Patent · US11712652B2 · B2 · US

Methods for the removal of CO2 from atmospheric air or other CO2-containing gas in order to achieve CO2 emissions reductions or negative CO2 emissions

(11) Publication number

US11712652B2

(21) Application number

16/344,065

(22) Filing date

2017-11-10

(30) Priority date

2016-11-29

(43) Publication date

2023-08-01

(45) Date of grant

2023-08-01

(52) CPC

B01D Separation: 53/0438, 2253/102, 2253/106, 2253/206, 2253/25, 2257/504, 2258/0283, 2258/05, 2258/06, 2259/40088, 53/04
C01B Non-metallic elements; compounds thereof; {metalloids or compounds thereof not covered by subclass C01C}: 3/24, 32/05, 32/205
C09C Treatment of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties; preparation of carbon black {; preparation of inorganic materials which are no single chemical compounds and which are mainly used as pigments or fillers}: 1/46, 1/48
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: 2/50
C25B Electrolytic or electrophoretic processes for the production of compounds or non-metals; apparatus therefor: 1/04
Y02C Capture, storage, sequestration or disposal of greenhouse gases [ghg]: 20/20, 20/40
Y02E Reduction of greenhouse gas [ghg] emissions, related to energy generation, transmission or distribution: 60/36
Y02P Climate change mitigation technologies in the production or processing of goods: 20/151

(73) Assignee

CLIMEWORKS AG

(54) Title

Methods for the removal of CO2 from atmospheric air or other CO2-containing gas in order to achieve CO2 emissions reductions or negative CO2 emissions

(57) Abstract

A process for the production of at least one of amorphous carbon or graphite, preferably of carbon black, from atmospheric air, biogas or flue gas CO2 is given, including at least the following steps: a) isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air, green house air or flue gas preferably by means of a cyclic adsorption/desorption process on amine-functionalized adsorbents; b) conversion of said captured CO2 into a gaseous or liquid saturated or unsaturated hydrocarbon by hydrogenation: c) cracking of said saturated or unsaturated hydrocarbon to at least one of amorphous carbon or graphite, preferably carbon black, wherein the H2 resulting from step c) is at least partially used in the hydrogenation of step b).

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Claims (25)

A method for the production of at least one of amorphous carbon or graphite from atmospheric air CO2 comprising at least the following steps: a) isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air performed by means of a cyclic adsorption/desorption process on solid support amine-functionalized adsorbents selected from the group consisting of (i) a weak ion exchange resin, (ii) an amine-functionalized cellulose, (iii) an amine-functionalized silica, and (iv) an amine-functionalized carbon, wherein the amine functions on the solid support amine-functionalized adsorbent are incorporated through covalent bonds, and wherein desorption of CO2 is performed by heating of the adsorbent to above 80° C.; b) conversion of said concentrated CO2 into a gaseous or liquid saturated or unsaturated hydrocarbon by hydrogenation; and c) cracking of said saturated or unsaturated hydrocarbon to yield H2 and at least one of amorphous carbon or graphite and sequestering the produced at least one of amorphous carbon or graphite underground, wherein the H2 resulting from step c) is at least partially used in the hydrogenation of step b), and wherein either one or a combination of the following is used to supply heat for CO2 desorption in step a): heat stored in the produced carbon and/or hydrogen in step c), and heat released from step b).
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected from the group consisting of: linear, branched or cyclic alkanes, linear, branched or cyclic alkenes, alkynes, or a mixture thereof.
The method according to claim 1, wherein further H2 required for step b) is provided via splitting of H2O.
The method according to claim 1, wherein further H2 required for step b) is provided via cracking of saturated or unsaturated hydrocarbon from fossil or biogenic sources in a step according to step c).
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein the further two moles H2 per mole CO2 required for step b) is provided via splitting of H2O.
The method according to claim 1, wherein heat release from step b), in the form of methanation reaction, is used to supply heat for the CO2 desorption step of the CO2 capture device.
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein cracking of methane in step c) is performed thermally above a temperature of 800° C.
The method according to claim 7, wherein methane cracking in step c) is performed in an electrically heated reactor.
The method according to claim 1, where at least one of steps a)-c) is performed continuously and/or cyclically.
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein methane cracking is step c) is performed in a liquid metal reactor.
The method according to claim 1, wherein atmospheric CO2 is provided in step a) by an adsorption/desorption process using an amine-functionalized adsorbent where desorption of CO2 is performed by heating of the adsorbent to above 90° C., without or in combination with reducing the pressure to below 500 mbar (abs).
The method according to claim 1, wherein the heat stored in the produced carbon and/or hydrogen in step c) is used to preheat methane, entering the reactor of step c) and/or is used to provide heat for the CO2 desorption step of the CO2 capture device in step a).
The method according to claim 1, wherein parts of the hydrogen needed for step b), is provided by recycling product hydrogen from the saturated or unsaturated hydrocarbon cracking reaction in step c), and a remainder of needed hydrogen is supplied by electrolysis of water using electricity, where electrolysis is performed by either alkali, polymer electrolyte membrane or solid oxide electrolyzers, and/or wherein the remainder hydrogen is supplied by cracking according to step c), of saturated or unsaturated hydrocarbon, from fossil or biogenic sources.
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein methane cracking is step c) is performed in a liquid metal reactor, using liquid tin.
The method according to claim 1, where the produced at least one of amorphous carbon or graphite is used in metallurgy as carburizer for tungsten carbide or silicon carbide, as reducing agent for solar grad silicon, as rubber filler, as addition for refractory bricks, as black pigment in plastics or concrete, as high temperature insulation, as asphalt or concrete binder or as construction aggregate or it is safely sequestered above or underground.
The method according to claim 1 for the production of carbon black, from atmospheric air, including at least the following steps: a) isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air; b) conversion of said captured CO2 into a gaseous or liquid saturated or unsaturated hydrocarbon by hydrogenation; c) cracking of said saturated or unsaturated hydrocarbon to yield H2 and carbon black, wherein the H2 resulting from step c) is at least partially used in the hydrogenation of step b).
The method according to claim 16, where the produced carbon black is used in metallurgy as carburizer for tungsten carbide or silicon carbide, as reducing agent for solar grad silicon, as rubber filler, as addition for refractory bricks, as black pigment in plastics or concrete, as high temperature insulation, as asphalt or concrete binder or as construction aggregate or it is safely sequestered above or underground.
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected from the group consisting of: methane, ethane, propane, butane, ethylene, propene, butylene, or a mixture thereof.
The method according to claim 1, wherein further H2 required for step b) is provided via splitting of H2O, wherein the splitting of H2O is a photocatalytic splitting, a photolectrochemical splitting, a radiolysis, a photobiological splitting, (thermal) plasma splitting or an electrolysis, or a combination thereof.
The method according to claim 1, wherein further H2 required for step b) is provided via thermal cracking of saturated or unsaturated hydrocarbon in a step according to step c), said saturated or unsaturated hydrocarbon stemming from fossil or biogenic sources, wherein the produced carbon is further used in metallurgy as carburizer for tungsten carbide or silicon carbide, as reducing agent for solar grad silicon, as rubber filler, as addition for refractory bricks, as black pigment in plastics or concrete, as high temperature insulation, as asphalt or concrete binder or as construction aggregate or it is safely sequestered above or underground.
The method according to claim 1, wherein further H2 required for step b) is provided via thermal cracking of methane from fossil or biogenic sources, in a step according to step c).
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein the further two moles H2 per mole CO2 required for step b) is provided via splitting of H2O, wherein the splitting of H2O is a photocatalytic splitting, a photolectrochemical splitting, a radiolysis, a photobiological splitting, (thermal) plasma splitting or an electrolysis, or a combination thereof.
The method according to claim 1, where isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air in step a) is performed by means of a cyclic adsorption/desorption process on amine-functionalized adsorbents, wherein the concentration of the concentrated CO2 provided in step a) is in the range of 50-100% v/v, or in the range of 90-100% v/v.
The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein cracking of methane in step c) is performed thermally above 900° C., or in a range of 1100° C.-1600° C.
The method according to claim 1, wherein the step c) in the form of methane cracking is carried out continuously.

Citations (13)

EP2682450A2
US4452676A
US5817287A
US7585434B2
US8840704B2
WO2008148641A2
WO2011003081A1
WO2012168346A1
WO2014170184A1
WO2015055349A1
WO2015185434A1
WO2016005226A1
WO2016161998A1

Record as JSON

{
  "publication_number": "US11712652B2",
  "country": "US",
  "kind": "B2",
  "title": "Methods for the removal of CO2 from atmospheric air or other CO2-containing gas in order to achieve CO2 emissions reductions or negative CO2 emissions",
  "abstract": "A process for the production of at least one of amorphous carbon or graphite, preferably of carbon black, from atmospheric air, biogas or flue gas CO2 is given, including at least the following steps: a) isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air, green house air or flue gas preferably by means of a cyclic adsorption/desorption process on amine-functionalized adsorbents; b) conversion of said captured CO2 into a gaseous or liquid saturated or unsaturated hydrocarbon by hydrogenation: c) cracking of said saturated or unsaturated hydrocarbon to at least one of amorphous carbon or graphite, preferably carbon black, wherein the H2 resulting from step c) is at least partially used in the hydrogenation of step b).",
  "claims": [
    "1. A method for the production of at least one of amorphous carbon or graphite from atmospheric air CO2 comprising at least the following steps: a) isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air performed by means of a cyclic adsorption/desorption process on solid support amine-functionalized adsorbents selected from the group consisting of (i) a weak ion exchange resin, (ii) an amine-functionalized cellulose, (iii) an amine-functionalized silica, and (iv) an amine-functionalized carbon, wherein the amine functions on the solid support amine-functionalized adsorbent are incorporated through covalent bonds, and wherein desorption of CO2 is performed by heating of the adsorbent to above 80° C.; b) conversion of said concentrated CO2 into a gaseous or liquid saturated or unsaturated hydrocarbon by hydrogenation; and c) cracking of said saturated or unsaturated hydrocarbon to yield H2 and at least one of amorphous carbon or graphite and sequestering the produced at least one of amorphous carbon or graphite underground, wherein the H2 resulting from step c) is at least partially used in the hydrogenation of step b), and wherein either one or a combination of the following is used to supply heat for CO2 desorption in step a): heat stored in the produced carbon and/or hydrogen in step c), and heat released from step b).",
    "2. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected from the group consisting of: linear, branched or cyclic alkanes, linear, branched or cyclic alkenes, alkynes, or a mixture thereof.",
    "3. The method according to claim 1, wherein further H2 required for step b) is provided via splitting of H2O.",
    "4. The method according to claim 1, wherein further H2 required for step b) is provided via cracking of saturated or unsaturated hydrocarbon from fossil or biogenic sources in a step according to step c).",
    "5. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein the further two moles H2 per mole CO2 required for step b) is provided via splitting of H2O.",
    "6. The method according to claim 1, wherein heat release from step b), in the form of methanation reaction, is used to supply heat for the CO2 desorption step of the CO2 capture device.",
    "7. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein cracking of methane in step c) is performed thermally above a temperature of 800° C.",
    "8. The method according to claim 7, wherein methane cracking in step c) is performed in an electrically heated reactor.",
    "9. The method according to claim 1, where at least one of steps a)-c) is performed continuously and/or cyclically.",
    "10. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein methane cracking is step c) is performed in a liquid metal reactor.",
    "11. The method according to claim 1, wherein atmospheric CO2 is provided in step a) by an adsorption/desorption process using an amine-functionalized adsorbent where desorption of CO2 is performed by heating of the adsorbent to above 90° C., without or in combination with reducing the pressure to below 500 mbar (abs).",
    "12. The method according to claim 1, wherein the heat stored in the produced carbon and/or hydrogen in step c) is used to preheat methane, entering the reactor of step c) and/or is used to provide heat for the CO2 desorption step of the CO2 capture device in step a).",
    "13. The method according to claim 1, wherein parts of the hydrogen needed for step b), is provided by recycling product hydrogen from the saturated or unsaturated hydrocarbon cracking reaction in step c), and a remainder of needed hydrogen is supplied by electrolysis of water using electricity, where electrolysis is performed by either alkali, polymer electrolyte membrane or solid oxide electrolyzers, and/or wherein the remainder hydrogen is supplied by cracking according to step c), of saturated or unsaturated hydrocarbon, from fossil or biogenic sources.",
    "14. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein methane cracking is step c) is performed in a liquid metal reactor, using liquid tin.",
    "15. The method according to claim 1, where the produced at least one of amorphous carbon or graphite is used in metallurgy as carburizer for tungsten carbide or silicon carbide, as reducing agent for solar grad silicon, as rubber filler, as addition for refractory bricks, as black pigment in plastics or concrete, as high temperature insulation, as asphalt or concrete binder or as construction aggregate or it is safely sequestered above or underground.",
    "16. The method according to claim 1 for the production of carbon black, from atmospheric air, including at least the following steps: a) isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air; b) conversion of said captured CO2 into a gaseous or liquid saturated or unsaturated hydrocarbon by hydrogenation; c) cracking of said saturated or unsaturated hydrocarbon to yield H2 and carbon black, wherein the H2 resulting from step c) is at least partially used in the hydrogenation of step b).",
    "17. The method according to claim 16, where the produced carbon black is used in metallurgy as carburizer for tungsten carbide or silicon carbide, as reducing agent for solar grad silicon, as rubber filler, as addition for refractory bricks, as black pigment in plastics or concrete, as high temperature insulation, as asphalt or concrete binder or as construction aggregate or it is safely sequestered above or underground.",
    "18. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected from the group consisting of: methane, ethane, propane, butane, ethylene, propene, butylene, or a mixture thereof.",
    "19. The method according to claim 1, wherein further H2 required for step b) is provided via splitting of H2O, wherein the splitting of H2O is a photocatalytic splitting, a photolectrochemical splitting, a radiolysis, a photobiological splitting, (thermal) plasma splitting or an electrolysis, or a combination thereof.",
    "20. The method according to claim 1, wherein further H2 required for step b) is provided via thermal cracking of saturated or unsaturated hydrocarbon in a step according to step c), said saturated or unsaturated hydrocarbon stemming from fossil or biogenic sources, wherein the produced carbon is further used in metallurgy as carburizer for tungsten carbide or silicon carbide, as reducing agent for solar grad silicon, as rubber filler, as addition for refractory bricks, as black pigment in plastics or concrete, as high temperature insulation, as asphalt or concrete binder or as construction aggregate or it is safely sequestered above or underground.",
    "21. The method according to claim 1, wherein further H2 required for step b) is provided via thermal cracking of methane from fossil or biogenic sources, in a step according to step c).",
    "22. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein the further two moles H2 per mole CO2 required for step b) is provided via splitting of H2O, wherein the splitting of H2O is a photocatalytic splitting, a photolectrochemical splitting, a radiolysis, a photobiological splitting, (thermal) plasma splitting or an electrolysis, or a combination thereof.",
    "23. The method according to claim 1, where isolation of concentrated CO2 of a concentration of at least 50% v/v from atmospheric air in step a) is performed by means of a cyclic adsorption/desorption process on amine-functionalized adsorbents, wherein the concentration of the concentrated CO2 provided in step a) is in the range of 50-100% v/v, or in the range of 90-100% v/v.",
    "24. The method according to claim 1, wherein the saturated or unsaturated hydrocarbon is selected to be methane, and wherein cracking of methane in step c) is performed thermally above 900° C., or in a range of 1100° C.-1600° C.",
    "25. The method according to claim 1, wherein the step c) in the form of methane cracking is carried out continuously."
  ],
  "cpc": [
    "B01D 53/0438",
    "B01D 2253/102",
    "B01D 2253/106",
    "B01D 2253/206",
    "B01D 2253/25",
    "B01D 2257/504",
    "B01D 2258/0283",
    "B01D 2258/05",
    "B01D 2258/06",
    "B01D 2259/40088",
    "B01D 53/04",
    "C01B 3/24",
    "C01B 32/05",
    "C01B 32/205",
    "C09C 1/46",
    "C09C 1/48",
    "C10G 2/50",
    "C25B 1/04",
    "Y02C 20/20",
    "Y02C 20/40",
    "Y02E 60/36",
    "Y02P 20/151"
  ],
  "assignees": [
    "CLIMEWORKS AG"
  ],
  "filing_date": "2017-11-10",
  "publication_date": "2023-08-01",
  "grant_date": "2023-08-01",
  "priority_date": "2016-11-29",
  "application_number": "US-201716344065-A",
  "family_id": "57442498",
  "citations": [
    "EP2682450A2",
    "US4452676A",
    "US5817287A",
    "US7585434B2",
    "US8840704B2",
    "WO2008148641A2",
    "WO2011003081A1",
    "WO2012168346A1",
    "WO2014170184A1",
    "WO2015055349A1",
    "WO2015185434A1",
    "WO2016005226A1",
    "WO2016161998A1"
  ]
}

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