WO2010094923A2 - Methods of absorption and desorption of carbon dioxide, and apparatus for each, for beneficial re-use of carbon dioxide - Google Patents

Methods of absorption and desorption of carbon dioxide, and apparatus for each, for beneficial re-use of carbon dioxide Download PDF

Info

Publication number
WO2010094923A2
WO2010094923A2 PCT/GB2010/000290 GB2010000290W WO2010094923A2 WO 2010094923 A2 WO2010094923 A2 WO 2010094923A2 GB 2010000290 W GB2010000290 W GB 2010000290W WO 2010094923 A2 WO2010094923 A2 WO 2010094923A2
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
gas
acid
absorption
absorbed
Prior art date
Application number
PCT/GB2010/000290
Other languages
French (fr)
Other versions
WO2010094923A3 (en
Inventor
Ian Houston
Original Assignee
Origo Industries Limited
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 Origo Industries Limited filed Critical Origo Industries Limited
Publication of WO2010094923A2 publication Critical patent/WO2010094923A2/en
Publication of WO2010094923A3 publication Critical patent/WO2010094923A3/en

Links

Classifications

    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • 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
    • B01D53/14—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 absorption
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • 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
    • B01D53/14—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 absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3251—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3253—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244—Non-macromolecular compounds
    • B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • B01J20/3255—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates in a first aspect to a method of absorbing carbon dioxide (CO 2 ) from a gas, and in a second aspect to a method of desorbing pre- absorbed carbon dioxide from a substrate in preparation for its use elsewhere.
  • the invention furthermore relates to CO 2 absorption/desorption apparatus.
  • the present invention relates to each of these aspects for the beneficial re-use of carbon dioxide.
  • amine-based sorbents to extract CO 2 from gas streams, especially exhaust/flue gas streams from industrial processes, such as power stations and chemical manufacturing operations.
  • the sorbents can be provided in solution, e.g. an aqueous solution, or in solid form, e.g. impregnated onto a porous substrate.
  • CO 2 absorption into an amine-based sorbent is a temperature-dependent process; above a certain threshold temperature, desorption of CO 2 occurs, often undesirably.
  • the present invention provides a method of absorbing
  • CO 2 from a gas that includes a volume, V 1 , of CO 2 (a CO 2 -containing gas) the method comprising: providing a CO 2 -absorption substrate, and contacting the gas with the substrate, whereby a volume, V 2 , of CO 2 is absorbed from the gas by the substrate leaving a
  • the substrate comprises a porous material, the composition of which comprises at least one chemical element having an atomic number of 13 or greater, onto which any one or more of the following CO 2 -absorbers is adsorbed: a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium compound.
  • the substrate may be organic or inorganic; if organic it will therefore comprise at least one chemical element other than hydrogen (atomic number of 1), carbon (atomic number of 6) and oxygen (atomic number of 8).
  • the CO 2 -absorbers may be adsorbed onto the surface of the porous substrate, including adsorption into the pores by treating the substrate with a solution of one or more CO 2 -absorbers in a suitable solvent to distribute them, and subsequently evaporating off the solvent.
  • the term "pore" and its derivates include both a depression in a surface and also a bottomless aperture in the surface. Once adsorbed, the CO 2 -absorbers are ready to absorb CO 2 molecules that come into contact with them.
  • the substrate is preferably a polymeric material having porosity suitable for adsorption of CO 2 -absorbers. Further preferably the polymeric material is a polysulfone.
  • the substrate is preferably in the form of a metallic network, further preferably a nickel foam.
  • a network material £ ⁇ inherently has porosity suitable for adsorption of CO 2 -absorbers.
  • V 1 V 2 .
  • the CO 2 -absorbers described above may be of the form R 1 R 2 R 3 N (and the quaternary ammonium compound similarly of the form R 1 R 2 R 3 R 4 N + ) wherein each of R 1 , R 2 and R 3 (and R 4 as appropriate) is independently selected from the group consisting of hydrogen, a linear alkyl, a branched alkyl, a cyclic alkyl, a substituted linear alkyl, a substituted branched alkyl, a substituted cyclic alkyl, an aryl, a substituted aryl, an arylated alkyl (aralkyl), a substituted aralkyl, a heterocyclic, a substituted heterocyclic, a hetero-aryl and a substituted hetero-aryl.
  • any two of R 1 , R 2 and R 3 (and R 4 as appropriate) may be independently selected from the group consisting of hydrogen and the non-sterically bulky substituents having between 1 and 6 carbon atoms inclusively, and the remaining R x is (are) a sterically bulky substituent(s) having at least 6 carbon atoms.
  • the CO 2 -absorber may be selected from any one or more of the following amines: dehydroabietylamine, butylamine, octylamine, benzylamine, ⁇ - methylbenzylamine, 2-amino-2-ethyl-1 ,3-propanediol, diphenylamine, ethanolamine, diethanolamine, triethanolamine, piperazine, 2-methylpiperazine, N- methylpiperazine, homopiperazine, piperidine, morpholine, pyrrolidine, ⁇ - aminopyridine, ⁇ -aminopyridine, ⁇ -aminopyridine and spermine.
  • the step of contacting the gas with the substrate preferably occurs in the presence of water (H 2 O), which is present in an amount such that the ratio of CO 2 : H 2 O is at least 1 :1.
  • H 2 O water
  • Advantageously water vapour may be comprised in the CO 2 -containing gas, especially where the gas is a product of hydrocarbons combustion, occurring in e.g. an internal combustion engine of a vehicle, a gas turbine, a refinery fluestack, a power station or in another industrial plant.
  • the gas may comprise at least 5 % by volume of CO 2 prior to contacting the substrate. However this may be at least 10 % or even 20 % depending upon the conditions of CO 2 emission.
  • the step of contacting the gas with the substrate may occur at a temperature of between 5 0 C and 100 0 C, preferably between 10 0 C and 85 0 C, and further preferably between 15 0 C and 70 0 C. Such a temperature is believed to be optimal for enabling absorption of CO 2 from the gas.
  • the method of the invention may further comprise the step of pre-treating the absorption substrate with an alkali metal compound, MX, such that the CO 2 -absorbers form an RiR 2 N M + intermediate prior to contacting the gas with the substrate.
  • This intermediate is a powerful base and may be used to drive the CO 2 and H 2 O equilibrium described above in the direction of the carbonate ion.
  • the metal, M is lithium.
  • Absorption of CO 2 by the substrate thus preferably forms of any one or more of the following absorption compounds: an amine carbonate, an amine hydrogen carbonate, a quaternary ammonium carbonate, a quaternary ammonium hydrogen carbonate.
  • the substrate is preferably provided in a re-sealable chamber which has a gas inlet, for introduction of the CO 2 -containing gas, and a gas outlet, for exhaustion of the CO 2 -deficient gas.
  • gas introduction to, and exhaustion from, the chamber may be performed continuously such that there is a negligible residence time of the gas in the chamber (subject to the gaseous flow rate through the chamber), and this maximum gaseous throughput to achieve increased absorption efficiency.
  • a method of desorbing CO 2 from a CO 2 -rich absorption substrate the substrate having any one or more of the following CO 2 -absorbers adsorbed onto it: a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium compound and a pre-absorbed volume, V 3 , of CO 2 , the method comprising: treating the substrate with an acid, thereby releasing a volume, V 4 , of the absorbed
  • a CO 2 -rich absorption substrate is one having a volume, V 3 , of CO 2 pre-absorbed onto it.
  • the substrate itself may be organic or inorganic, and is preferably porous.
  • the CO 2 -absorbers may be adsorbed onto the surface of the substrate, including adsorption into its pores, where such exist.
  • the acid used is an organic acid, which may be selected from the group consisting of: acetic acid, lactic acid, citric acid, malic acid and tartaric acid.
  • Such weak acids may the by-product of another industrial process or they may be formed by oxidation from a corresponding alcohol.
  • the acid preferably has a low "carbon footprint".
  • the acid may be an inorganic acid, in which case it may be selected from the group consisting of: sulphuric acid and phosphoric acid.
  • the acid used may furthermore be a mixture of different acids.
  • the ratio of V 3 to V 4 is dependent on the amount and/or concentration of acid used, and as such, CO 2 desorption is controllable.
  • the invention preferably further comprises the step of preheating the substrate so that the CO 2 -absorption compound forms a carbonate prior to treating it with the acid.
  • the substrate may be preheated to a temperature of at least 40 0 C, and preferably up to around 120 °C. This temperature range appears to be optimal in terms of carbonate formation, whilst maintaining the integrity of the substrate and preventing its degradation.
  • the method may also comprise the step of treating the acidified substrate with an alkali to regenerate the CO 2 -absorption property of the substrate.
  • the alkali is preferably an excess of aqueous ammonia.
  • the method of the invention may be performed in any environment in which it is desired to desorb a volume of absorbed CO 2 from a substrate, including both open and closed systems
  • the substrate is preferably provided in a re-sealable chamber which has an inlet, for introduction of the acid, and an outlet, for exhaustion of desorbed CO 2 .
  • the CO 2 may be pre-absorbed by the substrate according to the first aspect of the invention.
  • the two methods may be considered as complementary and may be co-operable with one another.
  • a CO 2 absorption/desorption apparatus comprising a re-sealable chamber having an inlet, for introduction of a CO 2 -containing gas and/or an acid, and an outlet, for exhaustion of a CO 2 -deficient gas and/or desorbed CO 2 .
  • One piece of apparatus may thus be suitable for sequentially performing each of the two methods of the invention without modification.
  • the apparatus comprises at least two such chambers adapted so as to be cyclically operable, such that when CO 2 absorption occurs in one chamber, previously absorbed CO 2 desorption occurs in the other chamber, in a complementary manner.
  • Carbon dioxide that has been absorbed for release may be beneficially re-used in other processes, especially those involving organic matter, such as feeding algae, in enzyme regeneration and in polymer regeneration.
  • a CO 2 -absorber solution was made by dissolving 20.Og (0.12 moles) of benzyltrimethylammonium hydroxide (a quaternary ammonium compound) in 100ml of water under ambient conditions.
  • the solution was mixed with methylated spirits and applied to a polysulfone substrate (the composition of which includes sulphur atoms, having an atomic number of 16).
  • the substrate was allowed to dry at room temperature, during which time the methylated spirits evaporated.
  • a suitable polysulfone substrate is available under the trade name UDELTM Polysulfone P-1700 from Solvay Advanced Polymers, Georgia, USA.
  • the substrate could be a nickel foam (the composition of which includes nickel atoms, having an atomic number of 28).
  • Such a metallic foam is available under the trade name IncoFoamTM from lnco Special Products (www.incosp.com).
  • the resultant CO 2 -absorption substrate was placed into a re-sealable stainless steel chamber, having a gas inlet and a gas outlet, which was then sealed to the atmosphere. Pure gaseous CO 2 was pumped into the sealed chamber through the gas inlet at a rate of 0.5 litres/minute for 2 minutes.
  • a gas analyzer GreenLine 8000 Flue Gas Analyzer available from E Instruments Group of Pennsylvania, USA was arranged to contemporaneously analyze the gas exiting the chamber via the gas outlet. The results showed 91 % absorption of CO 2 .
  • the resulting solution of benzyltrimethylammonium carbonate was then made up to a total volume of 100ml by addition of distilled water and cooled to a temperature of less than 20 0 C. Pure gaseous CO 2 was bubbled through the solution at a rate of 0.5 litres/minute for 2 minutes to form a solution of benzyltrimethylammonium hydrogen carbonate.
  • Example 2 Subsequent to analysis of the exiting gas from the sealed chamber in Example 1 , the substrate inside the chamber was treated with a slight excess of citric acid (a weak organic acid) until effervescence ceased.
  • the gas analyzer yielded the result that all of the absorbed CO 2 had been desorbed, i.e. the full 91 % was desorbed and detected.
  • the precipitate was filtered and titrated with more methylated spirits (95 %) and subsequently filtered and dried under ambient conditions to yield 84g of diethanolamine hydrogen carbonate, representing an 81 % recovery of CO 2 over the two stages.
  • a porous substrate such as a polysulfone or a metallic foam can be impregnated with an amine CO 2 -absorber, contacted with a gas containing CO 2 and have CO 2 (up to 100 %) absorbed from the gas by the substrate.
  • CO 2 can be desorbed from a CO 2 -rich absorption substrate, which may or may not be formed by the absorption method of the invention, using an acid, such as a weak organic acid, with subsequent regeneration of the absorption substrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A method of absorbing CO2 from a gas that includes a volume, V1, of CO2 comprising: providing a CC2-absorption substrate, and contacting the gas with the substrate, whereby a volume, V2, of CO2 is absorbed from the gas by the substrate, wherein the substrate comprises a porous material, the composition of which comprises at least one chemical element having an atomic number of 13 or greater, onto which any one or more of the following CO2-absorbers is adsorbed: a primary, secondary or tertiary amine, or a quaternary ammonium compound. Also a method of desorbing CO2 from a CO2-rich absorption substrate, the substrate having any one or more of the following CO2-absorbers adsorbed onto it: a primary, secondary or tertiary amine, or a quaternary ammonium compound and a pre-absorbed volume, V3, of CO2, the method comprising: treating the substrate with an acid, thereby releasing a volume, V4, of the absorbed CO2.

Description

METHODS OF ABSORPTION AND DESORPTION OF CARBON DIOXIDE, AND APPARATUS FOR EACH, FOR BENEFICIAL RE-USE OF CARBON DIOXIDE
The present invention relates in a first aspect to a method of absorbing carbon dioxide (CO2) from a gas, and in a second aspect to a method of desorbing pre- absorbed carbon dioxide from a substrate in preparation for its use elsewhere. The invention furthermore relates to CO2 absorption/desorption apparatus. Moreover the present invention relates to each of these aspects for the beneficial re-use of carbon dioxide.
Pollution management, especially air pollution management with an emphasis on CO2 emissions into the atmosphere, is currently high on the global political, economic and environmental agendas. This is because of an increasing amount of scientific evidence indicating that CO2 emissions are having an increasingly detrimental effect on both human health and the health of our ecosystems.
A number of solutions have been proposed to address the problem of increasing CO2 emission including: reduction in the levels of CO2 emissions themselves, for example by the use of cleaner hydrocarbon-based fuels and by the use of alternative fuels; capturing CO2 emissions from the atmosphere and treating for subsequent storage in another medium, e.g. by reaction with calcium oxide (quicklime) to form calcium carbonate (chalk).
In the latter group of solutions, it is furthermore known to use amine-based sorbents to extract CO2 from gas streams, especially exhaust/flue gas streams from industrial processes, such as power stations and chemical manufacturing operations. The sorbents can be provided in solution, e.g. an aqueous solution, or in solid form, e.g. impregnated onto a porous substrate. However CO2 absorption into an amine-based sorbent is a temperature-dependent process; above a certain threshold temperature, desorption of CO2 occurs, often undesirably.
It is therefore an aim of the invention to provide a method for improved CO2 absorption, especially improved absorption efficiency. It is a further aim of the invention to provide a method for controllable CO2 desorption, from which desorbed CO2 may then be taken for further processing, such as use in bio-fuel manufacture. It is moreover an aim of the invention to provide a suitable CO2 absorption/desorption apparatus.
Accordingly in a first aspect the present invention provides a method of absorbing
CO2 from a gas that includes a volume, V1, of CO2 (a CO2-containing gas) the method comprising: providing a CO2-absorption substrate, and contacting the gas with the substrate, whereby a volume, V2, of CO2 is absorbed from the gas by the substrate leaving a
CO2-deficient gas, wherein the substrate comprises a porous material, the composition of which comprises at least one chemical element having an atomic number of 13 or greater, onto which any one or more of the following CO2-absorbers is adsorbed: a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium compound.
The substrate may be organic or inorganic; if organic it will therefore comprise at least one chemical element other than hydrogen (atomic number of 1), carbon (atomic number of 6) and oxygen (atomic number of 8). The CO2-absorbers may be adsorbed onto the surface of the porous substrate, including adsorption into the pores by treating the substrate with a solution of one or more CO2-absorbers in a suitable solvent to distribute them, and subsequently evaporating off the solvent. For the avoidance of doubt, the term "pore" and its derivates include both a depression in a surface and also a bottomless aperture in the surface. Once adsorbed, the CO2-absorbers are ready to absorb CO2 molecules that come into contact with them.
In one embodiment of the invention, the substrate is preferably a polymeric material having porosity suitable for adsorption of CO2-absorbers. Further preferably the polymeric material is a polysulfone.
In an alternative embodiment of the invention, the substrate is preferably in the form of a metallic network, further preferably a nickel foam. Such a network material £ι inherently has porosity suitable for adsorption of CO2-absorbers.
Advantageously, the volume of CO2 absorbed from the gas by the substrate, V2, may be more or less equal to the volume of CO2 contained in the gas prior to its treatment, V1, that is to say V1 = V2. The closer V2 is to V1, the more efficient the absorption method is.
The CO2-absorbers described above may be of the form R1R2R3N (and the quaternary ammonium compound similarly of the form R1R2R3R4N+) wherein each of R1, R2 and R3 (and R4 as appropriate) is independently selected from the group consisting of hydrogen, a linear alkyl, a branched alkyl, a cyclic alkyl, a substituted linear alkyl, a substituted branched alkyl, a substituted cyclic alkyl, an aryl, a substituted aryl, an arylated alkyl (aralkyl), a substituted aralkyl, a heterocyclic, a substituted heterocyclic, a hetero-aryl and a substituted hetero-aryl.
However preferably any two of R1, R2 and R3 (and R4 as appropriate) may be independently selected from the group consisting of hydrogen and the non-sterically bulky substituents having between 1 and 6 carbon atoms inclusively, and the remaining Rx is (are) a sterically bulky substituent(s) having at least 6 carbon atoms.
Indeed the CO2-absorber may be selected from any one or more of the following amines: dehydroabietylamine, butylamine, octylamine, benzylamine, α- methylbenzylamine, 2-amino-2-ethyl-1 ,3-propanediol, diphenylamine, ethanolamine, diethanolamine, triethanolamine, piperazine, 2-methylpiperazine, N- methylpiperazine, homopiperazine, piperidine, morpholine, pyrrolidine, α- aminopyridine, β-aminopyridine, γ-aminopyridine and spermine.
The step of contacting the gas with the substrate preferably occurs in the presence of water (H2O), which is present in an amount such that the ratio of CO2 : H2O is at least 1 :1. An equilibrium exists between CO2 plus H2O and carbonic acid (H2CO3), the bicarbonate ion (HCO3 ") and the carbonate ion (CO3 2"), which is beneficial to the method of the invention.
Advantageously water vapour may be comprised in the CO2-containing gas, especially where the gas is a product of hydrocarbons combustion, occurring in e.g. an internal combustion engine of a vehicle, a gas turbine, a refinery fluestack, a power station or in another industrial plant. Typically the gas may comprise at least 5 % by volume of CO2 prior to contacting the substrate. However this may be at least 10 % or even 20 % depending upon the conditions of CO2 emission.
The step of contacting the gas with the substrate may occur at a temperature of between 5 0C and 100 0C, preferably between 10 0C and 85 0C, and further preferably between 15 0C and 70 0C. Such a temperature is believed to be optimal for enabling absorption of CO2 from the gas.
In addition to the foregoing, the method of the invention may further comprise the step of pre-treating the absorption substrate with an alkali metal compound, MX, such that the CO2-absorbers form an RiR2N M+ intermediate prior to contacting the gas with the substrate. This intermediate is a powerful base and may be used to drive the CO2 and H2O equilibrium described above in the direction of the carbonate ion. Advantageously the metal, M, is lithium.
Absorption of CO2 by the substrate thus preferably forms of any one or more of the following absorption compounds: an amine carbonate, an amine hydrogen carbonate, a quaternary ammonium carbonate, a quaternary ammonium hydrogen carbonate.
Although the method of the invention may be performed in any environment in which the level of CO2 in the atmosphere is desired to be reduced, including both open and closed systems, the substrate is preferably provided in a re-sealable chamber which has a gas inlet, for introduction of the CO2-containing gas, and a gas outlet, for exhaustion of the CO2-deficient gas. Beneficially gas introduction to, and exhaustion from, the chamber may be performed continuously such that there is a negligible residence time of the gas in the chamber (subject to the gaseous flow rate through the chamber), and this maximum gaseous throughput to achieve increased absorption efficiency.
Turning now to the second aspect of the invention, there is provided a method of desorbing CO2 from a CO2-rich absorption substrate, the substrate having any one or more of the following CO2-absorbers adsorbed onto it: a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium compound and a pre-absorbed volume, V3, of CO2, the method comprising: treating the substrate with an acid, thereby releasing a volume, V4, of the absorbed
CO2.
For the avoidance of doubt, a CO2-rich absorption substrate is one having a volume, V3, of CO2 pre-absorbed onto it. The substrate itself may be organic or inorganic, and is preferably porous. The CO2-absorbers may be adsorbed onto the surface of the substrate, including adsorption into its pores, where such exist.
Preferably the acid used is an organic acid, which may be selected from the group consisting of: acetic acid, lactic acid, citric acid, malic acid and tartaric acid. Such weak acids may the by-product of another industrial process or they may be formed by oxidation from a corresponding alcohol. In any case, the acid preferably has a low "carbon footprint".
Alternatively, the acid may be an inorganic acid, in which case it may be selected from the group consisting of: sulphuric acid and phosphoric acid. The acid used may furthermore be a mixture of different acids.
Advantageously the volume of CO2 desorbed/released, V4 may be more or less equal to the volume of pre-absorbed CO2, V3, that is to say V3 = V4. The ratio of V3 to V4 is dependent on the amount and/or concentration of acid used, and as such, CO2 desorption is controllable.
In addition to the foregoing steps for desorbing CO2, the invention preferably further comprises the step of preheating the substrate so that the CO2-absorption compound forms a carbonate prior to treating it with the acid.
Typically the substrate may be preheated to a temperature of at least 40 0C, and preferably up to around 120 °C. This temperature range appears to be optimal in terms of carbonate formation, whilst maintaining the integrity of the substrate and preventing its degradation.
Furthermore following the step of treating the substrate with the acid, the method may also comprise the step of treating the acidified substrate with an alkali to regenerate the CO2-absorption property of the substrate. The alkali is preferably an excess of aqueous ammonia.
Although the method of the invention may be performed in any environment in which it is desired to desorb a volume of absorbed CO2 from a substrate, including both open and closed systems, the substrate is preferably provided in a re-sealable chamber which has an inlet, for introduction of the acid, and an outlet, for exhaustion of desorbed CO2. Advantageously, in the method of desorbing CO2 described above according to the second aspect of the invention, the CO2 may be pre-absorbed by the substrate according to the first aspect of the invention. Thus the two methods may be considered as complementary and may be co-operable with one another.
Turning now to the third aspect of the invention, there is provided a CO2 absorption/desorption apparatus comprising a re-sealable chamber having an inlet, for introduction of a CO2-containing gas and/or an acid, and an outlet, for exhaustion of a CO2-deficient gas and/or desorbed CO2. One piece of apparatus may thus be suitable for sequentially performing each of the two methods of the invention without modification.
Preferably the apparatus comprises at least two such chambers adapted so as to be cyclically operable, such that when CO2 absorption occurs in one chamber, previously absorbed CO2 desorption occurs in the other chamber, in a complementary manner.
Carbon dioxide that has been absorbed for release may be beneficially re-used in other processes, especially those involving organic matter, such as feeding algae, in enzyme regeneration and in polymer regeneration.
For a better understanding the present invention will now be more particularly described by way of non-limiting example. Example 1 - CO? Absorption
A CO2-absorber solution was made by dissolving 20.Og (0.12 moles) of benzyltrimethylammonium hydroxide (a quaternary ammonium compound) in 100ml of water under ambient conditions. The solution was mixed with methylated spirits and applied to a polysulfone substrate (the composition of which includes sulphur atoms, having an atomic number of 16). The substrate was allowed to dry at room temperature, during which time the methylated spirits evaporated. A suitable polysulfone substrate is available under the trade name UDEL™ Polysulfone P-1700 from Solvay Advanced Polymers, Georgia, USA. Alternatively, the substrate could be a nickel foam (the composition of which includes nickel atoms, having an atomic number of 28). Such a metallic foam is available under the trade name IncoFoam™ from lnco Special Products (www.incosp.com).
The resultant CO2-absorption substrate was placed into a re-sealable stainless steel chamber, having a gas inlet and a gas outlet, which was then sealed to the atmosphere. Pure gaseous CO2 was pumped into the sealed chamber through the gas inlet at a rate of 0.5 litres/minute for 2 minutes. A gas analyzer (GreenLine 8000 Flue Gas Analyzer available from E Instruments Group of Pennsylvania, USA) was arranged to contemporaneously analyze the gas exiting the chamber via the gas outlet. The results showed 91 % absorption of CO2.
This result was confirmed with a laboratory experiment, in which pure gaseous CO2 was bubbled through the CO2-absorber solution at a rate of 0.5 litres/minute for 2 minutes. The resulting solution was heated under reflux for 45 minutes whilst being sparged with nitrogen. The exiting gas was passed through a fine glass sintered bubbler into aqueous sodium hydroxide. Back-titration of the aqueous sodium hydroxide yielded the result that 2.Og of CO2 had been absorbed (76 % absorption), with the concomitant formation of benzyltrimethylammonium carbonate.
The resulting solution of benzyltrimethylammonium carbonate was then made up to a total volume of 100ml by addition of distilled water and cooled to a temperature of less than 20 0C. Pure gaseous CO2 was bubbled through the solution at a rate of 0.5 litres/minute for 2 minutes to form a solution of benzyltrimethylammonium hydrogen carbonate.
The resulting solution was heated under reflux for 45 minutes whilst being sparged with nitrogen. The exiting gas was again passed through a fine glass sintered bubbler into aqueous sodium hydroxide. Back-titration of the aqueous sodium hydroxide yielded the result that 2.4g of CO2 had been absorbed (91 % absorption), with the concomitant formation of benzyltrimethylammonium carbonate.
Example 2 - CO? Desorption
Subsequent to analysis of the exiting gas from the sealed chamber in Example 1 , the substrate inside the chamber was treated with a slight excess of citric acid (a weak organic acid) until effervescence ceased. The gas analyzer yielded the result that all of the absorbed CO2 had been desorbed, i.e. the full 91 % was desorbed and detected.
Again this result was confirmed with a laboratory experiment. The benzyltrimethylammonium carbonate finally formed in the laboratory experiment described in Example 1 above was intermittently treated with a slight excess of citric acid and sparged with nitrogen until the observed effervescence ceased. The exiting gas was passed through a fine glass sintered bubbler into aqueous sodium hydroxide. Back-titration of the aqueous sodium hydroxide yielded the result that 2.8g of CO2 had been absorbed, representing a 91 % recovery of CO2 over the three stages (two in Example 1 and this in Example 2).
Example 3 - COg Desorption
A further laboratory experiment was performed to assess CO2 desorption. 104g (0.30 moles) of diethanolamine hydrogen carbonate (a CO2-absorption compound) was suspended in 500ml of isopropyl alcohol and heated to reflux whilst being sparged with nitrogen. The exiting gas was bubbled into a stirred solution of 20Og (0.62 moles) if diethanolamine in 2000ml of methylated spirits (95 %) at 0 0C whereupon a precipitate was formed.
The precipitate was filtered and titrated with more methylated spirits (95 %) and subsequently filtered and dried under ambient conditions to yield 84g of diethanolamine hydrogen carbonate, representing an 81 % recovery of CO2 over the two stages.
In summary, a porous substrate such as a polysulfone or a metallic foam can be impregnated with an amine CO2-absorber, contacted with a gas containing CO2 and have CO2 (up to 100 %) absorbed from the gas by the substrate. Furthermore CO2 can be desorbed from a CO2-rich absorption substrate, which may or may not be formed by the absorption method of the invention, using an acid, such as a weak organic acid, with subsequent regeneration of the absorption substrate.

Claims

CLAIMS:
1. A method of absorbing carbon dioxide (CO2) from a gas that includes a volume, V1, of CO2 (a CO2-containing gas) the method comprising: providing a CO2-absorption substrate, and contacting the gas with the substrate, whereby a volume, V2, of CO2 is absorbed from the gas by the substrate leaving a CO2-deficient gas, wherein the substrate comprises a porous material, the composition of which comprises at least one chemical element having an atomic number of 13 or greater, onto which any one or more of the following CO2-absorbers is adsorbed: a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium compound.
2. A method according to claim 1 wherein the substrate is a polymeric material.
3. A method according to claim 2 wherein the polymeric material is a polysulfone.
4. A method according to claim 1 wherein the substrate is a metallic network.
5. A method according to claim 4 wherein the metallic network is a nickel foam.
6. A method according to any preceding claim wherein V1 = V2.
7. A method according to any one of the preceding claims wherein the CO2- absorbers are of the form R1R2R3N (and the quaternary ammonium compound is similarly of the form R1R2R3R4N+) wherein each of R1, R2 and R3 (and R4 as appropriate) is independently selected from the group consisting of hydrogen, a linear alkyl, a branched alkyl, a cyclic alkyl, a substituted linear alkyl, a substituted branched alkyl, a substituted cyclic alkyl, an aryl, a substituted aryl, an arylated alkyl (aralkyl), a substituted aralkyl, a heterocyclic, a substituted heterocyclic, a hetero-aryl and a substituted hetero-aryl.
8. A method according to claim 7 wherein any two of R1, R2 and R3 (and R4 as appropriate) is independently selected from the group consisting of hydrogen and the non-sterically bulky substituents having between 1 and 6 carbon atoms inclusively, and the remaining Rx is (are) a sterically bulky substituent(s) having at least 6 carbon atoms.
9. A method according to claim 7 or claim 8 wherein the CO2-absorber is selected from any one or more of the following amines: dehydroabietylamine, butylamine, octylamine, benzylamine, α-methylbenzylamine, 2-amino-2-ethyl- 1 ,3-propanediol, diphenylamine, ethanolamine, diethanolamine, triethanolamine, piperazine, 2-methylpiperazine, N-methylpiperazine, homopiperazine, piperidine, morpholine, pyrrolidine, α-aminopyridine, β- aminopyridine, γ-aminopyridine and spermine.
10. A method according to any preceding claim wherein contacting of the gas with the substrate occurs in the presence of water (H2O), which is present in an amount such that the ratio of CO2 : H2O is at least 1 :1.
11. A method according to claim 10 wherein water vapour is comprised in gas.
12. A method according to claim 11 wherein the gas is a product of hydrocarbons combustion.
13. A method according to any preceding claim wherein the gas comprises at least 5 % by volume of CO2 prior to contacting the substrate.
14. A method according to any preceding claim wherein contacting the gas with the substrate occurs at a temperature of between 5 0C and 100 °C.
15. A method according to any of claims 7 to 14 further comprising the step of pre-treating the absorption substrate with an alkali metal compound, MX, such that the CO2-absorbers form an R1R2N M+ intermediate prior to contacting the gas with the substrate.
16. A method according to claim 15 wherein the metal, M, is lithium.
17. A method according to any preceding claim wherein absorption of CO2 by the substrate forms of any one or more of the following absorption compounds: an amine carbonate, an amine hydrogen carbonate, a quaternary ammonium carbonate, a quaternary ammonium hydrogen carbonate.
18. A method according to any preceding claim further comprising providing the substrate in a re-sealable chamber which has a gas inlet, for introduction of the CO2-containing gas, and a gas outlet, for exhaustion of the CO2-deficient gas.
19. A method according to claim 18 wherein gas introduction and exhaustion is performed continuously.
20. A method of desorbing CO2 from a CO2-rich absorption substrate, the substrate having any one or more of the following CO2-absorbers adsorbed onto it: a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium compound and a pre-absorbed volume, V3, of CO2, the method comprising: treating the substrate with an acid, thereby releasing a volume, V4, of the absorbed CO2.
21. A method according to claim 20 wherein the acid is an organic acid.
22. A method according to claim 21 wherein the organic acid is selected from the group consisting of: acetic acid, lactic acid, citric acid, malic acid and tartaric acid.
23. A method according to claim 20 wherein the acid is an inorganic acid.
24. A method according to claim 23 wherein the inorganic acid is selected from the group consisting of: sulphuric acid and phosphoric acid.
25. A method according to any of claims 20 to 24 wherein V3 = V4.
26. A method according to any of claims 20 to 25 further comprising preheating the substrate so that the CO2-absorption compound forms a carbonate prior to treating it with the acid.
27. A method according to claim 26 wherein the substrate is preheated to a temperature of at least 40 0C.
28. A method according to any of claims 20 to 27 further comprising treating the acidified substrate with an alkali to regenerate the CO2-absorption property of the substrate.
29. A method according to claim 28 wherein the alkali is an excess of aqueous ammonia.
30. A method according to any of claims 20 to 29 further comprising providing the substrate in a re-sealable chamber which has an inlet, for introduction of the acid, and an outlet, for exhaustion of desorbed CO2.
31. A method according to any of claims 20 to 30 wherein CO2 is pre-absorbed by the substrate according to the method of any of claims 1 to 19.
32. CO2 absorption/desorption apparatus comprising a re-sealable chamber having an inlet, for introduction of a CO2-containing gas and/or an acid, and an outlet, for exhaustion of a CO2-deficient gas and/or desorbed CO2.
33. CO2 absorption/desorption apparatus as claimed in claim 32 comprising at least two such chambers adapted so as to be cyclically operable, such that when CO2 absorption occurs in one chamber, previously absorbed CO2 desorption occurs in the other chamber.
34. A method of absorbing CO2 from a CO2-containing gas substantially as hereinbefore described.
35. A method of desorbing CO2 from a CO2-rich absorption substrate substantially as hereinbefore described.
36. CO2 absorption/desorption apparatus substantially as hereinbefore described.
PCT/GB2010/000290 2009-02-19 2010-02-19 Methods of absorption and desorption of carbon dioxide, and apparatus for each, for beneficial re-use of carbon dioxide WO2010094923A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0902800A GB2467921A (en) 2009-02-19 2009-02-19 Carbon dioxide absorption and desorption
GB0902800.2 2009-02-19

Publications (2)

Publication Number Publication Date
WO2010094923A2 true WO2010094923A2 (en) 2010-08-26
WO2010094923A3 WO2010094923A3 (en) 2010-11-18

Family

ID=40565372

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2010/000290 WO2010094923A2 (en) 2009-02-19 2010-02-19 Methods of absorption and desorption of carbon dioxide, and apparatus for each, for beneficial re-use of carbon dioxide

Country Status (2)

Country Link
GB (1) GB2467921A (en)
WO (1) WO2010094923A2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012120173A1 (en) * 2011-03-04 2012-09-13 Endesa, S. A. Method for capturing co2
WO2017040761A1 (en) * 2015-09-01 2017-03-09 Ohio State Innovation Foundation Membranes for gas separation
CN107073381A (en) * 2014-09-12 2017-08-18 庄信万丰股份有限公司 Sorbent material
CN114558549A (en) * 2020-11-27 2022-05-31 北京驭碳科技有限公司 Use of carboxylate compounds as absorbents for capturing carbon dioxide
CN114870587A (en) * 2022-05-05 2022-08-09 北京金隅水泥节能科技有限公司 Industrial flue gas carbon dioxide trapping agent and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116832580B (en) * 2023-08-21 2024-03-15 天府永兴实验室 Low energy carbon dioxide capture composition with hydrogen ion self-regulating property, capture method and application

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB850443A (en) * 1957-07-05 1960-10-05 Exxon Research Engineering Co Method and apparatus for fractionating gaseous mixtures
US4539020A (en) * 1983-07-10 1985-09-03 Kawasaki Steel Corporation Methods for obtaining high-purity carbon monoxide
JP2001070736A (en) * 1999-07-05 2001-03-21 Toray Ind Inc Adsorption element, air filter, air conditioner, oxygen- enriching apparatus, carbon dioxide removal apparatus, and fuel cell system
US6364938B1 (en) * 2000-08-17 2002-04-02 Hamilton Sundstrand Corporation Sorbent system and method for absorbing carbon dioxide (CO2) from the atmosphere of a closed habitable environment
US6547854B1 (en) * 2001-09-25 2003-04-15 The United States Of America As Represented By The United States Department Of Energy Amine enriched solid sorbents for carbon dioxide capture
JP3937016B2 (en) * 2003-09-19 2007-06-27 独立行政法人産業技術総合研究所 Regeneration method of carbon dioxide absorbing material
US7288136B1 (en) * 2005-01-13 2007-10-30 United States Of America Department Of Energy High capacity immobilized amine sorbents
WO2006094411A1 (en) * 2005-03-11 2006-09-14 University Of Ottawa Functionalized adsorbent for removal of acid gases and use thereof
US7795175B2 (en) * 2006-08-10 2010-09-14 University Of Southern California Nano-structure supported solid regenerative polyamine and polyamine polyol absorbents for the separation of carbon dioxide from gas mixtures including the air

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012120173A1 (en) * 2011-03-04 2012-09-13 Endesa, S. A. Method for capturing co2
ES2387791A1 (en) * 2011-03-04 2012-10-01 Endesa, S.A. Method for capturing co2
CN107073381A (en) * 2014-09-12 2017-08-18 庄信万丰股份有限公司 Sorbent material
CN107073381B (en) * 2014-09-12 2020-10-16 庄信万丰股份有限公司 Adsorbent material
WO2017040761A1 (en) * 2015-09-01 2017-03-09 Ohio State Innovation Foundation Membranes for gas separation
US10213747B2 (en) 2015-09-01 2019-02-26 Ohio State Innovation Foundation Membranes for gas separation
CN114558549A (en) * 2020-11-27 2022-05-31 北京驭碳科技有限公司 Use of carboxylate compounds as absorbents for capturing carbon dioxide
CN114870587A (en) * 2022-05-05 2022-08-09 北京金隅水泥节能科技有限公司 Industrial flue gas carbon dioxide trapping agent and preparation method thereof
CN114870587B (en) * 2022-05-05 2023-04-14 北京金隅节能科技有限公司 Industrial flue gas carbon dioxide trapping agent and preparation method thereof

Also Published As

Publication number Publication date
WO2010094923A3 (en) 2010-11-18
GB2467921A (en) 2010-08-25
GB0902800D0 (en) 2009-04-08

Similar Documents

Publication Publication Date Title
CA2933236C (en) System for the capture and release of acid gases
Ajhar et al. Siloxane removal from landfill and digester gas–A technology overview
WO2010094923A2 (en) Methods of absorption and desorption of carbon dioxide, and apparatus for each, for beneficial re-use of carbon dioxide
US9365423B2 (en) Method and device for separating hydrogen sulfide and hydrogen production system using the same
CN108993125B (en) Eutectic solvent for removing carbon dioxide in air and flue gas
AU2015269515B2 (en) Carbon dioxide recovery device, and method for treating exhaust gas
CN103623771A (en) Waste solution mercury removal adsorbent, preparation method and application method thereof
DE502007006314D1 (en) Method for removing mercury from combustion exhaust gases
KR102114062B1 (en) METHOD FOR REMOVING SOx FROM GAS USING POLYOL COMPLEX SOLUTION
CA2916141A1 (en) Methods, systems and apparatuses for capturing and sequestering carbon dioxide emitted from a vehicle
EP3378550A1 (en) Carbon dioxide adsorbent and carbon dioxide separation and recovery system
CN106563346A (en) Reaction type VOCs absorbent
AU2019202469B2 (en) Acidic gas absorbent, acidic gas removal method and acidic gas removal apparatus
RU2576634C1 (en) Adsorbent for trapping, concentration and storage of carbon dioxide
Chioyama et al. Temperature-dependent double-step CO2 occlusion of K2CO3 under moist conditions
CN110302759B (en) Nano-framework material for adsorbing hydrogen sulfide gas
KR101419589B1 (en) Carbon dioxide absorbent and recycle method thereof
WO2014011041A1 (en) Nitrosamine and/or nitramines reduction in a liquid medium
US20240173665A1 (en) Methods for capturing co2 from dilute co2 streams of varying humidity, including natural gas combine cycle exhaust streams and ambient air streams using kaust-7 based physisorbents
CN117160432B (en) Desorption liquid, preparation method, active carbon desorption method and active carbon
CN109439377B (en) Adsorbent for removing hydrogen sulfide
CN117529358A (en) Use of MOF-based physical adsorbents from air and diluted CO 2 Concentration of CO in stream 2 Is a method of (2)
Hussin et al. Green synthesis approach using deep eutectic solvents to enhance the surface functional groups on porous carbon for CO2 capture
KR20240139046A (en) Sorption material for CO2 capture, its use and method for producing same
WO2024176018A1 (en) Amine solvent-based carbon capture compositions

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: 10710090

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10710090

Country of ref document: EP

Kind code of ref document: A2

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 13.03.2012)

122 Ep: pct application non-entry in european phase

Ref document number: 10710090

Country of ref document: EP

Kind code of ref document: A2