Process for upcycle carbonaceous material obtained from waste recycling or pyrolysis of biomass as alternative material for fossil-based cokes

Abstract

The present invention comprises a process of upcycling of carbonaceous material obtained from waste recycling or pyrolysis of biomass as alternative material for fossil-based cokes, wherein said carbonaceous material is fed into a reactor chamber and used as bed material in the form of a fixed, fluidized or moving bed having a particle size of 0.1 mm to 10 mm, wherein a hydrocarbon feed are also fed into said reaction chamber and pyrolyzed at a pressure of 1 to 30 bar and a temperature of 800 to 1500°C to give a hydrogen-containing product stream and solid pyrolytic carbon and wherein said solid pyrolytic carbon deposits in the pores and on the surface of said carbonaceous material and wherein the deposition rate of the pyrolytic carbon is kept in a range of 2 to 20 wt.-% by a conversion rate of 25 to 85 % and by diluting said hydrocarbon feed with hydrogen to a volume ratio of H2 / C1+ of 0.5 to 25 of the diluted total feed stream, and if the ash content of said carbonaceous material is above 5 wt.-% said carbonaceous material is pretreated with an atmosphere of hydrogen and / or inert gases before starting the production mode of said pyrolysis process of hydrocarbons and wherein the time and temperature of said pretreatment is characterized by the formula T (min * °C) = time (min) multiplied by temperature (°C) and T is at least 10000 min * °C and wherein said temperature is at least 500°C of said pretreatment, and wherein during said pretreatment the carbon deposition rate of a pyrolysis process during the pretreatment, if any, is below 1 wt.-%.

Description

[0001] Process for upcycle carbonaceous material obtained from waste recycling or pyrolysis of biomass as alternative ma- terial for fossil-based cokes Description The present invention comprises a process of upcycling of carbonaceous material obtained from waste recycling or pyrolysis of biomass as alternative material for fossil-based cokes, wherein said carbonaceous material is fed into a reactor chamber and used as bed material in the form of a fixed, fluidized or moving bed having a particle size of 0.1 mm to 10 mm, wherein a hydrocarbon feed is also fed into said reaction chamber and pyrolyzed at a pressure of 1 to 30 bar and a temperature of 800 to 1500°C to give a hydrogen-containing product stream and solid pyrolytic carbon and wherein said solid pyrolytic carbon deposits in the pores and on the surface of said carbonaceous material and wherein the deposition rate of the pyrolytic carbon is kept in a range of 2 to 20 wt.-% by a conversion rate of 25 to 85 % and by diluting said hydrocarbon feed with hydrogen to a volume ratio of H2 / C1+ of 0.5 to 25 of the diluted total feed stream, and if the ash content of said carbonaceous material is above 5 wt.-% said carbonaceous material is pretreated and passivated with an atmosphere of hydrogen and / or inert gases before starting the production mode of said pyrolysis process of hydrocarbons and wherein the time and temperature of said pretreatment is characterized by the formula T (min * °C) = time (min) multiplied by temperature (°C) and T is at least 10000 min * °C and wherein the temperature is at least 500°C and wherein during said pretreatment the carbon deposition rate of a pyrolysis pro- cess, if any, is below 1 wt.-%. The present invention also comprises a core-shell particle comprising a core comprising carbonaceous material ob- tained from pyrolysis of biomass having a carbon-14 content of 0.5 to 2.0 ppt, based on total carbon, and a shell of pyrolytic carbon obtained by hydrocarbon pyrolysis having a carbon-14 content of below 0.5 ppt, based on total car- bon. State of the art The increasing concentration of carbon dioxide in the atmosphere has been linked to current and future global warm- ing. Various methods have been put forward to reduce the atmospheric concentration of carbon dioxide, either by reducing the carbon dioxide emissions or by sequestering the carbon dioxide. Currently, CO2 emissions are regulated by CO2 certificates e.g. in the European Union, which will most likely be- come more expensive year after year. It is under discussion whether CO2 emissions could be banned in the foresee- able future. In recent years, industries whose CO2 emissions are based on using carbon-containing material as an energy source started to reduce or even completely eliminate CO2 emissions with manageable effort, e.g. via electrification and the shift from oil and natural gas to hydrogen. It is expected that the need of hydrogen and renewable energy increases rapidly. However, carbon and carbon monoxide are typical reducing agents based on fossil-based petroleum coke as carbon source. These reducing agents are used in many industrial processes, mainly but not exclusively for metals. Either carbon is directly used as a reduction agent or carbon monoxide is generated from carbon e.g. with carbon dioxide C + CO2 ^ 2 CO or from carbon and oxygen 2 C + O2 ^ 2 CO and subsequently used as a reduction agent. Exam- ples (J. House: inorganic Chemistry, 2013 Academic Internet Publishers, M. Bertau et al: Industrielle Anorganische Chemie, 2013 Wiley-VCH) are the production of: calcium carbide CaO + 3 C ^ CaC2 + CO aluminum 2 Al2O3 + 3 C ^ 4 Al + 3 CO2 iron 2 Fe2O3 + 3 C ^ 4 Fe + 3 CO2 with reactions e. g. 2 C + O2 ^ 2 CO, FeO + CO ^ Fe + CO2, C + CO2 ^ 2 CO, Fe3O4 + CO ^ 3 FeO + CO2, 3 Fe2O3 + CO ^ 2 Fe3O4 + CO2. silicon carbide SiO2 + 3C ^ SiC + 2 CO silicon SiO2 + 2 C ^ Si + 2 CO lead PbO + CO ^ Pb + CO2 tin SnO2 + 2 C ^ Sn + 2 CO chromium Cr2O3 + 3 C ^ 2 Cr + 3 CO manganese oxide MnO2 + C ^ MnO + CO phosphorus 2 Ca3(PO4)2 + 6 SiO2 + 10 C ^ P4 + 10 CO + 6 CaSiO3. Said industries that use carbon-containing material as a reducing agent cannot stop their CO2 emission via electrifi- cation since carbon is necessary for production of the target product. These industries need an alternative reducing agent or alternative methods for emission reduction like Carbon Capture and Utilization (CCU) or Carbon Capture and Storage (CCS). RU223489 describes the need of bio-based carbon materials as substitute for fossil coke with a high bulk density, which can be used in the ferrous and non-ferrous metallurgy and in the chemical and electronic industries. It is de- scribed that hydrocarbon is blown through bio carbon which is decomposed by high temperature when passing through the porous biocarbon and carbon is deposited in the pores and at the surface of the biocarbon. It is further disclosed that under certain conditions, pyrocarbon formed on the surface of granules can glue the adjacent parti- cles, which leads to a decrease in the gravitational movement of the material being processed, the formation of ag- glomerates and even to complete blockage of the reactor. The disclosed solution of this formation of agglomeration is a periodic pulsed increase in pressure. The disadvantage of this periodic pressure increase is on the one hand the resulting stress on the reactor, especially on reactor internals, and on the other hand the complex controlling of the periodic cycles and the associated periodic uneven reaction rate. For example, the production of aluminum is carried out in electrolytic cells or pots (known as Hall-Héroult process). Electrolysis of Al2O3 occurs in a molten bath of cryolite layered between the carbon anodes and the molten metal. Aluminum ions within Al2O3 are reduced to form molten aluminum. The molten aluminum is collected at the bottom of the cell. The oxide ions react with the carbon anode producing carbon dioxide, thus, the carbon anode is con- sumed in the electrolytic reaction. Carbon consumption during electrolysis requires prebaked anodes to be replaced every 3 to 4 weeks depending on anode size and current density. Anodes in various stages of consumption are present in all cells due to the restriction of constant replacement and minimal disruption to cells. At the time of anode changing, approximately three-quarters of the anode is consumed. The remainder is called butts. Various reactions in the cell contribute to the consumption of the anode carbon. Those that do not result in metal re- duction contribute to excess carbon consumption like airburn (O2 + C → CO2, with O2 from ambient air), carboxy attack (CO2 + C → CO, with CO2 as product of the Aluminum-producing redox reaction) and selective oxidation (dusting). Dusting occurs as a secondary effect of CO2 attack due to reactivity imbalance between the different coke phases allowing fragments of solid C to fall out. The cost of carbon anode accounts for 15–20% of the total cost of aluminum electrolysis production. Hence, the quality of the carbon anode is of crucial importance and significantly influences the energy consumption and environ- mental effects of aluminum electrolysis. Anode quality is characterized by five main properties: - Reactivity, which determines the greater part of the excess carbon consumption per ton of aluminum produced. The lower the reactivity, the lower this excess carbon consumption. - Density, which is the main factor determining the lifetime of anodes in the pots. The greater the density, the longer the lifetime. Increasing anode lifetime decreases the number of anode changes that are necessary. - Thermal shock resistance, which determines whether or not cracking or fractures occur when anodes are placed in the pots, or during their cycles. - low electrical resistivity, which determines the electrical power loss due to the large electrical currents employed in the Hall cell - high chemical purity, which determines the quality of the aluminum product due to the direct consumption of the an- ode in the electrolytic cell, any metallic or other impurities it contains tend to be transferred to the aluminum product and may adversely affect it mechanical properties. A high chemical purity has also a positive effect on the reactivity. The anode's mechanical strength must meet the demands imposed by the electrolysis process. Porous carbon exhib- its enhanced wetting properties, allowing for better binder material adhesion compared to smooth carbon surfaces. This, in turn, contributes to improved mechanical strength following electrode production and calcination. However, excessive porosity results in increased binder consumption and compromises the performance of the final electrode during the electrolysis process. Therefore, achieving an optimal level of porosity is crucial to maximize electrode per- formance. The raw material used for the production of the dry recipe in prebaked anodes plants are typically calcined petroleum coke, coal tar pitch binder, crushed butts, green scrap (formed, but not baked anodes) and baked scrap (formed and baked anode, which are out of specification). Typically, prebaked anodes are made of about 65 % coke, 15 % pitch and 20% recycled anode butts. As the butts have a high content of Na, butts have to be mixed with fresh carbon with low Na content. Therefore, the total recycling percentage of butts is limited to about 20 %. The continued increase of the demand for aluminum metal combined with the decrease and fluctuations in the quality of aluminum anode grade coke with both the density and the purity of the cokes affected makes it more challenging for the anode manufacturing plants to deliver steady quality anodes. The low quality grade coke has higher reactivity resulting in higher carbon consumption in the smelter. In the last decades different attempts were made to blend or substitute petroleum cokes with different carbon sources like brown-coal, shot coke, graphite and pyrolytic carbon (e.g. US3427240). Recently it was disclosed in WO2020 / 016186 that pyrolytic carbon obtained in a methane pyrolysis process, particu- larly obtained as a deposit on a support consisting of petroleum coke, can be used as blend material in carbon-based aluminum anodes for the reduction of alumina oxide to aluminum. WO 2021 / 239831 discloses a circular carbon process including a methanation step, a methane pyrolysis step and the use of said pyrolytic carbon obtained in the methane pyrolysis as a reducing agent in a chemical process produc- ing carbon monoxide, whereas said carbon monoxide is used for the methanation step. These three process steps are preferably conducted on one side as a joint plant set-up. The benefit of WO 2021 / 239831 is that carbon can still be used as a reducing agent resulting in carbon oxide emissions, but this carbon oxide is not emitted to the atmos- phere but converted to methane resulting in a closed carbon cycle. The generic term methane pyrolysis covers a wide range of different process technologies. The best known and most advanced of these are: plasma pyrolysis, pyrolysis in a metal melting & metal salt melting reactor, moving bed & flu- idized bed and fixed bed (catalytic and non-catalytic) processes, and pyrolysis via partial combustion. They differ in the form of the energy used (thermal, electrical, etc.), the process conditions (temperature, pressure, etc.), the cata- lysts and / or auxiliary materials used, the process flow and the technical readiness level (TRL). Moving and fluidized bed reactors are disclosed for example in US 2,982,622, US 2022 / 0152568, US 2021 / 033 1918, WO 2023 / 57242. Many different solids (also called support or substrate) are disclosed as moving or fluidized bed material, for example inert coke or coal particle, particularly petroleum coke, and ceramic carrier particles on which the pyrolytic carbon can deposit. Although WO 2016 / 026562 disclosed a preferred carbon content of 98.-wt % of the support, it is disclosed that granular materials could be used as solid material that consists wholly or partly of low-grade coking plant coke based on brown coal or hard coal and / or of coke obtained from biomass. In case of us- ing carbonaceous solid materials these materials are typically solely used as starting material, during the continuous pyrolysis operation, the pyrolytic carbon content of said bed material will constantly grow and replace the initial car- bonaceous material. WO 2023 / 57242 discloses the need of highly pure carbonaceous material as support material with a carbon content of 99 to 100 wt.-%. If the amount of inorganic is too high, unwanted reactions or fouling might block the reactor by formation of soot or catalytic side reactions. In addition, highly catalytically active support material could lead to an inhomogeneous pyrolytic reaction resulting in high local deposition rates and thus local agglomerations blocking the reactor. WO 2024 / 115488 discloses the use of by-products streams from a cracking process as feedstock for a methane py- rolysis process. Said methane pyrolysis is operated in a moving bed reactor at 800 to 1500°C, wherein the by-prod- ucts streams used as feedstock is preferably diluted by a recycled hydrogen product stream resulting in a feedstock stream that contains 70 to 99 vol.-% hydrogen and 1 to 30 vol.-% hydrocarbons. WO 2021 / 102521 discloses a decomposition of a plastic pyrolysis gas on biochar with a particle size of 1 to 100 mi- crons at temperature from 500 to 900°C. It is disclosed that carbon nanotubes are formed at 700 and 900°C. Although the climate discussion and studies to achieve CO2 neutral production started more than 20 years ago, only a few studies on alternatives to carbon-based anodes has been disclosed yet. For example, US 6,551,489 discloses an inert anode assembly replacing the consumable carbon anode. Despite the use of fossil based pyrolytic carbon as an alternative for petroleum coke, there is a need for a better re- cycling and utilization of carbonaceous material and the need to use biogenic based carbonaceous material as an alternative for petroleum coke. Unfortunately, most of the characteristics of this carbonaceous material contradict to the characteristics of petroleum coke and thus the needed characteristics for carbon used as reducing material such as high chemical purity, high density and low porosity. Senanu et al. describes in “Biocarbon in the Aluminium Industry: A Review”, Conference Parer, 24.02.2021, pp 649- 656 that despite the advantage of being renewable and consequently contributing to a balanced CO2 emission, the use of bio-cokes or charcoal as a raw material in the aluminum industry comes with certain challenges relating to me- chanical strength, CO2 reactivity, porosity, density, electrochemical consumption, purity, etc. Analysis of the pilot an- odes showed that the anodes with charcoal had lower density, poor mechanical strength, and higher CO2 reactivity, especially due to the open pores that did not contribute to coal par pitch impregnation and the low density of said bio- cokes or charcoal. Due to said analysis it was not recommended to use said material in anode production for alumi- num industry. In addition, also Monson et al. pointed out in “CHARCOAL IN ANODES FOR ALUMINIUM PRODUCTION” Light Metals 2010 that charcoal cannot be recommended for use in anodes for aluminum production due to the low den- sity, open coral pore structure and high impurities increasing the CO2-reactivity, especially alkali content. In a nutshell, the needed characteristics for carbon used as reducing material: High purity (particularly in view of S, V, Na, Fe, Ni, Co, Ca), high density, low surface area, low porosity. However, the characteristics of biochar are: many contaminants (particularly O, S, N, Na, Ca and Fe) and a low car- bon content, high surface area, very high porosity resulting in a very low density. Task It is an object of the present invention to find a way of utilization of carbonaceous material from waste recycling or pyrolysis of biomass, preferably even carbonaceous material with varying qualities and / or even carbonaceous mate- rial with catalytically active centers. Another objective of the invention is to find a way of upcycling such carbona- ceous material from waste recycling or pyrolysis of biomass to improve chemical purity, especially increase carbon content and decrease oxygen, ash and sodium content, increase density, decrease surface area and / or decrease porosity and thus to increase fields of application, also outside the application of origin, like carbon mass from batter- ies and recovered / recycled carbon black from rubber applications (e.g. tires). Another objective of the invention is to utilize carbonaceous material from waste recycling or pyrolysis of biomass for the use as reducing agent, especially as electrode material. Invention The present invention comprises a process of upcycling of carbonaceous material obtained from waste recycling or pyrolysis of biomass as alternative material for fossil-based cokes, wherein said carbonaceous material is fed into a reactor chamber and used as bed material in the form of a fixed, fluidized or moving bed having a particle size of 0.1 mm to 10 mm, wherein a hydrocarbon feed are also fed into said reaction chamber, wherein the hydrocarbons are pyrolyzed at a pressure of 1 to 30 bar and a temperature of 800 to 1500°C to give a hydrogen-containing product stream and solid pyrolytic carbon and wherein said solid pyrolytic carbon deposits in the pores and on the surface of said carbonaceous material and wherein the deposition rate of the pyrolytic carbon is kept in a range of 2 to 20 wt.-% by a conversion rate of 25 to 85 % and by diluting said hydrocarbon feed with hydrogen to a volume ratio of H2 / C1+ of 0.5 to 25 of the diluted total feed stream, and if the ash content of said carbonaceous material is above 5 wt.-% said carbonaceous material is pretreated with an atmosphere of hydrogen and / or inert gases before starting the pro- duction mode of said pyrolysis process of hydrocarbons and wherein the time and temperature of said pretreatment is characterized by the formula T (min * °C) = time (min) multiplied by temperature (°C) and T is at least 10000 min * °C and wherein said temperature of said pretreatment is at least 500°C and wherein during said pretreatment the carbon deposition rate of a pyrolysis process, if any, is below 1 wt.-%. Said carbon deposition rate can be defined by reference time unit (see equation 7) or by weight-% (see equation 8), for the features in the claim, the definition by weight-% is taken so that said carbon deposition rate is defined by: ఛ^^^Δ^^ ^^^^^,^^^ ^^^ ⋅ ^^^^^^ = 100 ⋅ = 100 ⋅ ^,ௗ^^^^^௧^^^ ^,ௗ^^^^^௧^^^ ^^^^^^ ^^ ^^ ^^^^ ^^^^ = 100 ⋅^௧ୀ^ ^^ ^^^The reactor specific reference residence time is defined as follows: • Batch / Fixed bed: ^^^^^= total pyrolysis time • Moving bed: ^^^^^= mean residence time of carrier particles in the pyrolysis zone • Fluidized bed: ^^^^^= mean residence time of carrier particles in the pyrolysis zone Reference mass in [g]: • Batch / Fixed bed: ^^^= initial carrier mass in the reactor •Moving bed: ^^ = ^^^^^^^^^^^^ ∙ ^^ wit ^^^^^ ^^^ h the reactor inlet mass flow ^^^ ^^^^^^^^^^^^^^ in [g / s]• Fluidized bed: ^^^ = ^^^^^^^^^^^^ ∙ ^^^^^ with the reactor inlet mass flow ^^^^^^^^^^^^^^^^^^^^^ in [g / s] wherein ^^^ ^,ௗ^^^^^௧^^^ the carbon deposition rate [g / s]Δ^^^ is the carbon mass increase [g]^^^^^ is the reactor specific reference residence time [s]^^^^^^^ is the carbon deposition rate (per reference time unit) in [wt.%].Surprisingly, a pyrolysis process mode was found that allows using and thus upcycling catalytically active and / or con- taminated carbonaceous material as inert bed material without the expected agglomeration and blocking of the bed reactor. The upcycling of such carbonaceous material obtained from waste recycling or pyrolysis of biomass contributes to the concept of a circular economy by promoting the reuse and recycling of materials, reducing waste generation, and supporting sustainable practices. Such materials are sustainable alternatives to traditional carbon-based materials like petroleum coke, reducing the reliance on virgin resources and minimizing environmental impact. Definitions C1 stands for methane. C1+ stands for all hydrocarbons having one or more C-atoms in the molecule. C2+ stands for all hydrocarbon having two or more C-atoms in the molecule. The (total) reactor feed stream includes both the external feed stream and the internally recycled hydrogen-contain- ing product stream. Fossil-based cokes are for example petroleum coke and acetylene coke. Methods for determining the parameters Median pore diameter (volume) Definition: The median of the pore size distribution is the pore diameter at which 50% of the total cumulative pore volume is smaller and 50% is larger. Reference: ISO 15901-1:2016. Pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption - Part 1: Mercury porosimetry URL: ISO 15901-1:2016(en), Evaluation of pore size distribution and porosity of solid materials by mercury porosime- try and gas adsorption — Part 1: Mercury porosimetry Particle size Definition: The particle size is the diameter of an idealized sphere that corresponds to the real, irregularly shaped one. It corresponds to the smallest sieve perforation diameter through which the particle fits through. Reference: [1] DIN 66165-1:2022-06. Partikelgrößenanalyse - Siebanalyse - Teil 1: Grundlagen, 2022 [2] DIN 66165-2:2016-08. Partikelgrößenanalyse - Siebanalyse - Teil 2: Durchführung, 2016 URL: Siebanalyse Unterschiedliche Siebmethoden für vielfältige Anwendungen Thickness of shell Definition: The shell thickness is the thickness of the layer of pyrolysis carbon that is deposited on a carrier particle and completely or partially covers the carrier particle. The method for determining the layer thickness is based on the ASTM B487 standard. Reference: ASTM B487. Standard Test Method for Measurement of Metal and Oxide Coating Thickness by Micro- scopical Examination of Cross Section, 2013 URL: ASTM-B-487-yr-87-R-13.pdf H2 / C1+ ratio Definition: H2 / C1+ ratio is the ratio of the mole fraction of dilution hydrogen to the mole fraction of hydrocarbons in the gaseous feed stream of the reactor. For ideal gases, the mole fractions of the mixture components are identical to the volume fractions. These parameters were measured with a micro GC, Agilent Technologies, type 490 Micro GC. Carbon content Definition: The carbon content of a carbonaceous material is the ratio of the mass of carbon contained in relation to the total mass of the sample. Determination method: CHNS method Reference: Hendrik Wetzel. CHNS-ANALYSE / O-ANALYSE, 2025 URL: CHNS-O-Analyse - Fraunhofer IAP Ash content Definition: The ash content is the mass fraction of the non-combustible residues after combustion of the sample un- der precisely defined conditions (temperature, air supply, duration). Reference: ISO 1172. Kohle und Asche - Asche URL: ISO-1171-2010.pdf Surface concentration of metallic elements Definition: The elemental composition of the sample surface, expressed in weight-% relative to the total mass of the analyzed sample. Determination method: Energy dispersive X-ray spectroscopy (EDX) in combination with scanning electron micros- copy (SEM). The raw signal of EDX is the count rate per peak. The evaluation software translates this to the surface concentration in % by weight. Reference: ASTM F1375-92(2020). Standard Test Method for Energy Dispersive X-Ray Spectrometer (EDX) Analy- sis of Metallic Surface Condition for Gas Distribution System Components, 2020. URL: F 1375 - 92 (2020).pdf Trace component concentration in the gas phase Definition: Components that occur in a carrier gas mixture in very low concentrations. Determination method: In the FTIR technique, a Michelson interferometer records an interferogram of the intensity of broadband infrared (IR) radiation. By applying a Fourier transform to this interferogram across a wide range of wave- lengths, a spectrum is generated that comprises the spectral signatures of the gaseous components present in the measurement path. Analyzing these spectral signatures allows for to determine the concentrations of many different components simultaneously using the FTIR system. Reference: DIN EN 15483:2009-02. Luftqualität Messungen in der bodennahen Atmosphäre mit FTIR-Spektroskopie, 2008. URL: ISO-14577-1-2015.pdf e-module (Young modulus) & hardness Definition: The modulus of elasticity is a material-physical parameter that indicates the linear relationship between stress and deformation in the elastic (reversible) deformation range. Determination method: The hardness and modulus of elasticity of thin layers of pyrolysis carbon are measured using nanoindentation. Reference: DIN EN ISO 14577-1. Metallische Werkstoffe– Instrumentierte Eindringprüfung zur Bestimmung der Härte und anderer Werkstoffparameter– Teil1: Prüfverfahren, 2024 URL: ISO-14577-1-2015.pdf Detailed Description of the Invention Original Carbonaceous material The original carbonaceous material to be upcycled is preferably bio char, green coke, anode butts, recycled / recov- ered carbon black (from polymer recycling via pyrolysis) and / or black mass (from battery recycling). The chemical composition is typically in the following ranges: The carbon content of said carbonaceous material is typically in the range of 75 to 98 wt.%, more preferably 80 to 95 wt.%. The oxygen content is typically in the range of in the range of 0 to 20 wt.%, more preferably 0 to 10 wt.%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 20 wt.%, more preferably 0 to 10 wt.%, more preferably 0 to 5 wt.%. In view of bio char is the chemical composition in the following ranges: The carbon content of bio char material is typically in the range of 75 to 98 wt.-%, more preferably 80 to 95 wt.-%, even more preferably 85 to 92 wt.-%. The oxygen content is typically in the range of in the range of 0 to 20 wt.-%, more preferably 1 to 10 wt.-%, even more preferably 3 to 8 wt.-%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 10 wt.-%, more preferably 0.5 to 5 wt.-%, even more preferably 1 to 3 wt.-%. The sulphur content is typically in the range of 0 to 2 wt.-%, more preferably 0.01 to 1 wt.-%, even more preferably 0.01 to 0.5 wt.-%. The sodium content is typically in the range in the range of 0 to 1 wt.-%, more preferably 0 to 0.5 wt.-%, even more preferably 0 to 0.2 wt.-%. In view of green coke is the chemical composition in the following ranges: The carbon content of green coke material is typically in the range of 80 to 99 wt.-%, more preferably 85 to 95 wt.-%, even more preferably 88 to 92 wt.-%. The oxygen content is typically in the range of in the range of 0 to 10 wt.-%, more preferably 0.5 to 5 wt.-%, even more preferably 1 to 2 wt.-%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 5 wt.-%, more preferably 0 to 1 wt.-%, even more preferably 0 to 0.5 wt.-%. The sulphur content is typically in the range in the range of 0 to 5 wt.%, more preferably 0 to 2 wt.-%, even more preferably 0 to 1 wt.-%. In view of anode butts is the chemical composition in the following ranges: The carbon content of anode butts material is typically in the range of 90 to 99 wt.-%, more preferably 92 to 98 wt.-%, more preferably 94 to 97 wt.-%, even more preferably 95 to 97 wt.-%. The oxygen content is typically in the range of in the range of 0 to 0.5 wt.-%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 1 wt.-%, more preferably 0 to 0.5 wt.%, even more preferably 0 to 0.2 wt.-%. The sulphur content is typically in the range in the range of 0.1 to 5 wt.-%, more preferably 0.5 to 4 wt.-%, even more preferably 1 to 3 wt.-%. The chlorine content is typically in the range in the range of 0 to 10 ppm. The sodium content is typically in the range in the range of 0 to 0.1 wt.-%. In view of recovered carbon black is the chemical composition in the following ranges: The carbon content of recovered carbon black material is typically in the range of 70 to 90 wt.-%. The Al content is typically in the range of 100 to 5000 ppm. The Ca content is typically in the range of 5000 to 13000 ppm. The Fe content is typically in the range of 100 to 8000 ppm. The Zn content is typically in the range of 3000 to 50000 ppm. The S content is typically in the range of 30000 to 50000 ppm. The Si content is typically in the range of 20000 to 150000 ppm. The N content is typically in the range of 1000 to 10000 ppm. The Cl content is typically in the range of 200 to 1500 ppm. The Br content is typically in the range of 300 to 1000 ppm. The Co content is typically in the range of 25 to 200 ppm. In view of black mass, the chemical composition of the carbon composition is in the following ranges: 80 to 99.9 wt.- % carbon, depending on the cleaning effort, the main impurities are Al2O3 / aluminates and SiO2 / silicates in addition to TiO2, ZrO2, WO3, Cu, Li-oxides. The original BET surface area of said carbonaceous material is typically between 2 and 1500 m2 / g, preferably 2 and 500 m2 / g. In view of bio char is the BET surface area in the following ranges: 40 to 1500 m2 / g. In view of green coke is the BET surface area in the following ranges 5 to 20 m2 / g. In view of anode butts is the BET surface area in the following ranges: 2 to 10 m2 / g. In view of recovered carbon black is the BET surface area in the following range: 30-80 m² / g, after activation 400- 600 m² / g. In view of black mass, the BET surface area of the carbon composition is in the following ranges: 4 bis 20 m2 / g. In view of bio char is the density in the following ranges: 0.35 to 0.7 g / ml. In view of green coke is the density in the following ranges: 0.5 to 0.9 g / ml. In view of anode butts is the density in the following ranges 0.8 to 0.9 g / ml In view of recovered carbon black is the density in the following ranges: 250 – 600 kg / m³. In view of bio char is the porosity in the following ranges: 0.3 to 0.6 ml / g. In view of green coke is the porosity in the following ranges: 0.05 to 0.15 ml / g. In view of anode butts is the porosity in the following ranges: 0.1 to 0.24 ml / g. In view of recovered carbon black is the porosity in the following ranges: 20-70%. Pretreatment of the carbonaceous material before feeding into the reaction chamber The particle size of a bed material in the form of a fixed, fluidized or moving bed is typically 1 to 10 mm for a fixed bed material, 0.1 to 1 mm for a fluidized bed material and 1 to 10 mm for a moving bed material. The carbonaceous material to be upcycled is preferably grinded / milled or pelletized to said particle sizes. The carbonaceous material to be upcycled can be mixed with well-known bed material for fixed, fluidized or moving bed, like inert coke or coal particle, particularly petroleum coke, and / or ceramic carrier particles. Preferably, the car- bonaceous material to be upcycled can be mixed with granular petroleum coke, preferably in a mixing ratio of 2 to 50 wt.-% carbonaceous material to be upcycled, especially bio char, and 98 to 50 wt.-% petroleum coke, more prefera- bly 3 to 30 wt.-% carbonaceous material to be upcycled, especially bio char, and 97 to 70 wt.-% petroleum coke, even more preferably 5 to 20 wt.-% carbonaceous material to be upcycled, especially bio char, and 95 to 80 wt.-% petroleum coke. The present invention further comprises a bed material for fixed, fluidized or moving bed reactor containing of 2 to 50 wt.-% carbonaceous material to be upcycled, especially bio char, and 98 to 50 wt.-% petroleum coke, more prefera- bly 3 to 30 wt.-% carbonaceous material to be upcycled, especially bio char, and 97 to 70 wt.-% petroleum coke, even more preferably 5 to 20 wt.-% carbonaceous material to be upcycled, especially bio char, and 95 to 80 wt.-% petroleum coke. In addition, during a batch or continuous operation of the fixed, fluidized or moving bed fresh carbonaceous material obtained from waste recycling or pyrolysis of biomass to be upcycled can be added and mixed with the already partly upcycled carbonaceous material obtained from waste recycling or pyrolysis of biomass. Preferably said mixing is done before feeding the reactor with the bed material needed. Pyrolysis process of hydrocarbons The process of pyrolyzing hydrocarbons to produce hydrogen and solid carbon is well described in the state of the art. Typically the pyrolysis operates at 500 to 2000°C in a pressure range from atmospheric pressure to 30 bar. Typi- cal hydrocarbon feedstocks for pyrolysis processes are gaseous hydrocarbons, like natural gas, methane, ethane, biogas, like biomethane. Feedstock Typically, natural gas contains hydrocarbons with a ratio of C1 / C2+ of 3 to 100, more preferably 3 to 50, even more preferably 3 to 25, even more preferably 4 to 20, even more preferably 5 to 15. Typically, natural gas is used as (external) feed stream. The composition of natural gas is very depending on the lo- cation of extraction. Beside methane, other hydrocarbon gases like ethane, propane, and butane may be present in varying amounts. Additionally, the presence of impurities such as carbon dioxide, nitrogen, and sulfur compounds can impact the quality and usability of natural gas. Natural gas typically has the following composition: methane from 50 to 99 Vol.-%, preferably 85 to 99 Vol.-%, ethane from 0.5 to 25 Vol.-%, preferably from 1 to 15 Vol.-%, propane from 0 to 10 Vol.-%, preferably from 0.5 to 5 Vol.-%, butane from 0 to 10 Vol.-%, pentane from 0 to 5 Vol.-%, CO2 from 0 to 5 Vol.-% and N2 from 0 to 10 Vol.-%, preferably from 1 to 5 Vol.-%, sulfur components from 0 to 10 Vol.-%, preferably from 0 to 2 Vol.-%, of the total raw natural gas. Typically, natural gas contains hydrocarbons with a ratio of C1 / C2+ of 3 to 100, more preferably 3 to 50, even more preferably 3 to 25, even more preferably 4 to 20, even more preferably 5 to 15. In addition or alternatively to natural gas, synthetic methane, biogas, flare gas and / or industrial off gas, e.g. cracker off gas, can be used. Such external feed stream also preferably contains hydrocarbons with a ratio of C1 / C2+ of 3 to 100, more preferably 3 to 50, even more preferably 3 to 25, even more preferably 4 to 20, even more preferably 5 to 15. Methane Pyrolysis (Production Mode) Preferably, a methane pyrolysis is conducted to upcycle the carbonaceous material. The methane pyrolysis is con- ducted in a moving, fluidized or fixed bed reactor, preferably at temperatures ranging from 800 to 1500°C, preferably ranging from 900 to 1400°C preferably ranging from 1000 to 1300°C, even more preferably ranging from 1100 to 1250°C, and at pressures ranging from 1 to 30 bar, preferably from 2 to 25 bar, even more preferably 3 to 20 bar, particularly 5 to 15 bar. The deposition rate is a critical parameter for upcycling such a diverse and reactive material and is to be kept in a range of preferably 0.1 to 20 wt.-%, more preferably 1 to 15 %, more preferably 2 to 12 %, even more preferably 3 to 10 wt.-%, even more preferably 5 to 9 wt.-%, even more preferably 4 to 8 wt.-%. The definition of the carbon deposition rate, sometimes also referred to as carbon growth rate, depends on the reac- tor type and is defined in the following: The symbols and indices used are shown in Table 1. Table 1. Symbols and indices used for describing carbon deposition and growth rates. Symbol Description^^^^,ௗ^^^^^௧^^^ Carbon deposition rate [molC / s]^^^^ுସ,^ Molar flow [molC / s]^^ Conversion rate [-]^^^ ^,ௗ^^^^^௧^^^ Carbon deposition rate [g / s]^^^ Molar mass [g / mol]^^^^ Carbon deposition [g / g]Δ^^^ Carbon mass increase [g]^^^ Carbon mass [g]^^^^^ Carbon deposition rate in [g / g*s]τ Time unit [s]^^^^^^^ Carbon deposition rate (per reference time unit) [-] or in [wt.%]V Reactor volume [m3]Indices Description 0 Particle before pyrolysis or state feed gas 1 Particle after pyrolysis or state in pyrolysis gas in Reactor inlet ref Reference (e.g. time unit) The carbon deposition rate in [mol,C / s] results from the molar flow of CH4 in the feed gas and the conversion rate: ^^^^,ௗ^^^^^௧^^^ = ^^^^ுସ,^ ⋅ ^^(^^,^^,^^^ , ^^^^^^%ுଶ,^, ^^^^^^%^ுସ,^) 1Considering the ^^^ ^,ௗ^^^^^௧^^^ = ^^^ ^,ௗ^^^^^௧^^^ ⋅ ^^^ 2The CH4 conversion rate is ^^^^^ = ^ுସ,^ − ^^^^ுସ,^ ^^^^ுସ,^^^^ = 1 − 3^ுସ,^ ^^^ ^ுସ,^ The carbon deposition in [g / g] is defined as: Δ^^^^^^ = ^^^ 4^The carbon deposition rate in [g / (g*s)] follows from the initial mass and the carbon deposition rate in [mol,C / s]: ^^^^^^^^ = ^,ௗ^^^^^௧^^^^^ 5^The total increase in carbon mass Δ^^^ = ^^^ ^,ௗ^^^^^௧^^^ ⋅ τ 6Considering the reactor volume ^^ and the reactor type specific reference residence time leads to the carbon tion rate per reference time unit in [-]: ఛ^^^Δ^^ ^ ^^^^^ ^,^^^ ^^ ^,ௗ^^^^^௧^^^ ^^^ ^,ௗ^^^^^௧^^^ ⋅ ^^^^^^^^ = = ^ ^^^^ ^^^^ = 7The carbon ఛ^^^Δ^^ ^^^^ ^^^ ⋅ ^^^^^^^^ = 100 ⋅ ^,^^^^^ = 100 ⋅ ^ ^,ௗ^^^^^௧^^^ ^^^^ ^^^^ = 100 ⋅ ^,ௗ^^^^^௧^^^ ^^^^ 8^ The reactor specific • Batch / Fixed bed: ^^ = total • Moving bed: ^^^^^= mean residence time of carrier particles in the pyrolysis zone • Fluidized bed: ^^^^^= mean residence time of carrier particles in the pyrolysis zone Reference mass in [g]: • Batch / Fixed bed: ^^^= initial carrier mass in the reactor •Moving bed: ^^ = ^^^^^ ∙ ^^ with the r ^^^^^ ^^^^^^^ ^^^ eactor inlet mass flow ^^^ ^^^^^^^^^^^^^^ in [g / s]• Fluidized bed: ^^ = ^^^^^ ∙ ^^ with the ^^^^^ ^^^^^^^ ^^^ reactor inlet mass flow ^^^ ^^^^^^^^^^^^^^ in [g / s]Depending on the available instrumentation and analysis methods, different ways for the practical application of the described theoretical framework for the calculation of ^^^^^^^exist. It is important to note that the specific material property must be measured before the pyrolysis (index “0”) and after a pyrolysis time of ^^^^^(index “1”). Exemplary ways of application: • Using the Sauter mean diameter of the particle size distribution and the measured real density from helium or xylene pycnometer:^^ ^^^ = ଷ ^^ ଷ6 ^^ௌ^௨௧^^,^ ⋅ ^^ு^,^, ^^^ =6 ^^ௌ^௨௧^^,^ ⋅ ^^ு^,^ 9 • Using a reference volume ^^^^^ which contains the particle mass ^^^௨^^,^,^ to determine the bulk density:^^^௨^ ^^^^ = ^,^ ^௨^^,^^௨^^,^ ^^ , ^^^௨^^,^ =^^^ ^^^^^ 11 • Using the measured or , gas conver- sion rate, using the measured of calculated molar flow rates and applying the detailed formulas given above. Moving bed: The solid carbon mass from hydrocarbon pyrolysis deposed on one solid granule in one pass through the reactor divided by the mass of the said one solid granule before entering the reactor. The mass of the said solid particle before and after the pyrolysis is calculated by the Sauter mean diameter of the particle size distribution and the real density of the used granule. The reference residence time according to equations 7-8 is preferably between 0.1 and 15 h, preferably between 1 and 10 h and more preferably between 2 and 8 h. Fixed bed: The solid carbon mass from hydrocarbon pyrolysis deposed on one solid granule during its residence time in the reactor divided by the mass of the said one solid granule before entering the reactor. The mass of the said solid particle before and after the pyrolysis is calculated by the Sauter mean diameter of the particle size distribution and the real density of the used granule. The reference residence time according to equations 7-8 is preferably 0.1 to 90 h, more preferably 0.25 to 50 h, more preferably 0.5 to 25 h and even more preferably 1.0 to 10 h. Fluidized bed: The solid carbon mass from hydrocarbon pyrolysis deposed on one solid granule during one inner cir- culation through the reactor divided by the mass of the said one solid granule before entering the reactor. The mass of the said solid particle before and after the pyrolysis is calculated by the Sauter mean diameter of the particle size distribution and the real density of the used granule. In a fluidized one particle can circulate multiple times through the reactor during its residence time inside the reactor. The reference residence time according to equations 7-8 is preferably 0.1 to 90 h, more preferably 0.25 to 50 h, more preferably 0.5 to 25 h and even more preferably 1.0 to 10 h. Besides the temperature and the pressure, the deposition rate is preferably be controlled by diluting the hydrocarbon feed with hydrogen to a volume ratio of preferably H2 / C1+, particularly H2 / C1+, of 0.1 to 25, even more preferably 0.5 to 10, in particular 1 to 8, even more preferably 2 to 6. The deposition rate is preferably also be controlled by the conversion rate that is preferably 20 to 90 %, more prefer- ably 25 to 85 %, more preferably 30 to 80 %, even more preferably 50 to 80 % (based on the hydrocarbons in the feed stream, see equation 3). Preferably, the deposition rate is increased during the operation of the inventive process. Preferably, the deposition rate is increased during the operation of the inventive process if the ash and / or oxygen content of said carbonaceous material is above 1 wt.-% and / or the BET surface area is above 100 m2 / g. Preferably, the deposition rate is in- creased continuously (see details on pretreatment conditions below). The methane pyrolysis process can be heated in different ways known to the persons skilled in the art: heated carrier gas, resistance heating, induction or autothermal. Preferably the methane pyrolysis process is heated electrically, even more preferably by resistive heating (Joule heating) of the solid material as described for example in US 2982622, WO 2019 / 145279 and WO 2020 / 200522. The methane pyrolysis results in a hydrogen-containing product stream and solid carbon. Depending on the reaction conditions, the content of the hydrogen-containing product stream - related to the total volume of the hydrogen-containing product stream - is preferably: (i) hydrogen preferably between 30 vol-% and 99 vol-%, more preferably between 50 vol-% and 98 vol-%, and in particular between 60 vol-% and 98 vol-%, (ii) methane preferably between 1 and 60 vol-%, more preferably between 2 and 40 vol-% and in particular between 2 and 30 vol-%, (iii) the sum of the contents of all C2+ hydrocarbon components comprising e.g. C2H6, C2H4, C2H2, C3H8, C3H6, C3H4, C4H8, C4H6, C6H6, C7H8, C8H10 preferably between 0 and 1 mol%, more preferably between 0 and 0.5 mol% and in particular between 0 and 0.1 mol-%, (iv) nitrogen preferably between 0 and 20vol%, more preferably between 0 and 10 vol-% and in particular between 0 and 5 vol-%, carbon monoxide preferably between 0 and 2-vol%, more preferably between 0 and 1-vol% and in particular between 0 and 0.5 vol-%, carbon dioxide preferably between 0 and 2-vol%, more preferably between 0 and 1vol-% and in particular between 0 and 0.5 vol-% and the water preferably between 0 and 2vol-%, more pref- erably between 0 and 1vol-% and in particular between 0 and 0.5 vol-%. The hydrogen-containing stream preferably contains hydrocarbons with a ratio of C1 / C2+ of 4 to 10000, more prefer- ably 15 to 1000, even more preferably 20 to 500, even more preferably 30 to 250, even more preferably 50 to 200. H2 / C1+ ratio Preferably, the H2 / C1+ ratio of the total reactor feed stream ranges from 0.5 to 25, more preferably from 0.75 to 10, even more preferably from 1 to 8, even more preferably 2 to 6. Typically, the total reactor feed stream contains preferred 50 to 95 Vol.-% hydrogen, more preferred 65 to 85 Vol% hydrogen, 5 to 50 Vol.-% hydrocarbons, more preferred 35 to 15 vol% hydrocarbons, and 0 to 3 Vol.-% inert gases, particularly nitrogen and argon. The total reactor feed stream preferably contains hydrocarbons with a ratio of C1 / C2+ of 15 to 500, more preferably 17 to 100, even more preferably 20 to 50. There are several process layouts how to realize said H2 / C1+, particularly H2 / C1+ feed volume ratio. Without exclud- ing further options, preferred layouts are: - Direct gas recycle: a portion of the reactor effluent gas stream is recycled without any purification steps. Gas streams may or may not be cooled or heated. - Recycle after purification unit: The hydrogen depleted gas stream after any purification or gas separation unit is recycled to the reactor, while a fraction is purged. - Gas streams employed for pneumatic transport of solids are recycled to the reactor. - Hydrogen containing gas streams from different processes or other sources are mixed to the hydrogen feed stream. Preferably, an internal recycle of the hydrogen-containing product stream is used to dilute the feed stream and con- trol the H2 / C1+ volume ratio, that means, a portion of the raw hydrogen-containing product stream is recycled without any purification steps. Said recycled hydrogen-containing product stream may or may not be cooled, heated and / or compressed. The hydrogen-containing product stream leaving the reaction chamber preferably enters a separation unit. This sepa- ration unit typically includes a valve, a flow meter, and a meter to determine the H2 concentration. Preferably, 20 vol-% to 90 vol-% of the hydrogen-containing product stream is separated and recycled to the reaction chamber, more preferably 30 vol -% to 85 vol %, more preferably 40 vol- % to 85 vol -%, even more preferably 50 vol -% to 80 vol -%. The vol-% of the hydrogen-containing product stream taken for the internal direct recycle is prefera- bly adjusted to a volume ratio H2 / C1+ of the total reactor feed stream ranging from 0.1 to 25, more preferably from 0.5 to 10, even more preferably from 1 to 8. The recycled hydrogen-containing product stream is mixed with the external feed stream, e.g. natural gas, inside or outside the reaction chamber. Before mixing, the temperature of the internally recycled hydrogen-containing product stream is preferably between 10°C and 200°C, even more preferably between 15 and 150°C and in particular be- tween 20 and 100°C. Preferably, the external feed stream and the recycled hydrogen-containing product stream are mixed before entering the rection chamber, outside of the reactor. Alternatively, the streams are separately intro- duced into the reaction chamber. Therefore, the feed of the pyrolysis process contains at least two feed streams: (i) external feed stream containing hydrocarbons, preferably gaseous and liquid hydrocarbons, more preferably gaseous hydrocarbons, even more pref- erably methane and / or other light hydrocarbons feed stream, preferably natural gas and (ii) an internally recycled hy- drogen-containing product stream. Ratio of internally recycled hydrogen-containing product stream and external hydrocarbon stream The (total) reactor feed stream includes both the external feed stream and the internally recycled hydrogen-contain- ing product stream. Preferably the ratio of the volume of the internally recycled hydrogen-containing product stream to the volume of the external feed stream is between 0.1 to 20, more preferably between 0.3 and 8, even more preferably between 0.8 and 6. Typically, the total reactor feed stream contains preferred 50 to 95 Vol.-% hydrogen, more preferred 65 to 85 Vol-% hydrogen, 5 to 50 Vol.-% hydrocarbons, more preferred 35 to 15 vol-% hydrocarbons, and 0 to 3 Vol.-% inert gases, particularly nitrogen and argon. The total reactor feed stream contains hydrocarbons with a ratio of C1 / C2+ of 15 to 500, more preferably 17 to 100, even more preferably 20 to 50. Preferably, said volume ratio of the total reactor feed stream is at least increased by a factor of 1.1 to 2.5, more pref- erably 1.25 to 2, compared to said volume ratio of C1 / C2+ of the external feed. Degree of Upcycling The degree of upcycling can be adjusted in a broad range. Typically, the degree of upcycling is adjusted by the oper- ation time, especially by the time, the carbonaceous material to be upcycled is in the reaction zone of the pyrolysis. The degree of upcycling can be measured by the degree of increased carbon content and amount. The needed de- gree of upcycling is depending on the planed application of this material. The upcycling typically occurs preferably as a two-step process: a deactivation / calcination of the material and the increase of carbon content by deposition of pyrolytic carbon. The deposition of the carbon typically also occurs in a two-step process: filling of the pores and coating of the particles. The degree of upcycling can be measured by analyzing part of the bed material. This method is especially preferred by the fluidized and moving bed technology as the solid material is always recycled to the reactor and easily to be analyzed. Typically, the carbon content, the density, the specific surface area and / or the porosity is analyzed. Alternatively, or in addition to the analytics of the carbonaceous material, the hydrogen containing product stream can preferably be analyzed. Typically, if the conversion rate of the hydrocarbon is constant, the first step of the upcy- cling process, mainly the deactivation / calcination of the material, has finished. In addition, the oxygen content in the hydrogen containing product stream can preferably be analyzed, if the concentration of oxygen-containing products like water, carbon monoxide and carbon dioxide decrease and keep low, the deactivation / calcination of said material has finished. Therefore, the present invention also includes the following process step: Measuring the chemical composition of the hydrogen-containing product stream and / or analyzing the withdrawn upcycled carbonaceous material. After the needed degree of upcycling is reached, the upcycled carbonaceous material is withdrawn from the bed re- actor. This can be done batchwise and all material is withdrawn when the needed degree of upcycling is reached or continuously. Deactivation and Calcination via pretreatment of the carbonaceous material Preferably, if the ash content of said carbonaceous material to be upcycled is above 1 wt.-%, more preferably above 2 wt.-%, even more preferably above 3 wt.-%, even more preferably above 4 wt.-%, in particular above 5 wt.-% the bed of said carbonaceous material to be upcycled is preferably pretreated. In said pretreatment, preferably a pas- sivation, a deactivation and / or a calcination is conducted. Said pretreatment is preferably conducted if a moving bed or a fixed bed is used for the present upcycling. Preferably, if the ash and / or oxygen content of said carbonaceous material to be upcycled is above 1 wt.-%, more preferably above 2 wt.-%, even more preferably above 5 wt.-% and / or the BET surface area of said carbonaceous material to be upcycled is above 100 m2 / g, more preferably above 200 m2 / g, even more preferably above 300 m2 / g the bed of said carbonaceous material to be upcycled is preferably pretreated. In said pretreatment, preferably the deactivation and calcination is conducted. Said pretreatment is preferably conducted if a moving bed or a fixed bed is used for the present upcycling. For this pretreatment preferably an atmosphere of hydrogen and / or inert gases is used. Preferably the atmosphere contains 70 to 100 Vol.-%, related to the total atmosphere used for the treatment, of hydrogen and / or inert gases like nitrogen, argon, helium; more preferably 80 to 100 Vol.-% of hydrogen and / or inert gases, more preferably 90 to 100 Vol.-%, even more preferably 95 to 100 Vol.-%, even more preferably 98 to 100 Vol.-%, even more preferably 99 to 100 Vol.-%. The atmosphere contains 30 to 0 Vol.-% of gaseous hydrocarbons, preferably 20 to 0 Vol.-%, more pref- erably 10 to 0 Vol.-%, more preferably 5 to 0 Vol.-%, even more preferably 2 to 0 Vol.-%, even more preferably 1 to 0 Vol.-%, the methane content in said gaseous hydrocarbons is preferably 85to 100 Vol.-%, more preferably 90 to 100 Vol.-%, even more preferably 95 to 100 Vol.-%, in particular 99 to 100 Vol.-%. The time and temperature of said treatment is characterized by the formula T = time (min) multiplied by temperature (°C) and the T is at least 10000 (min * °C) and wherein the temperature is at least 500°C. Preferably T is at least 20000 (min * °C), more preferably T is at least 50000 (min * °C), even more preferably T is at least 100000 (min * °C). Preferably T is in the range of 3000 to 1500000 (min * °C), more preferably in the range of 10000 to 900000 (min * °C), more preferably in the range of 50000 to 700000 (min * °C), even more preferably in the range of 100000 to 300000 (min * °C). Preferably the temperature of said treatment is at least 600°C, more preferably at least 700°C, more preferably at least 800°C, more preferably at least 900°C, even more preferably at least 1000°C. Preferably the temperature of said treatment is in the range of 500°C to 2500°C, more preferably in the range of 600°C to 2000°C, more preferably in the range of 1000°C to 1500°C, even more preferably in the range of 1200°C to 1400°C. The time of said treatment is at least 5 min, more preferably at least 30 min, more preferably at least 60 min, more preferably at least 90 min, more preferably at least 120 min, even more preferably at least 180 min. Preferably the time / period of said treatment is in the range of 5 min to 10 days, preferably 5 min to 5 days, more pref- erably 5 min to 3 days, more preferably 5 min to 1 day, more preferably in the range of 10 min to 12 hours, even more preferably in the range of 30 min to 720 min. If a moving bed is using, the time / period of said treatment is pref- erably at least one passage of the solid material (moving bed) through the reactor (residence time), more preferably at least two passages through the reaction. Preferably one to ten passages of the moving bed through the reactor, more preferably one to five passages, even more preferably one to four passages, even more preferably two to four passages, even more preferably one to two passages. The operating time in pre-treatment mode preferably exceeds the treatment time required for a single particle. This is due to two main factors: first, a transition period is necessary to switch between production mode and pre-treatment mode, allowing for the adjustment of operating conditions and stabilization of the system to the desired target state. Second, pre-treatment is performed on a larger quantity of material to ensure sufficient supply for the intended runtime of the subsequent production cycle. Alternatively, the pre-treatment can be controlled until the carrier material meets specific criteria. For example, the composition of the outflowing gas stream can be measured, preferably using FTIR according to DIN EN 15483:2009- 02. Key components of interest include carbon monoxide, carbon dioxide, water vapor, and hydrogen sulfide. Pre- treatment continues until the concentration of these components drops below a specified threshold. The cumulative mole fraction of H2O, CO, CO2, H2S, CS2, and COS should be less than 1 vol.-%, preferably less than 0,5 vol.-%, and particularly less than 0,1 vol.-%, especially less than 0.05 vol.-%. Additionally, the surface concentration of metallic elements on the carrier and / or the loading of the carrier with pyroly- sis carbon serves as a measure of pre-treatment effectiveness. The surface concentration, defined as the mass of metal impurities relative to the outer surface of the carrier particles, should be determined semi-quantitatively by SEM / EDX according to ASTM F1375-92(2020). The acceptable surface concentration of metallic impurities should be less than 0.1 mg / cm² to 1 mg / cm². During said pretreatment, the carbon deposition rate of a pyrolysis process, if any, is preferably below 5 wt.-%, more preferably below 2 wt.-%, even more preferably below 1 wt.-%. Preferably, the deposition rate during said pretreat- ment is in the range of 0 to 5 wt.-%, more preferably 0 to 2 wt.-%, even more preferably 0 to 1 wt.-%. During said treatment, the conversion rate of the pyrolysis process, if any, is preferably below 75 %, more preferably below 50 %, even more preferably below 30 %, even more preferably below 20 % (based on the hydrocarbons in the feed stream). Preferably, the conversion rate during said treatment is in the range of 0 to 75 %, more preferably 0 to 50 %, even more preferably 0 to 30 %, even more preferably 0 to 20 %. After the pretreatment, the metal-content on the outer surface of the pretreated carbonaceous material obtained from waste recycling or pyrolysis of biomass (defined by the outer shell of 5 µm thickness), is preferably in the range 20 to 0.001 wt.%, more preferably 5 wt.% to 0.001 wt.%, more preferably 1 wt % to 0.001 wt%, even more preferably 0.5 wt.% to 0.001 wt.%. Adaption of the pyrolysis process parameters and the optional pretreatment process conditions The concrete preferred process conditions are depending on the bed material used. In principle, a person skilled in the art preferably adapts the process conditions of the optional pretreatment and the hydrocarbon pyrolysis as fol- lows: 1. Making an elemental analysis of the bed material. 2: Adjusting the pretreatment to the chemical composition: the higher the oxygen and ash content of the bed material the lower the deposition rate during the first operation time of the pretreatment. If oxygen and / or ash content is higher than 1 w.-%, pretreatment is preferred. Said pretreatment can preferably end, if an low content of oxygen containing site product, like water CO, CO2 is reached in the hydrogen containing product stream, e.g. water below 0.01 vol.-% and CO below 250 ppm, are present. After that, the pyrolysis process can preferably be started. 3. Adjusting the process conditions of the pyrolysis conditions, especially the deposition rate, preferably start with a low deposition rate like 1 wt.-% deposition and slowly increasing the deposition rate as the operation time increases, e.g. increase of 1 wt.-% in deposition rate after 10 min to 1 hour of operation time or increase of 1 wt.-% in deposition rate per passage of the bed material through a moving bed reactor. Upcycled carbonaceous material Due to the deposition of the pyrolytic carbon during the pyrolysis process, the original characteristics of said carbona- ceous material changes: The carbon content is increased, the oxygen, ash and sodium content is decreased. The density is increased. The porosity, especially the median pore diameter is decreased. The chemical composition of said upcycled carbonaceous material is typically in the following ranges: The carbon content is typically in the range of 95 to 99.9 wt.-%, more preferably 97 to 99 wt.%. The oxygen content is typically in the range of in the range of 0 to 2 wt.%, more preferably 0 to 1 wt.-%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 5 wt.%, more preferably 0 to 3 wt.-% In view of upcycled bio char is the chemical composition in the following ranges: The carbon content of said carbonaceous material is typically in the range of 90 to 99 wt.-%, more preferably 95 to 99 wt.-%, even more preferably 97 to 99.9 wt.-%. The oxygen content is typically in the range of in the range of 0 to 2 wt.%, more preferably 0 to 0.5 wt.-%, even more preferably 0 to 0.1 wt.-%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 10 wt.-%, more preferably 0.5 to 5 wt.%, even more preferably 1 to 3 wt.-%. The sulphur content is typically in the range in the range of 0 to 2 wt.%, more preferably 0 to 0.5 wt.%, even more preferably 0 to 0.01 wt.-%. The sodium content is typically in the range in the range of 0 to 1 wt.-%, more preferably 0 to 0.1 wt.-%, even more preferably 0 to 0.01 wt.-%.. In view of upcycled green coke is the chemical composition in the following ranges: The carbon content of said carbonaceous material is typically in the range of 95 to 99.9 wt.%, more preferably 98 to 99.9 wt.%, even more preferably 99 to 99.99 wt.%. The oxygen content is typically in the range of in the range of 0 to 0.5 wt.%, more preferably 0.0 to 0.2 wt.%, even more preferably 0 to 0.1 wt.%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 1 wt.%, more preferably 0 to 0.5 wt.%, even more preferably 0 to 0.2 wt.%. The sulphur content is typically in the range in the range of 0 to 2 wt.%, more preferably 0 to 1 wt.%, even more pref- erably 0 to 0.5 wt.%. In view of upcycled anode butts is the chemical composition in the following ranges: The carbon content of said carbonaceous material is typically in the range of 99 to 99 wt.%, more preferably 98 to 99.9 wt.%, even more preferably 99 to 99.99 wt.%. The oxygen content is typically in the range of in the range of 0 to 0.5 wt.%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is typically in the range in the range of 0 to 0.5 wt.%, more preferably 0 to 0.2 wt.%, even more preferably 0 to 0.1 wt.%. The sulphur content is typically in the range in the range of 0 to 5 wt.%, more preferably 0 to 2 wt.%, even more pref- erably 0 to 0.5 wt.%. The chlorine content is typically in the range in the range of 0 to 2 ppm. The sodium content is typically in the range in the range of 0 to 0.1 wt.%, more preferably 0 to 0.05 wt.%, even more preferably 0 to 0.01 wt.%. Preferably, in view of bio char is the density of said upcycled bio char in the following ranges: 0.7 to 1.3 g / ml, prefera- bly 0.8 to 1.2 g / ml, even more preferably 0.9 to 1.2 g / ml. The increase is preferably 10 to 300%. Preferably, in view of green coke is the density of said upcycled green coke in the following ranges: 0.6 to 1.3 g / ml, preferably 0.7 to 1.2 g / ml, even more preferably 0.8 to 1.2 g / ml. The increase is preferably 10 to 100% Preferably, in view of anode butts is the density of said upcycled anode butts in the following ranges: 0.8 to 1.3 g / ml, preferably 0.9 to 1.2 g / ml, even more preferably 1 to 1.2 g / ml. The increase is preferably 5 to 30%. Preferred Process Conditions: Moving Bed Preferably the solid material (also called substrate) is guided in form of a moving bed through the reaction chamber, with methane and / or other light hydrocarbons being passed advantageously in countercurrent to the substrate. For this purpose, the reaction chamber is preferably designed as a vertical reactor, which means that the movement of the moving bed is gravity driven. Flow through the moving bed is taking place, advantageously, homogeneously, and uniformly (see for example WO 2013 / 004398, WO 2019 / 145279 and WO 2020 / 200522). Methane and / or other light hydrocarbons are preferably introduced via the bottom of the reactor, preferably having a temperature of 10 to 200°C. The substrate is preferably introduced via the top of the reactor, preferably having a temperature of 10 to 200°C. The hydrogen-containing product gas is preferably taken off via the top of the reactor, preferably having a temperature of 10 to 200°C. The granular pyrolytic carbon is preferably taken off via the bottom of the reactor, prefer- ably having a temperature of 10 to 200°C. The discharged carbon is preferably at least partly recycled and introduced into the reactor again using it as sub- strate for the moving bed. As a result, a continuous process of the moving bed is achieved. The recycled carbon can optionally be mixed with fresh, initial solid material. The flow velocity of the substrate is advantageously in the range of 0.005 to 6.0 cm / s, more preferably 0.005 to 0.5 cm / s. The flow velocity of the gas flow is advantageously in the range of 0.025 to 10 m / s, more preferably 0.025 to 2 m / s. The gas residence time in the reactor is advantageously between 0.1 and 50 s, preferably between 1 and 20 s. The residence time of the substrate is preferably between 0.1 and 15 hours, preferably between 1 and 10 hours and more preferably between 2 and 8 hours. Solid material The solid material, also called substrate or carrier material, is preferably a granular material. The particle size of a preferred substrate is in the range of 0.1 to 10 mm, preferably 0.3 to 8 mm. The preferred substrate is a carbon-containing substrate, for example calcined petcoke (CPC), green coke, anode butts, bio char, recycled carbon black (from polymer recycling via pyrolysis), black mass (battery recycling) or the pyrolytic carbon itself. The carbon content is preferably in the range of 70 to 99 wt.%, more preferably 90 wt.% to 99.9 wt.%, more preferably 99 to 99.95 wt.%, even more preferably 99 to 99.99 wt.%. The oxygen content is preferably in the range of 20 to 0.001 wt.%, more preferably 5 wt.% to 0.1 wt.%, more prefera- bly 1 wt % to 0.5 wt%. The ash content, in particular Fe, Ni, Ca, Si, Al, Cr, K, Mg, Mn, Pb, V and Zn, is preferably in the range 20 to 0.001 wt.%, more preferably 5 wt.% to 0.1 wt.%, more preferably 1 wt % to 0.5 wt%. The Sulphur content is preferably in the range 5 to 0.0001 wt.%, more preferably 0.5 wt.% to 0.01 wt.%, more prefer- ably 0.1 wt % to 0.01 wt%. The chlorine content is preferably in the range 1 to 0.00001 wt.%, more preferably 0.1 wt % to 0.001 wt%, even more preferably 0.01 wt.% to 0.1 wt.%. Preferably, the metal-content on the outer surface (defined by the outer shell of 5 µm thickness), is preferably in the range 20 to 0.001 wt.%, more preferably 5 wt.% to 0.001 wt.%, more preferably 1 wt % to 0.001 wt%, even more preferably 0.5 wt.% to 0.001 wt.%. The BET surface area of the substrate is preferably between 0.001 and 100 m2 / g, preferably 0.01 and 50 m2 / g, in particular 0.05 to 30 m2 / g. Typically, the porosity of the solid material is between 0.1% to 90%, preferably between 1% to 80%, even more preferably 30% to 70% according to WO 2023 / 057242, even more preferably 30% to 60% (Hg porosimetry, DIN66133). Preferably, the density of the substrate is in the range of 1.5 to 2.5 g / cc (real density in xylene, ISO 8004). Preferably, the bulk density of the substrate is in the range of 0.5 to 1.5 g / cc. Pyrolytic granular carbon Typically, the density of the deposited pyrolytic carbon produced via the described methane pyrolysis process is in the range of 1.5 to 2.5 g / cc, preferably 1.7 to 2.4 g / cc, even more preferably 2.0 to 2.3 g / cc (real density in xylene, ISO 8004). Typically, the bulk density of the pyrolytic carbon is in the range of 0.5 to 1.5 g / cc, more preferably 0.7 to 1.3 g / cc. Typically, the ash content of the pyrolytic carbon is in the range of 0.001 to 1 weight-%, preferably 0.01 to 0.2 weight- %. Typically, the carbon content is in the range of 98 to 100 weight-%, more preferably 99.5 to 100 weight-%, even more 99.75 to 100 weight-%, even more 99.9 to 100 weight-%. Typically, the porosity of the granular pyrolytic carbon is between 0% to 15%, preferably 0.2% to 10%, most prefera- bly 0.2% to 5% (Hg porosimetry, DIN66133). Typically, the specific surface area of the pyrolytic carbon measured by Brunauer-Emmett-Teller (BET) is in the range of 0.001 to 20 m2 / g, preferably 0.001 to 10 m2 / g, even more prefera- bly 0.05 to 5 m2 / g. Preferred Moving Bed Method Preferably a moving bed technology is used for the methane pyrolysis of the present invention comprising: - a plurality of solid substrates is guided into the first heat integration zone and from there into the reaction zone, - the solid substrates are heated in the reaction zone, - the solid substrates are guided from the reaction zone into the second heat integration zone and are with- drawn from the second heat integration zone, - methane is introduced into the second heat integration zone and from there into the reaction zone, wherein methane in the second heat integration zone is heated against solid substrates coming from the reaction zone, wherein the solid substrates are cooled, and wherein the methane is contacted with the heated solid substrates in the reaction zone, wherein heat from the heated solid substrates is transferred to methane in order to heat methane in the reaction zone, wherein methane is decomposed to hydrogen and granular pyro- lytic carbon in the reaction zone, - hydrogen produced is guided from the reaction zone into the first heat integration zone, wherein the solid sub- strates in the first heat integration zone are preheated against hydrogen coming from the reaction zone, wherein hydrogen is cooled, and wherein - hydrogen is withdrawn from the first heat integration zone - granular pyrolytic carbon produced is deposited on solid substrates and withdrawn with the substrates - withdrawn substrate is preferably at least partly recycled and introduced into the reactor - withdrawn hydrogen is preferably at least partly recycled and introduced into the reactor. Preferred Reactor Preferably, the reactor for carrying out the methane pyrolysis, in which hydrogen and pyrolytic carbon are produced from hydrocarbons, preferably methane, comprises: - a reactor surrounding a reactor interior - the reactor is configured to provide a gravity-driven moving bed in a reaction zone of the reactor interior, which gravity-driven moving bed comprises a large number plurality of solid substrates, wherein the reactor is also configured to guide methane into the reaction zone, wherein, in order to heat methane, the reactor is configured to heat the solid substrates in the reaction zone by generating an electric current in the solid sub- strates between a pair of first and second electrodes such that, by transferring heat from the solid sub- strates to methane, - methane in the reaction zone can be heated to a reaction temperature to produce hydrogen and granular pyrolytic carbon, - and wherein the reactor interior also comprises a first heat integration zone in which heat from hydrogen produced in the reaction zone can be transferred to solid substrates of the reactor gravity driven moving bed which are to be guided into the reaction zone, and wherein the reactor interior also comprises a second heat integration zone in which heat from solid substrates of the reactor gravity driven moving bed coming from the reaction zone can be transferred to methane in order to preheat methane, wherein said reaction zone is arranged between said pair of first and second electrodes and said first heat integration zone is arranged above said first electrode and said second heat integration zone is arranged below said second electrode. The volume of the reaction section is preferably 1 m3 to 1000 m3, preferably 5 m3 to 750 m3, more preferably 0.5 m3 to 500 m3. The height of the reaction section is preferably 0.1 m to 50 m, preferably 0.5 to 20 m, more preferably 1 m to 10 m. The said moving bed reactor has several advantageous compared to other reactor types. - Heat integration enables a high efficiency since gas and solid are leaving the reactor at temperatures be- tween 10 °C – 200 °C - No additional equipment for heat recovery or special equipment for handling of gas solids with temperatures above 200 °C required. - Reproduceable carbon quality: Each particle is treated under the same conditions in the moving bed. Same residence time for each solid particle in the reaction zone. Preferred Fixed Bed Method Preferably a fixed bed technology is used for the methane pyrolysis of the present invention comprising: - a plurality of solid substrates having a particle size of 0.5 to 10 mm is introduced into the reactor and fixed in the reaction zone, preferably the substrates are introduced via the top of the reactor, - the solid substrates are heated in the reaction zone, preferably the solids are electrically heated, more prefer- ably the solids are heated via a direct electric Joule heating, - methane is introduced into the reaction zone, wherein the methane is contacted with the heated solid sub- strates in the reaction zone, wherein heat from the heated solid substrates is transferred to methane in order to heat methane in the reaction zone and wherein methane is decomposed to hydrogen and pyrolytic carbon that is deposited on the solid substrates in the reaction zone, preferably methane is introduced via the top of the reactor, - hydrogen is withdrawn from the reaction zone, preferably from the bottom of the reactor - By feeding hydrocarbon from the top into the reactor, the gas velocity is not limited by the fluidization regime of the solid particles, which allows higher space time yields compared to moving bed or fluidized bed reactors. Gas velocities in the reaction zone (calculated for an empty reactor) are 0,5 – 15 m / s and more preferred 1 – 10 m / s. In addition, the residence time of the substrate can be increased to 2 to 24 hours. - batchwise the solid substrates with pyrolytic carbon deposited on it are withdrawn from the reaction zone - withdrawn substrate is preferably at least partly recycled and introduced into the reactor - withdrawn hydrogen is preferably at least partly recycled and introduced into the reactor. Fixed bed reactors are known in the state of the art, e.g. [1] Eigenberger, Ruppel, Ullmanns’s encyclopedia of indus- trial chemistry Catalytic Fixed-Bed Reactors, 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Typically, several fixed bed reactors are combined in a cyclic mode operation e.g. One reactor is in production mode and carbon is deposed in the fixed bed until the maximum carbon deposition is reached. While the carbon is re- moved from this reactor, the next reactor starts with production and so on. With this cyclic operation mode, a continu- ous production is ensured. Preferred Fluidized Bed Method Preferably a fluidized bed technology is used for the methane pyrolysis of the present invention comprising: - a plurality of solid substrates having a particle size of 0.1 to 10 mm is introduced in the fluidization zone, the reaction zone, and placed on a distributor o optionally the substrates are heated externally and are introduced into the reactor at a temperature of 800 °C to 1500 °C - optionally the solid substrates are heated in the reaction zone, preferably the solids are electrically heated, - methane is introduced into the reactor via the bottom, distributed by the distributor fluidizing the solid sub- strates and guided through the reaction zone wherein methane is contacted with the heated solid substrates in the reaction zone, wherein heat from the heated solid substrates is transferred to methane in order to heat methane in the reaction zone, wherein methane is decomposed to hydrogen and pyrolytic carbon that is de- posited on the solid substrates in the reaction zone, o The Hydrocarbon concentration of the feed gas ranges preferably from 20 vol% - 100 vol %, more prefera- bly form 60 vol% to 100 vol % o Due to the relative motion of the particles in a fluidized, carbon deposition rates from the pyrolyzed gas on the solid granule per pass through the reactor are preferred above 10 w% and more preferred above 20 w%. The relative deposition is related to the mean solid particle mass flux out of the reactor. o The pressure is preferably 1 to 10 bar. - hydrogen is withdrawn from the reaction zone, preferably from the top of the reactor - preferably continuously, the solid substrates with pyrolytic carbon deposited on it are withdrawn from the reac- tion zone - withdrawn substrate is preferably at least partly recycled and introduced into the reactor - withdrawn hydrogen is preferably at least partly recycled and introduced into the reactor. Fluidized bed reactors are known in the state of the art, e.g[2]. Werther, Ullmanns’s encyclopedia of industrial chem- istry Fluidized Bed-Reactors, 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. A fluidized bed reactor may have more than one stage as described in WO2022081170 and US20210331918. H2 Purification The part of the hydrogen-containing product stream that is not internally recycled into the reaction chamber is typi- cally purified in a removal apparatus, e.g. using adsorption or membrane technologies. For example, the gaseous product stream can still contain hydrogen sulfide. Hydrogen sulfide can preferably be re- moved from the gaseous product stream via gas scrubbing, e.g. via ZnO, CuZnO, Fe(OH)3, Zeolites, MOFs, as known in the state of the art. Typical process conditions of the gas scrubbing are 60 to 180°C and 1 to 100 bar. For example, the gaseous product stream can still contain carbon oxide and inert gases, e.g. nitrogen. Correspond- ing hydrogen recovery apparatuses are common knowledge to the person skilled in the art, for example pressure swing adsorption or permeation. Recycle of purification off-gas Preferably, a part of the off-gas from the hydrogen recovery is additionally internally recycled to the reaction cham- ber, preferably 5 to 100 vol.-% of the total off-gas, more preferably 10 to 98 vol.-%, even more preferably 25 to 95 vol.-%, even more preferably 50 to 95 vol.-% even more preferably 70 to 95 vol.-% even more preferably 80 to 95 vol.-%. Preferably, the remaining part of said total off-gas from the hydrogen recovery is withdrawn. The preferred percentage of recycle and withdrawal is dependent on the amount of inert gases in the hydrogen-containing product stream, especially on the nitrogen content. Core-shell particle The present invention also comprises a core-shell particle comprising a core comprising carbonaceous material ob- tained from pyrolysis of biomass having a carbon-14 content of 0.5 to 2.0 ppt, based on total carbon, and a shell of pyrolytic carbon obtained by hydrocarbon pyrolysis having a carbon-14 content of below 0.5 ppt, based on total car- bon. Preferably the diameter of the core is from 0.1 mm to 10 mm, more preferably 0.5 to 8 mm. Preferably the thickness of the shell is from 10 µm to 10 mm, preferably 100 µm to 5 mm, 200 µm to 1 mm. The core is at least partially coated by pyrolytic carbon obtained by thermal decomposition of hydrocarbons, the shell; preferably the core is at least by 80 % of the outer surface of the core coated by pyrolytic carbon; preferably by 85 %, even more preferably by 90 %, even more preferably by 95 %. More preferably, the core is completely coated by said pyrolytic carbon resulting in a closed outer layer, the shell. Preferably, the second layer covers the outer surface of the first, underlying layer by at least by 80 % of the outer sur- face of the first layer; preferably by 85 %, even more preferably by 90 %, even more preferably by 95 %. Preferably, the first, underlying layer is completely covered / coated by the second layer. Along with the 13C stable isotope, a very small proportion of the carbon in a molecule will be of the naturally occur- ring radioactive form, 14C, also called radiocarbon. The 14C atoms are formed in the upper atmosphere due to inter- actions between cosmic rays and nitrogen atoms. The natural abundance of 14C in compounds is around 1 part per trillion (ppt; 10-12). This radioactive carbon isotope decays with a half-life of 5730 years such that after six half-lives, it is functionally undetectable in a sample. Carbon compounds that are derived from fossil sources such as oil or gas will contain no radiocarbon, as it will have decayed away during the millions of years needed to make such reserves. This contrasts with recently grown plant-based materials that do contain measurable amounts of 14C. Radioactive carbon can be measured using gas proportional counting, liquid scintillation counting, and accelerator mass spec- trometry (AMS). The latter approach is the most sensitive of the three. There are three naturally occurring of carbon on Earth (12C), which makes up 99% of all carbon on Earth; carbon- 13 (13C), which makes up 1%; and carbon-14 (14C), which occurs in trace amounts, making up about 1 or 1.5 atoms per 1012 atoms of carbon in the atmosphere. Carbon-12 and carbon-13 are both stable, while carbon-14 is unstable and has a half-life of 5700±30 years. Carbon-14 decays into nitrogen-14 (14N) through beta decay. The primary nat- ural source of carbon-14 on Earth is cosmic ray action on nitrogen in the atmosphere, and it is therefore a cosmo- genic nuclide. The natural abundance of carbon-14 (14C) is approximately 1 ppt (parts per trillion; 10-12; 10-10 atom-%), in general 0.5 to 2.0 ppt, based on the total carbon content. The shell of pyrolytic carbon preferably has (i) Carbon content 98 to 99.99 wt.-%, preferably 99 to 99.99 wt.-%, more preferably 99.5 to 99.99 wt.-% (ii) Particle size from 0.1 to 10 mm, preferably 0.5 to 10 mm, more preferably 1 to 8 mm (iii) Ash content 0 to 2 wt.-%, preferably 0 to 1 wt.-%, more preferably 0 to 0.5 wt.-% (iv) Specific surface area 5 to 25 m2 / g, preferably 7 to 20 m2 / g, more preferably 10 to 20 m2 / g (v) Median pore diameter (volume) from 0.005 to 1 µm, preferably 0.05 to 1 µm (vi) e-module being in the range of 5 to 35 GPa and (vii) hardness being in the range of 0.2 to 5 GPa, (viii) L-parameter of colour from 10 to 45 Advantages A broad utilization of such carbonaceous material obtained from waste recycling or pyrolysis of biomass and thus reducing the reliance on virgin resources and minimizing environmental impact contributes to the concept of a circu- lar economy by promoting the reuse and recycling of materials, reducing waste generation, and supporting sustaina- ble practices. Biochar is known for their ability to capture and store carbon, helping to mitigate climate change by re- ducing greenhouse gas emissions. Recycling back mass, recovered carbon black and aluminum butts helps to con- serve valuable resources by reusing materials that would otherwise be discarded as waste. Description of the Figures Figure 1 presents the internal recycle of the process Figure 2: presents SEM images of a carrier particle after methane pyrolysis at 1300 °C of Comparative Example 1. The surface of the carrier shows filament formation. Figure 3: presents SEM images of a carrier particle before (3a) and after (3b) methane pyrolysis at 1300 °C of In- ventive Example 1. The initial surface structure of the carrier is covered with smooth shaped pyrolysis carbon. Figure 4: presents SEM images of a carrier particle at initial state, after the experiment at 1150 °C (4b) and after the experiment at 1200 °C (4c) of Inventive Example 2. The initial surface structure of the carrier is covered with coral- like shaped pyrolysis carbon after each experiment. Figure 5a: The diagram shows the local carbon deposition along the reactor height for four CH4 concentrations in the feed gas, all at 1250°C in the reaction zone. Figure 5b: Normed reaction rate along the reactor height for four CH4 concentrations in feed gas and 1250°C in the reaction zone. Figure 5c: The diagram shows the local carbon deposition along the reactor height for 50% CH4 in the feed gas and different temperatures. Figure 6: The diagram shows the isolines of carbon deposition (CD) depending on temperature and CH4 concentra- tion in feed gas, where CDi < CDii < CDiii Example Comparative example 1. Using bio char as bed material in a pyrolysis reaction (high ash content, no pretreatment) Pyrolysis of methane was carried out in a fixed bed reactor. The utilized reactor was a fixed bed reactor filled over a total height of ~551 mm with solid carbon granule (Biochar “Desorex C33” having a BET surface aren of 1200 m2 / g and a carbon content of 86.3 wt.-%) in a ceramic tube with an inner diameter of 50 mm. A mixture of 20 % methane in hydrogen was used as feed mixture (total flow rate 300 nL / h). Pyrolysis was carried out for 4 h at a reactor pres- sure of 1 bara and a temperature of 1300 °C. The carbon deposition rate ^^^^^^^was 15.3 %. Very strong agglomeration of the carbon bed including filament formation was observed resulting ultimately in the formation of a massive agglomerate that could only be extracted with high effort from the reactor. Separation of the bed into single granules was not possible without damaging the granules. The SEM results shown in Figure 2 under- line this finding. The high level of agglomeration can be explained by the high oxygen, ash contents and high surface area of the car- rier that result in a high initial activity of the carrier material, which needs to be controlled in a systematic manner by our upcycling protocol to allow for a usage of such carrier materials in fixed bed, moving bed and fluidized bed reac- tors also at increased carbon deposition rates. Table: Elementary Analysis Original bio char [g / 100g] Petroleum coke Carbon 86.4 98.3 Sulfur 0.2 0.42 Oxygen 5.6 < 0.5 Na 0.13 < 0.5 Hydrogen 1.2 0.040 additional ash content Rest to 100 Rest to 100 Present invention 2. Upcycling Bio Char 1 (low ash content, no pretreatment) Pyrolysis of methane was carried out in a fixed bed reactor. The utilized reactor was a fixed bed reactor filled over a total height of ~558 mm with a commercially available solid carbon granule / bio char (“Alcarbon PH 55 / 4x8 C” having a granular dimension of a length of 55 mm and 8 mm diameter.) in a ceramic tube with an inner diameter of 50 mm. A mixture of 20 % methane (60 nL / h) in hydrogen (240 nL / h) was used as feed mixture. Pyrolysis was carried out for 4 h at a reactor pressure of 1 bara and a temperature of 1300 °C. Deposition rate 15 %. No formation of agglomer- ates or filaments was observed. The SEM results shown in Figure 3 underline this finding. 2.1 Chemical composition Table: Elementary Analysis Original bio char [g / 100g] Upcycled bio char [g / 100g] Petroleum coke Carbon 91 95.1 98.3 Sulfur 0.02 0.01 0.42 Oxygen 6.7 1.2 < 0.5 Na 0.048 0.0044 < 0.5 Hydrogen 0.8 <0.5 0.040 additional ash content Rest to 100 Rest to 100 Rest to 100 2.2 Porosity Table Original bio char Upcycled bio char 0,3661 mL / g (at 59.964,00 0,2084 mL / g (at 59.966,21 Total intrusion volume psia) psia) Median pore diameter 0,61480 μm (at 350,59 psia 0,49708 µm (at 433,62 psia (volume) and 0,183 mL / g) and 0,104 mL / g) 2.3 Bulk density Table Original bio char Upcycled bio char Increase of den- Petroleum coke sity (%) Bulk density 0.473 g / ml 0.582 g / ml 23 % 0.725 3. Upcycling Bio Char 2 (high ash content, pretreatment) Pyrolysis of methane was carried out in a fixed bed reactor. The utilized reactor was a fixed bed reactor in a ceramic tube with an inner diameter of 40 mm filled over a total height of ~551 mm with a commercially available solid carbon granule / bio char based on untreated wood residues from the company “Novocarbo” having a grain size in between 0-4 cm. Due to the higher ash and oxygen content the carrier material was first pretreated at lower temperature be- fore a higher temperature for the production mode of the methane pyrolysis was applied. The pretreatment was conducted for 2 h at 10 bara at a temperature of 1150 °C using a mixture of 20 % methane (120 nL / h) in hydrogen (480 nL / h). The carbon deposition rate ^^^^^^^was – 8 wt.-% (minus eight weight percent). After the pretreatment was finished, the reactor was cooled down, the carbon bed was weighted, and a carbon sam- ple was removed for analysis. Afterwards, the reactor was heated again and methane pyrolysis at a higher tempera- ture of 1200 °C at 10 bara was conducted for another 2 h using a mixture of 20 % methane (120 nL / h) in hydrogen (480 nL / h). After this experiment was finished, the reactor was cooled down, the carbon bed was weighted, and a carbon sample was removed for analysis. Afterwards, the reactor was heated again and methane pyrolysis at a higher temperature of 1300 °C at 10 bara was conducted for another 1 h using a mixture of 20 % methane (120 nL / h) in hydrogen (480 nL / h). The carbon deposition rate ^^^^^^^was 10 %. After the experiment, the reactor was cooled down, the carbon bed was weighted, and a carbon sample was removed for analysis. No formation of agglomerates was observed during any of said experiments. Results of porosity show a decreasing pore volume due to surface coverage and the filling of pores by pyrolysis carbon during the experiments. Results of the SEM analysis of the initial carrier and after each experiments show that even though a minor loss in carrier mass is observed during pretreatment owing to the release of volatile species, the surface of the carrier shows the coral- like shape of pyrolysis carbon typical for methane pyrolysis carbon under the reaction conditions chosen (s. Figures 2). 3.1 Chemical composition Table: Elementary Analysis Original bio char [g / 100g] Carbon 92.3 Sulfur 0.03 Oxygen 3.7 Na 0.2 Hydrogen 2.0 additional ash content Rest to 100

[0002] 3.2 Porosity Table: Original Biochar After experiment at After experiment at After experiment at 1150 °C 1200 °C 1300 °C Total intrusion 2.4965 mL / g (at 1.5310 mL / g (at 1.3451 mL / g (at 1.1671 mL / g (at volume 59,946.21 psia) 59,946.25 psia) 59,949.47 psia) 59,949.96 psia) 1.68030 μm (at 2.71770 μm (at 0.91053 μm (at Median pore 3.29578 μm (at 65.40 128.28 psia and 79.31 psia and 236.72 psia and diameter (volume) psia and 1.248 mL / g) 0.766 mL / g) 0.673 mL / g) 0.584 mL / g) 4. Upcycling Anode Butts Pyrolysis of methane was carried out in a fixed bed reactor. The utilized reactor was a fixed bed reactor filled over a total height of ~579 mm with a solid carbon granule (anode butts from aluminum production with a particle size of 2 – 4 mm.) in a ceramic tube with an inner diameter of 50 mm. A mixture of 20 % natural gas (60 nL / h) in hydrogen (240 nL / h) was used as feed mixture. Pyrolysis was carried out for 2 h at a reactor pressure of 1 bara and a temperature of 1300 °C. Deposition rate of ca.3 wt.-% 4.1 Chemical composition Table: Elementary Analysis Original Anode Butts Upcycled Anode Butts Petroleum coke [g / 100g] [g / 100g] Carbon 95.9 98.4 98.3 Sulfur 2.0 1.9 0.42 Oxygen < 0.5 < 0.5 < 0.5 Hydrogen < 0.5 < 0.5 < 0.5 Na 0.069 0.015 0.040 additional ash content Rest to 100 Rest to 100 Rest to 100 4.2 Porosity Table Original Anode Butts Upcycled Anode Butts 0,1620 mL / g (at 59.768,05 0,1044 mL / g (at 59.136,45 Total intrusion volume psia) psia) Median pore diameter (vol- 4,92841 μm (at 43,74 psia 0,36608 μm (at 588,79 psia ume) and 0,081 mL / g) and 0,052 mL / g) 4.3 Bulk density Table Original Anode Butts Upcycled Anode Butts Increase of den- Petroleum coke sity (%) Bulk density 0.849 g / ml 0.904 g / ml 6.5 % 0.725 5. Upcycling Green Coke Pyrolysis of methane was carried out in a fixed bed reactor. The utilized reactor was a fixed bed reactor filled over a total height of ~587 mm with a solid carbon granule (green coke (precursor for CPC production) with a particle size of 1 – 4.5 mm.) in a ceramic tube with an inner diameter of 50 mm. A mixture of 20 % natural gas (60 nL / h) in hydrogen (240 nL / h) was used as feed mixture. Pyrolysis was carried out for 1 h at a reactor pressure of 1 bara and a tempera- ture of 1300 °C. Deposition rate = -11 %* *Since green coke is a product from the petrochemical industry which contains a fraction of volatile organic com- pounds that are still incorporated in the structure and pores of the material. In a calcination process (comparable with the calcination in the production of CPC from Green Coke), which occurs during heat up and in parallel to the pyroly- sis reaction in the reactor, the volatile components, as well as other components like oxygen species are transferred to the gas phase. In the short pyrolysis step the weight losses by this calcination step were not yet compensated by the weight gains by the deposition of PyroC in the pyrolysis reaction. By increasing the reaction time / cycles in the reactor the weight losses can be compensated and a positive deposition rate can be achieved. 5.1 Chemical composition Table: Elementary Analysis Original Green Coke Upcycled Green Coke Petroleum coke [g / 100g] [g / 100g] Carbon 91.3 98.1 98.3 Sulfur 0.8 0.8 0.42 Oxygen 1.7 < 0.5 < 0.5 Hydrogen 3.8 < 0.5 < 0.5 Na 0.0046 0.0016 0.040 additional ash content Rest to 100 Rest to 100 Rest to 100 5.2 Porosity Table Original Green Coke Upcycled Green Coke Median pore diameter (vol- 74,03992 μm (at 2,91 psia 0,04648 μm (at 4.637,78 ume) and 0,055 mL / g) psia and 0,106 mL / g) 5.3 Bulk density Table Original Green Coke Upcycled Green Coke Increase of den- Petroleum coke sity (%) Bulk density 0.614 g / ml 0.697 g / ml 13.5 % 0.725 6. Measuring the porosity In Mercury Intrusion Porosimetry (MIP), a sample is subjected to increasing pressure using mercury as the intrusion fluid. The pressure is gradually increased, forcing the mercury to penetrate into the pores of the material. As the pressure increases, the mercury intrudes into smaller and smaller pores, allowing for the determination of the pore size distribution. The amount of mercury intruded into the sample is measured, and this data is used to calculate the pore volume, pore size distribution and pore surface assuming a cylindrical pore geometry. The maximum pressure was set to 4.13 *10^8 Pa which corresponds to a minimum pore size of 3nm. The measurements were performed on a Micromeritics Autopore 5 system with an SOP according to DIN 66133 and DIN ISO 15901-1. 7. Influence on H2 / C1+ ratio on reaction rate and carbon deposition rate For the examination of the H2 / C1+ ratio´s influence on reaction rate and carbon deposition, the following parameters are used: 1250°C in reaction zone, 1.4 bar(ü), 20 kg / h carbon (gas flow rate adjusted for heat integration). A 2D model implemented in COMSOL is used for the simulations. Four cases are studied at this temperature: (i) 15% CH4 in gas feed, (ii) 35% CH4 in gas feed, (iii) 50% CH4 in gas feed and (iv) 80% CH4 in gas feed, shown in Figure 5.a. Two more cases with 50% CH4 in gas feed, at 1170°C and 1120°C, were simulated, in order to show the influence of temperature on the achievable local carbon deposition, shown in Figure 5.c. The simulation was performed for a moving bed reactor operated in counter flow with solid particles moving from top to the bottom. Hence, the highest carbon deposition is at the bottom of the reactor. For the simulation, the pyrolysis was limited to the reaction zone and stopped in the heat integration zone. For the specific carbon deposition rate it can be seen, that the preferred range is reached with 15 vol% and 35 vol% at 1250°C. Higher CH4 concentration exceed the preferred range. By lowering the reaction temperature, the CH4 conversion decreases and the preferred specific deposition is reached with 50 vol% CH4 feed concentrations as well. Another advantage of the H2 dilution is revealed by the normed local reaction rate (Figure 5.b). By decreasing the CH4 concentration, a more homogeneous distribution of the reaction rate along the reactor length is reached, which lowers the probability for blocking. 8. Influence of temperature and H2 dilution on carbon deposition rate The interconnections between the parameters of temperature, pressure, H2 dilution, reference time and carrier po- rosity and their influence on the carbon deposition rate are complex. In order to give a visual representation of the relation between carbon deposition rate, temperature, and H2 dilution, a parametric variation has been performed using the model described in Section 6. The porosity and reference time are the same for the simulated operating points. The results can be seen in Figure 6, which shows isolines of carbon deposition rate in dependency of temper- ature and H2 dilution, where CDi < CDii < CDiii: an increasing temperature leads to an increase in carbon deposition rate, and a decreasing H2 / C1+ ratio, which means an increase in CH4 concentration, leads to an increase in carbon deposition rate.

Claims

Claims:

1. A process of upcycling of carbonaceous material obtained from waste recycling or pyrolysis of biomass as alternative material for fossil-based cokes, wherein said carbonaceous material is fed into a reactor chamber and used as bed material in the form of a fixed, fluidized or moving bed having a particle size of 0.1 mm to 10 mm, wherein a hydrocarbon feed is also fed into said reaction chamber and pyrolyzed at a pressure of 1 to 30 bar and a temperature of 800 to 1500°C to give a hydrogen-containing product stream and solid pyrolytic car- bon and wherein said solid pyrolytic carbon deposits in the pores and on the surface of said carbonaceous material and wherein the deposition rate of the pyrolytic carbon is kept in a range of 2 to 20 wt.-% by a con- version rate of 25 to 85% and by diluting said hydrocarbon feed with hydrogen to a volume ratio of H2 / C1+ of 0.5 to 25 of the diluted total feed stream, and if the ash content of said carbonaceous material is above 5 wt.- % said carbonaceous material is pretreated and passivated with an atmosphere of hydrogen and / or inert gases before starting the production mode of said pyrolysis process of hydrocarbons and wherein the time and temperature of said pretreatment is characterized by the formula T (min * °C) = time (min) multiplied by temperature (°C) and T is at least 10000 min * °C and wherein said temperature of said pretreatment is at least 500°C, and wherein during said pretreatment the carbon deposition rate of a pyrolysis process during the pretreatment, if any, is below 1 wt.-%.

2. Process according to claim 1, wherein said carbonaceous material is bio char, anode butts, green coke, re- covered carbon black and / or black mass having a carbon content in the range of 75 to 98 wt.-%.

3. Process according to claim 1 or 2, wherein said deposition rate is kept in a range of 4 to 15 wt.-%., wherein said carbon deposition rate is defined by: Δ^^^,^^^ ∗ 100 ^^^ ^,ௗ^^^^^௧ ⋅ ^^ ∗ 100^^^^ ^^^ ^^^^^^ =^^ =^ ^^^wherein the reactor specific reference residence time ^^^^^is defined as follows: • Fixed bed: ^^^^^= total pyrolysis time • Moving bed: ^^^^^= time of a particle to move through the pyrolysis zone • Fluidized bed: ^^^^^= time of a particle to complete a single inner circulation wherein^^^ ^,ௗ^^^^^௧^^^ is the carbon deposition rate [g / s]Δ^^^is the carbon mass increase [g]^^^^^ is the reactor specific reference residence time [s]^^^^ ^^^ is the carbon deposition rate (per reference time unit) in [wt.%].

4. Process according to any of claims 1 to 3, wherein said hydrocarbon feed is diluted by hydrogen to a volume ratio of H2 / C1+ of 1:

8.

5. Process according to any of claims 1 to 4, wherein 30 to 85 vol.-% of said hydrogen-containing product stream is recycled internally to said reaction chamber.

6. Process according to any of claims 1 to 5, wherein the conversion rate is 30 to 80 %.

7. Process according to any of claims 1 to 6, wherein said pyrolysis process is conducted at a temperature rang- ing from 1100 to 1400°C and a pressure ranging from 2.5 to 15 bar.

8. Process according to any of claims 1 to 7, wherein the degree of upcycling is controlled by measuring the chemical composition of the hydrogen-containing product stream and / or by analyzing the withdrawn upcycled carbonaceous material.

9. Process according to any of claims 1 to 8, wherein T is in the range of 100000 to 1500000 min * °C, the time of said treatment is in the range of 60 min to 12 hours and the temperature of said treatment is in the range of 1000°C to 1500°C.

10. Process according to any of claims 1 to 9, wherein the metal-content on the outer surface of the pretreated carbonaceous material is in the range 0.5 wt.% to 0.001 wt.% after said pretreatment.

11. Process according to any of claims 1 to 10, wherein the atmosphere of said pre-treatment contains 70 to 100 Vol.-%, related to the total atmosphere used for the treatment, of hydrogen and / or inert gases and 30 to 0 Vol.-% of gaseous hydrocarbons.

12. Process according to any of claims 1 to 11, wherein said carbonaceous material bed is in the form of a mov- ing bed and wherein said carbonaceous material is guided in countercurrent to the hydrocarbon feed.

13. Process according to any of claims 1 to 12, wherein said hydrogen-containing product stream is taken off via the top of said reaction chamber having a temperature of 10 to 200°C and said upcycled carbonaceous mate- rial is taken off via the bottom of said reaction chamber having a temperature of 10 to 200°C.

14. Core-shell particle comprising a core comprising carbonaceous material obtained from pyrolysis of biomass having a carbon-14 content of 0.5 to 2.0 ppt, based on total carbon, and a shell of pyrolytic carbon obtained by hydrocarbon pyrolysis having a carbon-14 content of below 0.5 ppt, based on total carbon, wherein the core diameter of the core is from 0.1 mm to 10 mm and the thickness of the shell is from 10 µm to 10 mm.

15. Core-shell particle according to claim 14, wherein the core diameter of the core is from 0.5 mm to 8 mm and the thickness of the shell is from 10 µm to 5 mm.

16. Core-shell particle according to claim 14 or 15, wherein said core is completely coated by said pyrolytic car- bon resulting in a closed outer layer, the shell.

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