bajohr: Review on methanation - From fundamentals to current projects; Fuel 166 (2016) 276-296 and can be selected and adapted by the skilled person.

[0144] The methanation reaction is for example a catalytic reaction using nickel on alumina catalysts, preferably a honeycomb shape catalyst, at 1 to 70 bar and 200 to 700 °C, preferably 5 to 60 bar, more preferably 10 to 45 bar and preferably 200 to 550 °C, more preferably 10 to 45 bar.

[0145] Methanol is another first product stream PS1 which can be manufactured from the gas stream GS2 by an optional further process FP1. Methanol can be produced from gas stream GS2 (synthesis gas) by a catalytic gas phase reaction generally at about 5 to 10 MPa and generally at a temperature of about 200 to about 300 °C in e.g., adiabatic reactors or quasi-isothermal reactors. The catalyst is for example a mixture of copper and zinc oxides, supported on alumina. The methanol synthesis and various options thereof suitable to be combined with the production system according to the present invention are known in the art and for example disclosed in Ullmann's Encyclopedia of Industrial Chemistry (2012), Chapter “Methanol”, p. 3 to 12.

[0146] Preferably, methanol is further converted e.g., by a methanol-to-olefins (MTO) process to olefins such as ethene and propene or by a methanol to gasoline (MTG) process to synthetic fuels.

[0147] In the MTG process, methanol is converted over a catalyst, generally a zeolite, preferably an acidic zeolite, like SAPO-34 or HZSM-5 to a hydrocarbon mixture of olefins, aliphatic hydrocarbons, and aromatic hydrocarbons, generally up to Cn hydrocarbons. Suitable reaction conditions are for example 350 to 400 °C, and atmospheric pressure. The hydrocarbon mixture obtained is suitable as synthetic fuel. 240746W001

[0148] 17

[0149] The MTO process is the catalytic conversion of methanol to lower olefins, especially ethene and / or propene. An interruption of the MTG reaction, by careful control over process conditions (T, space velocity), leads to the methanol-to-olefins process (MTO). As in the MTG process, generally a zeolite, preferably an acidic zeolite, like SAPO-34 or HZSM-5 is used as catalyst.

[0150] Further details regarding the MTG and the MTO process are known in the art and for example described in Makarand R. Gogate (2019) Methanol-to-olefins process technology: current status and future prospects, Petroleum Science and Technology, 37:5, 559-565, DOI: 10.1080 / 10916466.2018.1555589 and the literature mentioned therein.

[0151] Suitable MTG processes comprise the Mobile MTG Process, Topsoe improved gasoline synthesis (TiGAS) and Syngas to Gasoline plus Process (STG+). The products obtained from said processes are synthetic fuels.

[0152] The gas stream GS2 can also optionally be converted into hydrocarbons such as light synthetic crude oil in an optional Fischer-Tropsch (FT) reaction unit by the FT process. Such hydrocarbons are also denoted “Fischer-Tropsch hydrocarbons”. The “Fischer-Tropsch hydrocarbons”, generally in form of a light synthetic oil can be further converted to naphtha, light olefins, gasoline, synthetic fuels (“FT fuels”) like diesel fuel or jet fuel, most preferably jet fuel, generally by hydrocracking and / or isomerization. By said process, so called FT-SPK fuels and FT-SKA fuels are for example obtained. FT-SPK fuels are fuels using biomass resources (e.g. wood residues) and FT-SKA fuels are FT fuels with aromatics using biomass resources (e.g. wood residues). Suitable FT processes and reactors and suitable subsequent processes and reactors for obtaining naphtha, light olefins, gasoline, fuel (“FT fuels”) like diesel fuel or jet fuel are known in the art. For production of naphta, gasoline, jet fuel and light olefins, the FT process is generally operated in a temperature range of about 330 to about 350 °C and generally at a pressure of about 2.5 MPa (high-temperature FT-process), for production of waxes and / or diesel fuel, generally in a temperature range of about 220 °C to about 250 °C and generally at a pressure of about 2.5 to about 4.4 MPa (low-temperature FT-process). Suitable reactors for low-temperature FT-processes comprise for example tubular fixed-bed reactors and slurry bed reactors. Suitable reactors for high-temperature FT-processes comprise for example circulating fluidized-bed reactors and SAS (Sasol advanced synthol) reactors. Iron- and / or cobalt-based catalysts are for example used for the FT-process. The Fischer- Tropsch process and reactor and suitable subsequent processes and reactors for obtaining naphtha, light olefins, gasoline, fuel (“FT fuels”) like diesel fuel or jet fuel and various options thereof suitable to be combined with the process according to the present invention are for example disclosed in Ullmann's Encyclopedia of Industrial Chemistry (2012), Chapter “Coal Liquefaction”, p. 20 to 33 and Greg Perkins et al. Bioresource Technology 312 (2020) 123596 (https: / / doi.Org / 10.1016 / j.biortech.2020.123596) and the literature mentioned therein.

[0153] 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 240746W001

[0154] 18 wording of this term is to be understood by the skilled person as being synonymous to "The method of any of embodiments 1 , 2 and 3". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and thus, suitably supports the claims of the present invention.

[0155] 1 . Process for manufacturing synthesis gas from end-of-life tires, said process comprising the steps

[0156] (i) providing a first feedstock F1 wherein said first feedstock F1 comprises sorted fragments of end-of-life tires, said sorted fragments of end-of-life tires formed by sorting from a non-sorted end-of-life tires, wherein said non-sorted end-of-life tires comprise a tread and a carcass, and further comprise metal fragments, non-metallic inorganic fillers, rubber and at least one polymer P selected from the group consisting of polyamides, polyesters and mixtures thereof, wherein said non-sorted end-of-life tires are presorted to form the sorted fragments of end-of-life tires, preferably in this order, by a) optionally separating the tread from the carcass of the non-sorted end-of-life tires, b) reducing the size of non-sorted end-of-life tires and / or the size of the carcass separated in optional step a) from the tread, and thereby produce fragments of non-sorted end-of-life tires and / or fragments of the carcass, and c) separating at least a portion of said metal fragments, and optionally separating at least a portion of said non-metallic inorganic fillers and / or at least a portion of the at least one polymer P from the fragments formed in step b), and thereby form sorted fragments of end-of-life tires and / or sorted fragments of carcasses, whereby said sorted fragments of end-of-life tires and / or sorted fragments of carcasses is / are depleted in metal fragments and optionally also depleted in non-metallic inorganic fillers and / or in at least a portion of polymer P, and whereby optionally step b) and / or step c) is / are repeated at least once,

[0157] (ii) preferably providing at least one further feedstock F2,

[0158] (iii) converting said first feedstock F1 provided in step (i), optionally together with at least one further feedstock F2 provided in step (ii), in at least one plasma gasifier PG into a gas stream GS1 , said gas stream GS1 comprising synthesis gas wherein said synthesis gas comprises H2, CO and CO2 and wherein said at least one plasma gasifier PG comprises at least three plasma torches, said at least three plasma torches operated with electricity,

[0159] (iv) removing at least a portion of the CO2 comprised in the gas stream GS1 in a synthesis gas upgrading unit SUU and thereby forming a gas stream GS2 which is depleted in CO2, and

[0160] (v) optionally using at least a portion of the said CO2 removed from the gas stream GS2 in step (iv) as a further feedstock F2in step (iii). 240746W001

[0161] 19

[0162] 2. Process according to embodiment 1 wherein the tread and carcass of the non-sorted end-of-life tires are separated on optional step a) by a method selected from the group comprising or preferably consisting of mechanical shredding, manual cutting, automated cutting, degrading, and combinations thereof.

[0163] 3. Process according to embodiments 1 or 2 wherein the size reducing method in step b) is selected from the group comprising or preferably consisting of shredding, grinding, milling, sieving, classifying and combinations thereof.

[0164] 4. Process according to any one of embodiments 1 to 3 wherein at least 90 wt.-% of the fragments of non-sorted end-of-life tires and / or fragments of the carcass formed in step b) are smaller than 5 cm, preferably at least 95 wt.-% smaller than 5 cm and more preferably at least 95 wt.-% are smaller than 3 cm.

[0165] 5. Process according to any one of embodiments 1 to 4 wherein step c) comprises at least removing metal fragments from the fragments of end-of-life tires and / or the fragments of the carcasses.

[0166] 6. Process according to any one of embodiments 1 to 5 wherein step c) is selected from the group comprising or preferably consisting of magnetic separation, density separation, manual sorting and combinations thereof.

[0167] 7. Process according to embodiment 6 wherein the density separation is a method selected from the group comprising or preferably consisting of cyclone separation, jigging, air separation, sink-float separation and combinations thereof.

[0168] 8. Process according to any one of embodiments 1 to 7 wherein the sorted fragments of end-of-life tires and / or sorted fragments of carcasses obtained in step (i) c) (feedstock F1) preferably comprise 14 to 42 wt.-% natural rubber, 18 to 26 wt.-% synthetic rubber, up to 5 wt.-% reclaimed rubber, 28 to 44 wt.-% non-metallic inorganic fillers (mainly carbon black and silica), preferably by repeating step b) and / or step c) at least once .

[0169] 9. Process according to any one of embodiments 1 to 8 wherein the non-sorted end-of-life tires and / or the nonsorted carcasses and / or the sorted fragments of end-of life tires and / or the sorted fragments of carcasses are / is dried before step (iii).

[0170] 10. Process according to any one of embodiments 1 to 9 wherein the sorted fragments of end-of-life tires and / or the sorted fragments of carcasses comprises at least one polymer P, said at least one polymer P selected from the group consisting of polyamides, polyesters and mixtures thereof.

[0171] 11. Process according to any one of embodiments 1 to 10 wherein the rubber comprised in the sorted fragments of end-of-life tires and / or the sorted fragments of carcasses is selected from the group comprising or 240746W001

[0172] 20 preferably consisting of natural rubber, styrene-butadiene rubber, butyl rubber, ethylene propylene diene monomer rubber, neoprene, nitrile rubber, silicone rubber and mixtures thereof.

[0173] 12. Process according to any one of embodiments 1 to 11 wherein at least one further feedstock F2 is provided in step (ii).

[0174] 13. Process according to any one of embodiments 1 to 12 wherein at least one feedstock F2 is provided in step (ii), said at least one further feedstock F2 selected from the group comprising or consisting of biomass, refuse- derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from biomass, heating oils, vacuum residues, preferably vacuum distillation residues, crude oil residues, heavy crude oils, extra heavy crude oils, tar sand bitumen, visbreaker bottom residues, deasphalter bottom residues, C5 asphalthene fraction, high viscous residues, fuel oils, pyrolysis gasolines, tire pyrolysis oils (TPO), waste oils, used oils, municipal solid waste (MSW), coal, tar oils, natural gas, CO2, waste streams from tire production, pre-sorted automotive shredder residue (ASR), and mixtures thereof.

[0175] 14. Process according to any one of embodiments 1 to 13 wherein the at least one further feedstock F2 optionally provided in step (ii) is selected from the group comprising or consisting of biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from end-of-life tires, pyrolysis oils made from biomass, municipal solid waste (MSW), coal, CO2, and mixtures thereof.

[0176] 15. Process according to any of embodiments 1 to 14 wherein the optional at least one further feedstock F2 is pre-treated before step (ii) by a method selected from the group comprising or preferably consisting of sorting, sieving, milling, grinding, pyrolysis, torrefaction, metal sorting and combinations thereof.

[0177] 16. Process according to any one of embodiments 1 to 14 wherein the weight ratio “first feedstock F1 : further feedstock F2” preferably ranges from 10 : 1 to 1 : 10, more preferably from 1 : 2 to 1 : 10 and most preferably from 1 : 5 to 1 : 10.

[0178] 17. Process according to any one of embodiments 1 to 16 wherein at least one plasma torch is installed in the part of the at least one plasma gasifier PG where the first feedstock F1 and / or the optional at least one further feedstock F2 are / is fed onto said at least one plasma gasifier PG and two plasma torches, preferably at least two plasma torches, are installed in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG.

[0179] 18. Process according to embodiment 17 wherein said at two plasma torches, preferably at least two plasma torches, are installed in an arrangement which forces the synthesis gas to pass said two plasma torches, preferably at least two plasma torches, in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG. 240746W001

[0180] 21

[0181] 19. Process according to any one of embodiments 1 to 18 wherein the electricity used for operating the at least three plasma torches of the at least one plasma gasifier PG is generated from a renewable source, whereby the product carbon footprint (PCF) of the synthesis gas comprised in gas stream GS1 is reduced.

[0182] 20. Process according to any one of embodiments 1 to 19 wherein the electricity used for operating the at least one plasma torch of the at least one plasma gasifier PG is generated from at least one source selected from the group consisting of solar energy, wind energy, tidal energy, nuclear energy, geothermal energy, and combinations thereof.

[0183] 21. Process according to any one of embodiments 1 to 20 wherein the plasma in the at least one plasma gasifier PG is generated from at least one plasma source PS selected from the group comprising or consisting of steam, oxygen, CO2, air, and combinations thereof.

[0184] 22. Process according to any one of embodiments 1 to 21 wherein the ratio “electrical power applied to the plasma torches : mass of gas stream GS1 produced” preferably ranges from 0.1 to 15 kW / h : kg, more preferably from 0.5 to 10 kW / h : kg and most preferably from 1 to 8 kW / h : kg.

[0185] 23. Process according to any of embodiments 1 to 22 wherein the at least one plasma gasifier PG is a fixed-bed plasma gasifier.

[0186] 24. Process according to any one of embodiments 1 to 23 wherein steam is co-fed into the at least one plasma gasifier PG in step (iii).

[0187] 25. Process according to any one of embodiments 1 to 24 wherein steam is co-fed into the at least one plasma gasifier PG in step (iii) and wherein the weight ratio “(first feedstock F1 and optional further feedstock F2 combined) : steam” preferably ranges from 1 : 1 to 10 : 1 , more preferably from 2 : 1 to 10 : 1 and most preferably from 5 : 1 to 10 : 1 or higher.

[0188] 26. Process according to any one of embodiments 1 to 25 wherein the synthesis gas formed in step (iii) preferably comprises < 15 Vol.-% CO2, more preferably < 10 Vol.-% CO2 and most preferably < 8 Vol.-% CO2.

[0189] 27. Process according to any of embodiments 1 to 26 wherein at least a portion of the CO2 is removed in step (iv) in a synthesis gas upgrading unit SUU by a method selected from the group comprising or consisting of absorption, adsorption, membrane separation, cryogenic separation, and combinations thereof. 240746W001

[0190] 22

[0191] 28. Process according to any of embodiments 1 to 27 wherein the ratio “CO2 : feedstocks F1 and F2 combined” fed into the at least one plasma gasifier in step (v) ranges from 0 to 2, preferably from 0 to 1 .5 and more preferably from 0 to 1.

[0192] 29. Process according to any one of embodiments 1 to 28 wherein the process comprises a further step (vi), said further step (vi) selected from the group comprising or consisting of separating H2 and CO in the gas stream GS2 from each other, compressing said gas stream GS2 and / or said H2 and / or said CO, combinations of the aforementioned, subjecting the gas stream GS2 to a Fischer-Tropsch process, subjecting gas stream GS2 to a methanization and subjecting gas stream GS2 to a methanol synthesis.

[0193] 30. Process according to any one of embodiments 1 to 28 wherein the gas stream GS2 is then subjected to a further process FP1 in a step (vi), said further process FP1 selected from the group comprising methanization, methanol synthesis and Fischer-Tropsch synthesis, whereby at least one first product stream PS1 is formed.

[0194] 31. Process according to any one of embodiments 1 to 30 wherein a synthetic is manufactured from at least a portion of the gas stream GS2 formed in step (iv).

[0195] 32. Use of plasma gasification in at least one plasma gasifier PG to convert fragments sorted end-of-life tires and / or fragments of sorted carcasses into a gas stream GS1 , said fragments sorted end-of-life tires and / or fragments of sorted carcasses formed by sorting from non-sorted end-of-life tires, wherein said non-sorted end-of-life tires comprise a tread and a carcass, and further comprise metal fragments and non-metallic inorganic fillers, rubber and at least one polymer selected from the group consisting of polyamides, polyesters and mixtures thereof, wherein said non-sorted end-of-life tires are sorted to form the fragments sorted end-of- life tires and / or fragments of sorted carcasses formed by sorting from non-sorted end-of-life tires, by optionally a) separating the carcass and the tread from each other, b) of non-sorted end-of-life tires or the size of the carcass separated in optional step a) from the tread and thereby obtain fragments of non-sorted end-of-life tires or fragments of the carcass, and c) separating at least a portion of said metal fragments and optionally separating at least a portion of said non- metallic inorganic fillers from the fragments formed in step b) and thereby form sorted fragments of end-of-life tires and / or sorted fragments of carcasses and wherein said at least one plasma gasifier PG comprises at least three plasma torches.

[0196] 33. Use according to embodiment 32 wherein the at least one plasma gasifier PG is a fixed-bed plasma gasifier.

[0197] 34. Use according to embodiment 32 or 33 wherein at least a portion of the gas stream GS2 is converted into a synthetic fuel.

[0198] The invention will be further explained by the following non-limiting examples. 240746W001

[0199] 23

[0200] Examples

[0201] For the examples, a fixed-bed plasma gasifier PG is compared with a conventional gasifier combination of a nonplasma fluidized bed gasifier G1 and an entrained flow gasifier G2, wherein gasifier G2 is downstream of and fluidically connected to gasifier G1 . As a main feed, a first feedstock F1 obtained from step (i) is used. Said feedstock F1 had the following composition: 85.9 wt.-% carbon (sum of carbon composed in rubber and carbon of carbon black), 8 wt.-% hydrogen, 0.4 wt.-% nitrogen, 1 wt.-% sulfur, 2.3 wt.-% oxygen, 2.4 wt.-% ash (i.e., non-metallic inorganic fillers other than carbon black). Further, the first feedstock F1 comprised 66.5 wt.-% volatiles, 30.3 wt.-% fixed carbon, 0.8 wt.-% moisture, and had a gross calorific value of 40 MJ / kg.

[0202] Example 1 (invention)

[0203] The plasma fixed-bed gasifier PG was fed with a mass ratio (kg : kg) “first feedstock F1 : first gas stream GS1 produced” = 0.44. The plasma was generated from steam, for the desired amount of plasma, a mass ratio (kg : kg) “steam : gas stream GS1 produced” = 0.56 was used. The steam had a pressure of 5.4 bar and a temperature of 180 °C. The ratio (kW / h : kg) “electrical power applied to the three plasma torches : mass of gas stream GS1 produced” = 1 .95 to reach the desired gas phase temperature of 1350 °C at the outlet of the fixed-bed plasma gasifier PG. The fixed-bed plasma gasifier PG was operated at atmospheric pressure conditions. The complete produced CO2in the gas stream GS1 was separated therefrom in the gas treatment unit GTU in step (iv) and fed as second feedstock F2 into the fixed-bed plasma gasifier PG. Accordingly, no CO2 is emitted from the process. The molar ratio H2: CO in the gas streams GS1 and GS2 was 1 .53. Furthermore, undesired fouling caused by deposition of tar in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG was suppressed.

[0204] Example 2 (comparative)

[0205] For comparison a conventional solid feed gasifier combination of 1 . a fluidized-bed gasifier G1 and 2. an entrained- flow gasifier G2 was simulated (the fluidized-bed gasifier G1 produced a raw first gas stream GS1 r from the first feedstock F1 which is then converted into a gas stream GS1 comprising synthesis gas in the entrained-flow gasifier G2). The fluidized-bed gasifier G1 was fed with mass ratio (kg : kg) “first feedstock F1 : first gas stream GS1 r produced” = 0.52 kg. Additionally, oxygen was fed with a ratio of 0.31 kg per kg synthesis gas comprised in the first gas stream GS1 r produced, and steam was fed for fluidization with a mass ratio (kg : kg) “steam : raw gas stream GS1 r produced” = 0.17 kg per kg raw synthesis gas produced. The steam had a pressure of 5.4 bar and a temperature of 180 °C. The raw first gas stream GS1 r leaving the fluidized-bed gasifier G1 had a temperature of 850 °C and a pressure of 4 bar. In gasifier G2, the raw gas stream GS1 r was heated up by introduction of additional oxygen with a mass ratio (kg : kg) “oxygen : first gas stream GS1 produced” = 0.17 kg. A temperature of 1350 °C was reached at the exit of gasifier G2. In step (iv), CO2of a CO2ratio 0.07 kg per / kg synthesis gas comprised in the gas stream GS2 produced is separated and afterwards emitted. The molar ratio H2: CO in the gas streams GS1 and GS2 was 0.74. Accordingly, undesired CO2is emitted in the process of the comparative example. Furthermore, the gas stream GS2 had a much lower molar ratio H2: CO than stream GS2 produced in Example 1 which renders the 240746W001

[0206] 24 synthesis gas stream GS2 produced in the comparative example less suited for a further process FP1 in a step (vi), said further process FP1 selected from the group comprising methanization, methanol synthesis and Fischer- Tropsch synthesis, whereby at least one first product stream PS1 is formed.

Claims

240746W00125Claims1 . Process for manufacturing synthesis gas from end-of-life tires, said process comprising the steps(i) providing a first feedstock F1 wherein said first feedstock F1 comprises sorted fragments of end-of-life tires, said sorted fragments of end-of-life tires formed by sorting from a non-sorted end-of-life tires, wherein said non-sorted end-of-life tires comprise a tread and a carcass, and further comprise metal fragments, non-metallic inorganic fillers, rubber and at least one polymer P selected from the group consisting of polyamides, polyesters and mixtures thereof, wherein said non-sorted end-of-life tires are presorted to form the sorted fragments of end-of-life tires, preferably in this order, by a) optionally separating the tread from the carcass of the non-sorted end-of-life tires, b) reducing the size of non-sorted end-of-life tires and / or the size of the carcass separated in optional step a) from the tread, and thereby produce fragments of non-sorted end-of-life tires and / or fragments of the carcass, and c) sorting out at least a portion of said metal fragments, and optionally sorting out at least a portion of said non-metallic inorganic fillers and / or at least a portion of polymer P from the fragments formed in step b), and thereby form sorted fragments of end-of-life tires and / or sorted fragments of carcasses, whereby said sorted fragments of end-of-life tires and / or sorted fragments of carcasses is / are depleted in metal fragments and optionally also depleted in non-metallic inorganic fillers and / or in at least a portion of the at least one polymer P, and whereby optionally step b) and / or step c) is / are repeated at least once,(ii) preferably providing at least one further feedstock F2,(iii) converting said first feedstock F1 provided in step (i), preferably together with at least one further feedstock F2 provided in step (ii), in at least one plasma gasifier PG into a gas stream GS1 , said gas stream GS1 comprising synthesis gas wherein said synthesis gas comprises H2, CO and CO2 and wherein said at least one plasma gasifier PG comprises at least three plasma torches , said at least three plasma torches operated with electricity,(iv) removing at least a portion of the CO2comprised in the gas stream GS1 in a synthesis gas upgrading unit SUU and thereby forming a gas stream GS2 which is depleted in CO2, and(v) optionally using at least a portion of the said CO2removed from the gas stream GS2 in step (iv) as a further feedstock F2 in step (iii).

2. Process according to claim 1 wherein the step b) is selected from the group comprising or consisting of shredding, grinding, milling, degrading, sieving, classifying and combinations thereof.

3. Process according to claim 1 or 2 wherein at least 90 wt.-% of the fragments of non-sorted end-of-life tires and / or fragments of the carcass formed in step b) are smaller than 5 cm, preferably at least 95 wt.-% smaller than 5 cm and more preferably at least 95 wt.-% are smaller than 3 cm.240746W001264. Process according to any one of claims 1 to 3 wherein step c) is selected from the group comprising or consisting of magnetic separation, density separation, manual sorting and combinations thereof.

5. Process according to any one of claims 1 to 4 wherein the sorted fragments of end-of-life tires and / or sorted fragments of carcasses obtained in step (i) c) (feedstock F1) preferably comprise 14 to 42 wt.-% natural rubber, 18 to 26 wt.-% synthetic rubber, up to 5 wt.-% reclaimed rubber, 28 to 44 wt.-% non-metallic inorganic fillers (mainly carbon black and silica) preferably by repeating step b) and / or step c) at least once.

6. Process according to any one of claims 1 to 5 wherein at least one feedstock F2 is provided in step (ii), said at least one further feedstock F2 selected from the group comprising or consisting of biomass, refuse-derived fuel (RDF), pyrolysis oils made from plastic waste, pyrolysis oils made from biomass, heating oils, vacuum residues, preferably vacuum distillation residues, crude oil residues, heavy crude oils, extra heavy crude oils, tar sand bitumen, visbreaker bottom residues, deasphalter bottom residues, C5 asphalthene fraction, high viscous residues, fuel oils, pyrolysis gasolines, tire pyrolysis oils (TPO), waste oils, used oils, municipal solid waste (MSW), coal, tar oil, natural gas, CO2, waste streams from tire production, pre-sorted automotive shredder residue (ASR), and mixtures thereof.

7. Process according to any one of claims 1 to 6 wherein at least one plasma torch is installed in the part of the at least one plasma gasifier PG where the first feedstock F1 and / or the optional at least one further feedstock F2 are / is fed into said at least one plasma gasifier PG and two plasma torches, preferably at least two plasma torches, are installed in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG.

8. Process according to claim 7 wherein said two plasma torches, preferably at least two plasma torches are installed in an arrangement which forces the synthesis gas to pass said two plasma torches, preferably at least two plasma torches, in the part of said at least one plasma gasifier PG where the synthesis gas leaves said at least one plasma gasifier PG.

9. Process according to any one of claims 1 to 8 wherein the electricity used for operating the at least one plasma torch of the at least one plasma gasifier PG is generated from a renewable source, whereby the product carbon footprint (PCF) of the synthesis gas comprised in gas stream GS1 is reduced.

10. Process according to any one of claims 1 to 9 wherein the ratio “electrical power applied to the plasma torches : mass of gas stream GS1 produced” preferably ranges from 0.1 to 15 kW / h : kg, more preferably from 0.5 to 10 kW / h : kg and most preferably from 1 to 8 kW / h : kg.240746W0012711. Process according to any one of claims 1 to 10 wherein steam is co-fed into the at least one plasma gasifier PG in step (iii) and wherein the weight ratio “(first feedstock F1 and optional further feedstock F2 combined) : steam” preferably ranges from 1 : 1 to 10 : 1 , more preferably from 2 : 1 to 10 : 1 and most preferably from 5 : 1 to 10 : 1 or higher.

12. Process according to any one of claims 1 to 11 wherein at least a portion of the CO2 is removed in step (iv) by a method selected from the group comprising or consisting of absorption, adsorption, membrane separation, cryogenic separation, and combinations thereof.

13. Process according to any one of claims 1 to 12 wherein the ratio “CO2 : feestocks F1 and F2 combined” fed into the at least one plasma gasifier in step (iii) ranges from 0 to 2, preferably from 0 to 1 .5 and more preferably from 0 to 1.

14. Process according to any one of claims 1 to 13 wherein the gas stream GS2 is then subjected to a further process FP1 in a step (vi), said further process FP1 selected from the group comprising methanization, methanol synthesis and Fischer-Tropsch synthesis, whereby at least one first product stream PS1 is formed.

15. Use of plasma gasification in at least one plasma gasifier PG to convert fragments sorted end-of-life tires and / or fragments of sorted carcasses into a gas stream GS1 , said fragments sorted end-of-life tires and / or fragments of sorted carcasses formed by sorting from non-sorted end-of-life tires, wherein said non-sorted end-of-life tires comprise a tread and a carcass, and further comprise metal fragments and non-metallic inorganic fillers, rubber and at least one polymer selected from the group consisting of polyamides, polyesters and mixtures thereof, wherein said non-sorted end-of-life tires are sorted to form the fragments sorted end-of- life tires and / or fragments of sorted carcasses formed by sorting from non-sorted end-of-life tires, by optionally a) separating the carcass and the tread from each other, b) of non-sorted end-of-life tires or the size of the carcass separated in optional step a) from the tread and thereby obtain fragments of non-sorted end-of-life tires or fragments of the carcass, and c) separating at least a portion of said metal fragments and optionally separating at least a portion of said non- metallic inorganic fillers from the fragments formed in step b) and thereby form sorted fragments of end-of-life tires and / or sorted fragments of carcasses and wherein said at least one plasma gasifier PG comprises at least three plasma torches.