WO2021180483A1 - Procédé pour déterminer des conditions de traitement optimisées pour un processus de production de gaz de synthèse par gazéification - Google Patents

Procédé pour déterminer des conditions de traitement optimisées pour un processus de production de gaz de synthèse par gazéification Download PDF

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Publication number
WO2021180483A1
WO2021180483A1 PCT/EP2021/054725 EP2021054725W WO2021180483A1 WO 2021180483 A1 WO2021180483 A1 WO 2021180483A1 EP 2021054725 W EP2021054725 W EP 2021054725W WO 2021180483 A1 WO2021180483 A1 WO 2021180483A1
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Prior art keywords
gasification
synthesis gas
carbon
composition
containing material
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PCT/EP2021/054725
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English (en)
Inventor
Christian DREISER
Olaf Wachsen
Stefan Brand
Maximilian HUNGSBERG
Alfons Drochner
Bastian Etzold
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Clariant International Ltd
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Priority claimed from EP20162983.9A external-priority patent/EP3878807A1/fr
Priority claimed from EP20163007.6A external-priority patent/EP3878927A1/fr
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of WO2021180483A1 publication Critical patent/WO2021180483A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/723—Controlling or regulating the gasification process
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/06—Modeling or simulation of processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/123—Heating the gasifier by electromagnetic waves, e.g. microwaves
    • C10J2300/1238—Heating the gasifier by electromagnetic waves, e.g. microwaves by plasma
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1246—Heating the gasifier by external or indirect heating

Definitions

  • the invention is directed to a method for determining optimized process conditions for a process for synthesis gas production by gasification of carbon-containing material using a gasification agent.
  • the composition of the gasification agent is determined as one process condition based on the atomic ratios O)C and H:C of at least one operational composition, which is a mixture of the carbon-containing material and the gasification agent, wherein the method utilizes a non-stoichiometric equilibrium model for gasification, in particular the non-stoichiometric equilibrium model is used for determining the synthesis gas product composition, the non- stoichiometric equilibrium model of the inventive method includes the calculation of the equilibrium composition of a system, comprising the considered product species, and the at least one operational composition is defined based on the non- stoichiometric equilibrium model for gasification and is defined based on at least one process criterion, selected from molar fraction of synthesis gas, synthesis gas ratio, solid carbon content in the synthesis gas, carbon efficiency, carbon dioxide emission, and water content in the
  • the invention is directed to the use of said method for process control, process monitoring, quality control and/or process engineering of a process for synthesis gas production by gasification.
  • Gasification is commonly defined as thermochemical conversion of solid or liquid carbon-containing materials into a gaseous product, known as synthesis gas, which mainly consists of hydrogen (H 2 ) and carbon monoxide (CO).
  • synthesis gas which mainly consists of hydrogen (H 2 ) and carbon monoxide (CO).
  • H 2 hydrogen
  • CO carbon monoxide
  • the conversion takes place at high temperatures with the use of a gasification agent in an oxygen starving environment.
  • air, pure oxygen, steam and combinations thereof are used as gasification agents in known gasification processes.
  • N 2 nitrogen
  • the gasification process produces a gas phase and a solid residue (also referred to as char or ashes).
  • gasification reactor types are for example fixed-bed gasifiers (e.g. Lurgi gasifier), fluidized-bed gasifiers (e.g. Winkler generator) and entrained-flow gasifiers (e.g. entrained-flow gasifier of Koppers und Totzek).
  • fixed-bed gasifiers e.g. Lurgi gasifier
  • fluidized-bed gasifiers e.g. Winkler generator
  • entrained-flow gasifiers e.g. entrained-flow gasifier of Koppers und Totzek.
  • Gasification processes are typically differentiated in direct (or autothermic) and indirect (or allothermic) processes, wherein the energy required for the endothermic gasification process can be supplied directly in an autothermic process or indirectly in an allothermic process.
  • Allothermic (indirect) gasification means that the energy required for the gasification process is supplied indirectly, for example via a heat exchanger or a circulating heat carrier.
  • gasification by means of plasma, such as microwave plasma or arc torch plasmas, which may be generated by an external power source.
  • Plasma as highly ionized gas, contains a significant number of electrically charged particles and is classified as the fourth state of matter. As plasma contains an equal number of free positive and negative charges, it is electrically neutral. Plasma processes may be largely classified into thermal and non-thermal hot plasma processes.
  • Plasma gasification of carbon-containing feedstock material using thermal plasma and arc torch plasmas are for example described in WO 2012/39751 and US 2010/0199557. Further, the use of microwave plasma in biomass gasification is described in WO 2018/187741.
  • waste-to-X concepts e.g. power-to-synthesis gas
  • power-to-value e.g. power-to-synthesis gas
  • waste-to-energy (WtE) concepts utilize the thermal energy of waste materials, e.g. by conversion of heat or convert the combustibles to electricity in a power plant.
  • waste to-X (WtX) also referred to as waste-to-value) concepts allow the use of waste materials as raw material for the production of chemicals, e.g. synthesis gas.
  • the synthesis gas product of gasification processes is used for generating power or for producing chemicals wherein the latter requires the production of chemical grade synthesis gas.
  • downstream processes for producing chemicals are catalytic synthesis reactions, such as methanol synthesis, mixed alcohol synthesis, Fischer-Tropsch synthesis, oxo-synthesis or methanation.
  • synthesis gas for use in downstream catalytic synthesis reactions (also referred to as chemical grade synthesis gas) requires a high ratio of H 2 to CO of about 2:1. Therefore, normally the ratio of H 2 to CO is adjusted via so called water-gas shift reaction downstream the gasification reaction.
  • water-gas shift reaction the synthesis gas is brought in contact with steam, wherein the carbon monoxide reacts with steam according to CO + H 2 O ⁇ CO 2 + H 2 (water-gas shift reaction, WGSR).
  • the synthesis gas product contains impurities besides carbon monoxide (CO) and hydrogen (H 2 ), such as tars, volatile or semi-volatile organic compounds, sulfur compounds, ammonia, nitrogen oxides, sulfur oxides, hydrogen chloride and ashes.
  • impurities besides carbon monoxide (CO) and hydrogen (H 2 ), such as tars, volatile or semi-volatile organic compounds, sulfur compounds, ammonia, nitrogen oxides, sulfur oxides, hydrogen chloride and ashes.
  • impurities besides carbon monoxide (CO) and hydrogen (H 2 ), such as tars, volatile or semi-volatile organic compounds, sulfur compounds, ammonia, nitrogen oxides, sulfur oxides, hydrogen chloride and ashes.
  • CO carbon monoxide
  • H 2 hydrogen
  • the production of chemical grade synthesis gas for use in downstream catalytic synthesis reactions requires the removal of such impurities and purification steps.
  • High levels of impurities require cost-intense synthesis gas clean-up for further processing.
  • a process for using biomass or waste to produce conversion products, such as synthesis gas for value-added products, is still challenging because of the above mentioned draw-backs of gasification technologies and the variations in bio-based raw material quality.
  • the processes and plants are designed for a specific raw material.
  • One object of the present invention is to provide a method for determining optimized process conditions for gasification, in particular for plasma gasification, that meet the above mentioned need and overcomes the drawbacks of the state of the art.
  • one object of the invention is to provide a gasification process, that is easy to implement and that uses readily available apparatus.
  • thermodynamic equilibrium model can advantageously be used to study the capability of plasma gasification, in particular in waste-to-value concepts, and to optimize the achievable total amount of synthesis gas and the synthesis gas ratio.
  • optimal process conditions namely temperature and gasification agent composition, in particular gasification agent composition, can be found based on thermodynamic equilibrium modelling, wherein it is possible to react on changes in feedstock composition and to tune the product gas composition through the flexible use of gasification agent.
  • the term process condition refers to the gasification agent composition.
  • the present invention is directed to a method for determining optimized process conditions for a process for synthesis gas production by gasification of carbon- containing material using a gasification agent, which comprises at least one gas selected from carbon dioxide, steam, oxygen, hydrogen, methane and air, wherein the composition of the gasification agent is determined as one process condition based on the atomic ratios O:C and H:C of at least one operational composition, which is a mixture of the carbon-containing material and the gasification agent, wherein the method utilizes a non-stoichiometric equilibrium model for gasification, the non- stoichiometric equilibrium model of the inventive method includes the calculation of the equilibrium composition of a system, comprising the considered product species, and the at least one operational composition is defined based on the non-stoichiometric equilibrium model for gasification and is defined based on at least one process criterion, selected from molar fraction of synthesis gas, synthesis gas ratio, solid carbon content in the synthesis gas, carbon efficiency, carbon dioxide emission, and water content in the synthesis
  • the inventive method allows easily adjusting relevant process parameters according to the given feedstock material, comprising or consisting of the carbon- containing material, and depending on arbitrary desired process criteria, for example specifications in view of the yield of synthesis gas, water content in synthesis gas, solid carbon content in the synthesis gas, etc.
  • the inventive method allows the use of different carbon-containing material, wherein the desired synthesis gas ratio and synthesis gas yield can be obtained by the adjustment of the composition of the gasification agent.
  • the process conditions for indirect (allothermic) gasification process can flexibly be used for different carbon-containing raw materials without the need of changes in the technical equipment. Further different operating conditions, such as the omission of oxygen, can be utilized in the gasification process.
  • inventive method allows to evaluate the suitability of a given carbon- containing feedstock material for a gasification process, in particular a plasma gasification process, having defined process criteria.
  • inventive method allows controlling a process for the indirect (allothermic) gasification of a carbon-containing feedstock material based on given process criteria.
  • synthesis gas means a gas mixture comprising (or preferably essentially consisting of) hydrogen and carbon monoxide.
  • synthesis gas exhibits a molar ratio of hydrogen to carbon monoxide in the range of 1 :1 to 2.5:1.
  • the molar ratio of hydrogen to carbon monoxide (H 2 /CO) is referred to as synthesis gas ratio.
  • an allothermic processes in particular an allothermic gasification (or also indirect gasification), means that the required energy for the endothermic gasification process is at least partly supplied indirectly as external energy. In particular at least 10 % of the required energy is supplied via external energy.
  • steam means water in the gaseous state.
  • the elemental composition of the, preferably solid, carbon- containing material, also referred to as feedstock, with its dry ash free weight Wdaf and weight fractions referring to carbon (C), oxygen (O), hydrogen (H) and moisture (H 2 O) are preferably known or analyzed.
  • the mass flow of the carbon-containing material in particular the mass flow of the dry ash free weight of the carbon- containing material, referring to the carbon-containing material without the moisture contained therein, or the mass flow of the ash free weight of the carbon- containing material, referring to the carbon-containing material including moisture, respectively, is preferably chosen and/or set.
  • a desired operational composition in particular a desired operational window comprising several desired operational compositions (cf. a-f in figure 12), is preferably determined in dependency of at least one process criterion which is aimed at, selected from at least one of molar fraction of synthesis gas, synthesis gas ratio, solid carbon content in the synthesis gas, carbon efficiency, carbon dioxide emission, and water content in the synthesis gas product.
  • a gasification agent in particular a distinct composition of the gasification agent, to start the preferably iterative method with, is preferably chosen.
  • the mixture of the carbon-containing material and the gasification agent forms preferably a resulting operational composition and more preferably the desired operational composition.
  • the mass flow of the resulting or desired operational composition is preferably chosen.
  • Composition and molar flows of the resulting or desired operational composition and/or the gasification agent, respectively, are preferably determined applying mass balances of the mixture of the carbon-containing material and the gasification agent.
  • the O:C and H:C ratios and the molar flows of the components, such as C, O, H, comprised in the carbon-containing material (af) and/or the dry and ash free weight of the carbon-containing material (daf) are preferably determined.
  • the carbon- containing material can be dried or assumed to be dried for the method for determining optimized process conditions resulting in a dried carbon-containing material (dried) having a moisture content, which is lower than the moisture content of the carbon- containing material (af), which is supplied initially to the process.
  • the O:C and H:C ratios and the molar flows of the carbon-containing material (af) and the dry and ash free weight of the carbon-containing material (daf), are preferably determined by the following equations, which reflect the calculation of intersection points of straight lines in the diagram of figure 1.
  • M is the molecular weight.
  • the ash free carbon-containing material is labelled with the index af.
  • the index daf stands for the dry and ash free weight of the carbon-containing material, Feed for the total flow of the ash free carbon-containing material and the dry and ash free weight of the carbon-containing material, respectively, and Moist for water initially comprised in the carbon-containing material. Further illustration of the meaning of indices af and daf is given in figure 1 at hand of the example of lignin.
  • the O:C and/or H:C ratios for the carbon-containing material, as determined above, and the desired operational composition are preferably compared with each other and the water content of the carbon-containing material can be adjusted by drying the carbon-containing material. Then, O:C and/or H:C ratios for the dried carbon- containing material are preferably calculated. If the O:C and/or H:C ratios for the carbon-containing material or the dried carbon- containing material are higher than O:C and/or H:C ratios for the desired operational composition, the carbon-containing material is dried or the dried carbon-containing material is further dried in a preferred embodiment. Drying is effectuated in particular until at least the H:C ratio of the desired operational composition is reached.
  • H: C dried H:C 0p.Comp
  • H: C dried is the H:C ratio which is achieved for the dried or further dried carbon-containing material, respectively.
  • Index dried stands for the dried or further dried carbon-containing material, respectively.
  • H:C 0p.Comp is the H:C ratio in the desired operational composition.
  • the molar flow of water which is preferably withdrawn from the carbon-containing material during drying, is calculated by equation (12). is the resulting elemental molar flow of hydrogen in the dried carbon-containing material, for the H:C ratio H: C dried of the dried carbon-containing material.
  • the O:C ratio for the dried carbon-containing material can be calculated by equation (14).
  • the molar flow of elemental oxygen for the dried carbon-containing material is given in equation (15).
  • the carbon-containing material is further dried or the desired operational composition is changed.
  • the addition of the gasification agent is considered, resulting in the m ixture comprising the carbon-containing material or dried carbon-containing material, respectively, and the gasification agent.
  • the gasification agent comprises at least H 2 O (steam), more preferably O 2 and/or H 2 O (steam) or CO 2 and/or H 2 O (steam).
  • the mixture comprising the carbon-containing material or dried carbon-containing material, respectively, and the gasification agent, is preferably set to equal the desired operational composition and the composition and mass or molar flow of the gasification agent is preferably calculated. More preferably, the molar flow of the individual components or gases of the gasification agent, which is required to reach the desired operational composition, is calculated. In particular, the molar flow of steam to be present in the gasification agent and, preferably in a subsequent step, the molar flow of oxygen to be present in the gasification agent in form of molecular oxygen is calculated.
  • equation (16) is used to calculate the amount of steam required as part of the gasification agent to obtain the desired operational composition, in particular in the case where the gasification agent comprises O 2 and/or H 2 O (steam).
  • the Index GA refers to the gasification agent.
  • the amount of molecular oxygen required as part of the gasification agent to obtain the desired operational composition is preferably determined by equation (17).
  • equation (18) is used to calculate the amount of steam required as part of the gasification agent to obtain the desired operational composition, in the case where the gasification agent comprises CO 2 and/or H 2 O (steam), in particular H 2 O (steam).
  • the amount of molecular CO 2 required as part of the gasification agent to obtain the desired operational composition is preferably determined by equation (19).
  • the carbon-containing material is preferably further dried, an alternative and/or additional gasification agent is used or an alternative desired operational composition is chosen.
  • the desired operational composition is achieved with the considered composition of the gasification agent and the method for determining optimized process conditions is preferably stopped.
  • the respective considered component is not required in the gasification agent.
  • inventive method encompasses the definition of the composition of at least carbon-containing material composition or a group of such compositions (also referred to as a starting window) defined by atomic O:C and H:C ratios within the O:C / H:C plot (also known as van-Kreve!en-plot).
  • determining the composition of the gasification agent is carried out by the following step:
  • Combinations as defined above are selected based on the non-stoichiometric equilibrium model for gasification.
  • the method for determining optimized process conditions for a process for synthesis gas production comprises the following steps: i) defining the composition of at least one carbon-containing material or a group of such compositions (starting window) within the O:C / H:C plot; ii) defining at least one operational composition or group of operational compositions (operational window) within the O:C / H:C plot based on the non- stoichiometric equilibrium model for gasification, and based on at least one process criterion, selected from molar amount of synthesis gas, synthesis gas ratio, solid carbon content in the synthesis gas, carbon dioxide emission, and water content in the synthesis gas product; iii) defining at least one suitable combination of carbon-containing material composition (within the starting window) and operational composition (within the operational window), wherein the operational composition is reached within the O:C / H:C plot starting from the carbon-containing material compositions by the addition of at least one gas selected from carbon dioxide, steam, oxygen, hydrogen, methane
  • the gasification is an allothermic gasification, wherein external energy obtained from electric power, preferably from electric power generated by renewable energy, is supplied in the gasification step.
  • the gasification is an arc-plasma gasification.
  • the gasification includes supplying external energy obtained from electric power, wherein the external energy causes the gasification reaction of the carbon- containing material, in the presence of the gasification agent.
  • the process for synthesis gas production is carried out as continuous process.
  • the present invention is directed to a method for determining optimized process conditions, e.g. optimal process conditions, for a process for synthesis gas production by gasification, wherein the composition of the gasification agent is determined as one process condition based on the atomic ratios O:C and H:C of at least one operational composition.
  • process conditions are understood as being process parameters that are set using the inventive method in order to obtain optimal or desired process results, such as one or more of the process criteria as described below.
  • the composition of the gasification agent is determined as one process condition.
  • the composition of the gasification agent is given by the molar fraction (given in mol%) for at least one gas selected from carbon dioxide, steam, oxygen, hydrogen, methane and air, or ranges thereof.
  • the temperature has only a minor influence on relevant process criteria and a temperature invariant product composition can be achieved for a given feedstock.
  • This allows for a stable and tolerant operation regime, in which particular suitable synthesis gas ratios and low solid carbon contents can be obtained within the ratio of O:C and H:C of the chosen operational window.
  • the method for determining optimized process conditions is directed to a process for synthesis gas production via plasma gasification which is carried out at a temperature in range of 1 ,400 to 1 ,800 K, in the gasification step.
  • the synthesis gas (also referred to as syngas) produced via the gasification process comprises hydrogen and carbon monoxide, wherein the sum of hydrogen and carbon monoxide in the produced synthesis gas is from 80 to 100 mol%, typically 80 to 95 mol%, based on the total synthesis gas, and calculated without inert gases, such as nitrogen.
  • the synthesis gas produced in the gasification of carbon-containing material may comprise further components besides hydrogen and carbon monoxide, such as common impurities and/or inert components. Typically, such further components may be present up to 1000 ppm.
  • the synthesis gas may comprise one or more further components besides hydrogen (H 2 ) and carbon monoxide (CO) selected from carbon dioxide (CO 2 ), methane (CH 4 ), steam, nitrogen (N 2 ), noble gases (e.g. argon), other nitrogen compounds, such as nitrogen oxides (NOx), ammonia (NH 3 ), and hydrogen cyanide (HCN); sulfur compounds, e.g. hydrogen sulfide (H 2 S), sulfur dioxide (SO 2 ), carbonyl sulfide (COS), carbon disulfide (CS 2 ), methane thiol (CH 3 SH), thiophene, benzothiophene and/or halogen compounds, such as hydrogen chloride (HCI).
  • gaseous impurities in the synthesis gas may be selected from at least one of nitrogen (N 2 ), ammonia (NH3), hydrogen cyanide (HCN), and hydrogen chloride (HCI).
  • the content of solid carbon in the synthesis gas product is less than 1 % (mol%), more preferably from 0.1 to 0.8 % (mol%).
  • the method is directed to the production of chemical grade synthesis gas.
  • chemical grade synthesis gas exhibits a composition and content of impurities in such way that it can be used for typical downstream processes, such as methanol synthesis, mixed alcohol synthesis, Fischer-Tropsch synthesis, oxo- synthesis (also referred to as hydroformylation), and methanation.
  • the synthesis gas has a synthesis gas ratio in the range of 1 :1 to 2.5:1 , more preferably in the range of 1.5:1 to 2.1 :1.
  • the composition of the synthesis gas e.g. the hydrogen to carbon monoxide ratio
  • the synthesis gas is used in a methanol synthesis process and has a synthesis gas ratio in the range of 2.0 : 1 to 2.5 : 1.
  • the synthesis gas is used in a Fischer-Tropsch process and has a synthesis gas ratio in the range 1.5 : 1 to 2.5 : 1 , preferably 2.0 : 1 to 2.5 : 1.
  • Carbon-containing material e.g. the hydrogen to carbon monoxide ratio
  • inventive method encompasses the definition of the composition of at least one carbon-containing material or a group of such compositions (also referred to as an starting window) defined by atomic O:C and H:C ratios in particular within the O:C / H:C plot (also known as van-Krevelen plot or Krevelen plot).
  • the process for synthesis gas production by gasification comprises feeding a feedstock, comprising at least one carbon-containing material, and a gasification agent into a gasifier.
  • the feedstock (or also referred to as feedstock material) consists of the one or more carbon-containing material(s) as described in the following.
  • the carbon-containing material is a mixture of different carbon-containing materials as described in the following, for example a mixture of different waste materials.
  • the composition of the carbon-containing material based on the atomic ratios O:C and H:C, e.g. within the range of CH 0.0-2.2 O 0.0- 1.3 can be adjusted via mixing of different carbon-containing materials.
  • the starting window, in particular within the O:C / H:C plot, can be defined via the mixture of different carbon-containing materials.
  • composition of said unknown carbon-containing material based on the atomic ratios O:C and H:C is determined via ultimate analysis and said composition (e.g. ratios O:C and H:C) is used in the inventive method.
  • an unknown carbon-containing material wherein the carbon-containing material, e.g. a plastic waste material, is characterized by a known analysis method, e.g. ultimate analysis, infrared spectroscopy, and the composition of said unknown carbon-containing material is defined based on the results of the said analysis method and the atomic ratios O:C and H:C commonly known and/or described in literature.
  • the carbon-containing material used in the inventive method for determining optimized process conditions for a process for synthesis gas production are selected from materials comprising carbon, hydrocarbons or mixtures thereof.
  • the carbon-containing material is selected from coal, biomass (e.g. wood or straw), cellulose-containing materials, lignin-containing materials, hydrocarbons, organic matter, waste material, such as municipal waste (e.g. municipal solid waste MSW), plastic solid waste materials (PSW), non-recyclable waste materials (e.g. thermographic paper), waste materials from chemical industry processes (e.g. solvents or residues) (referred to as chemical process waste materials), sludges, rubbers, and mixtures thereof.
  • waste material such as municipal waste (e.g. municipal solid waste MSW), plastic solid waste materials (PSW), non-recyclable waste materials (e.g. thermographic paper), waste materials from chemical industry processes (e.g. solvents or residues) (referred to as chemical process waste materials), sludges, rubbers, and mixtures thereof.
  • the carbon-containing material is selected from coal, cellulose-containing materials, and lignin-containing materials, more preferably from coal, lignin and cellulose.
  • the carbon-containing material has a composition in the range defined by
  • the carbon-containing material used in the inventive method for determining optimized process conditions is selected from coal, preferably having a composition CH 0.0-0.9 O 0.0-0.1 ; lignin, preferably having a composition CH 0.6-1.6 O 0.0-0.9 ; and cellulose, preferably having a composition CH 1.0-2.2 O 0.3-1.3 . More preferably, the carbon-containing material can be selected from coal, having a composition CH 0.6 O 0.02 ; lignin having a composition CH 1.1 O 0.4 ; and cellulose, having a composition CH 1.65 O 0.8 .
  • the inventive method is directed to a process for synthesis gas production which is utilized as waste-to-value (WtV) process, wherein the value is for example synthesis gas or a downstream product, e.g. methanol, Fischer-Tropsch waxes, Fischer-Tropsch fuels, alcohols (from mixed alcohol synthesis), aldehydes (from hydroformylation) or methane (from methanation).
  • WtV waste-to-value
  • the carbon-containing material is selected from waste materials comprising hydrocarbons, in particular selected from agricultural waste, industrial organic waste, industrial biogenic waste, and municipal waste.
  • the carbon-containing material is selected from one or more plastic solid waste (PSW) materials.
  • the carbon-containing material is selected from non-recyclable waste materials (e.g. thermographic paper).
  • the inventive method is directed to a process of the allothermic gasification of plastic solid waste (PSW).
  • PSW plastic solid waste
  • the composition of the gasification agent can be adjusted in view of the used plastic solid waste material and/or the desired synthesis gas ratio in the produced synthesis gas.
  • Plastic solid waste is for example selected from automotive shredder residue (ASR), post-consumer plastic waste, household plastic waste and/or commercial plastic waste.
  • ASR automotive shredder residue
  • post-consumer plastic waste household plastic waste and/or commercial plastic waste.
  • plastic solid waste is a mixture of commonly used plastic materials.
  • the plastic solid waste comprises one or more plastic materials selected from styrene polymers (e.g. GPPS, HIPS), styrene copolymers (e.g. ABS, ASA), polyesters (e.g. PBT, PET), polyvinylchloride (PVC), polyolefins (e.g. PE, PP, HDPE, LDPE, LLDPE), polyether ether ketone (PEEK), polyvinylacetate (PVA), polyurethane (PU), polyamides (e.g. PA6), acrylate polymers (e.g. PMMA), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polycarbonate (PC) and polyoxomethylene (POM).
  • styrene polymers e.g. GPPS, HIPS
  • styrene copolymers e.g. ABS, ASA
  • the plastic solid waste (PSW) comprises (preferably consists of) one or more plastic materials selected from polystyrene (PS), general purpose polystyrene (GPPS), high impact polystyrene (HIPS), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyether ether ketone (PEEK), and polyvinyl acetate (PVA).
  • the plastic solid waste (PSW) comprises (preferably consists of) one or more plastic materials selected from polyethylene (PE), polypropylene (PP), polystyrene (PS) and polyether ether ketone (PEEK).
  • the carbon-containing material comprises only one of the above mentioned plastic materials (single-sort recycled PSW).
  • the carbon-containing material comprises two or more of the above mentioned plastic materials (mixed-sort recycled PSW).
  • the carbon-containing material in particular PSW, exhibits an atomic ratio of O:C (oxygen to carbon) in the range of 0.0 to 0.7; more preferably in the range of 0.0 to 0.1; and/or an atomic ratio H:C (hydrogen to carbon) in the range of 0.4 to 2.2; most preferably in the range of 1.8 to 2.2.
  • the carbon- containing material has a composition CH0.4-2.2O0.0-0.7; more preferably a composition CH 1.8-2.2 O 0.0-0.1 .
  • the carbon-containing material is at least one plastic solid waste having a composition in the range defined by CH 0.4-2.2 O 0.0-0.7 ; most preferably CH 1.8-2.2 O 0.0-0.1 .
  • the carbon-containing material may be pretreated before fed into the gasifier.
  • the feedstock comprising at least one carbon-containing material is dried before feeding into the gasifier.
  • drying the carbon-containing material, to adjust the moisture content in the carbon-containing material, if appropriate, can be considered with the inventive method before the addition of the gasification agent.
  • the feedstock comprising at least one carbon-containing material may be reduced to small particles, e.g. by cutting, crushing, grinding.
  • the pretreatment may encompasses separating and sorting of the feedstock material.
  • the carbon-containing material has a water content of up to 50 % by weight, preferably up to 30 % by weight, more preferably in the range of 0 to 50 % by weight, most preferably 0.001 to 40 % by weight.
  • the carbon-containing material is selected from plastic solid waste material and has a water content of up to 5 % by weight, more preferably up to 1 % by weight, most preferably in the range of about 0 to 1 % by weight.
  • the gasification agent comprises at least one gas selected from carbon dioxide, steam, oxygen, hydrogen, methane, and air, preferably selected from carbon dioxide, steam, oxygen, hydrogen and methane; more preferably selected from carbon dioxide, steam, hydrogen, and methane, in particular from oxygen, carbon dioxide, and steam.
  • the gasification agent is a mixture of two or more of the gases mentioned before.
  • the gasification agent comprises (preferably consists of):
  • 1 to 98 mol% preferably 5 to 80 mol%, more preferably 10 to 60 mol%, of steam; 1 to 98 mol%; preferably 5 to 80 mol%, more preferably 10 to 60 mol%, of oxygen;
  • further components preferably further gaseous components, e.g. selected from carbon monoxide and gaseous impurities, e.g. impurities comprising sulfur compounds and/or nitrogen compounds.
  • the gasification agent may comprise impurities, in particular gaseous impurities, in the ppb or ppm range, for example in the amount of 0.001 ppm to 100 ppm.
  • impurities are selected from sulfur compounds, nitrogen compounds and halogen compounds as mentioned above in connection with the synthesis gas impurities.
  • the gasification agent may comprise carbon monoxide in an amount of from 0 to 30 mol%, preferably of from 0.0001 to 10 mol%. In an embodiment the gasification agent comprises less than 1 mol%, preferably less than 0.1 mol%, of nitrogen.
  • the gasification agent may comprise methane obtained from bio gas production.
  • the inventive method encompasses the definition of at least one operational composition, which is a mixture of the carbon-containing material and the gasification agent, based on the atomic ratios O:C and H:C, in particular within the O:C / H:C plot (also known as van-Krevelen-plot).
  • the inventive method encompasses the definition of a group of operational compositions (also referred to as an operational window) defined by atomic O:C and H:C ratios, preferably represented as a box within the O:C / H:C plot.
  • the operational composition or operational window is defined based on criteria set for relevant process parameter (also referred to as process criteria in the following).
  • process criteria are for example synthesis gas ratio, yield of synthesis gas, carbon efficiency, and solid carbon content in the synthesis gas.
  • the operational composition or operational window is defined using the non- stoichiometric equilibrium model for gasification. It is also possible to use a simulation based on said non-stoichiometric equilibrium model for gasification. In particular, the operational composition or operational window is defined based on said non- stoichiometric equilibrium model for gasification, wherein one or more process parameters as described below are set as constraints on the synthesis gas composition (product gas composition) calculated by the non-stoichiometric equilibrium model for gasification.
  • the at least one operational composition, or the operational window is defined based on the non-stoichiometric equilibrium model for gasification and is defined based on at least one process criterion, selected from molar fraction of synthesis gas (yield of synthesis gas), synthesis gas ratio, solid carbon content in the synthesis gas, carbon efficiency (yield of carbon monoxide), carbon dioxide emission, and water content in the synthesis gas product.
  • the operational composition is at least one composition selected from compositions having an atomic ratio of O:C in the range of 1.0 to 1.7; preferably in the range of 1.2 to 1.5; and/or an atomic ratio H:C in the range of 2.0 to 4.0; preferably in the range of 3.0 to 3.4.
  • the operational composition is at least one composition selected from the range defined by CH 2.0-4.0 O 1.0-1.7 ; more preferably CH 2.7-3.7 O 1.1-1 .6 , also preferably CH 3.0-3.4 O 1.2-1 .5 , most preferably the operational composition is CH 3.2 O 1.4 .
  • the operational window has an atomic ratio of O:C in the range of 1.0 to 1.7; preferably in the range of 1.2 to 1.5; and/or an atomic ratio H:C in the range of 2.0 to 4.0; preferably in the range of 3.0 to 3.4.
  • the operational window is CH 2.0-4.0 O 1.0-1.7 ; more preferably CH 2.7-3.7 O 1.1- 1.6 , also preferably CH 3.0-3.4 O 1.2-1.5 .
  • the operational composition is at least one composition selected from compositions having an atomic ratio of O:C in the range of 1.1 to 1.4 and/or an atomic ratio H:C in the range of 2.0 to 4.0.
  • the operational composition is at least one composition selected from CH 2.0-4.0 O 1.1-1.4 .
  • the operational window has an atomic ratio of O:C in the range of 1.1 to 1.4 and/or an atomic ratio H:C in the range of 2.0 to 4.0.
  • the operational composition is at least one composition selected from CH 2.0-4.0 O 1.1-1 .4 .
  • the process criteria as described in the following may be used to define at least one suitable operational composition or preferably an operational window (i.e. the group of suitable or preferred operational compositions), in particular within the O:C / H:C plot, based on the non-stoichiometric equilibrium model for gasification.
  • an operational window i.e. the group of suitable or preferred operational compositions
  • the process criterion used in the inventive method is one or more selected from molar amount of synthesis gas (yield of synthesis gas), synthesis gas ratio, solid carbon content in the synthesis gas product, carbon efficiency (yield of carbon monoxide), carbon dioxide emission, and water content in the synthesis gas product; more preferably selected from molar fraction of synthesis gas (yield of synthesis gas) and synthesis gas ratio.
  • molar amount of synthesis gas yield of synthesis gas
  • synthesis gas ratio solid carbon content in the synthesis gas product
  • carbon efficiency yield of carbon monoxide
  • carbon dioxide emission carbon dioxide emission
  • water content in the synthesis gas product more preferably selected from molar fraction of synthesis gas (yield of synthesis gas) and synthesis gas ratio.
  • two or more, preferably two to five, more preferably two to three process criteria are used in the inventive method in order to define the operational composition(s) or the operational window.
  • the molar amounts are given as molar flow in a continuous process.
  • the inventive method is based on maximum molar amount of synthesis gas as relevant process criteria.
  • a molar amount of synthesis gas of at least 70 %, more preferably at least 80 %, even more preferably in the range of 70 to 100 %, most preferably 80 to 95 %, is used as process criterion in the inventive method.
  • the molar amounts are given as molar flow in a continuous process.
  • a synthesis gas ratio in the range of 1 :1 to 2.5:1 , more preferably 1.1 :1 to 2.5:1 , even more preferably 1.5:1 to 2.5:1 , most preferably 2:1 to 2.1 :1 , in particular 1 :1 to 2:1 , for example 2:1 , is used as process criterion in the inventive method.
  • solid carbon content (SCC) in the synthesis gas is given in % by:
  • the molar amounts are given as molar flow in a continuous process.
  • the inventive method is based on minimum solid carbon content in the synthesis gas as one relevant process criteria.
  • solid carbon content (SCC) of below 1 %, more preferably in the range of 0 to 0.9 %, most preferably 0.1 to 0.8 %, is used as process criterion in the inventive method.
  • the molar amounts are given as molar flow in a continuous process.
  • the inventive method is based on maximum carbon efficiency as relevant process criteria.
  • a carbon efficiency of at least 60 %, more preferably at least 80 %, even more preferably in the range of 60 to 100 %, most preferably 80 to 95 %, is used as process criterion in the inventive method.
  • the invention method for determining optimized process conditions for synthesis gas production by gasification utilizes a non-stoichiometric equilibrium model for gasification.
  • the non-stoichiometric equilibrium model is utilized for determining the synthesis gas product composition.
  • the utilization of the non-stoichiometric equilibrium model includes the solution of a system of equations as described below, resulting from minimization of the total Gibbs free energy.
  • the non-stoichiometric equilibrium model for gasification may be implemented in the inventive method via generally known computer programs including the possibility for solving systems of non-linear algebraic equations, e.g. Matlab, Mathematica and Microsoft Excel Solver add-in.
  • inventive method can for example be based on a simulation which is based on said non-stoichiometric equilibrium model for gasification.
  • suitable simulation methods are known in the art and are carried out using commonly known computer programs, for example Aspen One® simulation software (from Aspen Technology, Inc., US).
  • the equilibrium composition of a system comprising (preferably consisting of) the desired product species, is calculated by minimization of the total Gibbs free energy of the system G s , wherein the total Gibbs free energy of the system G s is defined as: where n, is the amount of substance of considered product species i;
  • N is the number of considered product species; and ⁇ i is the chemical potential of considered product species i.
  • the chemical potential ⁇ i of species i which are considered as ideal gases, is given by:
  • ⁇ G° f,i is the standard Gibbs free energy of formation of the species i; R is the ideal gas constant; T is the temperature of the species or of the system; n i is the amount of substance of product species i; and n total is the total amount of substance of all N product species considered.
  • product species selected from solid carbon (C (s)), gaseous carbon monoxide (CO (g)), gaseous carbon dioxide (CO 2 (g)), gaseous methane (CH 4 (g)), gaseous hydrogen (H2 (g)), and gaseous water (steam, H 2 O (g)) are considered.
  • the non-stoichiometric equilibrium model of the inventive method includes the calculation of the equilibrium composition of a system, comprising the considered product species, by minimization of the total Gibbs free energy of the system G s , wherein the objective function of the minimization problem (minimization of G s ) is given by formula (22): wherein the symbols are as defined above.
  • the inventive method may include the calculation of the equilibrium composition as described for different temperatures T within a given range, more preferably for a temperature range of from 800 to 1 ,800 K, most preferably for a temperature range of from 1 ,400 to 1,800 K.
  • the standard Gibbs free energies of formation of the considered species ( ⁇ G° f,i ) and their temperature dependence are determined based on standard databases, e.g. NIST-JANAF database.
  • the standard Gibbs free energies of formation of the considered species ( ⁇ G° f,i ) at the given temperature can be approximated by polynomial functions given in said standard data bases.
  • Aj is the total number of atoms of the j-th element (in particular C, H, O), present in the reaction mixture, a i,j is the number of atoms of element j in product species i; n i is the amount of substance of product species i, and N is the number of considered product species.
  • the mass balances according to formula (23) of the elements C (carbon), H (hydrogen) and O (oxygen) are considered as constraints for the calculation of the synthesis gas product composition by the non-stoichiometric equilibrium model.
  • the input species needs to be specified in order to determine available atoms Aj for the non-stoichiometric equilibrium model.
  • the input of feedstock (carbon-containing material), feedstock moisture and gasification agents are considered in the model, e.g. in the mass balances of formula (23).
  • the gasification agents considered in the non-stoichiometric equilibrium model for gasification are as described above.
  • at least oxygen, steam and carbon dioxide are considered.
  • the feedstock (carbon-containing material) is given in form of a carbon- normalized composition CHxOy .
  • CHxOy is calculated according to the following formulas (24) and (25): where
  • W daf is the weight fractions on dry basis; and M is the molar mass.
  • the production of synthesis gas by gasification encompasses process steps including the gasification reaction carried out in a gasifier, and typically additional pretreatment steps and/or subsequent steps of purification or the so called water gas shift.
  • the method for determining optimized process conditions is directed to a process for synthesis gas production by gasification comprising the steps: a) feeding a feedstock, comprising at least one carbon-containing material, and a gasification agent, comprising at least one gas, selected from carbon dioxide, steam, oxygen, hydrogen, methane and air, as feed stream into a gasifier, wherein a product stream comprising raw synthesis gas is generated; b) removing the raw synthesis gas as product stream from the gasifier and optionally cooling the product stream; c) separating the solid ingredients from the gaseous ingredients in the raw synthesis gas product stream; d) feeding the product stream obtained in step c) into a water-gas shift reactor, wherein a part of the carbon monoxide of the synthesis gas is transformed together with steam into hydrogen and carbon dioxide and wherein a modified synthesis gas product stream is obtained; e) optionally removing sulfur compounds from the modified product stream in a desulfurizing step; f) removing and separating carbon dioxide at least partially from the modified product
  • the synthesis gas product stream obtained in step f) or g) can be used in a downstream synthesis process, wherein at least one downstream synthesis product and an exhaust gas comprising carbon dioxide is obtained.
  • the at least one carbon-containing material used as feedstock may be in solid and/or liquid form.
  • the carbon-containing material used as feedstock in the gasification process of the inventive method is in solid form.
  • the gasification is carried out as an allothermic gasification, wherein external energy is supplied in the gasification step a), preferably external energy obtained from electric power, more preferably external energy obtained from electric power generated by renewable energy.
  • the renewable energy for generating the electric power is based on biomass, hydroelectricity, wind power, geothermal energy, and/or solar energy (e.g. photovoltaic electricity, solar thermal power, concentrated solar power).
  • the external energy is supplied in the gasifier in step a) in form of a plasma, preferably an arc plasma.
  • the inventive method is directed to the production of synthesis gas by plasma gasification of carbon- containing material.
  • the utilization of plasma as external power source can be advantageous due to higher flexibility as the external power source can be adapted depending on the carbon containing raw material and the process conditions.
  • a plasma is defined as an ionized gas, which contains a significant number of electrically charged particles (ions and electrons) and is classified as the fourth state of matter.
  • a plasma is electrically conductive and it is electrically neutral, as plasma contains an equal number of free positive and negative charges.
  • the degree of ionization can typically be less than 1 % or up to 100 %.
  • a plasma can be generated by suppling external energy, e.g. in form of thermal energy, strong electro- magnetic fields, into a gas in the ground state.
  • the plasma used in gasification step a) may be a non-thermal plasma or a thermal plasma.
  • a non-thermal plasma or also referred to as non-equilibrium plasma is a plasma that is not in a thermodynamic equilibrium due to the different temperature of the different particle species (electrons and heavy species, i.e. neutrals, ions).
  • a thermal plasma or also referred to as equilibrium plasma is a plasma that is in a thermodynamic equilibrium due to the same temperature of the different particle species.
  • the gasification is carried out in step a) using a plasma as external energy and at a temperature in the range of 1 ,400 K to 1 ,800 K.
  • the plasma used the gasification of the inventive method may be generated by using various commonly known methods, such as by using an arc plasma torch, gliding arc discharge, a plasma pencil, a plasma needle, a plasma jet, a dielectric barrier discharge, a resistive barrier discharge, a piezoelectric direct discharge, a glow discharge or a microwave plasma generation.
  • an arc plasma torch gliding arc discharge, a plasma pencil, a plasma needle, a plasma jet, a dielectric barrier discharge, a resistive barrier discharge, a piezoelectric direct discharge, a glow discharge or a microwave plasma generation.
  • the external energy is supplied in form of an arc plasma in the gasification step a).
  • Arc plasma electrical arc plasma
  • Arc plasma is defined as a plasma generated in an electrical arc, via electrical discharge and ionization of a gas.
  • plasma torches for arc plasma generation are commonly known by a skilled person (e.g. from Westinghouse Plasma Corporation).
  • the external energy is supplied in the gasifier in step a) in form of plasma, preferably an arc plasma generated by a plasma torch operated in the power range of 80 to 4000 kW, preferably 300 to 3000 kW.
  • the gasification in step a) is carried out at a temperature above 1 ,400 K (operational temperature), preferably in the range of 1 ,400 to 1 ,800 K, wherein the external energy is supplied in the gasifier in step a) in form of a plasma, preferably an arc plasma.
  • the temperature given above for the gasification in step a) is directed to the gas temperature of the product stream leaving the gasifier in step a), said temperature can also be referred to as operational temperature in gasification step a).
  • the core temperature of the plasma can be more than 2,000 K, for example the core temperature of the plasma can be in the range of 5,000 to 50,000 K in an arc plasma.
  • gasification reaction in step a) can be carried out using commonly known types of gasifiers, for examples fluidized-bed gasifiers, fixed-bed gasifiers, entrained-flow gasifiers or combinations thereof.
  • the raw synthesis gas obtained in the gasification step a) exhibits a synthesis gas ratio (molar H 2 /CO) in the range of 1 : 1 to 2.1 : 1 , preferably 1 : 1 to 1.5 : 1.
  • Suitable subsequent steps are commonly known and described in the state of the art, such as separation of the solid ingredients in the raw synthesis gas product stream which is removed from the gasifier from the gaseous ingredients, e.g. by means of cyclones, filters (e.g. moving bed filters, ceramic filter candles), electrostatic filters (ESP), and (solvent) scrubbers.
  • filters e.g. moving bed filters, ceramic filter candles
  • electrostatic filters ESP
  • solvent scrubbers solvent
  • raw synthesis gas obtained in the gasification step is fed into a water-gas shift reactor, optionally together with steam, wherein a part of the carbon monoxide of the synthesis gas is transformed together with steam into hydrogen and carbon dioxide according to the water-gas shift reaction according to CO + H 2 O ⁇ CO 2 + H 2 , and wherein a modified synthesis gas product stream is obtained.
  • a water-gas shift reaction and apparatus therefore are commonly known and described in the state of the art, e.g. in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, 2011 , Vol. 16, p. 483-493, Gas Production, 3. Gas Treating, Boll et al.
  • sulfur compounds such as hydrogen sulfide (H 2 S) and/or carbonyl sulfide (COS)
  • H 2 S hydrogen sulfide
  • COS carbonyl sulfide
  • HCI and CO 2 impurities
  • desulfurizing step can be carried out using known wet and/or dry processes as known in the state of the art.
  • the gasification process encompasses removing and separating the carbon dioxide at least partially from the modified synthesis gas product stream, wherein an exhaust gas comprising carbon dioxide may be obtained.
  • carbon dioxide can be removed from the synthesis gas product stream by chemical and physical absorption with at least one liquid solvent or by adsorption with at least one solid adsorbent. Suitable processes are described in the state of the art, such as Thermal Swing Adsorption (TSA) or Pressure Swing Adsorption (PSA).
  • further purification of the synthesis gas product stream may be necessary to fulfill the requirements for chemical grade synthesis gas that can be used in a downstream synthesis reaction, in particular a catalytic downstream synthesis reaction.
  • further purification includes the removal or reduction of contaminants, such as chlorine compounds (e.g. hydrogen chloride HCI), nitrogen compounds (e.g. NH 3 , HCN), sulfur compounds (e.g. H 2 S, COS, SOx ) , water, alkali and earth alkali compounds.
  • contaminants such as chlorine compounds (e.g. hydrogen chloride HCI), nitrogen compounds (e.g. NH 3 , HCN), sulfur compounds (e.g. H 2 S, COS, SOx ) , water, alkali and earth alkali compounds.
  • such purification may be carried out by wet scrubbing or by dry adsorption processes, e.g. by adsorption to a solid adsorbent, in particular zinc oxide (ZnO) or iron oxid (FeO).
  • the synthesis gas can be used as an intermediate product in a downstream synthesis process for the production of downstream products (i.e. secondary products of synthesis gas), such as methanol, Fischer-Tropsch waxes, Fischer-Tropsch fuels, alcohols (from mixed alcohol synthesis), aldehydes (from hydroformylation) or methane (from methanation), preferably methanol.
  • downstream products i.e. secondary products of synthesis gas
  • secondary products of synthesis gas such as methanol, Fischer-Tropsch waxes, Fischer-Tropsch fuels, alcohols (from mixed alcohol synthesis), aldehydes (from hydroformylation) or methane (from methanation), preferably methanol.
  • the invention is directed to the use of the method for determining optimized process condition as described above for process control for synthesis gas production by gasification, process monitoring of a process for synthesis gas production by gasification, quality control of a process for synthesis gas production by gasification, evaluation of carbon-containing material for a process for synthesis gas production by gasification, adaption of process conditions for a process for synthesis gas production by gasification depending on variation of carbon-containing material (feedstock material) and/or process engineering for a process for synthesis gas production by gasification.
  • the inventive method can be used for adjusting the composition of the gasification agent, based on a given feedstock material (carbon-containing material). Further, the inventive method can be used for adjusting the composition of the gasification agent depending on arbitrary desired process criteria, for example specifications in view of the yield of synthesis gas, water content in synthesis gas, solid carbon content in the synthesis gas, etc.
  • the use of the inventive method can for example be directed to process monitoring, quality control of the synthesis gas product, and process engineering.
  • the inventive method allows to evaluate the suitability of a given carbon- containing feedstock material for a gasification process (in particular a plasma gasification process), for example based on defined process criteria.
  • a gasification process in particular a plasma gasification process
  • the inventive method can also be used for unknown carbon-containing material based on results of ultimate analysis or for mixtures of different carbon containing materials.
  • the inventive method allows controlling and/or engineering a process for the indirect (allothermic) gasification of a carbon-containing feedstock material based on given process criteria.
  • Figure 1 shows the O:C / H:C plot including compositions of suitable carbon-containing feedstock materials and illustrates the change by addition of gasification agent, i.e. CH 4 , H 2 O, CO 2 .
  • the carbon-containing feedstock materials are dry-ash-free coal (“Coal, daf” ); dry-ash-free lignin (“Lignin, daf” ); dry-ash-free cellulose (“Cellulose, daf” ); and ash-free lignin (“Lignin, af”).
  • said plot shows the variety of feedstock compositions and illustrates the shift in the O:C / H:C plot by adding different gasification agent.
  • Figure 2 shows the results of the parametric study for the gasification of coal (CH 0.6 O 0.02 ) for different temperatures (from 800 K to 1 ,800 K).
  • Figure 2a) shows the molar amount of synthesis gas in dependency of the addition of oxygen.
  • Figure 2b) shows the synthesis gas ratio in dependency of the amount of oxygen.
  • Figures 2c) and 2d) show the molar amount of synthesis gas and the synthesis gas ratio respectively for different amounts of water as gasification agent.
  • figures 2e) and 2f) the influence of the addition of hydrogen is shown for the molar amount of synthesis gas and the synthesis gas ratio.
  • Figure 3 shows the results of the parametric study for the gasification of lignin (CH 1.1 O 0.4 ) for different temperatures (from 800 K to 1,800 K).
  • Figure 3a) shows the molar amount of synthesis gas in dependency of the addition of oxygen.
  • Figure 3b) shows the synthesis gas ratio in dependency of the amount of oxygen.
  • Figures 3c) and 3d) show the molar amount of synthesis gas and the synthesis gas ratio for different amounts of water as gasification agent, respectively.
  • figures 3e) and 3f) the influence of the addition of hydrogen is shown for the molar amount of synthesis gas and the synthesis gas ratio.
  • Figure 4 shows the results of the parametric study for the gasification of cellulose (CH 1.65 O 0.8 ) for different temperatures (from 800 K to 1 ,800 K).
  • Figure 4a) shows the molar amount of synthesis gas in dependency of the addition of oxygen.
  • Figure 4b) shows the synthesis gas ratio in dependency of the amount of oxygen.
  • Figures 4c) and 4d) show the molar amount of synthesis gas and the synthesis gas ratio for different amounts of water as gasification agent, respectively.
  • figures 4e) and 4f) the influence of the addition of hydrogen is shown for the molar amount of synthesis gas and the synthesis gas ratio.
  • Figures 5 show the molar amount of synthesis gas for gasification of coal (CH0.6O0.02), lignin (CH 1.1 O 0.4 ) and cellulose (CH 1.65 O 0.8 ) at 1,400 K.
  • Figure 5a) shows the molar amount of synthesis gas in dependency of the added oxygen amount.
  • Figure 5b) represents the synthesis gas amount versus the O:C-ratio of the operational composition.
  • figure 5c) the molar amount of synthesis gas is shown for different H:C- ratios at a constant O:C-ratio of 1.8. It is demonstrated that desired process criteria, i.e. the molar amount of synthesis gas, can be illustrated independent from the carbon- containing material (feedstock) using the plots in relation of O:C and H:C ratios.
  • Figure 6 illustrates the determination of the borderlines in the O:C / H:C plot based on the process criteria and utilizing the non-stoichiometric equilibrium model.
  • Figure 6a) shows the borderlines resulting for molar amount of synthesis gas (>0.94; >0.80 and >0.70, corresponding to >94 %,>80 %; >70 %).
  • Figure 6b) shows the borderlines resulting for synthesis gas ratio (4.0, 3.0, 2.0 and 1.0).
  • Figure 6c) shows the borderlines resulting for solid carbon content ( ⁇ 0.1 , ⁇ 0.01 ; ⁇ 0.001 ; corresponding to ⁇ 10 %, ⁇ 1 %; ⁇ 0.1 %).
  • Figure 7 illustrates the determination of the operational window in the O:C / H:C plot based on the process criteria: molar amount of synthesis gas, synthesis gas ratio, and solid carbon content in synthesis gas.
  • the process criteria applied are molar amount of synthesis gas of at least 70 % (>0.70), synthesis gas ratio from 1 to 2, and solid carbon content of equal or less than 1 % ( ⁇ 0.01 ).
  • the operational window is the area denoted with +.
  • Figure 8 illustrates the addition of water/steam (H 2 O), oxygen (O 2 ) or carbon dioxide (CO 2 ) starting from ash free (af) lignin in order to reach the operational window.
  • H 2 O water/steam
  • O 2 oxygen
  • CO 2 carbon dioxide
  • Figure 9 shows the results of the validation of the inventive method for conventional gasification.
  • the results for the composition of the synthesis gas product (raw synthesis gas after gasification) described in literature (x-axis “Experiment”) were compared with the results obtained via the non-stoichiometric equilibrium model for gasification (y-axis “Simulation”).
  • the amounts of CO ( ⁇ ), CO 2 ( ⁇ ), H 2 ( ⁇ ) and CH 4 ( ⁇ ) (given in vol.-% based on dry gases) in the raw synthesis gas are indicated.
  • Figure 10 shows the results of the validation of the inventive method for plasma gasification.
  • the results for the composition of the synthesis gas product (raw synthesis gas after gasification described in literature (x-axis “Experiment”) were compared with the results obtained via the non-stoichiometric equilibrium model for gasification (y-axis “Simulation”).
  • the amounts of CO ( ⁇ ), CO 2 ( ⁇ ), H 2 ( ⁇ ) and N 2 ( ⁇ ) (given in vol.-% based on dry gases) in the raw synthesis gas product are indicated.
  • Figure 11 shows a schematic flow chart of a preferred embodiment of the inventive gasification process, wherein the reference signs have the following meaning:
  • feedstock (11) comprising carbon- containing material
  • Solid removal e.g. particulate filter
  • Feedstock carbon material e.g. solid feed
  • FIG. 12 shows the O:C / H:C plot including compositions of suitable plastic solid waste (PSW) materials (points 1 to 5) and suitable feed stream compositions /operational compositions (points a to f).
  • PSW plastic solid waste
  • the O:C / H:C plot (also referred to as van Krevelen plot) in figure 2 shows the atomic ratio of hydrogen to carbon (H:C) versus the atomic ratio of oxygen to carbon (O:C).
  • Figure 13 illustrates the method for determining the feed stream compositions /operational composition of point (a) starting from the solid plastic waste materials 1 to 5 via the addition of carbon dioxide and/or steam as gasifying agent.
  • Figure 14 illustrates the method for determining the feed stream compositions /operational composition of point (e) starting from the solid plastic waste materials according to points 1 to 5 via the addition of carbon dioxide and/or steam as gasifying agent.
  • Example I Determining optimized process conditions for different feedstock materials a. General set-up of the method for determining optimized process conditions
  • the gasification agent was defined as being a oxygen, steam and/or carbon dioxide.
  • the defined minimization problem consisting of the objective function (22) with its variables n, and the constraints (26) to (28) was solved by using the Microsoft Excel Solver add-in.
  • n i the solver function estimated the equilibrium composition, which minimizes Gs within given constrains and at temperature T.
  • thermodynamic data for water, carbon monoxide and carbon dioxide as given in tables S1 and S2 were used in the equilibrium model.
  • the Gibbs free energy of formation for the elements was zero at all temperatures of interest.
  • the pressure for all data was 0.1 MP.
  • Tabell S2 Coefficients for fit of the thermodynamic data shown in table S1.
  • b Results of the method using non-stoichiometric equilibrium model for gasification of coal, lignin and cellulose
  • Figure 5a compares the obtainable molar amount of syngas for the three carbon- containing materials (feedstocks), i.e. coal, lignin, cellulose, and different amounts of oxygen added as gasification agent. For all feedstocks a maximum was observed, which shifted for the more functionalized feeds towards lower oxygen addition. This was caused by the different oxygen amount required to reach a stoichiometric O:C- ratio.
  • the plot (see Figure 5b)) of the molar amount of synthesis gas versus the oxygen to carbon ratio of the operational composition (feedstock plus the gasification agent) provided a better comparison. It was found that the maximum was always at an O:C- ratio of one while the resulting curves showed similar characteristics.
  • the process criteria were set as follows: molar amount of synthesis gas of at least 70 % (see borderlines in Figure 6a)), synthesis gas ratio from 1 to 2 (see borderlines in figure 6b)), and solid carbon content of equal or less than 1 % (see borderlines in figure 6c)).
  • Figure 7 which can be regarded as a combination of figures 6a)-6c), illustrates the determination of the operational window in the O:C / H:C plot based on the process criteria: molar amount of synthesis gas, synthesis gas ratio, and solid carbon content in synthesis gas.
  • the three target variables (process criteria), molar amount of synthesis gas, synthesis gas ratio, and solid carbon content are illustrated as lines in the O:C / H:C plot in dependency of the operational composition.
  • the operational window is denoted with +. It is revealed by requirements of a synthesis gas ratio greater than 1 , a molar amount of synthesis gas of at least 70 % (indicated with lines > 0.70 in Figure 7) and less than 1 % solid carbon.
  • Figure 8 illustrates the addition of water/steam (H 2 O), oxygen (O 2 ) or carbon dioxide (CO 2 ) starting from ash free (af) lignin in order to reach the operational window. It is shown that it is possible to shift an operational composition (lignin, af) into the operational window in order to meet the defined requirements.
  • the requirements reflected by the operational window are synthesis gas ratio greater than 1 , a molar amount of synthesis gas of at least 70 % and a solid carbon content lower than 1 %.
  • Lignin (af) is the moist, ash-free feedstock composition.
  • the arrows represent possible shifts by adding the labelled gasification agent.
  • a synthesis gas sum of at least 80 % and a carbon content of less than 1 % exclude a synthesis gas ratio of 2 and above as shown in Figure 7.
  • Example III Determination of process parameters The following PSW materials were used as feedstock composition in order to set the range of atomic ratio H:C and O:C:
  • feed stream compositions CH 2.0-4.0 O 1.0-1.7
  • Preferred combinations of feedstock compositions points 1 to 5 in figure 12
  • operational compositions points a to f in figure 12
  • O:C / H:C plots are commonly known and also referred to as van Krevelen plot (van Krevelen, D.W., 1957, Coal science: aspects of coal constitution, Elsevier Publishing Company, Amsterdam).
  • Example IV Plasma Gasification process
  • the process parameters as determined in example III and summarized in table S3 were used in plasma gasification process simulation (ASPEN One ® ) employing a non- stoichiometric equilibrium model, wherein the equilibrium composition was calculated by minimization of the total Gibbs free energy of the system Gs.
  • the gasification process was based on a process as described in flow chart of figure 11. The following exemplary conditions were used:
  • Carbon capture efficiency for (G1) is 98 %
  • table S7 It is shown in table S7 that the desired operational compositions (O:C and H:C ratios) were obtained for the combinations of table S3. The obtained operational compositions for all other combinations are summarized in table S7. The results for the preferred combinations according to table S3 are summarized in the following tables S4 and S5.
  • mol/mol(FS) means “mol/mol(feedstock)”.
  • Total CO 2 is the total molar amount (or molar flow) of CO 2 in the product stream obtained in the process after water-gas shift reaction in step d) given in mol/mol(feedstock) (mol/mol(FS)).
  • the carbon capture efficiency is 98 % for step f) employing gas scrubbing with an amine solvent, i.e. the molar amount of the exhaust gas obtained in the CO 2 separation step (step f) is 98 % of “total CO 2 ” (“total CO 2 ” times 0.98).
  • Molar flow CO is the molar flow of CO (given in mol/mol (feedstock)) in the synthesis gas product stream obtained in the process;
  • Molar flow C in feedstock is the molar amount of carbon in the added feedstock based on ultimate analysis (plastic solid waste compositions 1 to 5) (given in mol/mol(feedstock)).
  • brackets in formula (I) is only relevant for examples which requires the addition of external CO 2 (negative values for CE1 ).
  • CE1 (given in %) is the CO 2 emission per mole CO obtained in the synthesis gas with recycling of CO 2 (recycling of exhaust stream obtained in step f) at least partly into the gasification step a).
  • CE1 is given by the following formula (II):
  • Molar flow CO is the molar flow of CO (given in mol/mol (feedstock)) in the synthesis gas product stream obtained in the process.
  • Negative values for “CE1” in table S5 mean that it is necessary to add CO 2 from an external CO 2 source.
  • CE2 (given in %) is the CO 2 emission per mole CO obtained via the synthesis gas product without recycling of CO 2 .
  • CE2 is given by the following formula (III): with “Molar flow CO” is the molar flow of CO (given in mol/mol (feedstock)) in the synthesis gas product stream obtained in the process.
  • compositions of the gasification agent and recycling rates are summarized in table S6 for the examples with recycling of carbon dioxide (recycling of exhaust gas obtained in step f) at least partially into the gasifier in step a)).
  • Tabie S6 Composition of gasification agent and recycling rate
  • the CO 2 in the gasification agent is completely recycled CO 2 .
  • the recycling rate (given in %) is the internal recycling rate of the process defined as:
  • Table S7 shows the simulation results for all combinations 1-5 and a-f.
  • the amounts of CO 2 and H 2 O are given as mol/mol (Feedstock) [mol/mol(FS)].
  • Table S7 Parameters and results for process simulation.

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Abstract

L'invention concerne un procédé pour déterminer des conditions de traitement optimisées pour un processus de production de gaz de synthèse par gazéification par plasma d'un matériau contenant du carbone à l'aide d'un agent de gazéification, la composition de l'agent de gazéification étant déterminée en tant que condition de traitement sur la base des rapports atomiques O : C et H : C d'au moins une composition fonctionnelle, qui est un mélange du matériau contenant du carbone et de l'agent de gazéification, et en outre, l'invention concerne l'utilisation dudit procédé pour la commande de processus, la surveillance de processus, la commande de qualité et/ou l'ingénierie de processus d'un processus de production de gaz de synthèse par gazéification.
PCT/EP2021/054725 2020-03-13 2021-02-25 Procédé pour déterminer des conditions de traitement optimisées pour un processus de production de gaz de synthèse par gazéification WO2021180483A1 (fr)

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EP20162983.9A EP3878807A1 (fr) 2020-03-13 2020-03-13 Procédé de production de gaz de synthèse par gazéification allothermique à réduction de dioxyde de carbone contrôlée
EP20163007.6A EP3878927A1 (fr) 2020-03-13 2020-03-13 Procédé pour déterminer des conditions de processus optimales pour un processus de production de gaz de synthèse par gazéification

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