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WO2025073661A1 - Procédé de préparation de méthanol à partir d'hydrogène pyrolytique - Google Patents

Procédé de préparation de méthanol à partir d'hydrogène pyrolytique Download PDF

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Publication number
WO2025073661A1
WO2025073661A1 PCT/EP2024/077540 EP2024077540W WO2025073661A1 WO 2025073661 A1 WO2025073661 A1 WO 2025073661A1 EP 2024077540 W EP2024077540 W EP 2024077540W WO 2025073661 A1 WO2025073661 A1 WO 2025073661A1
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methanol
gas
carbon
hydrogen
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Inventor
Frederik SCHEIFF
Maximilian Vicari
David SCHLERETH
Johannes BODE
Laila Raquel PASIN E MATOS
Grigorios Kolios
Daniela Rieck
Jens Peter JOHANNSEN
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BASF SE
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BASF SE
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    • 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
    • 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
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/28—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using moving solid particles
    • 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
    • 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
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/085—Methods of heating the process for making hydrogen or synthesis gas by electric heating

Definitions

  • the hydrogen feedstock may in principle come from a wide variety of different sources. Examples include the supply of hydrogen from other production plants in which hydrogen is formed as a by-product, for example from steamcrackers or refineries, from the processing of synthesis gas, from the cracking of hydrocarbons or from the electrolysis of water.
  • WO 2013/4391 and WO 2014/95661 describe a process for producing synthesis gas by reacting natural gas, blast furnace gases, associated gases and/or biogases/biomethane and carbon dioxide in a reaction chamber in a bed of carbon-containing solids to give a gaseous product stream containing hydrogen and carbon monoxide, wherein said bed is guided through the reaction chamber as a moving bed.
  • synthesis gas can be used as a feedstock for methanol production. No details are given to any purification step of the natural or pyrolytic hydrogen.
  • stage (a) a feed stream (I) containing light hydrocarbons and optionally carbon oxides and sulfur compounds is fed into a methane pyrolysis unit and pyrolyzed and hydrogenated into (ai) a crude pyrolytic gaseous product stream (III) containing hydrogen, residual methane and optionally carbon oxides and hydrogen sulfide and into (aii) solid carbon (IV).
  • the feed stream (I) containing light hydrocarbons, preferably gaseous C2-C4 alkanes, even more preferably methane, is preferably natural gas, associated gas, industry off-gas and/or biogas/biomethane.
  • Such feed streams typically comprise light hydrocarbons like methane, ethane, ethylene, propane, propylene and butane, carbon monoxide and carbon dioxide, inert gases like nitrogen, and sulfur components.
  • additional carbon oxides (II) might be needed for the methanol synthesis.
  • the amount of carbon oxides (II) to be fed is found from the mass balance of the streams supplied to and removed from the methanol synthesis unit (C).
  • the additional carbon oxides stream (II) can preferably be mixed with the feed stream (I) and/or fed into the methane pyrolysis unit (A) separately.
  • the use of carbon dioxide plus hydrogen instead of synthesis gas has the benefit that carbon dioxide is often easily available as a by-product or waste. Carbon dioxide may, for example, easily come from sources such as fossil based power plants, steal processes, cement industry, chemical production complexes or direct air capture. Using carbon dioxide as carbon source, this methanol process can become CO2-neutral or even CO2-negative while using biogas/biomethane as feedstock.
  • the solid carbon type generated in the methane pyrolysis depends on the reaction conditions, reactor and heating technology. Examples are
  • the pyrolysis processes using molten metals or molten metal salts use the heat from the melt for pyrolysis.
  • metals can be selected that have a catalytic effect, so that pyrolysis can take place at relatively low temperatures of approx. 800 - 1200 °C.
  • the ethane rich natural gas or ethane rich off-gas is fed into the molten metal; the bubbles formed in the process rise upwards in the reactor, whereby the hydrocarbons decompose and form mainly methane, hydrogen and solid carbon.
  • Catalysts can also be used to reduce the high reaction temperatures (see for example WC2011029144, WC2016154666).
  • a very cost-effective alternative is the use of iron oxide catalysts. Reaction temperatures of approx. 700 to 1000°C can be realized.
  • the reactions take place, for example, in the fluidized bed, with the catalyst as the fluidized material.
  • the hydrocarbon is decomposed at the catalytic surface.
  • the pyrolysis process is preferably heated electrically, even more preferably by resistive heating (Joule heating) of the substrate material as described for example in US 2982622, WO 2019/145279 and WO 2020/200522.
  • the reaction chamber is preferably rationally designed as a vertical reactor, which means that the movement of the moving bed is gravity driven. Flow through the moving bed is taking place, advantageously, homogeneously, and uniformly (see for example WO 2013/004398, WO 2019/145279 and WO 2020/200522).
  • Methane and/or other light hydrocarbons are preferably introduced via the bottom of the reactor, preferably having a temperature of 10 to 200°C.
  • the substrate is preferably introduced via the top of the reactor, preferably having a temperature of 10 to 200°C.
  • Hydrogen is preferably taken off via the top of the reactor, preferably having a temperature of 10 to 200°C.
  • the granular pyrolytic carbon produced preferably deposited on solid substrates and withdrawn with the substrates via the bottom of the reactor, preferably having a temperature of 10 to 200°C.
  • the flow velocity of the substrate is advantageously in the range of 0.005 to 0.5 cm/s.
  • the flow velocity of the gas flow is advantageously in the range of 0.025 to 2 m/s.
  • the gas residence time in the reactor is advantageously between 0.5 and 50 s, preferably between 1 and 20 s.
  • the residence time of the substrate is preferably between 0.5 and 15 hours, preferably between 1 and 10 hours and more preferably between 2 and 8 hours.
  • the substrates are carbonaceous materials that are macro-structured carbonaceous materials, wherein the porosity of the carbonaceous material is in the range of 30 to 70 vol.-% and the carbonaceous material contains of a carbon content of 98 wt.-% to 100 wt.-%, preferably 99 wt.-% to 100 wt.-%, even more preferably 99.5 wt.-% to 100 wt.-% and a content of alkaline-earth metals, transition metals and metalloids of 0 and 2 wt.-%, preferably 0 to 1 wt.-%, even more preferably 0 to 0.5 wt.-%, in relation to the total mass of solid carbonaceous material (see WO 2023/057242).
  • the BET surface area of the substrate is preferably between 0.1 and 100 m2/g, preferably 0.1 and 50 m2/g, in particular 0.1 to 30 m2/g.
  • the real density of the substrate is in the range of 1 .5 to 2.5 g/cc (real density in xylene, ISO 8004).
  • the bulk density of the substrate is in the range of 0.5 to 1 .5 g/cc.
  • the real density of the granular pyrolytic carbon (IV) produced via the described methane pyrolysis process of stage (a) two is in the range of 1 .5 to 2.5 g/cc, preferably 2.0 to 2.3 g/cc (real density in xylene, ISO 8004).
  • the bulk density of the granular pyrolytic carbon (IV) is in the range of 0.5 to 1 .5 g/cc, more preferably 0.7 to 1 .3 g/cc.
  • the ash content of the granular pyrolytic carbon (IV) composition is in the range of 0.001 to 1 weight-% of the composition, preferably 0.01 to 0.2 weight-%.
  • 95 weight-% of the carbon of the granular pyrolytic carbon (IV) is not-functionalized, preferably 98 weight- %, wherein carbon functionalization refers to a reaction in which a carbon-carbon bond is broken and replaced by a carbon-X bond (where X is usually hydrogen, oxygen, sulfur, phosphorus, nitrogen, halogens, and/or metals).
  • the cation exchange capacity (CEC) of granular pyrolytic carbon (IV) is about 0.01 to 1 .5 cmol/kg, preferably 0.025 to 0.75 cmol/kg.
  • the particle size of the granular pyrolytic carbon (IV) directly resulting of the pyrolysis of gaseous hydrocarbons - without any agglomeration step - is in the range of 0.3 mm (d10) to 8 mm (d90), preferably 0.5 mm (d10) to 5 mm (d90), more preferably 1 mm (d10) to 4 mm (d90).
  • the porosity of the granular pyrolytic carbon (IV) is between 0% to 15%, preferably 0.2% to 10%, most preferably 0.2% to 5% (Hg porosimetry, DIN66133).
  • the specific surface area of the granular pyrolytic carbon (IV) measured by Hg porosimetry is in the range of 0.001 to 10 m2/g, preferably 0.001 to 5 m2/g, even more preferably 0.05 to 2 m2/g.
  • the crude methanol water mixture is depressurized form methanol synthesis loop pressure down to lower 10 bar(abs.) and fractionated to off-gas stream (XI), pure methanol stream (IX) and water and high boilers stream (X).
  • the catalyst is cooled by boiling water with a temperature of 212°C for making methanol from H2, CO and CO2 and 240°C for making methanol from H2, and mainly CO2.
  • the reactor inlet pressure is 73 bar(abs.).
  • the concentration of inert components at the methanol synthesis reactor is 30 vol-% for all inventive examples using crude H2.
  • the concentration of inert components at the methanol synthesis reactor is ⁇ 2.0 vol-%.
  • the inert components are N2, CH4 and C2H6.
  • the gas hourly space velocity (GHSV Nm 3 /(m 3 K at*h)) is kept constant with 6127 1/h.
  • the stoichiometric constant Ks for all examples is 3.4 .
  • the H2 yield of the H2 recovery section is in all examples 83%.
  • the CH4 slip through the H2 recovery section is a 0.1 %.
  • the methanol synthesis is operated with the reactive components mixture of H2, CO and CO 2 .
  • the crude H2 (stream III) is desulfurized at a Cu/ZnO catalytic absorber.
  • the H2S builds very stable NiS, hence the sulfur concentration after the Cu/ZnO catalytic absorber is lower than 0.1 vol. ppm.
  • Such a low sulfur content in the synthesis-gas is beneficial for the activity and lifetime of the methanol synthesis catalyst.
  • To prepare an appropriate make-up gas (stream VI) for the methanol synthesis the desulfurized crude H2 and the H2 from H2 recovery unit are mixed. This mixture is enriched in CO2 and CO for a CO2 concentration of 3.5 vol.-% and a CO concentration of 26.7 vol.-%.
  • the required stoichiometric constant Ks of the make-up gas stream (VI) is 2.050 to ensure a Ks of 3.4 before the methanol synthesis reactor.
  • the 233 Nm 3 /tMeOH purge-gas stream (XII) with a H2 content of 50.5 vol.% is withdrawn from the methanol synthesis loop and fed to the H2 recovery section. From this stream 97 Nm 3 /t Me oH nearly pure H2 with a H2 content of 99.9 vol.-% is recovered and sent back to the inlet of the methanol synthesis loop to the make-up gas stream.
  • the off-gas of the H2 recovery section together with the off-gases of the methanol purification section are sent to thermal used by combustion.
  • the carbon yield is 87.1% and the crude bfe-demand is 1595 Nm 3 /t Me oH.
  • the CO2 emissions are 0.200 tco2 1 IMSOH.
  • the carbon yield is the ratio of all carbon fed to the process, including inert components like CH4, and C2H4 and the carbon in the valued product methanol.
  • the methanol synthesis is operated with the reactive components mixture of H2, CO and CO2 but without CO2 emission.
  • the crude H2 (stream III) is desulfurized at a Cu/ZnO catalytic absorber.
  • the H2S builds very stable NIS, hence the sulfur concentration after the Cu/ZnO catalytic absorber is lower than 0.1 vol. ppm.
  • Such a low sulfur content in the synthesis-gas is beneficial for the activity and lifetime of the methanol synthesis catalyst.
  • To prepare an appropriate make-up gas (stream VI) for the methanol synthesis the desulfurized crude H2 and the H2 from H2 recovery unit are mixed. This mixture is enriched in CO for a CO concentration of 25.6 vol.-%.
  • the CO2 generated by the OxyFuel combustion and CO2 recovery section is quantitatively reused for the methanol synthesis.
  • the CO2 content in the make-up gas stream (VI) is 4.4 vol.-% and marginally higher than in the 1 st inventive example with 3.5 vol.-%.
  • the required stoichiometric constant Ks of the make-up gas stream (VI) is 2.047 to ensure a Ks of 3.4 before the methanol synthesis reactor.
  • the 242 Nm 3 /tMeOH purge-gas stream (XII) with a H2 content of 50.9 vol.% is withdrawn from the methanol synthesis loop and fed to the H2 recovery section. From this stream 102 Nm 3 /tMeOH nearly pure H2 with a H2 content of 99.9 vol.-% is recovered and sent back to the inlet of the methanol synthesis loop to the make-up gas stream.
  • the off-gas of the H2 recovery section together with the off-gases of the methanol purification section are sent to the OxyFuel combustion section.
  • the carbon yield (table 3) is 100% and the crude Fh-demand is 1617 Nm 3 /tMeOH. This slightly higher than in the 1 st inventive example with 1595 Nm 3 /tMeOH caused by the slightly higher CO2 content in the make-up gas.
  • the carbon containing components in the make-up gas like CH4 and C2H6, are converted to methanol too.
  • the methanol synthesis is operated with the reactive components mixture of H2 and CO2 only, no additional CO is added to the make-up gas (stream VI).
  • the crude H2 (stream III) is desulfurized at a Cu/ZnO catalytic absorber.
  • the H2S builds very stable NIS, hence the sulfur concentration after the Cu/ZnO catalytic absorber is lower than 0.1 vol. ppm.
  • Such a low sulfur content in the synthesis-gas is beneficial for the activity and lifetime of the methanol synthesis catalyst.
  • To prepare an appropriate make-up gas (stream VI) for the methanol synthesis the desulfurized crude H2 and the H2 from H2 recovery unit are mixed.
  • This mixture is enriched in CO2 for a CO2 concentration of 22.8 vol.-%.
  • the required stoichiometric constant Ks of the make-up gas stream (VI) is 2.145 to ensure a Ks of 3.4 before the methanol synthesis reactor.
  • the 430 Nm 3 /tMeOH purge-gas stream (XII) with a H2 content of 56.7 vol.% is withdrawn from the methanol synthesis loop and fed to the H2 recovery section. From this stream 202 Nm eOH nearly pure H2 with a H2 content of 99.9 vol.-% is recovered and sent back to the inlet of the methanol synthesis loop to the make-up gas stream.
  • the off-gas of the H2 recovery section together with the off-gases of the methanol purification section are sent to thermal used by combustion.
  • the carbon yield is 82.0 % and the crude Hfe-demand is 2301 Nm 3 /t Me oH.
  • the CO2 emissions are 0.297 t C o2 1 t Me oH. 4 th Example (inventive)
  • the crude H2 (stream III) is desulfurized at a Cu/ZnO catalytic absorber.
  • the H2S builds very stable NiS, hence the sulfur concentration after the Cu/ZnO catalytic absorber is lower than 0.1 vol. ppm.
  • Such a low sulfur content in the synthesis-gas is beneficial for the activity and lifetime of the methanol synthesis catalyst.
  • an appropriate make-up gas (stream VI) for the methanol synthesis the desulfurized crude H2 and the H2 from H2 recovery unit are mixed.
  • This mixture is enriched in CO2 with external CO2 and CO2 generated by the OxyFuel combustion and CO2 recovery section.
  • This CO2 stream is quantitatively reused for the methanol synthesis.
  • the required stoichiometric constant Ks of the make-up gas stream (VI) is 2.145 to ensure a Ks of 3.4 before the methanol synthesis reactor.
  • the 430 Nm 3 /tMeOH purge-gas stream (XII) with a H2 content of 56.7 vol.% is withdrawn from the methanol synthesis loop and fed to the H2 recovery section. From this stream 202 Nm 3 /tMeOH nearly pure H2 with a H2 content of 99.9 vol.-% is recovered and sent back to the inlet of the methanol synthesis loop to the make-up gas stream.
  • the off-gas (XIII) of the H2 recovery section (F) together with the off-gases (XI) of the methanol purification section (E) are sent to the OxyFuel combustion section. From the flue-gas of the OxyFuel combustion section the 151 Nm 3 /tMeOH CO2 is recovered and sent back to the methanol synthesis loop and mixed in the in the make-up gas stream VI.
  • the crude F -demand is 2301 Nm 3 /tMeOH.
  • the F -demand is equal to the inventive example 3, because the recycled CO2 from OxyFuel combustion section and CO2 recovery section substitutes fresh CO2 and the carbon yield at this inventive example 4 (table 4) is 100%.
  • the CO2 emissions are 0.0 tco2 1 IMSOH.
  • Table 9 In the comparative example 1 the methanol synthesis is operated with the reactive components mixture of H2, CO and CO2 .
  • the separation of the inert components from the crude H2 (F) is located before the methanol unit (C).
  • the methanol synthesis loop operates nearly without inert components like N2, CH4 and C2H6 and needs no or a minimum purge gas stream (XII).
  • the natural gas is upfront desulfurized at a Cu/ZnO catalytic absorber.
  • the H2S builds very stable NIS, hence the sulfur concentration after the Cu/ZnO catalytic absorber is lower than 0.1 vol. ppm.
  • Such a low sulfur content in the synthesis-gas is beneficial for the activity and lifetime of the methanol synthesis catalyst.
  • the desulfurized natural gas (la) is fed into a methane pyrolysis unit (A) and pyrolyzed into a crude H2 stream (III') and solid carbon (IV).
  • the crude H2 (stream III') is purified from the inert components like N2, CH4 and C2H6. Then the H2 concentration is 99.9 vol.-% like the H2 coming the H2 recovery section in inventive examples 1 - 4.
  • stream VI an appropriate make-up gas for the methanol synthesis
  • the desulfurized purified H2 stream is enriched in CO2 and CO for a CO2 concentration of 3.5 vol.-% and the CO concentration of 29.3 vol.-%.
  • the off-gas (XIII) of the frontend H2 recovery section (F) together with the off-gases (XI) of the methanol purification section (E) are sent to thermal used by combustion.
  • the carbon yield is 86,6% and the crude F -demand is 1896 Nm 3 /tMeOH.
  • the CO2 emissions are 0.208 tco2 1 IMSOH.
  • the crude H2 demand of this comparative example 1 is 19% higher than in the inventive example 1 with 1595 Nm 3 /t Me oH.
  • the whole H2 stream to the methanol synthesis loop is purified (1898 Nm 3 /tMeOH with 93.0 vol.-% H2) and in the inventive example 1 only the H2 from the purge gas stream (233 Nm 3 /tMeOH with 50.5 vol.-% H2) has to be recovered.
  • the methanol synthesis is operated with the reactive components mixture of H2 and CO2 only, no additional CO is added to the make-up gas (stream VI)
  • the separation of the inert components from the crude H2 is located before the before the methanol unit (C).
  • the methanol synthesis loop operates nearly without inert components like N2, CH4 and C2H6 and needs no or a minimum purge gas stream (XII).
  • the natural gas is upfront desulfurized at a Cu/ZnO catalytic absorber.
  • the H2S builds very stable NiS, hence the sulfur concentration after the Cu/ZnO catalyt- ic absorber is lower than 0.1 vol. ppm.
  • Such a low sulfur content in the synthesis-gas is beneficial for the activity and lifetime of the methanol synthesis catalyst.
  • the desulfurized natural gas (la) is fed into a methane pyrolysis unit (A) and pyrolyzed into a crude H2 stream (III') and solid carbon (IV).
  • the crude H2 (stream III') is purified from the inert components like N2, CH4 and C2H6. Then the H2 concentration is 99.9 vol.-% like the H2 coming the H2 recovery section in inventive examples 1 - 4.
  • the required stoichiometric constant Ks of the make-up gas stream (VI) is 1 .949 to ensure a Ks of 3.4 before the methanol synthesis reactor.
  • the off-gas (XIII) of the frontend H2 recovery section (F) together with the off-gases (XI) of the methanol purification section (E) are sent to thermal used by combustion.
  • the carbon yield is 82.6% and the crude F -demand is 2721 Nm 3 /t Me oH.
  • the CO2 emissions are 0.284 t C o2 1 t Me oH.
  • the crude H2 demand of this comparative example 2 is 18% higher than in the inventive example 3 with 2301 Nm 3 /tMeOH.
  • the whole H2 stream to the methanol synthesis loop is purified (2721 Nm 3 /tMeOH with 93.0 vol.-% H2) and in the inventive example 3 only the H2 from the purge gas stream (430 Nm 3 /tMeOH with 56.7 vol.-% H2) has to be recovered.

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Abstract

La présente invention concerne un procédé de préparation de méthanol par (a) pyrolyse et hydrogénation d'un flux d'alimentation (I) contenant des hydrocarbures légers et éventuellement des oxydes de carbone et des composés soufrés en (al) un flux de produit gazeux pyrolytique brut (III) contenant de l'hydrogène, du méthane résiduel, et éventuellement des oxydes de carbone et du sulfure d'hydrogène et en (ail) du carbone solide (IV) ; (b) séparation de carbone solide (IV) du flux de produit gazeux pyrolytique brut (III) ; (c) séparation éventuelle de sulfure d'hydrogène du flux de produit gazeux pyrolytique brut (III) conduisant à (ci) un flux de produit gazeux pyrolytique de départ (VI) contenant de l'hydrogène, du méthane résiduel et éventuellement des oxydes de carbone et (cii) éventuellement du soufre adsorbé (V) ; (d) conversion dudit flux de produit gazeux pyrolytique brut ou de départ (III) ou (VI) avec des oxydes de carbone (II) en méthanol brut (VII) ; (e) séparation du flux de gaz non condensé, gaz de purge (XII) dudit méthanol brut (VII), un flux de méthanol (VIII) étant obtenu ; (f) purification dudit flux de méthanol (VIII) ; (g) séparation d'hydrogène (XIV) dudit gaz de purge (XII) ; (h) recyclage dudit hydrogène (XIV) vers l'unité de synthèse de méthanol de l'étape (d).
PCT/EP2024/077540 2023-10-06 2024-10-01 Procédé de préparation de méthanol à partir d'hydrogène pyrolytique Pending WO2025073661A1 (fr)

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