GB2305139A - Coated absorbent particles for a carbon dioxide scrubber system - Google Patents
Coated absorbent particles for a carbon dioxide scrubber system Download PDFInfo
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- GB2305139A GB2305139A GB9618219A GB9618219A GB2305139A GB 2305139 A GB2305139 A GB 2305139A GB 9618219 A GB9618219 A GB 9618219A GB 9618219 A GB9618219 A GB 9618219A GB 2305139 A GB2305139 A GB 2305139A
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- United Kingdom
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- pieces
- substrate
- absorbent particles
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- substrate material
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- 239000002245 particle Substances 0.000 title claims abstract description 45
- 239000002250 absorbent Substances 0.000 title claims abstract description 41
- 230000002745 absorbent Effects 0.000 title claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract description 96
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 51
- 239000001569 carbon dioxide Substances 0.000 title abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 51
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000008187 granular material Substances 0.000 claims abstract description 31
- 239000006096 absorbing agent Substances 0.000 claims abstract description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000011449 brick Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 11
- 230000029058 respiratory gaseous exchange Effects 0.000 abstract description 5
- 230000000241 respiratory effect Effects 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 10
- 229910001868 water Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 239000007931 coated granule Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000034964 establishment of cell polarity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 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
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
-
- 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
- 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
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
-
- 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
- B01J20/3231—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
- B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
- B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/302—Alkali metal compounds of lithium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention provides CO 2 -absorbent particles for a CO 2 scrubber system comprising a plurality of pieces of substrate material, the pieces being coated with an at least partly enveloping outer layer formed of a CO 2 absorber, wherein the particles have a substantially inert core of substrate material and an average particle sizes in the range of about 6-14 mesh, and wherein the volume of the coating layer is about 20-40% of the substrate volume. The substrate is preferably magnesium oxide granules and the absorber lithium hydroxide. The scrubber system is used to remove carbon dioxide from air or fuel streams supplying metal-air or fuel cell batteries or respiratory breathing systems.
Description
IMPROVED CARBON DIOXIDE - ABSORBENT PARTICLES
FOR CARBON DIOXIDE SCRUBBER SYSTEM
The present invention relates to CO2-absorbent particles for a scrubber system for removing carbon dioxide from air or fuel streams supplying a metal-air or fuel cell battery, or from respiratory breathing systems and to processes for the preparation thereof.
More particularly, the present invention relates to improved CO2 absorbent particles for zinc-air battery scrubber systems of the type described in U.S. application 08/210,333 and corresponding EPC application 95301398.4, the teachings of which are incorporated herein by reference.
As is known, and as described, e.g., in U.S. Patent
No. 3,909,206, alkali electrolyte fuel cells and metal-air batteries require a clean fuel and a clean oxidant to generate power. Many oxidants, such as air and all but the most pure, and therefore the most expensive, oxygen supplies and some fuels contain carbon dioxide (CO2) which, when brought into contact with the electrolyte, combines with the electrolyte to form carbonates. The formation and presence of carbonates in the electrolyte decreases the voltage of the cells and batteries, and eventually causes their failure.
For this reason, a CO2 scrubber system is applicable to a metal-air or fuel cell battery (e.g., zinc-air battery, hydrogen-air fuel cell) with an alkaline electrolyte (e.g., aqueous KOH) and incorporating an air electrode, supplied with air as the cathodic reactant. Regular air contains about 400 ppm of CO2, and if this CO2 is not removed, the CO2 can react with the KOH to form potassium carbonate (K2 CO3), which will gradually build up in the alkaline electrolyte.
2KOH + CO2 = K2CO3 + H2O (1)
K2 CO3 not only reduces the conductivity and alkalinity of the KOH, giving poorer cell polarization characteristics, but, being less soluble than KOM, can deposit carbonate crystals in the pores of the air electrode, especially in the presence of other sparingly soluble ions, such as zincates and aluminates in the electrolytes of zinc-air and aluminum-air cells respectively. These crystals can cause leaks and shorten the life of air electrodes.
In a related field, respiratory breathing systems in naval or aerospace units have CO2 scrubbers which maintain the CO2 concentration at a safe low level for breathing use.
The general absorption reaction of CO2 by alkali metal hydroxide (MOH) may be written:
2MOH + CO2 = M2C03 + H O (2)
The prior art has therefore suggested the use of a scrubber system containing alkali hydroxide granules, held as a compact bed in a suitable container whose dimensions, the granule size, the granule loading and degree of packing of the granules are determined by such factors as the required air flow rate and flow time through to the battery, permitted pressure drop across the granule bed, permitted CO2 exit concentration and degree of absorption required within the bed. Advantageously, the granules are retained between plastic screens somewhat finer than the granule dimensions, and the scrubber system may be advantageously fitted with dust-retaining filters and/or moisture or droplet-retaining demisters.When the bed is no longer effective for scrubbing and C02 breakthrough occurs, as shown, for example, visually (by a color change of a chemical indicator impregnated on the granules, which signals chemical exhaustion of the bed) or electronically (by the output of a CO2 detector, for example of the infra-red type, showing C02 levels above a certain predetermined value, for example, 50 ppm), the bed must be replaced.
There is therefore a need for a scrubber system of special application to serviceable batteries of the above type (e.g., mechanically-rechargeable zinc-air) or breathing equipment wherein there is a need to periodically maintain the CO2 scrubber system, and it is desirable, for economical and/or ecological reasons, to reprocess the spent scrubber active material rather than simply disposing of spent scrubber material and using of fresh material.
U.S. Patent No. 3,909,206 teaches a scrubber using finely-ground alkali hydroxide particles mixed with fine particles of a hydrophobic material, such as polytetrafluoroethylene, for removing carbon dioxide from a gas stream to a concentration of less than 0.25 ppm.
Although CO2 levels may be reduced to less than 0.25 ppm, no means are provided for reprocessing the scrubber material, or for extending the effective life thereof.
U.S. Patent No. 3,990,912 for hydrogen-air fuel cells with alkaline electrolytes uses electrochemical means to convert K2CO3 in the cell electrolyte back to KOH, by means of an additional regenerator cell system with circulating electrolyte that consumes hydrogen when it operates. This may be too complex, heavy and parasitic as to power needs for a mobile system application (e.g., an electric vehicle) and, requiring a source of hydrogen, will not be applicable to non-hydrogen systems (e.g., aluminum-air).
U.S. Patent No. 4,047,894 describes a scrubber element comprised of spaced-apart corrugated layers of porous PVC impregnated with CO2-absorbing solution (e.g., 10 Moles/ liter aqueous KOH). Although means for reuse of the element are described (column 3, lines 49-52), comprising rinsing with water, drying and reimpregnation with absorption solution, no means are given for reprocessing of the spent absorber to give fresh absorbent free of carbonate deposits, or for extending the effective life thereof by mechanical means.
As stated hereinbefore in co-pending U.S. application 08/210,333 and corresponding EPC application 95301398.4, the teachings of which are incorporated herein by reference, there is described and claimed a scrubber system for removing carbon dioxide from a metal-air or fuel cell battery. In said co-pending specification the CO2 absorbent material used comprises a solution of Group la metal hydroxide in water absorbed into porous granules of an alkali-resistant material.
More particularly, the scrubber system described in said earlier co-pending specification was based on the use of a coarse, granular type CO2 -absorbent material (3-30 mesh), comprising an alkali metal hydroxide (e.g., selected from LiOH, NaOH, KOH). The hydroxide therein is described as being in the solid phase (either anhydrous or hydrated form), when advantageously a certain minimum porosity (50% minimum) of the granules will ensure some utilization of the inner portions of said granules.
Alternatively, especially when the air to the scrubber/ battery is prehumidified, the hydroxide may be in the form of an impregnated phase as an aqueous solution (e.g., 30-40 wt.% MOH) absorbed into porous carrier granules of an alkali-resistant plastic, ceramic or elastomer in foam, floc, chip or felt form. Examples of such materials are polyethylene, polypropylene, PVC, polystyrene, nylon, low-density brick, or rubber.
It has now been found that this approach is associated with a low utilization of the CO2 absorbing material at the time of CO2 breakthrough and that only the outer core of the granule, comprising typically 30-40% of the weight or volume of the active material, reacts.
This figure is very low and results in a large quantity of unreacted absorber having to be replaced or regenerated each time the scrubber is serviced. Unfortunately, the unreacted material is at the core of the granule, or absorbed within the substrate core, and no easy separation route exists. Some scrubber materials such as LiOH or its hydrate are preferred absorber materials for CO2 because of the low weight ratio.
weight of absorbent taking un 1 mole CO weight of 1 mole CO2 associated with the CO2 absorption reaction,
2MOH+C02 = M2C03 + H20 but these materials are expensive and their utilization should be increased.
With this state of the art in mind there is now provided, according to the present invention, CO2-absorbent particles for a CO2 scrubber system comprising a plurality of pieces of substrate material, said pieces being coated with an at least partly enveloping outer layer formed of a CO2 absorber, wherein said particles have a substantially inert core of substrate material and an average particle size in the range of about 6-14 mesh, and wherein the volume of said coating layer is about 20-40% of the substrate volume.
In preferred embodiments of the present invention said substrated inert core substrate pieces have an average major axis of about 1-2 mm, and said coating has a thickness of about 100-500 microns.
In especially preferred embodiments of the present invention said substrate material is porous and has a porosity of at least 50% and a coarse pored structure with pore diameters in the range of 100-500 microns.
In another aspect of the present invention there is provided a process for the preparation of CO2-absorbent particles for a CO2 scrubber system comprising preparing porous pieces of substrate material, having a porosity of at least 50% and a coarse pored structure with pore diameters in the range of 100-500 microns, preparing a slurry of a CO2 absorber material, placing said pieces of substrate material in a filtering container, and pouring said slurry over said pieces to form a coating layer on said pieces, followed by heating, wherein said formed particles have a substantially inert core of substrate material and an average particle size in the range of about 6-14 mesh, and wherein the volume of said coating layer is about 20-40% of the volume of the substrate pieces.
The invention also provides a process for the preparation of
CO2-absorbent particles for a CO2 scrubber system comprising preparing pieces of substrate material, preparing a slurry of a CO2 absorber material or using the absorbent material directly and compressing said slurry or absorbent material onto the surface of said pieces of substrate material to form a coating layer on said pieces, wherein said formed particles having a substantially inert core of substrate material and an average particle size in the range of about 6-14 mesh, and wherein the volume of said coating layer is about 20-40% of the volume of the substrate pieces.
Thus, according to the present invention, there has now been developed a novel CO2 absorbent material comprising porous granules of substrate, coated with CO2 absorbent material.
LiOH and its hydrate are preferred CO2 absorbents of choice, though other Group Ia metal hydroxides may be used, and other CO2 absorbers such as soda lime, sodium hydroxide with barium hydroxide, and amines. Similar to US Application 08/210,333 the substrate material may be porous pieces of an alkali resistant plastic, ceramic, carbon or elastomer in foam, floc, chip granule, or felt form. Examples of such materials are polyethylene, polypropylene, PVC, polystryrene, nylon, rubber, carbon and low density clay, rock or brick.However, in order for the coating of the absorber to adhere to the substrate granules (the absorbent material preferably being applied via the solid phase as a powder or a slurry onto the substrate granules, followed by heating as will be described below), there has been found that the substrate material should have a porosity of at least 50%, and a coarse pored structure with pore diameters in the range of 100-500 micron. Furthermore, the coated substrate, (which should have a particle size in the 6-14 mesh range for reasons discussed above), should conform to an optimum volume distribution between the coating volume and the substrate volume, such that the coating volume is about 30% of the substrate volume. In practical terms for the aforementioned coated granule size of 6-14 mesh (2-4 mm diameter particles) the appropriate substrate diameter would be from 1-2 mm.At CO2 breakthrough, the utilization of absorbent material may be doubled or trebled by means of this strategy.
A preferred substrate material for use in the present invention is magnesium oxide (MgO). The lithium hydroxide absorber, which is available (as raw material or from regeneration) as a fine powder whose particle size is in the 1-10 micron range, is first prepared as a 30 wt % slurry in a suitable carrier phase such as isopropyl alcohol or a saturated solution of 10 wt % lithium hydroxide in water.
The magnesium oxide granules are placed into a filter funnel and are agitated gently by means of a plastic impeller. The lithium hydroxide slurry is then added into the filter funnel and the liquid phase continuously filtered off. The process is terminated when the apparent volume of lithium hydroxide corresponding to 30% the apparent volume of the magnesium oxide has been added and the liquid phase of the slurry has been substantially filtered off. The contents of the filter funnel are then turned out onto a plastic tray and heated at 50-1500C in a stream of CO2 free air and/or subjected to vacuum. The coated granules may then be used as CO2 scrubber material. Due to the viscous nature of the slurry liquid phase only a small quantity of dissolved LiOH enters the MgO granules.In a further embodiment, substrate pieces in fabricated form, for example plastic granules with one or more external cavities, can be loaded with absorbent slurry or absorbent powder by coating or compressing means into the cavity area, and then heated as above. Compression 2 pressures range from 1-2 tons/cm While the invention will now be described in connection with certain preferred embodiments in the following examples so that aspects thereof may be more fully understood and appreciated, it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as may be included within the scope of the invention as defined by the appended claims.Thus, the following examples which include preferred embodiments will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of formulation procedures as well as of the principles and conceptual aspects of the invention.
Example 1
Magnesium oxide substrate granules of porosity 70% and particle size 1-2mm were made by high temperature sintering of magnesium oxide powder (70 micron grade). Porosity measurements (Micrometrics)showed the predominant surface pores on the granules to be at least 150 microns in diameter. The CO2 absorbent material taken to coat the magnesium oxide granules was lithium hydroxide powder (10-100 micron grade). A 50 gm sample of magnesium oxide granules was placed in a Buchner filter funnel and filter flask assembly fitted with a Whatman No. 41 filter paper and the granules could be agitated by means of a plastic impeller connected to an overhead stirrer.With the plastic impeller gently activated and the Buchner assembly connected to a water pump, a slurry comprising 30 gm of lithium hydroxide powder in a saturated solution of 70 gm of 10 wt% lithium hydroxide in water was slowly poured over the magnesium oxide granules. After the liquid phase had been evacuated, the contents of the filter funnel were turned out onto a plastic tray and heated in a stream of CO2 - free air at 55 for one hour. Inspection of the coated granules showed that the coating was quite firm and keyed in onto the coarse pored magnesium oxide cores and the mesh size of the coated granules fell in the 6-14 mesh range. By measuring the bulk volume of the substrate before and after coating it was shown that the coating comprised about 30% of the net substrate volume.
Example 2
The coated granules of Example 1 (30gm content lithium hydroxide) were compared as to scrubbing efficiency with an equivalent volume of 6-14 mesh commercial granules comprising only LiOH (50gm) by forcing regular air (400 ppm
CO2) at a flow rate of 150ml/minute over the packed granules in separate scrubber columns for two successive experiments until breakthrough occurred ( > 50 ppm CO2 via an infra red CO2 detector observed in the air exit stream). The coated material lasted about the same time till breakthrough as the commercial granules, showing a much higher utilization of available lithium hydroxide.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative examples and that the present invention may be embodied in other specific forms without departing from the essential attributes thereof, and it is therefore desired that the present embodiments and examples be considered in all respects as illustrative and not restrictive, reference being made to the appended claims, rather than to the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (16)
1. CO2-absorbent particles for a CO2 scrubber system comprising a plurality of pieces of substrate material, said pieces being coated with an at least partly enveloping outer layer formed of a CO2 absorber, wherein said particles have a substantially inert core of substrate material and an average particle size in the range of about 6-14 mesh, and wherein the volume of said coating layer is about 20-40% of the substrate volume.
2. CO2-absorbent particles according to claim 1, wherein said substrated inert core substrate pieces have an average major axis of about 1-2 mm, and wherein said coating has a thickness of about 100-500 microns.
3. CO2-absorbent particles according to claim 1, wherein said CO2 absorber is selected from the group consisting of
Group la metal hydroxides and hydrates thereof, soda lime, sodium hydroxide, barium hydroxide, amines and combinations thereof.
4. CO2-absorbent particles according to claim 1, wherein said CO2 absorber is LiOH or a hydrate thereof.
5. CO2-absorbent particles according to claim 1, wherein said substrate pieces are formed of a material selected from the group consisting of alkali-resistant plastic, ceramic, carbon or elastomer in foam, floc, chip, granule, felt or fabricated carrier form.
6. CO2 absorbent particles according to claim 5, wherein the substrate pieces have at least one external cavity for receiving CO2 absorbent material by coating or compressing means.
7. CO2-absorbent particles according to claim 1, wherein said substrate material is selected from the group consisting of polyethylene, polypropylene, polyvinylchloride, polystyrene, nylon, rubber, carbon, and low density clay, rock and brick.
8. CO2-absorbent particles according to claim 1, wherein the volume of said coating layer is 25-35% of the substrate volume.
9. CO2-absorbent particles according to claim 1, wherein said substrate material is porous and has a porosity of at least 50% and a coarse pored structure with pore diameters in the range of 100-500 microns.
10. A process for the preparation of CO2-absorbent particles for a CO2 scrubber system comprising preparing porous pieces of substrate material, having a porosity of at least 50% and a coarse pored structure with pore diameters in the range of 100-500 microns, preparing a slurry of a CO2 absorber material, placing said pieces of substrate material in a filtering container, pouring said slurry over said pieces to form a coating layer on said pieces, and heating the resultant particles, wherein said formed particles have a substantially inert core of substrate material and an average particle size in the range of about 6-14 mesh, and wherein the volume of said coating layer is about 20-40% of the volume of the substrate pieces.
11. A process for the preparation of CO2-absorbent particles for a CO2 scrubber system according to claim 10, wherein said substrate material is magnesium oxide.
12. A process for the preparation of CO2-absorbent particles for a CO2 scrubber system according to claim 10, wherein said CO2 absorber is lithium hydroxide.
13. A process for the preparation of CO2-absorbent particles for a CO2 scrubber system according to claim 10, wherein said pieces of substrate material are placed in a filtering apparatus and agitated gently by means of an impeller during the addition of said slurry thereto.
14. A process for the preparation of CO2-absorbent particles for a CO2 scrubber system comprising preparing pieces of substrate material, preparing a slurry of a CO2 absorber material or using solid absorbent material directly and compressing said slurry or absorbent material onto the surface of said pieces of substrate material to form a coating layer on said pieces, and heating the resultant particles, wherein said formed particles have a substantially inert core of substrate material and an average particle size in the range of about 6-14 mesh, and wherein the volume of said coating layer is about 20-40% of the volume of the substrate pieces.
15. CO2-absorbent particles for a CQ scrubber system as claimed in claim 1 substantially as hereinbefore described in Example 1.
16. A process for the preparation of CO2-absorbent particles as claimed in claim 10 substantially as hereinbefore described in Example 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52689595A | 1995-09-12 | 1995-09-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9618219D0 GB9618219D0 (en) | 1996-10-09 |
| GB2305139A true GB2305139A (en) | 1997-04-02 |
Family
ID=24099269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9618219A Withdrawn GB2305139A (en) | 1995-09-12 | 1996-08-30 | Coated absorbent particles for a carbon dioxide scrubber system |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE19636648A1 (en) |
| GB (1) | GB2305139A (en) |
| IT (1) | IT1284497B1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002059993A3 (en) * | 2001-01-24 | 2002-12-27 | Casio Computer Co Ltd | Integrated fuel pack, reformer and gas purification device for fuel cell power generation system____________ |
| WO2007078785A2 (en) * | 2005-12-21 | 2007-07-12 | General Electric Company | Gas scrubber and method related thereto |
| EP2893322A4 (en) * | 2012-08-20 | 2016-03-30 | Sabic Global Technologies Bv | Real-time online determination of caustic in process scrubbers using near infrared spectroscopy and chemometrics |
| EP3146583A4 (en) * | 2014-05-19 | 2018-01-17 | Gencell Ltd. | Scrubbing device for gas used in a fuel cell and method of scrubbing gas using the device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10157552B4 (en) * | 2001-11-23 | 2012-05-31 | Air Liquide Deutschland Gmbh | Gas cleaning mass for the removal of carbon dioxide from dry gases and their use |
| DE102008010349A1 (en) * | 2008-02-13 | 2009-08-20 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg(ZSW) | As CO2 absorbent and for use as bed material in fluidized beds suitable material and its preparation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3684712A (en) * | 1970-02-02 | 1972-08-15 | Ato Inc | Carbon dioxide absorbing chemical |
| WO1984002283A1 (en) * | 1982-12-08 | 1984-06-21 | Lindstroem Ab Olle | Means and procedure for removal of carbon dioxide |
| EP0677883A1 (en) * | 1994-03-18 | 1995-10-18 | Electric Fuel (E.F.L.) Limited | Scrubber system for removing carbon dioxide from a metal-air or fuel cell battery |
-
1996
- 1996-08-30 GB GB9618219A patent/GB2305139A/en not_active Withdrawn
- 1996-09-10 IT IT96MI001854A patent/IT1284497B1/en active IP Right Grant
- 1996-09-10 DE DE19636648A patent/DE19636648A1/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3684712A (en) * | 1970-02-02 | 1972-08-15 | Ato Inc | Carbon dioxide absorbing chemical |
| WO1984002283A1 (en) * | 1982-12-08 | 1984-06-21 | Lindstroem Ab Olle | Means and procedure for removal of carbon dioxide |
| EP0677883A1 (en) * | 1994-03-18 | 1995-10-18 | Electric Fuel (E.F.L.) Limited | Scrubber system for removing carbon dioxide from a metal-air or fuel cell battery |
Non-Patent Citations (1)
| Title |
|---|
| Abstracts of JP 04133328 A (Meidensha Corp.) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002059993A3 (en) * | 2001-01-24 | 2002-12-27 | Casio Computer Co Ltd | Integrated fuel pack, reformer and gas purification device for fuel cell power generation system____________ |
| US6777118B2 (en) | 2001-01-24 | 2004-08-17 | Casio Computer Co., Ltd. | Power supply system, fuel pack constituting the system, and device driven by power generator and power supply system |
| WO2007078785A2 (en) * | 2005-12-21 | 2007-07-12 | General Electric Company | Gas scrubber and method related thereto |
| WO2007078785A3 (en) * | 2005-12-21 | 2007-09-20 | Gen Electric | Gas scrubber and method related thereto |
| EP2893322A4 (en) * | 2012-08-20 | 2016-03-30 | Sabic Global Technologies Bv | Real-time online determination of caustic in process scrubbers using near infrared spectroscopy and chemometrics |
| EP3146583A4 (en) * | 2014-05-19 | 2018-01-17 | Gencell Ltd. | Scrubbing device for gas used in a fuel cell and method of scrubbing gas using the device |
| US10530001B2 (en) | 2014-05-19 | 2020-01-07 | Gencell Ltd. | Scrubbing device for gas used in a fuel cell and method of scrubbing gas using the device |
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI961854A1 (en) | 1998-03-10 |
| GB9618219D0 (en) | 1996-10-09 |
| DE19636648A1 (en) | 1997-03-13 |
| IT1284497B1 (en) | 1998-05-21 |
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