[go: up one dir, main page]

WO2024245821A1 - Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une charge riche en dioxyde de carbone - Google Patents

Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une charge riche en dioxyde de carbone Download PDF

Info

Publication number
WO2024245821A1
WO2024245821A1 PCT/EP2024/063954 EP2024063954W WO2024245821A1 WO 2024245821 A1 WO2024245821 A1 WO 2024245821A1 EP 2024063954 W EP2024063954 W EP 2024063954W WO 2024245821 A1 WO2024245821 A1 WO 2024245821A1
Authority
WO
WIPO (PCT)
Prior art keywords
synthesis
synthesis gas
methanol
gas stream
main
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/063954
Other languages
English (en)
Inventor
Luca Basini
Antonio Batistini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NextChem SpA
Original Assignee
NextChem Tech SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NextChem Tech SpA filed Critical NextChem Tech SpA
Publication of WO2024245821A1 publication Critical patent/WO2024245821A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/386—Catalytic partial combustion
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • 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
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process

Definitions

  • the present invention relates to a process for the production of fuels and chemicals from waste materials by utilizing carbon dioxide-rich feedstock.
  • the invention also relates to an apparatus for carrying out this process.
  • the CO2 concentration in the atmosphere has overcome, in 2016, the 400 ppm after having remained between 100 ppm and 300 ppm for thousands of years before, during and after the industrial revolution periods.
  • GHG greenhouse gases
  • CO2 is also a synthon but being a highly stable molecule, its transformations require a relevant energy input and/or complex biological cycles.
  • WO 2008130260 Al discloses a waste to liquid hydrocarbon refinery system designed to convert municipal and industrial wastes, biomass and other carbon containing feedstock into diesel, gasoline and other products.
  • the system involves a high temperature liquid iron bed that generates row syngas from solid and liquid feedstocks and a very high temperature plasma to convert contaminants in the row syngas into ions.
  • WO2022078915 Al discloses a process for producing synthesis gas from waste materials and/or biomass through the steps of: i) gasifying with an oxygen containing feed waste materials and/or biomass materials to produce a first raw synthesis gas stream, ii) passing the raw synthesis gas into a second reaction zone producing partial oxidation reactions, iii) decontaminate the obtained synthesis gas stream, iii) combine the obtained synthesis gas with an H2 flow obtained from a steam electrolysis utilizing renewable electric energy sources, iv) subjecting the obtained synthesis gas mixture to a conversion step that could be constituted preferentially by a Fischer-Tropsch (F-T) process, but also by other conversion processes such as NH3 synthesis or methanol synthesis.
  • F-T Fischer-Tropsch
  • US Pat. N° 6,455,011 B l discloses a method and apparatus for treating wastes into two-stage gasification which recovers metals or ash content in the wastes in such a state that they can be recycled and gases containing carbon monoxide (CO) and hydrogen gas (H2) for use as synthesis gas for ammonia (NH3) or the other chemicals production.
  • CO carbon monoxide
  • H2 hydrogen gas
  • CN103242134 discloses an invention related to household garbage treatment method, where the waste is subjected to a thermal cracking to form mixed combustible gases containing CO, CO2, H2, nitrogen (N2) and inert argon (Ar) by a full gasification process.
  • the syngas is purified and separated, and then are used for synthesizing methanol and/or dimethyl ether (DME), generating power and synthesizing urea.
  • DME dimethyl ether
  • US 2014/0364517 Al discloses a process and system for producing liquid and gas fuels and other useful chemicals from carbon containing source materials comprises cool plasma gasification and/or pyrolysis to produce syngas which in turn could be used for producing hydrocarbon, methanol, ammonia, urea and other products.
  • the system is carbon neutral but is relatively complex and expensive, requires relatively large amount of energy for the plasma gasification and has quite high cost for maintenance.
  • RDF refuse derived fuels
  • MSW waste converter technology
  • the described syngas purification comprises an acidic scrubbing, a basic scrubbing, a mist removal with a Wet Electrostatic Precipitator (WESP); while the syngas composition is adjusted for achieving a ratio (H2-CO2)/(CO+CO2) ca 2 v/v by employing a water gas shift step (WGS) described with equation [3] in the following of the document, and CO2 removal sections.
  • WESP Wet Electrostatic Precipitator
  • US 2013/0149767 Al describes a process for the conversion of carbon-based materials combining direct liquefaction via hydrotreating and indirect liquefaction via non-catalytic partial oxidation (POx), thereby producing syngas which is then converted into hydrocarbons via a Fischer-Tropsch (F-T) process.
  • POx non-catalytic partial oxidation
  • F-T Fischer-Tropsch
  • US 2010/294994 Al describes a process for the production of syngas by means of a reactor provided with four sections (I, II, III, IV, Fig. 2) in which the first and the second zones include: i) a device for the nebulization of a liquid hydrocarbon feedstock and ii) a nebulization and mixing chamber for providing a reactant mixture that is subsequently converted into synthesis gas in a reaction zone included in section III having a cylindrical shape and layered catalytic structures for converting the mixture of nebulized liquid hydrocarbons with the oxidant flow.
  • the state-of-the-art processes include at least two GHG and concentrated CO2 emission points that cannot be avoided.
  • An aspect of the present invention is a process to produce methanol and/or hydrocarbons from waste materials comprising the steps of: a) Oxidative gasification of said waste materials with production of a main synthesis gas stream; b) Cleaning of said main synthesis gas stream produced in said step a); c) Production of hydrogen and oxygen streams by electrolysis of steam or water; d) Addition of the hydrogen produced in said step c) to said main synthesis gas stream produced in said step a) to modify its composition to achieve: i) a ratio (H2-CO2/(CO+CO2) from 1.5 to 2.5 v/v, preferably from 1.7 to 2.3 v/v, more preferably from 1.8 to 2.2 v/v, useful for the methanol synthesis, thereby avoiding any CO2 separation from the main syngas stream; or ii) a ratio H2/CO from 1.5 to 2.5 v/v, preferably from 1.7 to 2.3 v/v, more preferably from
  • Another aspect of the invention is an apparatus for producing additional synthesis gas utilizing the recycle gases and/or the tail gases of the methanol synthesis and Fischer Tropsch process defined above and the oxygen produced from the electrolysers, comprising a short contact time catalytic partial oxidation reactor including a first portion having a cylindrical shape consisting of an inlet a mixing zone and a thermal shield zone, a second portion containing a catalytic bed having a truncated cone shape, and a third portion having a cylindrical shape with a diameter greater than the diameter of said first cylindrical portion, followed by a second thermal shield zone, wherein: a) in said second portion having the shape of a truncated cone the upper base is smaller than the bottom base; b) said upper base of said truncated cone is joined to said first cylindrical portion and said bottom base is joined to said third cylindrical portion; and c) the external angle (a) of said truncated cone at the upper base is lower than 85° and preferably lower than 75°.
  • waste materials designates any carbon containing waste of organic nature, including municipal waste, biomass, agricultural waste, animal waste, plastics.
  • SCT-CPO short contact time catalytic partial oxidation
  • electrolysis of steam or “steam electrolysis” means the High-temperature electrolysis; as known in the field.
  • associated gas designates a gas produced as a byproduct of the production of crude oil. Associated gas is generally regarded as an undesirable byproduct, which is either reinjected, flared, or vented.
  • off-gas designates a gas produced as a byproduct of a chemical process.
  • tail gas designates gases and vapors released into the atmosphere from an industrial process after all reactions and treatments have taken place.
  • the present disclosure concerns the conversion of waste materials into fuels and chemicals with process schemes and technologies allowing the avoidance of CO2 and the other GHG emissions.
  • a CO2 containing gas can also be integrated in the innovative process solutions for providing a pathway for CO2 utilization and its conversion in fuels and/or chemicals.
  • waste materials e.g., municipal wastes, refuse derived fuel, industrial or agricultural wastes
  • waste materials e.g., municipal wastes, refuse derived fuel, industrial or agricultural wastes
  • the Fischer-Tropsch (F-T) process for obtaining liquid hydrocarbons and/or olefins and the methanol synthesis require the initial conversion of wastes and of the CO2 rich streams into synthesis gas mixtures with different features.
  • the ratio (Fh-CCh CO+CCF) between the main components of the synthesis gas need to reach varies from 1.5 to 2.5 v/v, preferably from 1.7 to 2.3 v/v, more preferably from 1.8 to 2.2 v/v.
  • the H2/CO ratio inside the synthesis gas typically needs to be from 1.5 to 2.5 v/v, preferably from 1.7 to 2.3 v/v, more preferably from 1.8 to 2.2 v/v.
  • the amount of the other molecules inside the synthesis gas needs to be contained at low percentages (typically the CH4 content typically needs to be lower than 3% v/v in and the CO2 content must be minimized possibly at values below 5%).
  • AE Alkaline Electrolysis
  • PEME Polymer Electrolyte Membrane Electrolysis
  • SOEC Solid Oxide Electrolyte Cells
  • the process solutions according to the invention allow the utilization of the co-produced O2 stream associated to the H2 production with steam/water electrolysis either in the SCT-CPO and/or in the waste gasification units.
  • the SCT-CPO reactor is particularly advantageous for utilizing the recycle gases, tail gases and/or the purge gas streams of the methanol synthesis or of F-T synthesis loops since the high-temperature catalytic reactions produced with this technology, are extremely selective towards partial oxidation products.
  • recycle gases, tail gases and the purge gas compositions either of the F-T synthesis and of the methanol synthesis contain relevant amounts of unconverted H2 and CO molecules and relatively minor amounts of small gaseous hydrocarbons and CO2.
  • SCT-CPO reactors are particularly suitable for utilizing CO2 rich feedstock since the reactivity features are not limited by the carbon formation reactions affecting the steam- CO2 reforming reactors, the autothermal reactors, the non-catalytic partial oxidation reactions. It has been found that the presence of the CO2 in the SCT-CPO reactor has an inhibiting effect towards the parasitic gaseous phase radical reactions that, particularly at high pressure conditions, are the only reactions that could lead to unsaturated hydrocarbon molecules formation that could possibly evolve and decompose producing carbonaceous deposits.
  • the hydrocarbons content of the recycle loop and/or the purge gas produced either in the methanol synthesis or in the F-T synthesis can be drastically decreased through partial oxidation reactions producing a synthesis gas with high H2 and CO content; ii) the presence of CO2 in the reactant mixture strongly inhibits the propagation of the unselective radical reactions inside the reactant/product gaseous mixture progressing inside the SCT-CPO reactor; iii) the CO2 participates the heterogeneous chemistry inside the catalytic bed after that relevant amounts of hydrocarbons have been already transformed into partial oxidation products that are the main desired components of the synthesis gas; iv) the CO2 reacts inside SCT-CPO reactors with the produced H2 through an internal RWGS in the last section of the SCT-CPO reactor catalytic bed.
  • SCT-CPO short contact time catalytic partial oxidation
  • FIG. 1 Simplified state-of-the art process scheme described in EP 3,433,341 B l that describes a method for producing methanol from syngas originated from wastes gasification. The process determines two main CO2 and GHG emission points that cannot be avoided by recycling these gases into the syngas generation reactors.
  • Figure 2. Simplified block diagram process scheme in which the syngas production and cleaning from waste materials is utilized for High Temperature (HT) and Low Temperature (LT) F-T synthesis for originating a plurality of hydrocarbons.
  • HT High Temperature
  • LT Low Temperature
  • FIG. 3 Simplified block diagram process scheme describing a method for producing methanol from syngas originated from wastes gasification.
  • the process avoids the utilization of a WGS and of a CO2 removal unit by including a steam or water electrolyzer system that produces the H2 useful for the achievement of an appropriate (H2-CO2)/(CO+CO2) ratio in the synthesis gas and consequently avoids one major CO2 emission point.
  • the steam/water electrolysis unit also provide an 02 stream for the waste gasification step.
  • FIG. 4 Simplified block diagram process scheme describing a method for producing hydrocarbon fuels and chemicals from syngas originated from wastes gasification.
  • the process solution by including a steam electrolyzer unit that produces the H2 allows the achievement of an appropriate H2/CO ratio in the synthesis gas and avoids the utilization of a CO2 removal unit and consequently one major CO2 emission point.
  • the steam/water electrolysis unit also provide an O2 stream for the waste gasification step.
  • FIG. 5 Simplified block diagram process scheme describing a method for producing methanol from syngas originated from waste gasification.
  • the process avoids the utilization of a WGS and of a CO2 removal unit by including a steam electrolyzer system that produces the H2 useful for the achievement of an appropriate (H2-CO2)/(CO+CO2) ratio in the synthesis gas and consequently avoids one major CO2 emission point.
  • the steam/water electrolysis unit also provide an O2 stream for the waste gasification step.
  • the process solution includes an SCT-CPO reactor able to process the purge of recycle gas for producing additional synthesis gas thus avoiding the second major GHG emission point.
  • the SCT-CPO reactor can also receive NG or other CO2 rich hydrocarbon (HC) feedstock and in case steam, for boosting the syngas production with appropriate (H2-CO2)/(CO+CO2) ratios.
  • HC CO2 rich hydrocarbon
  • FIG. 6 Simplified block diagram process scheme describing a method for producing methanol from syngas originated from wastes gasification.
  • the process avoids the utilization of a WGS and of a CO2 removal unit by including a steam electrolyzer system that produces the H2 useful for the achievement of an appropriate H2/CO ratio in the synthesis gas and consequently avoids one major CO2 emission point.
  • the steam/water electrolysis unit also provide an O2 stream for the waste gasification step.
  • the process solution includes an SCT-CPO reactor able to process the purge of the F-T recycle gases for producing additional synthesis gas thus avoiding the second major GHG emission point.
  • the SCT-CPO reactor can also receive NG or other CO2 rich hydrocarbon (HC) feedstock and in case steam, for boosting the syngas production with appropriate H2/CO ratios.
  • HC CO2 rich hydrocarbon
  • Figures 1 and 2 show that the process schemes deriving from the known literature information when utilizing synthesis gas produced by urban, industrial, and agricultural wastes cannot avoid two main CO2 and GHG emission points either in the production of methanol and in the production of liquid fuels and chemicals.
  • the first CO2 emission point is determined by the necessity of removing some CO2 molecules from the partially shifted synthesis gas produced by the waste gasification and cleaning steps, to adjust the ratio (H2- CO2)/(CO+CO2) to values around 2 v/v.
  • the WGS step is not mandatory but also in this case a CO2 removal section is necessary to achieve the desired H2/CO v/v ratio (ca. 2 v/v).
  • the second GHG emission point is determined by the necessity of purging either the methanol synthesis recycle loop and the F-T synthesis recycle loop. These purges are necessary for avoiding the accumulation of molecules that are not active in these two chemical processes namely CH4 and other gaseous hydrocarbon molecules and an excess of CO 2 . Noteworthy, the purge operations are not selective towards these molecules and the purge streams also contain relevant amounts of H2 and CO.
  • the Figures 3 and 5 show how the steam electrolysis providing a stream of pure H2 and a stream of pure O2 avoids either: i) the necessity of introducing a WGS step for adjusting the (H2-CO2)/(CO+CO2) ratios and ii) the necessity of a CO2 removal section.
  • the addition of the hydrogen produced by electrolysis to the main synthesis gas stream produced by gasification of waste allow to modify its composition to achieve a ratio (H2-CO2/(CO+CO2) from 1.5 to 2.5 v/v, preferably from 1.7 to 2.3 v/v, more preferably from 1.8 to 2.2 v/v, thereby avoiding any CO2 separation from the main syngas stream.
  • Figure 5 also shows that the utilization of SCT-CPO allows the conversion of the purge gas into additional synthesis gas also utilizing the O2 stream produced by the steam electrolysis.
  • the production of synthesis gas with SCT-CPO can also utilize other gaseous hydrocarbon streams and in particular CO2 rich hydrocarbon stream.
  • the flexibility towards the feedstock composition and the operation conditions of this technology allows to produce a synthesis gas stream with an appropriate composition for contributing to the final syngas flow to be utilized in the methanol synthesis reactor.
  • the SCT-CPO reactor allows using the purge of recycle gas for producing additional synthesis gas, thus avoiding a major GHG emission point.
  • the SCT-CPO reactor can also receive NG or other CO2 rich hydrocarbon (HC) feedstock and in case steam, for boosting the syngas production with appropriate (H2-CO2)/(CO+CO2) ratios.
  • HC CO2 rich hydrocarbon
  • Figure 6 also shows that the utilization of SCT-CPO allows the conversion of the purge gas into additional synthesis gas also utilizing the O2 stream produced by the steam electrolysis. Noteworthy, also in this case, the production of synthesis gas with SCT-CPO can also utilize other gaseous hydrocarbon streams and in particular CO2 rich hydrocarbon stream. The flexibility towards the feedstock composition and the operation conditions of this technology allow to produce a synthesis gas stream with an appropriate composition for contributing to the final syngas flow to be utilized in the F-T synthesis reactor.
  • Figures 2, 4 and 6 also show that the proposed process scheme solution consider either the possibility of: a) operating in parallel low temperature and high temperature F-T processes for obtaining a plurality of hydrocarbon products, b) operating only low temperature F-T processes or high temperature F-T processes.
  • thermo-chemical properties of the reaction environment produced in short contact time conditions during the SCT-CPO in a heterogeneous catalytic fixed bed reactor fed with a premixed CH4, Steam, CO2 and O2 stream, can be discussed considering the system composed by the by equations [1-5]
  • the exothermic total oxidation reaction [1] has the highest probability to occur at the beginning of the bed, while the endothermic steam-CO2 reforming reactions [5] and [6] and the mildly endothermic (RWGS) reaction [4] would have the highest probability to occur in following zone.
  • reaction [4] is favored with respect to reaction [3] and also favored with respect to steam-CCh reforming [5] and [6].
  • the solid catalyst temperatures reach values higher than 1000 °C while the gas remains relatively cool by utilizing a reaction environment geometry that allows to reduce the contact time at the entrance of the catalytic bed to few milliseconds and that allows the expansion of the reaction volume when the temperature and the mole flow increases due to the progressing of the reaction.
  • This effect is obtained by adopting a truncated shape geometry of the catalytic bed and catalyst geometrical features that allow to reduce the pressure drop inside the reaction zone.
  • Figure 8 shows the main zones of the SCT-CPO reactor including a truncated cone reaction zone; these include:
  • the cylindrical first portion includes a mixing inlet zone and a first thermal shield pre-heating zone.
  • the central second portion includes a reaction zone
  • the cylindrical third portion includes a second thermal shield and a reactor exit zone.
  • the angle a shown in Figure 8 is clearly lower than 85° and preferentially comprised between 75° and 30°.
  • the ratios R1/R2 have to be comprised between 0.9 and 0.1 and preferentially between 0.8 and 0.4 and the shapes of the filling of the catalyst bed need to be defined for minimizing the pressure drop conditions by utilizing pelletized or monolith structures and their combinations.
  • thermo-chemical properties of the SCT environments performed after optimization of the reaction environment characteristics, are synthesized as follows: i) the temperature of the solid phase raises steeply at the beginning of the bed and the temperature profiles are smoothed through radiative and conduction mechanisms in the axial and radial directions; ii) temperature differences are originated between the gas and the solid phases; iii) local surface temperatures values result higher than the adiabatic temperatures; iv) gas temperatures are always lower than the adiabatic temperatures and gradually increase from the entrance to the exit of the bed.
  • the CO2 emissions are mainly related to the E.E. consumption required for: - compressing the feedstock (compression energy that would be required for any syngas production technology),
  • ASU Air Separation Unit
  • the described SCT-CPO reactor has unique features that allow: i) the utilization of CO2 rich feedstock and ii) the utilization of the F-T tail gases and of the other offgases produced in the separation and/or upgrading of the primary F-T products as well as iii) of the tail gas of the methanol synthesis loop.
  • These streams can be utilized for producing additional synthesis gas useful to the F-T synthesis as well as to the MeOH synthesis allowing the incorporation of CO2 molecules in the reaction products and the avoidance of GHG emissions associated to the purge-gas, tail-gas and the other off-gas streams associated the operation of the F-T and/or MeOH synthesis processes.
  • reactions [7] and [9-10] are the primary sources of carbon that can be divided into three typologies: i) whisker carbon, ii) gum (encapsulating carbon), and iii) pyrolytic carbon.
  • Gum formation and pyrolytic carbon are especially associated with the presence of hydrocarbons with more than two carbon atoms in the feedstock and can be avoided by removing these molecules with a pre-reformer unit upstream dry reforming.
  • whisker carbon can only be avoided by operating in condition having a low thermodynamic affinity towards this species which, once formed, brings to the catalyst pellet destruction and to the plant shut down due to the necessity of avoiding that the heat flow from the furnace not adsorbed by the endothermic reactions could lead to tubes overheating and fracturing.
  • the SCT-CPO reactor and process solutions here described overcome the drawbacks related to the occurrence of carbon formation reactions and allow, as already mentioned, the inclusion of the CO2 molecules and of the saturated and unsaturated hydrocarbon molecules of the tail gases, purge gases and off-gases produced in the F-T and MeOH synthesis.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un processus de production de combustibles et de produits chimiques à partir de déchets comprenant les étapes de : a) la gazéification par oxydation desdits déchets pour produire un gaz de synthèse ; b) le nettoyage dudit gaz de synthèse ; c) la production de flux d'hydrogène et d'oxygène par électrolyse de vapeur ou d'eau ; d) l'ajout de l'hydrogène produit dans ladite étape c) audit gaz de synthèse pour modifier sa composition pour obtenir un rapport souhaité (H2-CO2/(CO+CO2) ; e) l'utilisation dudit gaz de synthèse pour produire du méthanol avec la synthèse de méthanol et/ou des hydrocarbures avec la synthèse de Fischer-Tropsch.
PCT/EP2024/063954 2023-05-30 2024-05-21 Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une charge riche en dioxyde de carbone Pending WO2024245821A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/EP2023/064433 WO2024245542A1 (fr) 2023-05-30 2023-05-30 Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une matière première riche en dioxyde de carbone
EPPCT/EP2023/064433 2023-05-30

Publications (1)

Publication Number Publication Date
WO2024245821A1 true WO2024245821A1 (fr) 2024-12-05

Family

ID=86771294

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/EP2023/064433 Pending WO2024245542A1 (fr) 2023-05-30 2023-05-30 Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une matière première riche en dioxyde de carbone
PCT/EP2024/063954 Pending WO2024245821A1 (fr) 2023-05-30 2024-05-21 Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une charge riche en dioxyde de carbone

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/EP2023/064433 Pending WO2024245542A1 (fr) 2023-05-30 2023-05-30 Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une matière première riche en dioxyde de carbone

Country Status (1)

Country Link
WO (2) WO2024245542A1 (fr)

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0640559A1 (fr) 1993-08-27 1995-03-01 SNAMPROGETTI S.p.A. Procédé pour l'oxydation partielle de gaz naturel pour obtenir le gaz de synthèse et le formaldehyde
EP0725038A1 (fr) 1995-02-03 1996-08-07 SNAMPROGETTI S.p.A. Matériau de type hydrotalcite ayant une structure en couches et son utilisation
WO1997037929A1 (fr) 1996-04-11 1997-10-16 Snamprogetti S.P.A. Materiel destine a des reactions d'oxydation partielle
US6455011B1 (en) 1996-04-23 2002-09-24 Ebara Corporation Method and apparatus for treating wastes by gasification
WO2005023710A2 (fr) 2003-09-11 2005-03-17 Eni S.P.A. Procede d'oxydation partielle catalytique permettant d'obtenir un gaz de synthese
US20050211604A1 (en) 2002-05-24 2005-09-29 Snamprogetti S.P.A. Process for catalytic partial oxidation reactions
WO2006034868A1 (fr) 2004-09-30 2006-04-06 Eni S.P.A. Equipement permettant la pulverisation d'un flux de liquide au moyen d'un flux gazeux de dispersion et le melange du produit pulverise avec un flux gazeux adequat additionnel dans un dispositif d'oxydation catalytique partielle et procede connexe d'oxydation catalytique partielle
WO2007045457A1 (fr) 2005-10-21 2007-04-26 Eni S.P.A. Dispositif de mélange de fluide inséré dans ou combiné avec un réacteur
WO2008130260A1 (fr) 2007-04-18 2008-10-30 Sgc Energia Sgps, S.A. Système de raffinage déchets en hydrocarbure liquide
US20090127512A1 (en) 2007-11-21 2009-05-21 Eni S.P.A. Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses
WO2009065559A1 (fr) 2007-11-23 2009-05-28 Eni S.P.A. Procédé de production de gaz de synthèse et d'hydrogène à partir d'hydrocarbures liquides ou gazeux
WO2011072877A1 (fr) 2009-12-16 2011-06-23 Eni S.P.A. Procédé de production d'hydrogène à partir d'hydrocarbures liquides, gazeux et/ou de composés oxygénés également issus de biomasses
US20110160313A1 (en) 2009-12-31 2011-06-30 Conocophillips Company Recycling Methane-Rich Purge Gas to Gasifier
WO2011151082A1 (fr) 2010-06-03 2011-12-08 Eni S.P.A. Système catalytique pour traitements catalytiques d'oxydation partielle à courte durée de contact
US20130149767A1 (en) 2011-12-07 2013-06-13 IFP Energies Nouvelles Process for the conversion of carbon-based material by a hybrid route combining direct liquefaction and indirect liquefaction in the presence of hydrogen resulting from non-fossil resources
CN103242134A (zh) 2013-04-25 2013-08-14 深圳市炬能生物质气化科技有限公司 一种生活垃圾热解气化净化方法
US20140364517A1 (en) 2012-01-24 2014-12-11 Sge Scandgreen Energy Ab COMBINED PROCESSES FOR UTILIZING SYNTHESIS GAS with LOW CO2 EMISSION AND HIGH ENERGY OUTPUT
WO2016016253A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré de reformage par oxydation catalytique partielle/chauffé au gaz à temps de contact court pour la production de gaz de synthèse
WO2016016257A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré d'oxydation catalytique partielle à temps de contact court pour la production de gaz de synthèse
WO2016016251A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé de production sct-cpo/sr intégré pour la production de gaz de synthèse
WO2016016256A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré d'oxydation catalytique partielle à temps de contact court/reformage autotherme (sct-cpo/atr) pour la production de gaz de synthèse
EP3433341B1 (fr) 2017-01-17 2021-03-17 NextChem S.p.A. Procédé et appareil pour la fabrication de bio-methanol pur à partir de syngas issu de la gaséification de déchet
US20220119720A1 (en) * 2020-10-21 2022-04-21 Exxonmobil Research And Engineering Company Integrated biomass gasification and electrolysis
WO2022078915A1 (fr) 2020-10-14 2022-04-21 Velocys Technologies Ltd Procédé de gazéification

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0640559A1 (fr) 1993-08-27 1995-03-01 SNAMPROGETTI S.p.A. Procédé pour l'oxydation partielle de gaz naturel pour obtenir le gaz de synthèse et le formaldehyde
EP0725038A1 (fr) 1995-02-03 1996-08-07 SNAMPROGETTI S.p.A. Matériau de type hydrotalcite ayant une structure en couches et son utilisation
WO1997037929A1 (fr) 1996-04-11 1997-10-16 Snamprogetti S.P.A. Materiel destine a des reactions d'oxydation partielle
US6455011B1 (en) 1996-04-23 2002-09-24 Ebara Corporation Method and apparatus for treating wastes by gasification
US20050211604A1 (en) 2002-05-24 2005-09-29 Snamprogetti S.P.A. Process for catalytic partial oxidation reactions
WO2005023710A2 (fr) 2003-09-11 2005-03-17 Eni S.P.A. Procede d'oxydation partielle catalytique permettant d'obtenir un gaz de synthese
WO2006034868A1 (fr) 2004-09-30 2006-04-06 Eni S.P.A. Equipement permettant la pulverisation d'un flux de liquide au moyen d'un flux gazeux de dispersion et le melange du produit pulverise avec un flux gazeux adequat additionnel dans un dispositif d'oxydation catalytique partielle et procede connexe d'oxydation catalytique partielle
WO2007045457A1 (fr) 2005-10-21 2007-04-26 Eni S.P.A. Dispositif de mélange de fluide inséré dans ou combiné avec un réacteur
WO2008130260A1 (fr) 2007-04-18 2008-10-30 Sgc Energia Sgps, S.A. Système de raffinage déchets en hydrocarbure liquide
US20090127512A1 (en) 2007-11-21 2009-05-21 Eni S.P.A. Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses
WO2009065559A1 (fr) 2007-11-23 2009-05-28 Eni S.P.A. Procédé de production de gaz de synthèse et d'hydrogène à partir d'hydrocarbures liquides ou gazeux
US20100294994A1 (en) 2007-11-23 2010-11-25 Eni S.P.A. Process for the production of synthesis gas and hydrogen starting from liquid or gaseous hydrocarbons
WO2011072877A1 (fr) 2009-12-16 2011-06-23 Eni S.P.A. Procédé de production d'hydrogène à partir d'hydrocarbures liquides, gazeux et/ou de composés oxygénés également issus de biomasses
US20120301391A1 (en) * 2009-12-16 2012-11-29 Eni S.P.A. Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses
US20110160313A1 (en) 2009-12-31 2011-06-30 Conocophillips Company Recycling Methane-Rich Purge Gas to Gasifier
WO2011151082A1 (fr) 2010-06-03 2011-12-08 Eni S.P.A. Système catalytique pour traitements catalytiques d'oxydation partielle à courte durée de contact
US20130149767A1 (en) 2011-12-07 2013-06-13 IFP Energies Nouvelles Process for the conversion of carbon-based material by a hybrid route combining direct liquefaction and indirect liquefaction in the presence of hydrogen resulting from non-fossil resources
US20140364517A1 (en) 2012-01-24 2014-12-11 Sge Scandgreen Energy Ab COMBINED PROCESSES FOR UTILIZING SYNTHESIS GAS with LOW CO2 EMISSION AND HIGH ENERGY OUTPUT
CN103242134A (zh) 2013-04-25 2013-08-14 深圳市炬能生物质气化科技有限公司 一种生活垃圾热解气化净化方法
WO2016016253A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré de reformage par oxydation catalytique partielle/chauffé au gaz à temps de contact court pour la production de gaz de synthèse
WO2016016257A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré d'oxydation catalytique partielle à temps de contact court pour la production de gaz de synthèse
WO2016016251A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé de production sct-cpo/sr intégré pour la production de gaz de synthèse
WO2016016256A1 (fr) 2014-07-29 2016-02-04 Eni S.P.A. Procédé intégré d'oxydation catalytique partielle à temps de contact court/reformage autotherme (sct-cpo/atr) pour la production de gaz de synthèse
EP3433341B1 (fr) 2017-01-17 2021-03-17 NextChem S.p.A. Procédé et appareil pour la fabrication de bio-methanol pur à partir de syngas issu de la gaséification de déchet
WO2022078915A1 (fr) 2020-10-14 2022-04-21 Velocys Technologies Ltd Procédé de gazéification
US20220119720A1 (en) * 2020-10-21 2022-04-21 Exxonmobil Research And Engineering Company Integrated biomass gasification and electrolysis

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BASINI, L.: "Fuel rich catalytic combustion: Principles and technological developments in short contact time (SCT) catalytic processes", CATALYSIS TODAY, vol. 117, no. 4, 15 October 2006 (2006-10-15), pages 384 - 393, XP025116884, DOI: 10.1016/j.cattod.2006.06.043
BASINI, LUCA: "Issues in H and synthesis gas technologies for refinery, GTL and small and distributed industrial needs", CATALYSIS TODAY, vol. 106, no. 1-4, October 2005 (2005-10-01), pages 34
G. IAQUANIELLOE. ANTONETTIB. CUCCHIELLAE. PALOA. SALLADINIA. GUARINONIA. LAINATIL. BASINI, NATURAL GAS CATALYTIC PARTIAL OXIDATION: A WAY TO SYNGAS AND BULK CHEMICALS PRODUCTION | INTECHOPEN
L.E. BASINIA. GUARINONI: "Short Contact Time Catalytic Partial Oxidation (SCT-CPO) for Synthesis Gas Processes and Olefins Production", IND. ENG. CHEM. RES., vol. 52, 2013, pages 17023 - 17037, XP093124801, DOI: 10.1021/ie402463m

Also Published As

Publication number Publication date
WO2024245542A1 (fr) 2024-12-05

Similar Documents

Publication Publication Date Title
US9856426B2 (en) Combined processes for utilizing synthesis gas with low CO2 emission and high energy output
CA2770290C (fr) Procede de gazeification de materiaux qui contiennent du carbone, par decomposition thermique de methane et conversion de dioxyde de carbone
WO2009113982A1 (fr) Procédé et appareil pour la production d'hydrogène et de carbone par dissociation d'hydrocarbures catalysée par un aérosol de carbone
KR102026419B1 (ko) 이산화탄소 및 메탄 함유 매립지 가스 또는 바이오 가스로부터 합성가스 및 메탄올 제조 방법
EP4121390A1 (fr) Production d'hydrocarbures
CN102781818A (zh) 使用化石燃料来增加生物质基燃料效益
TWI872354B (zh) 捕捉的方法
WO2022038090A1 (fr) Combustible à base d'hydrogène à faible teneur en carbone
CA2330302A1 (fr) Procede et appareil de production de gaz de synthese
BR112014004278B1 (pt) Método para reforma do gás da gaseificação
Uchida et al. Hydrogen energy engineering applications and products
JP7715554B2 (ja) 合成燃料の製造方法
CN115667129B (zh) 涉及催化剂的用于将二氧化碳转化为一氧化碳的方法和反应器
WO2024245821A1 (fr) Processus de production de combustible et de produits chimiques à partir de déchets au moyen d'une charge riche en dioxyde de carbone
Chen et al. Plasma-assisted chemical-looping dry reforming of methane for hydrogen generation at room temperature
EP4471111A1 (fr) Procédé de production de composés hydrocarbonés synthétiques à l'aide d'une charge d'alimentation riche en dioxyde de carbone
JP7715555B2 (ja) 合成燃料の製造方法
Udemu et al. Steam Reforming Process for Conversion of Hydrocarbons to Hydrogen
WO2024245540A1 (fr) Procédé de production d'acides carboxyliques et de composés carbonyle à l'aide d'une charge riche en dioxyde de carbone
US20250115478A1 (en) Process and reactor design for the conversion of carbon dioxide to synthesis gas
JP2001026788A (ja) 合成ガスの製造方法及びその製造装置
US20240417626A1 (en) Fuel Generation System and Process
Udemu et al. 3 Steam Reforming
GB2637133A (en) Process
KR20250112236A (ko) H2와 co2를 함유하는 오프가스의 합성연료로의 전환

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24730896

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)