WO2024022800A1 - Amélioration de procédé dans des procédés de conversion d'energie en un autre vecteur energetique (power-to-x (ptx)) - Google Patents

Amélioration de procédé dans des procédés de conversion d'energie en un autre vecteur energetique (power-to-x (ptx)) Download PDF

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Publication number
WO2024022800A1
WO2024022800A1 PCT/EP2023/069145 EP2023069145W WO2024022800A1 WO 2024022800 A1 WO2024022800 A1 WO 2024022800A1 EP 2023069145 W EP2023069145 W EP 2023069145W WO 2024022800 A1 WO2024022800 A1 WO 2024022800A1
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WO
WIPO (PCT)
Prior art keywords
membrane
gas
gas stream
regular
biogas
Prior art date
Application number
PCT/EP2023/069145
Other languages
English (en)
Inventor
Tilman J. Schildhauer
Original Assignee
Paul Scherrer Institut
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
Priority claimed from EP22187488.6A external-priority patent/EP4311852A1/fr
Application filed by Paul Scherrer Institut filed Critical Paul Scherrer Institut
Publication of WO2024022800A1 publication Critical patent/WO2024022800A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/225—Multiple stage diffusion
    • B01D53/226—Multiple stage diffusion in serial connexion
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/10—Recycling of a stream within the process or apparatus to reuse elsewhere therein
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/26—Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/46—Compressors or pumps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/548—Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel

Definitions

  • the present invention is related to a method and a system for the optimization of the part load capabilities of a biogas based PtX (power-to-X) conversion.
  • Biogas based PtX conversion processes are widely used. These processes will form part in the replacement of fossil fuel for the energy and/or heat generation.
  • hydrocarbons e.g. methane, methanol, Diesel, kerosene
  • an appropriate part load of the biogas with hydrogen is desired.
  • the objective of the present invention is to provide a method and a system for the optimization of the part load capabilities of a biogas based PtX conversion that offer a better capability of using hydrogen that is generated or has not been consumed in the hydrocarbon synthesis process (e.g. methanation) for further process steps, such as a recycling into the synthesis process.
  • a biogas based PtX conversion that offer a better capability of using hydrogen that is generated or has not been consumed in the hydrocarbon synthesis process (e.g. methanation) for further process steps, such as a recycling into the synthesis process.
  • a method for the optimization of the part load capabilities of a biogas based PtX conversion comprising the steps of: a) converting the CO2 fraction of the biogas at least partially with hydrogen in a hydrocarbon synthesis reactor, into a CH4-rich product gas stream, preferably using a condensation unit to separate a fluid comprising water and/or condensable hydrocarbons, such as methanol, gas oil or kerosene, from the CH4 enrichted product gas stream; b) treating the CH4-enriched product gas stream by using a regular membrane upgrading unit that at least comprises a main membrane separating C02 from methane to yield injectable CH4 enriched gas and a C02 cleaning membrane recovering permeated methane downstream of the main membrane from C02 ; and c) leading the CH4-enriched product gas stream over a polymeric gas separation membrane thereby positioning the polymeric gas separation membrane in addition to the regular membrane upgrading unit downstream of the hydrocarbon synthesis reactor and upstream of the regular membrane upgrading unit.
  • a system for the optimization of the part load capabilities of a biogas based PtX conversion comprising : a) a hydrocarbon synthesis reactor, enabled to convert a gas feed, such as the biogas (3) , into a CH4-rich product gas stream, and preferably a condensation unit to separate a fluid comprising water and/or condensable hydrocarbons, such as methanol, gas oil or kerosene, from the CH4-enriched product gas stream; b) a regular membrane upgrading unit enabled to treat the CH4-enriched product gas stream wherein the regular membrane upgrading unit at least comprises a main membrane being enabled to separate C02 from methane to yield injectable CH4 enriched gas and a C02 cleaning membrane being enabled to recover permeated methane downstream of the main membrane from C02 ; and c) a polymeric gas separation membrane being enabled to treat the CH4-enriched product gas stream wherein the polymeric gas separation membrane is in addition to the regular membrane upgrading unit and is positioned downstream of the fluid
  • the method and the system allow to increase the recycle rate of hydrogen in the process and therefore reduce its loss through the off gas stream.
  • the present invention also allows to decrease the slip of the generated hydrocarbon through the same path and reduce the energy loss through the off gas stream.
  • the permeate side of the polymeric gas separation membrane can be flushed with a retentate gas stream of the CO2 cleaning membrane; ii) the permeate side of the polymeric gas separation membrane can be flushed with raw feed gas, e.g. biogas; iii) a gas feed can be to the hydrocarbon synthesis reactor comprising hydrogen, carbon oxides (CO and/or CO2 ) and methane, stemming e.g. from a gasification or a pyrolysis step; and/or.
  • raw feed gas e.g. biogas
  • a gas feed can be to the hydrocarbon synthesis reactor comprising hydrogen, carbon oxides (CO and/or CO2 ) and methane, stemming e.g. from a gasification or a pyrolysis step; and/or.
  • a gas feed preferably stemming from a direct gasification or a pyrolysis step with air as oxidation mean, can hydrogen, carbon oxides (CO and/or CO2 ) and nitrogen, wherein the nitrogen content can be extracted as retentate of the regular membrane upgrading unit.
  • the figure shows the introduction of a polymeric gas separation membrane 4 in addition to a regular membrane upgrading unit 6 that usually comprises a main membrane 8 (that separates C02 from the hydrocarbon, such as methane, to yield injectable gas for a gas grid 14) and a C02 cleaning membrane 10 (that recovers permeated hydrocarbons from the CO2 before it is vented with the off gas stream 12) .
  • the off gas can also be used for sequestration, this way allowing for negative CO2 emissions.
  • the present invention allows thus to increase the recycle rate of hydrogen in the process at an early stage and therefore reduce its loss through an off gas stream 12. At the same time, the present invention also allows to decrease the slip of the generated hydrocarbons, such as CH4, through the same path and reduce the energy loss due to recompression .
  • the polymeric gas separation membrane 4 - also called hereinafter sweep membrane - can be applied in a raw product gas stream 16 coming from the hydrocarbon synthesis reactor 18 optionally followed by a condensation unit 19 to separate a fluid 21 comprising water and/or condensable hydrocarbons, such as methanol, Diesel or kerosene, and being disposed upstream of the regular membrane upgrading unit 6, optionally also mixed with unreacted raw gas (due to the part load) .
  • the polymeric gas separation membrane 4 separates at least a part of the hydrogen already before the raw product gas stream 16 enters the regular membrane upgrading system 6.
  • the hydrocarbon synthesis reactor can be for example a methanation reactor in fix bed or fluidized bed layout .
  • CO2 may be transferred from the recycle stream to the retentate side. This leads to an accumulation of CO2 and therefore a replacement of H2 with CO2 in the membrane upgrading unit 6.
  • a scheme for the sweep membrane process indication the desired and undesired permeating flow in the sweep membrane is illustrated in the figure.
  • the left arrow over the sweep membrane 4 represents the desired H2 permeation (light-grey color) while the right arrow over the sweep membrane represents the blocking function of the sweep membrane 4 for the undesired permeation of CO2 and the hydrocarbons, such as CH4 (dark-grey color) .
  • This additional sweep membrane 4 is equipped with an inlet at the permeate side for a so-called sweep stream (see Figure) .
  • the recycle stream of the plant corresponding to the retentate of the second upgrading stage in the membrane upgrading unit, directly forms the sweep-stream 20.
  • the advantage of feeding the recycle stream as a sweep stream 20 to the permeate side is, that it lowers the partial pressure difference of CO2 and the hydrocarbon, such as CH4.
  • the raw feedgas e.g. biogas
  • the raw feedgas could be used as sweep stream, too.
  • the polymeric gas separation membrane 4 can be made from polymers, such as poly-imide, poly-propylene etc. Ceramic and metallic membranes are often a bit more selective than polymeric membranes but they require significantly higher temperatures (as compared to ambient temperatures or slightly elevated temperatures above ambient temperature) and often also higher pressure gradients over the membrane.
  • the polymeric membranes further enables the operator of the system 2 to support the adjustment of specific selectivity of the permeation conditions by an appropriate adjustment of the content in the sweep gas stream 20 without losing any permeability for the desired H2 permeation in the respective sweep membrane 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'objet de la présente invention est de fournir un procédé et un système permettant d'optimiser les capacités de charge partielle d'une conversion basée sur la PtX biogaz ou d'une conversion basée sur du gaz de gazéification qui offrent une meilleure capacité d'utilisation de l'hydrogène généré ou qui n'a pas été utilisé dans le procédé de synthèse d'hydrocarbures pour d'autres étapes de traitement, telles qu'un recyclage dans le procédé de synthèse. La présente invention concerne un procédé et un système (2) pour l'optimisation des capacités de charge partielle d'une conversion PtX à base de biogaz, comprenant les étapes consistant à : a) convertir la fraction CO2 du biogaz (3) au moins partiellement avec de l'hydrogène dans un réacteur de synthèse d'hydrocarbures (18), en un flux de gaz produit riche en CH4 (16), de préférence à l'aide d'une unité de condensation (19) pour séparer un fluide (21) comprenant de l'eau et/ou des hydrocarbures condensables, tels que le méthanol, gas-oil ou kérosène, du flux de gaz produit enrichi en CH4 (16); b) traiter le flux de gaz produit enrichi en CH4 (16) à l'aide d'une unité de valorisation à membrane régulière (6) qui comprend au moins une membrane principale (8) séparant le CO2 du méthane pour produire du gaz enrichi en CH4 injectable et une membrane de nettoyage au CO2 (10) récupérant le méthane imprégné en aval de la membrane principale (8) à partir de CO2; et c) amener le flux de gaz produit enrichi en CH4 (16) sur une membrane de séparation de gaz polymère (4), ce qui permet de positionner la membrane de séparation de gaz polymère (4) en plus de l'unité de valorisation de membrane régulière (6) en aval du réacteur de synthèse d'hydrocarbures (18) et en amont de l'unité de valorisation de membrane régulière (6). La membrane de séparation de gaz polymère supplémentaire permet au procédé et système d'augmenter le taux de recyclage de l'hydrogène dans le procédé et, par conséquent, de réduire sa perte par le flux de gaz d'échappement. En même temps, la présente invention permet également de réduire la perte d'efficacité de CH4 par le même chemin et de réduire la perte d'énergie due à la recompression.
PCT/EP2023/069145 2022-07-28 2023-07-11 Amélioration de procédé dans des procédés de conversion d'energie en un autre vecteur energetique (power-to-x (ptx)) WO2024022800A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP22187488.6 2022-07-28
EP22187488.6A EP4311852A1 (fr) 2022-07-28 2022-07-28 Mise à niveau de l'amélioration des processus dans les processus power-to-x (ptx)
EP22189058.5 2022-08-05
EP22189058 2022-08-05

Publications (1)

Publication Number Publication Date
WO2024022800A1 true WO2024022800A1 (fr) 2024-02-01

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012048078A1 (fr) * 2010-10-06 2012-04-12 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé d'élimination du dioxyde de carbone
US20190381449A1 (en) * 2018-06-14 2019-12-19 Uop Llc Multi-stage membrane systems with polymeric and microporous zeolitic inorganic membranes for gas separations

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012048078A1 (fr) * 2010-10-06 2012-04-12 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé d'élimination du dioxyde de carbone
US20190381449A1 (en) * 2018-06-14 2019-12-19 Uop Llc Multi-stage membrane systems with polymeric and microporous zeolitic inorganic membranes for gas separations

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GANTENBEIN ANDREAS ET AL: "Flexible application of biogas upgrading membranes for hydrogen recycle in power-to-methane processes", CHEMICAL ENGINEERING SCIENCE, OXFORD, GB, vol. 229, 8 August 2020 (2020-08-08), XP086315247, ISSN: 0009-2509, [retrieved on 20200808], DOI: 10.1016/J.CES.2020.116012 *
WITTE JULIA ET AL: "Direct catalytic methanation of biogas - Part II: Techno-economic process assessment and feasibility reflections", ENERGY CONVERSION AND MANAGEMENT, ELSEVIER SCIENCE PUBLISHERS, OXFORD, GB, vol. 178, 15 October 2018 (2018-10-15), pages 26 - 43, XP085524760, ISSN: 0196-8904, DOI: 10.1016/J.ENCONMAN.2018.09.079 *

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