EP2337629A2 - Élément adsorbant et procédé pour fabriquer un élément adsorbant - Google Patents
Élément adsorbant et procédé pour fabriquer un élément adsorbantInfo
- Publication number
- EP2337629A2 EP2337629A2 EP09771470A EP09771470A EP2337629A2 EP 2337629 A2 EP2337629 A2 EP 2337629A2 EP 09771470 A EP09771470 A EP 09771470A EP 09771470 A EP09771470 A EP 09771470A EP 2337629 A2 EP2337629 A2 EP 2337629A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- adsorber
- suspension
- adsorberelement
- layer
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 38
- 239000003463 adsorbent Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000012876 carrier material Substances 0.000 claims abstract description 7
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000010457 zeolite Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000000084 colloidal system Substances 0.000 abstract description 4
- 239000002808 molecular sieve Substances 0.000 description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 29
- 239000000758 substrate Substances 0.000 description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000003507 refrigerant Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000002318 adhesion promoter Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000011491 glass wool Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010943 off-gassing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000035939 shock Effects 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
- 230000001464 adherent effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- 230000005653 Brownian motion process Effects 0.000 description 1
- 241001415825 Bubo bubo Species 0.000 description 1
- 241001340534 Eido Species 0.000 description 1
- 241000883510 Kolla Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 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
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
-
- 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
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28023—Fibres or filaments
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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
- B01J20/30—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
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3223—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating by means of an adhesive agent
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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
- B01J20/30—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
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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
- B01J20/30—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
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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
- B01J20/30—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
- B01J20/3238—Inorganic material layers containing any type of zeolite
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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
- B01J20/30—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
- B01J20/324—Inorganic material layers containing free carbon, e.g. activated carbon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
- F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
Definitions
- the invention relates to an adsorber element according to the preamble of patent claim 1 and to a method for producing an adsorbing element according to the preamble of patent claim 15.
- Adsorbentbasis for example: silica, activated carbon or zeolite [then molecular sieve base]
- Adsorbentbasis for example: silica, activated carbon or zeolite [then molecular sieve base]
- refrigerant adsorption gives off heat
- refrigerant desorption adsorbent absorbs heat
- Adsorbents are generally crystalline solids whose particle size is usually in the range of a few micrometers. Advantageous for use in a heat pump is a good connection of these Adsorbentpumble to a material of very good thermal conductivity, as it represents, for example, aluminum or copper.
- adsorbent particles are generally not The use of adhesion promoters (binder materials), which adhere the particles to one another and to the metal, is necessary. These bonding agents must meet two criteria. They should not hinder the adsorption of refrigerant into the adsorbent and, more generally, should not hinder the function of the heat pump. They should also consist of environmentally friendly and economically enforceable materials.
- the heat pump operates under pure refrigerant vapor pressure at different temperatures. Increasing the existing pressure in the heat pump leads by the presence of inert gases to a reduction in performance of the heat pump up to a complete failure. For this reason, the adsorbent layer must not release any gases for a desired service life of 15 years, i. H. in particular, the adhesion promoter (binder material) used must not release any gases.
- metal knits metal wool
- metal mesh being attached to metal walls, for example, by a heat pump.
- the method is described in DE 44 05 669 Al by the same applicant as insufficient.
- the metal mesh with zeolite is released from the metal walls during cyclic stresses.
- the high-temperature binder Sauerfeisenzement type 8 from SeppZeug GmbH contains no alkali metal silicates, but magnesium oxide, magnesium phosphate and zirconium silicate.
- this material is used as a binder, so massive Shrinkage cracks up. Shrink cracks generally have their cause in the decrease in volume of the solidifying suspension due to the evaporation of liquid, for example, they can often be observed in dried, loamy river banks.
- the adsorbent layer adheres very instable to aluminum sheet and falls off with slight vibrations immediately. The same problem occurs with the high temperature binder Ceramabond from Kager GmbH.
- This binder contains as well as the acid rice type 8 no alkali silicates, but especially corundum in fine particle size. Experiments show that adsorbent coatings made with this binder also have numerous shrinkage cracks and immediately peel off the metal at a temperature load (16O 0 C).
- the performance and, in particular, the stability of molecular sieve layers can be improved by the use of glass wool nonwovens as likewise described in DE 44 05 669 A1.
- a glass wool nonwoven is applied directly to metal and then glued to the molecular sieve / binder suspension.
- a disadvantage of this approach is that such a glass wool nonwoven can be applied only in easily accessible geometries of the metal body.
- Organic adhesion promoters have the inherent disadvantage that outgassing reactions of the organic substances within the heat pump can occur over long periods of time, which then impair the function of the heat pump. This is done against the background that the layers in the cyclic operation of the heat pump temperatures above 150 0 C from are set and organic substances tend to decompose at these temperatures.
- a zeolite layer which is produced by the use of organic polymer binders is provided.
- JP 63291809 A, JP 59213615 A, DE 693 20 195 T2 and DE 103 09 009 Al describe methods by which zeolites grow directly on substrates.
- alumina substrates JP 63291809 A
- glass JP 59213615 A
- ceramic DE 103 09 009 Al
- metals or metal alloys such as aluminum or steel
- the disadvantage is that the manufacturing method can not generally be applied to all substrate materials and is very expensive.
- moldings to be coated (the substrates) must be placed in reactors and typically maintained at high pressures and temperatures over a period of several days.
- Just untreated and reactive aluminum as it is very advantageous for this production method, but is undesirable in heat pumps, because it can come to so-called hydrogen corrosion over a longer period.
- water reacts with aluminum to form aluminum hydroxide and / or alumina hydroxide and / or alumina and hydrogen.
- the formation of hydrogen is highly undesirable in a heat pump, since this gas increases the operating pressure of the heat pump.
- the invention has for its object to improve an adsorber element or a method for producing an adsorber of the type described above.
- metal bodies are coated by the application of a liquid, preferably aqueous suspension and a subsequent drying process.
- a liquid preferably aqueous suspension
- the suspension contains adsorbent particles, fibers and a colloidal binder.
- Colloids from Greek kolla “glue” and eidos “form, appearance" are particles or droplets which are finely dispersed in another medium (solid, gas or liquid), the dispersion medium.
- the single colloid is typically between 1 nanometer and 10 microns in size. If they are mobile (eg in a liquid dispersion medium), colloids usually show Brownian motion.
- Both the fibers and the colloidal binder are selected from the class of inorganic, inert or substantially inert materials, so that there can be no chemical reactions and / or outgassing during heat pump operation.
- colloidal silicon oxides or colloidal aluminum oxides / hydroxides are used as colloidal binders for the bonding of adsorbent particles.
- Fibers are used to impart elasticity and strength to the layer and to prevent shrinkage cracks, since such may occur particularly during drying of the suspension.
- the layer As the layer is constantly exposed to temperature changes, tensions occur between the various materials present; H. Metal, adhesion promoters, fibers and adsorbent. These substances have different thermal expansion coefficients and therefore undergo different volume and length changes when heated, resulting in the mentioned stresses. In order to achieve a permanent strength of the layer, it follows that the layer must be elastic within limits - it must be able to "breathe”. In order to obtain a certain relaxation capacity of the layer with relatively brittle materials such as glass, the particular binder material used is preferably used in fiber form.
- fibers of different sizes can be used with particular advantage. Larger fibers impart stability and elasticity over long distances of the layer, while smaller fibers connect the individual adsorbent particles with each other and with the larger fibers and the substrate over short distances (see also FIG. 1, which schematically shows the structure of such a layer).
- fiber materials offer two further advantages. On the one hand, a layer crosslinked by fibers is less prone to failure. If, for example, the layer is detached from the metal at one point due to heavy mechanical stress, it will nevertheless adhere to the substrate surface in its entirety, since other sites may still provide sufficient adhesion.
- the second advantage lies in the thermal conductivity of the layer. In addition to adhesion and elasticity, this is crucial for the successful implementation of the overall concept. If fibers with a good thermal conductivity are used, the thermal conductivity of the entire layer is increased.
- a colloidal binder is necessary as an adhesive to bond together fibers, adsorbent particles and substrate or metal surface at the molecular level. It has the advantage over common adhesives that it does not have to be organic - commercially available adhesives such as eagle owl, epoxy resin, pattex etc. - consist of organic substances with the mentioned disadvantages - nor that it completely pores the adsorbent or can partially bond. A complete bonding of Adsorbentporen is to be avoided when used in a heat pump, because so the adsorbent is prevented from adding or desorbing refrigerant.
- One possible disadvantage of the technique shown with the aid of fibers to create a partially elastic layer is the possibly generated preferred orientation of fibers by directed shear forces during the application process.
- Such preferred orientation can cause shrinkage cracks to occur during the drying process of the suspension.
- the mechanical reinforcement of the adsorbent layer can only take place in the direction of the longitudinal axis of the fibers.
- a statistical distribution of the fibers is preferable. Such a statistical distribution can be achieved largely by spraying the suspension onto the respective substrate, which leads to irregularly acting, weak shearing forces. Fibers can no longer orient themselves in this way.
- a second way is to add a gas generator which is added to the suspension and which is present in the layer homogeneously distributed during the drying process of the suspension and leads to a statistically distributed orientation of the fibers by gas bubble formation.
- gas bubbles escape from the still liquid suspension before drying, these lead to an irregular and statistically distributed turbulence of the suspension, as a result of which the fibers present are distributed irregularly as desired.
- the gas bubble formation additionally leads to a loosening of the dried layer, forming cavities and channels facilitate the diffusion of water molecules, but complicate on the other hand, the heat transport within the layer.
- the gas generator must be selected from the group of reactive and / or volatile substances, so that after the drying process of the suspension, no gas is formed which could influence the function of the heat pump. Further advantages and details of the invention are:
- Firmly adherent layers can be obtained by intimately mixing ground fibers having an average length of about 100 microns and a diameter of 5-12 microns with adsorbent powder and adding an alumina / silica-based colloidal binder. The resulting aqueous suspension is intimately mixed again and then applied to any substrate. After a drying process, these layers adhere to different materials having a hydrophilic surface such as copper, glass, aluminum, porcelain.
- the resulting oxygen escapes and leads to the drying of the layer to pores, which are about 50 microns in size.
- Iron (III) chloride is given here only as an example of a catalyst which decomposes the hydrogen peroxide, there are a large number of further suitable catalysts which can be selected depending on the circumstances.
- Other examples which may be mentioned are: MnO 2 , colloidal MnO 2 , MnCl 2 , Fe (OH) 2 , Fe (OH) 3 , colloidal Fe (OH) 3 .
- colloidal forms of certain transition metal hydroxides / oxides may be advantageous because they have a high catalytic activity for the decomposition of H 2 O 2 , that is to say they have to be added only in very small amounts, and because they have sufficient catalyst particle size can not penetrate into the Adsorbentporen, which could lead to a reduction in performance.
- a heat exchanger in which a plurality of fibers with a heat-conducting Adhesive film to be fixed on a wall.
- the individual fibers are coated with a sorbent.
- An adsorber element or a process in which the adsorber layer is applied in the form of a suspension is not disclosed in this document.
- a sorbent molding and a method for its preparation and use is known.
- the powder used or the granules used are in this solution but not in the form of a layer, but as a so-called heap (mixture of solid particles that are loosely mixed or firmly pressed together or baked) are arranged within a cage.
- adsorbent layers shown in examples a) to e) adhere firmly to the aluminum sheets used and do not detach from the sheets even under thermal stress.
- the coated sheets were subjected to several thermal shocks. They were brought in an oven to about 160 0 C and immediately placed in a bucket filled with ice water. Thereafter, the procedure was repeated up to three times.
- the layers were brought to 2O 0 C with the aid of a special test structure to 120 0 C and after 10 minutes. When heating was dry air and when cooling humid air flowed over the samples. After 15,000 cycles of this type, the samples had no stability problems.
- the average layer thickness of the created layers is about 350 to 450 micrometers.
- the adsorbent content in all the layers shown in the examples including the comparative examples is 70% (by mass) based on fully hydrated adsorbent.
- Example h Use of molecular sieve FAM from Mitsubishi and high temperature binder Ceramabond 569 from Kager Industrietechnik GmbH. The procedure was as in Example h). Shrinkage cracks are in contrast to Example i) recognizable only with a magnifying glass, but the layer is only marginally more stable than the one created in Example i), and drops after a slight shock.
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Abstract
L'invention concerne un élément adsorbant et un procédé pour le fabriquer, cet élément comportant un matériau support (1) sur lequel sont disposées des particules d'adsorbant (3) avec un liant (2) pour former une couche d'adsorbant. Selon l'invention, la couche d'adsorbant comporte des fibres inorganiques (4) et le liant (2) est colloïdal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008050926A DE102008050926A1 (de) | 2008-10-10 | 2008-10-10 | Adsorberelement und Verfahren zur Herstellung eines Adsorberelements |
| PCT/DE2009/001370 WO2010040335A2 (fr) | 2008-10-10 | 2009-10-02 | Élément adsorbant et procédé pour fabriquer un élément adsorbant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2337629A2 true EP2337629A2 (fr) | 2011-06-29 |
Family
ID=41728258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP09771470A Withdrawn EP2337629A2 (fr) | 2008-10-10 | 2009-10-02 | Élément adsorbant et procédé pour fabriquer un élément adsorbant |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20110183835A1 (fr) |
| EP (1) | EP2337629A2 (fr) |
| JP (1) | JP2012505071A (fr) |
| KR (1) | KR20110069119A (fr) |
| CN (1) | CN102176964A (fr) |
| DE (1) | DE102008050926A1 (fr) |
| WO (1) | WO2010040335A2 (fr) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010004344A1 (de) | 2010-01-11 | 2011-07-14 | Viessmann Werke GmbH & Co KG, 35108 | Beschichtungsverfahren und Adsorberelement |
| DE102010021692A1 (de) | 2010-05-27 | 2011-12-01 | Viessmann Werke Gmbh & Co Kg | Lamellenwärmeübertrager |
| DE102011011688A1 (de) | 2011-02-18 | 2012-08-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Beschichtung einer Wärmetauscherstruktur, beschichtete Wärmetauscherstruktur und deren Verwendung |
| DE102012014335A1 (de) | 2012-07-19 | 2014-01-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Dispersion, Verfahren zur Beschichtung von Gegenstädenmit dieser Dispersion und Verwendung der Dispersion |
| US8794373B1 (en) | 2013-03-15 | 2014-08-05 | Bose Corporation | Three-dimensional air-adsorbing structure |
| DE102013226732A1 (de) | 2013-12-19 | 2015-06-25 | MAHLE Behr GmbH & Co. KG | Adsorberstruktur |
| RU2020117132A (ru) * | 2015-07-09 | 2020-09-17 | ИНДЖЕВИТИ САУТ КАРОЛИНА, ЭлЭлСи | Система хранения газообразных веществ, способы ее изготовления и ее использования |
| CN109952148B (zh) * | 2016-11-14 | 2023-01-20 | 3M创新有限公司 | 包括含金属的聚合物材料的复合颗粒 |
| DE102017208201A1 (de) | 2017-05-16 | 2018-11-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Bauteil, Verfahren zu dessen Herstellung und dessen Verwendung |
| DE102018132348A1 (de) | 2018-12-14 | 2020-06-18 | Sorption Technologies GmbH | Beschichtungsmaterial zur Herstellung einer adsorbierenden, porösen, flexiblen Beschichtung für einen Wärmetauscher und Verfahren zu dessen Herstellung |
| CN114130128B (zh) * | 2020-09-02 | 2023-05-02 | 杭州科百特科技有限公司 | 一种空气过滤器 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002066152A2 (fr) * | 2001-01-05 | 2002-08-29 | Questair Technologies, Inc. | Compositions de revetement adsorbantes, stratifies et elements d'adsorption comprenant ces compositions et leurs procedes de fabrication et d'utilisation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59213615A (ja) | 1983-05-13 | 1984-12-03 | Toa Nenryo Kogyo Kk | 膜状合成ゼオライト及びその製造方法 |
| DE3347700C2 (de) * | 1983-12-31 | 1994-07-07 | Zeolith Tech | Zeolithformling mit hoher Wärmeleitung und Verfahren zur Herstellung |
| JP2501825B2 (ja) | 1987-05-26 | 1996-05-29 | 出光興産株式会社 | 膜状合成ゼオライトの製造方法 |
| US4800187A (en) * | 1987-10-28 | 1989-01-24 | Corning Glass Works | Method of crystallizing a zeolite on the surface of a monolithic ceramic substrate |
| DE4041725C2 (de) * | 1990-12-24 | 1995-05-18 | Kernforschungsz Karlsruhe | Verfahren zum Erzeugen einer regenerierfähigen Sorptionsschicht auf einer metallischen Oberfläche und die nach diesem Verfahren hergestellte Sorptionsschicht |
| JPH0523584A (ja) * | 1991-07-25 | 1993-02-02 | Kawata Mfg Co Ltd | 吸着性セラミツク多孔体およびその製造方法 |
| US5316661A (en) * | 1992-07-08 | 1994-05-31 | Mobil Oil Corporation | Processes for converting feedstock organic compounds |
| DE4405669A1 (de) * | 1994-02-23 | 1995-08-24 | Zeolith Tech | Adsorptionsmittelbeschichtung auf Metallen und Verfahren zur Herstellung |
| GB9613211D0 (en) * | 1996-06-24 | 1996-08-28 | Johnson Matthey Plc | Improvements in heat transfer materials |
| US5768904A (en) * | 1997-05-02 | 1998-06-23 | Uop Llc | Processes for integrating a continuous sorption cooling process with an external process |
| WO2002045847A2 (fr) | 2000-12-06 | 2002-06-13 | Uop Llc | Feuille adsorbante, procede de preparation et procede de dessechement destines a mettre en oeuvre la feuille |
| DE10309009A1 (de) | 2003-03-01 | 2004-09-09 | Scheffler, Michael, Dr.rer.nat. | Zeolith-Beschichtung |
| US20080251027A1 (en) * | 2003-07-11 | 2008-10-16 | Bradley Kirsch | Shaped Absorbent Particles |
| GB0318027D0 (en) * | 2003-08-01 | 2003-09-03 | Accentus Plc | Catalyst structure and catalytic reactor |
| JP4975970B2 (ja) * | 2005-01-21 | 2012-07-11 | 日本エクスラン工業株式会社 | 収着式熱交換モジュールおよびその製法 |
| DE102005000022A1 (de) * | 2005-03-16 | 2006-09-28 | Füsting, Bernd | Sorbierender Formkörper, Verfahren zur Herstellung und Verwendung |
| DE102006028372A1 (de) * | 2005-06-17 | 2007-02-01 | Behr Gmbh & Co. Kg | Wärmeübertrager, insbesondere Sorptions-, Reaktions- und/oder Wärmerohr |
| WO2006137163A1 (fr) * | 2005-06-24 | 2006-12-28 | Ibiden Co., Ltd. | Corps à structure en nid d’abeilles |
| JP5061581B2 (ja) * | 2005-11-04 | 2012-10-31 | 三菱化学株式会社 | 吸着素子およびそれを用いた調湿用空調装置 |
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2008
- 2008-10-10 DE DE102008050926A patent/DE102008050926A1/de not_active Ceased
-
2009
- 2009-10-02 WO PCT/DE2009/001370 patent/WO2010040335A2/fr not_active Ceased
- 2009-10-02 EP EP09771470A patent/EP2337629A2/fr not_active Withdrawn
- 2009-10-02 JP JP2011530361A patent/JP2012505071A/ja active Pending
- 2009-10-02 US US12/998,319 patent/US20110183835A1/en not_active Abandoned
- 2009-10-02 CN CN2009801402432A patent/CN102176964A/zh active Pending
- 2009-10-02 KR KR1020117009266A patent/KR20110069119A/ko not_active Ceased
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| WO2002066152A2 (fr) * | 2001-01-05 | 2002-08-29 | Questair Technologies, Inc. | Compositions de revetement adsorbantes, stratifies et elements d'adsorption comprenant ces compositions et leurs procedes de fabrication et d'utilisation |
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| See also references of WO2010040335A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110183835A1 (en) | 2011-07-28 |
| WO2010040335A2 (fr) | 2010-04-15 |
| JP2012505071A (ja) | 2012-03-01 |
| DE102008050926A1 (de) | 2010-04-15 |
| WO2010040335A3 (fr) | 2010-07-15 |
| KR20110069119A (ko) | 2011-06-22 |
| CN102176964A (zh) | 2011-09-07 |
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