GB2428038A - Process for the extraction of carbon dioxide from a gas - Google Patents
Process for the extraction of carbon dioxide from a gas Download PDFInfo
- Publication number
- GB2428038A GB2428038A GB0513866A GB0513866A GB2428038A GB 2428038 A GB2428038 A GB 2428038A GB 0513866 A GB0513866 A GB 0513866A GB 0513866 A GB0513866 A GB 0513866A GB 2428038 A GB2428038 A GB 2428038A
- Authority
- GB
- United Kingdom
- Prior art keywords
- carbon dioxide
- gas
- ceramic
- conduit
- metal oxide
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 137
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 23
- 238000000605 extraction Methods 0.000 title claims abstract description 5
- 239000000919 ceramic Substances 0.000 claims abstract description 48
- 230000036961 partial effect Effects 0.000 claims abstract description 13
- 239000012466 permeate Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims description 32
- 150000004706 metal oxides Chemical class 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000006096 absorbing agent Substances 0.000 claims description 21
- 239000004927 clay Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 230000004888 barrier function Effects 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 239000004566 building material Substances 0.000 claims description 2
- 239000003337 fertilizer Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000292 calcium oxide Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 description 79
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 56
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 238000003795 desorption Methods 0.000 description 11
- 239000000446 fuel Substances 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 235000010216 calcium carbonate Nutrition 0.000 description 6
- 229910021532 Calcite Inorganic materials 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011236 particulate material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000001960 triggered effect Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
- C01B3/384—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 the catalyst being continuously externally heated
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- 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
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- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
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- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
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- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/04—Clay; Kaolin
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/057—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on calcium oxide
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- 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
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- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C01B2203/06—Integration with other chemical processes
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- 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
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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Abstract
A process for the extraction of carbon dioxide from a carbon dioxide-containing gas by calcium oxide by formation of calcium carbonate, said process comprising flowing said carbon dioxide-containing gas past or through a gas-porous, calcium oxide-containing ceramic member 1 disposed in a reactor vessel whereby said carbon dioxide-containing gas may permeate said member, and preferably subsequently heating said member and/or exposing said member to a gas having a lower carbon dioxide partial pressure than said carbon dioxide-containing gas whereby to cause calcium carbonate therein to release carbon dioxide, said member defining at least part of the inner wall of a gas flow conduit within said reactor vessel. Also disclosed are a conduit device, a process for the production of a ceramic product and a ceramic.
Description
Process This invention relates to a process for the extraction of carbon
dioxide from the gaseous product of methane reformation (generally using natural gas or a natural gas derived material as the starting material for the process) or combustion (e.g. from flue or exhaust gases), to apparatus therefor and to ceramics and ceramic-containing elements suitable for use therein.
Methane reformation involves the reaction of methane and water at elevated temperature to produce hydrogen and carbon dioxide. The resultant hydrogen may be used for many purposes but it is of particular interest for use in fuel cells, in chemical processes or as a fuel gas.
Where the hydrogen produced is used in fuel cells, reformation effectively centralizes the environmental problems of generating energy from methane since the carbon dioxide generated can be captured at the site of the reactor used for the methane reformation.
The gaseous output of a methane reformation reactor is generally referred to as synthesis gas (or syngas) and comprises hydrogen, water, carbon dioxide, some carbon monoxide and some methane. The carbon monoxide may be converted by reaction with water in a shift reactor to produce hydrogen and carbon dioxide and thus the output from the combination of reformer and shift reactors is hydrogen, water, carbon dioxide and some methane and/or carbon monoxide.
It has been proposed in US-B-6667022 to pass steam and the syngas from a reformer through a fluidized bed in a first reactor comprising a fluidized bed of particulate calcium oxide and ferric oxide whereby the calcium oxide reacts with the carbon dioxide to produce calcium carbonate and the carbon monoxide is transformed to carbon dioxide by a combination of a shift reaction and reduction of the ferric oxide. The upper part of the particulate bed is fed, together with the gas output (essentially wet hydrogen) into a second fluidized bed in a second reactor which functions to separate the gas from the solid and perhaps also to some extent as a shift reactor to transform any remaining carbon monoxide to carbon dioxide which can react with remaining calcium oxide. Gas essentially comprising wet hydrogen is drawn out of the top of this reactor while the particulate material from the base of this reactor is fed into a fluidized bed in a third reactor. The bed in this third reactor is fluidized with oxygen and steam which serves to oxidize the ferrous oxide back to ferric oxide and to regenerate calcium oxide from the calcium carbonate as a result of the heat emitted by the oxidation reaction.
The gas drawn off from the top of the third reactor is essentially a mixture of water, carbon dioxide, oxygen and some methane. The regenerated particulate mass is drawn off the base of this reactor and recycled into the base of the first reactor.
This procedure, while attractive as a means of separating the hydrogen in syngas from carbon monoxide and carbon dioxide, is undesirably complicated as it requires a particulate mass to be circulated between three separate reactors in which the particulate components undergo cyclical chemical changes which will of course result in their structural integrity, and hence their ability to withstand the physical cycling procedure, being reduced.
We have now found that carbon dioxide removal may be effected particularly advantageously using a static metal carbonate/oxide bed which is cycled between conditions which cause carbon dioxide absorption and conditions which cause carbon dioxide release. The bed may be particulate, in which case it will be retained in place along a length of a gas transmitting conduit by a porous retainer, e.g. a porous metal or ceramic inner wall, or it may be a self-supporting ceramic in which case it may be placed within or form some or all of the inner wall of that length of conduit.
Thus viewed from one aspect the invention provides a process for the extraction of carbon dioxide from a carbon dioxide-containing gas (preferably a gas which contains hydrogen and/or methane and optionally which contains water, especially a gas produced in a methane reformation process, in particular syngas) by a metal oxide, especially an alkaline earth metal oxide, by formation of the corresponding metal carbonate (and preferably for the release of carbon dioxide from said metal carbonate to regenerate said metal oxide), said process comprising flowing said carbon dioxide- containing gas past or through a gas-porous member disposed in a reactor vessel and containing said metal oxide whereby said carbon dioxide- containing gas may permeate said member, and preferably subsequently heating said member and/or exposing said member to a gas having a lower carbon dioxide partial pressure than said carbon dioxide-containing gas whereby to cause metal carbonate therein to release carbon dioxide, said member defining at least part of the inner wall of a gas flow conduit within said reactor vessel.
Viewed from a further aspect the invention also provides a carbon dioxide separation apparatus comprising a vessel having a gas inlet and a gas outlet and a gas flow conduit linking said inlet and outlet, at least part of an inner wall of said conduit being provided by a gas porous member containing a metal oxide and/or carbonate, wherein carbon dioxidecontaining gas flowing through said conduit permeates said member permitting carbon dioxide in said gas to react with metal oxide in said member to form metal carbonate, said apparatus being arranged such that said member may be heated and/or exposed to a gas having a lower carbon dioxide partial pressure than said carbon dioxide-containing gas whereby to cause metal carbonate therein to release carbon dioxide into said conduit.
Particularly desirably, the apparatus comprises a first such member and a second such member in thermal contact with each other via a gasimpermeable, thermally conducting barrier (e.g. a metal barrier) whereby the first member may in one stage of operation serve to absorb carbon dioxide from a conduit while the second member is functioning to release carbon dioxide into a conduit and in a further stage of operation the second member may serve to absorb carbon dioxide from a conduit while the first member is functioning to release carbon dioxide into a conduit. In this embodiment, the apparatus is preferably provided with a valve which may be operated to direct the carbon dioxide-containing gas alternatively past the first or second member and also desirably a further valve which may be operated to direct an essentially hydrogen-free gas past the other member.
Thus, for example, in one preferred embodiment, the members may be arranged concentrically between inner and outer concentric conduits with an intervening concentric gas impermeable barrier, and preferably within an outer concentric gas-impermeable shell. In an alternative preferred embodiment, two or more parallel conduits are separated by one or more gas impermeable barriers, with the members either forming the walls of the conduits or being disposed on either side of the barrier(s) between adjacent conduits. In this way an array of two or more conduits, e.g. 1x2, 1x4, 2x2, 2x3, 2x4 or 4x4 conduits may simultaneously operate to absorb or release carbon dioxide from or into the gas passing through them.
In a further preferred embodiment, the members are enclosed by a gasimpermeable, thermally conducting barrier and have extending therethrough a gas flow conduit.
In a yet further preferred embodiment the members have extending therethrough a first gas flow conduit from which gas may permeate the member and a second conduit having a gas-impermeable, thermally conducting wall whereby gas therein may not permeate the member.
The conduit through the members may be a single conduit or a plurality of conduits from which gas may permeate the same volumes of the member, i.e. it may provide multiple flow paths so as to increase the efficiency of carbon dioxide uptake or release.
Such conduit arrangements are novel and form a further aspect of the invention. Viewed from this aspect the invention provides a conduit device comprising an outer gas-impermeable wall containing therein a conduit and a gas permeable member containing a metal oxide transformable by carbon dioxide uptake to a metal carbonate or a said metal carbonate transformable on heating to said metal oxide, whereby gas from said conduit may permeate said member, said conduit device having a gasimpermeable thermally conductive portion (preferably a barrier) wherefrom heat may be transferred to or from said member. If desired, the barrier may be provided by the said outer wall.
Particularly desirably the members are formed from a porous ceramic material. However they may alternatively comprise containers having a porous wall (e.g. a perforated or sintered metal or ceramic wall) behind which is disposed a particulate material comprising the metal oxide/carbonate. In this latter case, the particulate may also comprise an inert filler, e.g. a silicate (for example sand), in order to maintain gas porosity of the particulate material.
The metal of the metal oxide/carbonate is preferably, for reasons of economy and efficiency, calcium. However other metals which can be cycled between their oxide and carbonate forms, e.g. alkaline earth metals such as magnesium, may be used in place of or in addition to calcium.
The particulate or ceramic may also if desired contain a material which may function as a catalyst in one or more stages of methane reformation or water-shift reactions, for example an iron oxide.
Where the metal oxide / carbonate is present in a ceramic, some or all of the remaining material making up the ceramic is preferably a clay. For this purpose, any clay from which a ceramic can be prepared may be used.
The preferred clays and preferred means of manufacturing the ceramic are discussed further below. Generally however the metal oxide / carbonate content (expressed in terms of the content of the metal oxide / carbonate when in metal carbonate form) of the dry ceramic will preferably be from 30 to 9O wt, more preferably 50 to 85, especially 60 to 85%, particularly 75 to 8O& wt.
At too high a metal carbonate content, the ceramic becomes friable and difficult to handle; at too low a metal carbonate content, the amount of carbon dioxide absorbable per unit volume is undesirably low. In general, gas porosity is substantially similar at 50 to wt. metal carbonate content.
Where the apparatus of the invention is to be used on a Continuous basis, it can desirably be provided with an expansion tank or tanks arranged to receive the gas flow to or from the conduit during changeover from CO2 absorption to CO2 release in specific lengths of the conduit or alternatively it may be provided with extra lengths of conduit so that each such length is either in CO2 uptake, CO2 release or changeover mode. During changeover mode, the gas content of any such length may be driven out by a gas which does not cause any significant CO2 release or uptake as desired.
It is also preferred that the apparatus be provided with sensors to monitor CO2 uptake by the members (e.g. weight sensors or CO2 sensors) in order that cycling between CO2 uptake and CO2 release may be achieved most efficiently. Typically such sensors will be functionally connected to a controller, e.g. a computer, which will switch from CO2 uptake once a predetermined amount of CO2 has been taken up, e.g. at least 50%-, more preferably at least 75%-, for example less than 80%- of the theoretical maximum determinable in laboratory conditions for the material used. The use of such a sensor is particularly desirable when the members are fresh or are reaching the end of their operating lives.
It is not necessary to monitor CO2 uptake along the whole length of the CO2 uptake conduit; desirably this is done at a small number of points, e. g. 1 to 6 points, along the length, preferably including at least one between 20 and 80%- of the distance along this length.
The apparatus of the invention has four particularly preferred formats. In the first it comprises a methane reformation reactor, a shift reactor and a carbon dioxide absorber in series; in the second it comprises a carbon dioxide absorber, optionally fed by a combustion apparatus (e.g. an engine or a heat and power generator); in the third it comprises a combined methane reformation reactor, shift reactor and carbon dioxide absorber (i.e. a fully integrated reactor); and in the fourth it comprises a methane reformation reactor and a combined shift reactor and carbon dioxide absorber (i.e. a partially integrated reactor).
Where the apparatus comprises a methane reformation reactor, this may for example be a steam reformer or a thermal reformer. Since the process performed within the reformation reactor generates carbon dioxide, the reactor may comprise a gas porous metal oxide/carbonate member as described herein which will operate to remove some of the carbon dioxide that is generated. As described, it is preferred that these members be arranged so that they can be switched between absorption and desorption modes so allowing continuous operation of the reactor.
Where the apparatus comprises a shift reactor, this may for example be a tilOWle temperature shift reactor or a "high" temperature shift reactor, or both may be present. As described above, the shift reactor may comprise a gas porous metal oxide/carbonate member as described herein which will operate to remove some of the carbon dioxide that is generated and that is present in the gas fed into the shift reactor. Once again, it is preferred that these members be arranged so that they can be switched between absorption and desorption modes so allowing continuous operation of the reactor.
Where the apparatus comprises a separate carbon dioxide absorber, this will preferably comprise a gas porous metal oxide/carbonate member as described herein which will operate to remove some of the carbon dioxide that is present in the gas fed into the absorber. Once again, it is preferred that these members be arranged so that they can be switched between absorption and desorption modes so allowing continuous operation of the absorber.
Typically the reactor temperature in a steam reformer for methane (normally natural gas, optionally desuiphurized by conventional techniques) is in the range 500 to 1100 C, more preferably 700 to 1020 C. The inlet gas is a steam/methane mixture and the outlet gas a steam/hydrogen/carbon dioxide/carbon monoxide/methane mixture. However, when this is done, the operating temperature is preferably kept below 1000 C, especially below 950 C to avoid undue inactivation of the carbon dioxide absorber.
Where the reformation is by thermal reformation (i.e. also involving addition of oxygen), the operation temperatures are similar, although operation towards the higher ends of the ranges specified may be preferred.
The outlet gas from the reformer is preferably passed through a heat exchanger before passing into a shift reactor in which the carbon monoxide is transformed to carbon dioxide by reaction with steam and optionally also with a reducable inorganic agent, e.g. Fe203.
Typically either co-called low or high temperature shift reactors (or a combination of both) may be used. Low temperature shift reactors typically operate at 200 to 350 C, while high temperature shift reactors typically operate at 350 to 750 C. The preferred operational temperature range is generally 400 to 700 C. The outlet gas from the shift reactor is essentially wet hydrogen, possibly with some relatively low content of CO and CO2.
Any remaining carbon oxide content may be removed by passing the outlet gas through a methanation or PROX (preferential oxygenation) reactor whereafter heat is removed (and water is condensed out of the hydrogen flow) by passage through a heat exchanger. The hydrogen may then be fed to a fuel cell and subsequently to an afterburner. The exhaust gas from the afterburner may then be fed to a further carbon dioxide absorber, optionally using a metal oxide containing material according to the invention. Heat from the afterburner and the heat exchangers may be used to bring the inlet gases for the steam reformer to the desired temperature.
If desired, two shift reactors, in series, may be used, the first being a high temperature shift reactor and the second a low temperature shift reactor.
As an alternative to a methanation or PROX reactor, a pressure swing absorber (PSA) may be used to produce a high pressure pure hydrogen stream. The purge gas from the PSA may then be used to produce a second fuel stream.
In a further alternative, the output gas from the steam reformer may be passed to a PSA to produce a high pressure hydrogen stream which may be fed to a fuel cell. The purge gas from the PSA may then be fed into a shift reactor and CO2 absorber lined with a metal oxide containing material according to the invention. The output from the shift reactor thus provides a second fuel stream.
If desired the shift reactors may not function as carbon dioxide absorbers but instead may be followed by carbon dioxide absorbers in which the gas flow conduit is lined with a metal oxide containing material according to the invention. The gas temperatures in the absorber will typically be in the range 350 to 975 C, preferably 400 to 860 C. The absorber may if desired be preceded or followed by a PSA.
At these operating temperatures, the metal oxide containing material readily serves to absorb carbon dioxide from the gases flowing through the reactor while it undergoes the reformation and shift reactions. By diverting gas flow to alternative conduits through the reactors (or carbon dioxide absorbers), the now metal carbonate containing material, which will remain at similar temperatures, will then release carbon dioxide into the conduits from which it may be drawn off.
Carbon dioxide release may be triggered by increasing temperature, reducing pressure or reducing carbon dioxide partial pressure, or a combination of these.
Reference to Figure 12 of the accompanying drawings will show how, at a given temperature (or carbon dioxide partial pressure), a change in carbon dioxide partial pressure (or temperature) can move the metal oxide! carbonate system from carbon dioxide absorbing to carbon dioxide desorbing or vice versa. Preferably however, any temperature increase to promote carbon dioxide desorption will not be to a temperature above 1100 C, especially not to one above 1000 C. In general however a temperature increase to a temperature above 860 C may be appropriate.
For the carbon dioxide desorption phase, the metal oxide/carbonate system may be contacted with an inert gas (e.g. nitrogen) so as to reduce the carbon dioxide partial pressure. However this results in an effluent gas which is not essentially only carbon dioxide. It is therefore preferred to use a condensable gas (e.g. steam or less preferably an organic solvent) or carbon dioxide. However, during the desorption phase there is no requirement for a gas flow through the desorbing part of the apparatus: desorption may be effected without gas flow, with the desorbed carbon dioxide subsequently being flushed from the apparatus. In general therefore there are four main options for the desorption phase: flush with steam; reduce pressure, e.g. with a vacuum pump; increase temperature; or flush with carbon dioxide at an elevated temperature.
The retrieved carbon dioxide is preferably compressed or liquefied for transport and disposal e.g. by injection into subterranean formations.
The operating temperature in any portion of the apparatus according to the invention which contains a metal oxide/carbonate ceramic carbon dioxide absorbing member according to the invention will preferably be below 1100 C, more preferably below 1000 C so as to avoid inactivation.
As mentioned earlier, the metal oxide / carbonate containing material is preferably a ceramic. This may for example be prepared as follows: clay and water are mixed and allowed to stand so that coarse particles (e.g. mode particle sizes above 60 I.Lm) settle out; the upper layer of water and clay is separated of f; coarser metal carbonate particles (e.g. mode particle size of less than 100 e.g. 2 to 50 m) are mixed in with the separated clay and water to the desired content); the mixture is poured into a mould and dried; the dried material is sintered (e.g. in air, vacuum or C02); and, optionally, the sintered material is exposed to carbon dioxide (e.g. to facilitate transport and storage) Thus viewed from a further aspect the invention provides a process for the production of a ceramic product, said process comprising: mixing clay and water; adding metal carbonate particles to the desired content; extruding or moulding the resulting mixture; drying and sintering the extruded or moulded product; and, optionally, exposing the sintered material to carbon dioxide.
The carbon dioxide released on sintering is preferably captured for disposal.
The metal carbonate used is preferably calcite or dolomite.
The mould used in this process, a process which forms a further aspect of the invention, is preferably a water- absorbent material, e.g. gypsum, so as to prevent deformation during drying.
Sintering is preferably effected at 800 to 1000 C, especially preferably 850 to 925 C.
Exposure to carbon dioxide is preferably effected at a temperature above 520 C, e.g. above 550 C, to avoid formation of metal hydroxide and to expedite the reaction.
The material may be extruded or moulded into blocks which can be Cut and/or built up so as to form structures of the desired shape for use according to the invention; alternatively they can be extruded or moulded in the desired shape, e.g. with channels or voids which will function as the gas flow conduits. In this latter case, the mixture may be added to the mould stepwise so as to build up the desired shape gradually.
The ceramic material may also be produced in particulate or pelletized form, for example for use in an embodiment of the invention in which the ceramic is contained within a porous-walled container.
Viewed from a further aspect the invention provides a ceramic containing at least 60 wt. of an alkaline earth metal carbonate or oxide (calculated as the carbonate) The clay used may be any clay suitable for ceramic formation. Examples of preferred clays are set out in WO 02/081409, the content of which is incorporated herein by reference. WO 02/081409 describes preparation via a calcium hydroxide stage of building blocks which have a relatively low calcium carbonate content in order to have the strength necessary for the desired end use.
The ceramic of the invention, when in the metal oxide containing state, may also be used as a carbon dioxide absorber in other circumstances than in methane reformation, e.g. to absorb carbon dioxide from the exhaust gas of a hydrocarbon burner, for example a heat and/or power generator. For such uses, the ceramic is preferably preconditioned by being subjected to at least one, preferably at least two, e.g. 3 to 10, carbon dioxide absorption and release cycles, as in this way performance is improved. The carbon dioxide loaded ceramic may be collected from the fuel burning site for centralized regeneration and subsequent re-use or it may simply be disposed of as landfill or on fields. The carbon dioxide loaded ceramic material may also be used as a building material or as a fertilizer. Ceramic used in methane reformation may similarly be disposed of.
Such disposal represents an environmentally friendly means of carbon dioxide disposal.
Such use of the ceramic of the invention forms a further aspect of the present invention.
The reader will appreciate that using metal oxide/ carbonate ceramics according to the invention allows processes such as methane reformation and shift processes to be effected at higher pressures than is feasible otherwise and that this also allows facile incorporation into the ceramic of catalysts desirable for use in such processes.
Preferred embodiments of the process, apparatus and ceramics of the invention will now be described further with reference to the following non-limiting Examples and the accompanying drawings in which: Figures 1 to 7 are schematic drawings of integrated apparatus for methane reformation; Figures 8 to 11 are schematic drawings of ceramic-walled gas flow conduits for use in methane reformation apparatus; and Figure 12 is a plot of temperature versus carbon dioxide partial pressure showing the thermodynamic equilibrium between calcium oxide and calcium carbonate.
Example 1
Ceramic Production Blue clay from Tr ndelag was mixed with water. In order to remove the largest fractions of the clay, and any impurities such as stones and sand, sedimentation in water was used to separate out the clay fraction finer than 25 tim. (The mixture of clay and water is allowed to stand so that coarse particles settle out and the upper layer of water and clay is separated off) A sample of the mixture of water and clay (<25 tim) was dried in order to find the dry weight of the mixture (the weight content of the clay). Calcite was then added to produce samples containing 20 to 50% wt clay (e.g. 25% wt) and 80 to 50% wt calcite (e.g. 75% wt) on a dry solids basis using the clay/water mixture (which had a 25% wt clay content). These samples were stirred and dried in a plaster mould. The calcite was bought from Franzefoss Kalk AS (Franzit Micro with specification (average) (6 Lm) 98% CaCO3, 0.8% MgCO3, 0.4% Si02, 0.2% A1203 and 0.15% Fe203, <0.1% Na20) The samples were sintered in an atmosphere of air, vacuum, or CO2 in an oven. The sintering temperature was typically 850-1000 C, preferably below 950 C (lower sintering temperatures gave better ability to absorb CD2) . Calcination takes place in the temperature range 600-1100 C depending on the partial pressure of CO2. The sintering time was e.g. 2-6 hours (dependent on the temperature, e.g. 2 hours at 1050 C). The oven was heated relatively slowly up and cooled slowly down, e.g. 300 C/h, in order not to break the ceramics.
The sintering temperature is preferably 850-925 C.
The ceramics are ready to absorb CO2 after the sintering.
However, if the material is to be transported or stored it might be beneficial to expose the ceramic to C02, e.g. at 700 C for 10-20 hours. The ceramic is stronger when it has absorbed CO2 and CaD is transformed into CaCO3.
However, then the material needs to be treated to desorb the CO2 before it can be used to capture CO2. This can be done either by changing the partial pressure of CO2 in the ceramics atmosphere or elevating the temperature (as described before).
Referring to Figures 1 to 7, there are shown schematically apparatus arrangements for methane reformation according to the invention. The boxes represent different reactors or vessels for different process steps. A dotted walled box indicates that the reactor or vessel is optional. Dashed lines indicate that the gas flow indicated is optional. HT and LT represent high and low temperature. Q represents energy removal, e.g. by heat exchange. FC represents fuel cell. SOFC represents solid oxide fuel cell. Alt. Fuel indicates that the gas may be used as a combustible fuel.
Referring to Figure 8, there is shown a reactor element 1 having concentric gas flow conduits 2 and 3 separated by two concentric ceramic tubes 4 and 5 which are separated by a gas impermeable, thermally conducting metal barrier 6. While the inner ceramic tube is absorbing C02, the outer ceramic tube is desorbing CO2.
When the inner tube has reached its absorption limit, gas flow is switched and the outer ceramic tube is used for CO2 absorption. Operating at similar temperatures, CO2 desorption may be triggered for example by lowering the partial pressure of CO2 in the conduit into which CO2 is to be released.
Figure 9 shows a reactor element 7 operating on the same principle as that of Figure 8 but with a plurality of parallel gas flow conduits 8, 9, 10,11, 12, 13 in two ceramic blocks 14 and 15 separated by a barrier 16.
Figure 10 shows two reactor elements 17 and 18 provided with gas flow conduits 19 and 20, uclosedu conduits 20 being separated from the ceramic blocks 21 by gas impermeable barriers 22. In this way the gas flow from the reformer may be passed through the closed conduits of element 18 before entering the CO2 absorber section in which it flows through the "open" conduits 19 of element 17. In element 17 the closed conduits are used for coolant flow. When element 17 has reached its CO2 absorption limit, gas flow may be switched. In element 18, the closed conduits are used to carry a heated gas so as to raise the temperature of the element and cause CO2 desorption into the open conduits.
Figure 11 shows reactor element arrays 23 and 24 each comprising four ceramic blocks 25, surrounded by a gas impermeable barrier 26 which serves as a heat exchange surface, and having running through their centres a gas flow conduit 27. Array 23 may be used for CO2 absorption while array 24 is used for CO2 desorption and vice versa.
Claims (10)
- Claims: 1. A process for the extraction of carbon dioxide from a carbondioxide- containing gas (e.g. syngas) by a metal oxide, especially an alkaline earth metal oxide, by formation of the corresponding metal carbonate (and preferably for the release of carbon dioxide from said metal carbonate to regenerate said metal oxide), said process comprising flowing said carbon dioxide- containing gas past or through a gas-porous member disposed in a reactor vessel and containing said metal oxide whereby said carbon dioxide- containing gas may permeate said member, and preferably subsequently heating said member and/or exposing said member to a gas having a lower carbon dioxide partial pressure than said carbon dioxide-containing gas whereby to cause metal carbonate therein to release carbon dioxide, said member defining at least part of the inner wall of a gas flow conduit within said reactor vessel.
- 2. A carbon dioxide separation apparatus comprising a vessel having a gas inlet and a gas outlet and a gas flow conduit linking said inlet and outlet, at least part of an inner wall of said conduit being provided by a gas porous member containing a metal oxide and/or carbonate, wherein carbon dioxide-containing gas flowing through said conduit permeates said member permitting carbon dioxide in said gas to react with metal oxide in said member to form metal carbonate, said apparatus being arranged such that said member may be heated and/or exposed to a gas having a lower carbon dioxide partial pressure than said carbon dioxide-containing gas whereby to cause metal carbonate therein to release carbon dioxide into said conduit.
- 3. A conduit device comprising an outer gas- impermeable wall containing therein a conduit and a gas permeable member containing a metal oxide transformable by carbon dioxide uptake to a metal carbonate or a said metal carbonate transformable on heating to said metal oxide, whereby gas from said conduit may permeate said member, said conduit device having a gas-impermeable thermally conductive portion (e.g. a barrier) wherefrom heat may be transferred to or from said member.
- 4. A process for the production of a ceramic product, said process comprising: mixing clay and water; adding metal carbonate particles to the desired content; extruding or moulding the resulting mixture; drying and sintering the extruded or moulded product; and, optionally, exposing the sintered material to carbon dioxide.
- 5. A ceramic containing at least 60 wt. of an alkaline earth metal carbonate or oxide (calculated as the carbonate)
- 6. A ceramic as claimed in claim 5 further containing a catalyst.
- 7. The use of a ceramic as claimed in claim 5 as a carbon dioxide absorber.
- 8. The use of a ceramic as claimed in claim 5 for repeated cycles of carbon dioxide absorption and release.
- 9. Use as claimed in either of claims 7 and 8 as a recyclable carbon dioxide absorber.
- 10. The use of a ceramic as claimed in claim 5 as a fertilizer or building material following its use as a carbon dioxide absorber.
Priority Applications (2)
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GB0513866A GB2428038B (en) | 2005-07-06 | 2005-07-06 | Carbon dioxide extraction process |
PCT/GB2006/002511 WO2007003954A1 (en) | 2005-07-06 | 2006-07-06 | Carbon dioxide extraction process |
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GB0513866A GB2428038B (en) | 2005-07-06 | 2005-07-06 | Carbon dioxide extraction process |
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GB0513866D0 GB0513866D0 (en) | 2005-08-10 |
GB2428038A true GB2428038A (en) | 2007-01-17 |
GB2428038A8 GB2428038A8 (en) | 2007-09-21 |
GB2428038B GB2428038B (en) | 2011-04-06 |
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GB0513866A Expired - Fee Related GB2428038B (en) | 2005-07-06 | 2005-07-06 | Carbon dioxide extraction process |
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Also Published As
Publication number | Publication date |
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GB2428038B (en) | 2011-04-06 |
GB0513866D0 (en) | 2005-08-10 |
WO2007003954A1 (en) | 2007-01-11 |
GB2428038A8 (en) | 2007-09-21 |
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