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WO2025027431A1 - Système de valorisation de biogaz - Google Patents

Système de valorisation de biogaz Download PDF

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Publication number
WO2025027431A1
WO2025027431A1 PCT/IB2024/056915 IB2024056915W WO2025027431A1 WO 2025027431 A1 WO2025027431 A1 WO 2025027431A1 IB 2024056915 W IB2024056915 W IB 2024056915W WO 2025027431 A1 WO2025027431 A1 WO 2025027431A1
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WO
WIPO (PCT)
Prior art keywords
biomethanol
biomethane
mol
unit
plant
Prior art date
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Pending
Application number
PCT/IB2024/056915
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English (en)
Inventor
Flavio MANENTI
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Politecnico di Milano
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Politecnico di Milano
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Publication of WO2025027431A1 publication Critical patent/WO2025027431A1/fr
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Classifications

    • 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
    • C01B3/32—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
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • 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
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas

Definitions

  • biomethane biogas The upgrading of biomethane biogas is a technology of great interest both nationally and internationally : it allows to produce biomethane, which can be used as an alternative to fossil methane, starting from a renewable energy resource (biogas ) for example generated by water treatment plants , from wet waste fraction and many other wastes of industrial and agricultural origin .
  • biogas renewable energy resource
  • the biogas produced by the anaerobic digestion from water treatment sludge has great potential to reduce the use of fossil fuel : once appropriately processed and converted into biomethane through an " upgrading" process , it can be used for example as a biofuel for the automotive industry or introduced into the natural gas distribution network .
  • the biogas produced by the anaerobic digestion from water treatment sludge is a gas mixture which mainly contains (Moretta et al . , 2022 ) :
  • the high methane content in the biogas resulting from said anaerobic digestion processes does not allow to use it as a widespread energy carrier . Furthermore, the high CO2 content does not allow to introduce methane into the public supply system or to use it as methane for the automotive industry .
  • Biomethane is introduced into the gas supply network, while the flow of carbon dioxide is released into the atmosphere or it is introduced into cylinders for use as inert in some industrial sectors .
  • the current biogas and biomethane production plants operate according to the block flow diagram of Figure 1 .
  • Agricultural and/or food wastes the sludge from animal faeces or the organic fraction of municipal solid waste are digested anaerobically in a digester .
  • Anaerobic digestion generates biogas (Moretta et al . , 2022 ) , that is a current process .
  • Such current also referred to as crude biogas , is sent to a f iltering/washing system for reducing the impurities and subsequently :
  • the biogas upgrading system mainly consists of :
  • the membrane-based upgrading technique is widely used .
  • Biogas is compressed up to 8 bar, preferably up to at least 15 bar (two compression stages ) .
  • the compression system is often provided with a dehumidifier, except for the cases of dry biogas or upstream dehumidification .
  • the biogas heats and the temperature should be preferably corrected .
  • the compressed biogas is sent to the membrane-based system which carries out the splitting between methane and carbon dioxide .
  • the methane is further compressed (third stage, at times even fourth stage based on the pressure drops astride the membranebased system) up to beyond 60 bar, that is up to a pressure useful for its injection into the natural gas distribution network and its temperature is corrected once again .
  • Carbon dioxide is released into the atmosphere after lamination .
  • a particularly critical aspect of the current plant s lies in the high cost with respect to the production volume .
  • the costs of the plant become a major factor and for the biogas market it is important to have cost-effective, non-pollutant , safe and low thermal budget technologies .
  • the present invention overcomes the problem relating to high ( investment , operating and maintenance ) costs , minimising the size of the conversion plant ; furthermore, the present invention advantageously minimises the residual emissions of carbon dioxide (eliminating them in an embodiment ) .
  • the present invention also allows to obtain an excellent conversion of biogas into biomethanol.
  • FIG. 1 Block Flow Diagram (BFD) of a plant for producing biomethane from biogas:
  • MSW agri-food residues sludge treatment
  • FIG. 1 Main operations for a conventional biogas plant for producing electrical energy:
  • MSW agri-food residues sludge treatment
  • FIG. 3 Main operations for a biomethane biogas upgrading plant :
  • MSW agri-food residues sludge treatment
  • blower 27 crude biogas
  • FIG. 4 BFD of the present invention: 42 : agri-food residues sludge treatment (MSW) 43: biogas plant 44: digested fertilizers 45: biogas 46: upgrading biogas 47 : Residual CO2 48: SN ratio CO2 49: biomethane 50: subject of the invention 51 : biomethanol
  • FIG. 5 Main operations of the present invention highlighting the new units (67, 74, 76) to be inserted ex novo into a biomethane plant : 52 : agri-food residues sludge treatment (MSW)
  • Figure 7 Diagram of the reaction section with single shell units.
  • the tube bundles of the catalytic reactors are necessarily vertical: 91 : syngas 92 : single shell heater 93: deflector 94 : single shell reactor 95: single shell cooling device 96: syngas 97 : syngas 98 : methanol water 99: methanol water 100: syngas 101: methanol water
  • FIG. 8 Layout for the embodiment "Biomethane and biomethanol upgrading plant with one-step reforming and two conversion stages": 102 : biogas 103: HP biomethane 104: reforming steam 105: SR OUT 106: H2O make-up 107: fresh syngas 108: CO2 to mixing 109: CO2 purging 110: syngas recycling 111: methanol synthesis 112: methanol crude 1 113: methanol synthesis 114 : purging 115: methanol crude 2 116: methanol 117: H2O 118: methanol and water recycling 119: off-gas
  • Figure 9 and Figure 10 data relating to the implementation Layout of Figure 8.
  • the present invention relates to a biomethane to biomethanol upgrading system, said system comprising
  • biomethane upgrading system comprises
  • a reforming unit (67) arranged after said splitting unit to form syngas (synthesis gas) , wherein the reactions below are carried out in said reforming unit:
  • the outflow of the biomethane exiting from said splitting unit ( 64 ) is comprised in the range from 15-25 bar, even more preferably between 20-25 bar .
  • said reaction [R3 ] is carried out with two steps comprising the following steps :
  • a recycling current deriving from said purification and separation consisting of o water comprised in the range from 50-100% mol, preferably 80-100%mol, even more preferably 85- 100%mol ; o biomethanol comprised in the range from 0-50%mol, preferably 0-20%mol, even more preferably 0- 0 . 15%mol, at a pressure equal to or greater than said reforming unit (typically 20 bar) . and vaporised and heated to a temperature up to 280 ° C, preferably up to 300 ° C;
  • Said catalytic system is selected from the group consisting of : at least one catalytic bed, at least one methanol cell and/or combinations thereof .
  • the effluents coming from said reforming unit are sent to a phase separator, wherein : - the remaining water condenses by lamination and/or heat exchange ; and
  • the syngas is sent downstream of the reforming unit and mixed with syngas flowing out from said reforming unit .
  • said reaction [R3 ] is carried out in a single step comprising the pumping, upstream of the reforming unit , a recycling current derived from said purification and separation consisting of
  • - water comprised in the range from 50-100%mol, preferably 80-100%mol, even more preferably 99 . 85-100%mol;
  • - biomethanol comprised in the range from 0-50%mol, preferably 0-20%mol, even more preferably 0-0 . 15%mol, and mixed with replenishing water .
  • the present invention exploits the operations already present in the biomethane production plant s to the uttermost , significantly reducing the CAPEX .
  • the present invention converts the whole biomethane current and part of the C02 current , otherwise released to the atmosphere, into biomethanol .
  • the present invention provides for a reforming unit (not bireforming or tri-reforming like in other technologies , for instance : Manenti, BIGSQUID, 2016 ) .
  • the present invention intercepts the biomethane current and transforms it into synthesis gas ( syngas ) rich in hydrogen through a classic steam methane reforming operation according to the reaction [Rl ] reported above .
  • said current is mixed with an appropriate fraction of carbon dioxide coming from the venting line to the atmosphere, before decompression so as to obtain an SN ratio that is excellent for methanol synthesis (Bozzano and Manenti, 2016 ) .
  • the dosage of CO2 is optimised in real time .
  • the present invention does not provide for any water-gas shift operation .
  • the present invention provides for recovering the secondary compressor of the biomethane process to compress the conditioned syngas up to the methanol synthesis pressure .
  • the present invention provides for reutilising the thermal exchange already envisaged for biomethane, and then sending the syngas to the new units for the synthesis of methanol and purification of the methanol/water mixture .
  • the water is then recycled to the reforming system so as to reduce the demi-water consumptions , but also to maximise the yield in methanol through syngas reconversion of the residual methanol contained in such water current and superior alcohols typically produced through parasitic reactions in the methanol synthesis .
  • the present invention simplifies the stage by stage nature of the synthesis section by using partially shared units .
  • Figure 7 shows the case of three reaction stages :
  • each reaction stage consists of three tube bundles , respectively for pre-heating, converting and cooling, and a separator for removing the methanol and water mixture .
  • the "Utility" side does not depend on the number of stages and there is a single jacket for the pre-heating section, a jacket with vertical baffles for the conversion section and a single jacket for the cooling section .
  • the first stage is the most efficient in terms of synthesis and therefore it is to be considered as a limiting element when designing the pre-heating and cooling .
  • bypasses for individually controlling the temperatures of each conversion stage are provided for the conversion section .
  • the purification is significantly reduced with respect to a common methanol synthesis process (for example, the purification sections were accurately described by Douglas and Hoadley ( 2006 ) ) .
  • said purification comprises two phase separators combined with only one distillation tower to reach the market specifications ( 99 . 85% of purity) .
  • the wastewater is recycled upstream of the reformer for full recovery within the process .
  • the data of the purification section are contained in the spreadsheet of the Tables of Figures 9 and 10 .
  • the present invention relates to plants comprising the biomethane to biomethanol upgrading system of the present invention .
  • said plant is selected from the group consisting of : biomethane production plants , biogas production plants , biomethanol and derivatives production plants , gasification plants (biomasses , plastics , sludges , Organic Fraction of Municipal Solid Waste, other) , pyrolysis plants (biomasses , plastics , sludges , Organic Fraction of Municipal Solid Waste, other) , gas plants provided with flaring system, plants with co-presence of methane and carbon dioxide ; plants with presence of methane and exogenous carbon dioxide, methanation plant .
  • the present invention allows a morphological minimisation of the biogas conversion units , capital and operating costs .
  • the present invention has an optimisation of the reuse of C02 and the production of biomethanol and derivatives .
  • the present invention leads to environmental and energy self-sustainability .
  • the system of the present invention relates :
  • thermal or catalytic treatment section including compression - a synthesis section with possible further compres sion and storage and
  • a single purification section with said purification section suitably oversized to receive multiple streams (at least two) of methanol and/or derivatives not to specification coming from an equal number of synthesis distributed on the area and with said section located in third position, preferably barycentric, with respect to such synthesis plants or at only one of them, and it is capable of generating a waste current , mainly aqueous , to be recycled to the original synthesis plants for its complete reconversion and obtaining a zeroresidue circular process network .
  • the transfer of the stream of methanol or derivatives not to specification and the waste aqueous mixture is carried out through road, railway or sea/river transport , preferably creating a tight network around the purification centre .
  • Such purification centre may also in turn convert methanol into derivatives such as , by way of non-limiting example, dimethyl ether, acetic acid, propionic acid, hydrogen .
  • the carbon dioxide generated is in turn recycled upstream of the original plants , where useful for the further reconversion to methanol and derivatives or reused locally for efficient carbon sink syntheses , such as for example acetic acid .
  • the streams are therefore to be considered transported by road, railway or sea and the purification section is to be considered suitably oversized depending on the number of plants to be received .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un système de valorisation de biogaz, et des installations comprenant ledit système.
PCT/IB2024/056915 2023-08-01 2024-07-17 Système de valorisation de biogaz Pending WO2025027431A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102023000016320 2023-08-01
IT102023000016320A IT202300016320A1 (it) 2023-08-01 2023-08-01 Sistema di upgrading del biogas

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WO2025027431A1 true WO2025027431A1 (fr) 2025-02-06

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801842A (zh) * 2007-08-16 2010-08-11 Dge京特博士工程有限公司 用于从生物气生产合成气的方法和设备
WO2019003213A1 (fr) * 2017-06-30 2019-01-03 Politecnico Di Milano Installation polyvalente pour convertir du biogaz en produits chimiques à haute valeur ajoutée

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801842A (zh) * 2007-08-16 2010-08-11 Dge京特博士工程有限公司 用于从生物气生产合成气的方法和设备
WO2019003213A1 (fr) * 2017-06-30 2019-01-03 Politecnico Di Milano Installation polyvalente pour convertir du biogaz en produits chimiques à haute valeur ajoutée

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
G. BOZZANO, ET AL.: "Efficient methanol synthesis: Perspectives, technologies and optimisation strategies", PROGRESS IN ENERGY AND COMBUSTION SCIENCE, vol. 56, 5 July 2016 (2016-07-05), Elsevier, Oxford, GB, pages 71 - 105, XP029666945, ISSN: 0360-1285, DOI: 10.1016/j.pecs.2016.06.001 *

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IT202300016320A1 (it) 2025-02-01

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