WO2015060356A1 - 酸素吸収剤の保存方法 - Google Patents
酸素吸収剤の保存方法 Download PDFInfo
- Publication number
- WO2015060356A1 WO2015060356A1 PCT/JP2014/078132 JP2014078132W WO2015060356A1 WO 2015060356 A1 WO2015060356 A1 WO 2015060356A1 JP 2014078132 W JP2014078132 W JP 2014078132W WO 2015060356 A1 WO2015060356 A1 WO 2015060356A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxygen
- aqueous solution
- oxygen absorbent
- alloy
- component
- Prior art date
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000001301 oxygen Substances 0.000 title claims abstract description 143
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000006096 absorbing agent Substances 0.000 title abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 61
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 56
- 239000000956 alloy Substances 0.000 claims abstract description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000011282 treatment Methods 0.000 claims abstract description 24
- 239000002738 chelating agent Substances 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 238000004438 BET method Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000002250 absorbent Substances 0.000 claims description 78
- 230000002745 absorbent Effects 0.000 claims description 78
- 150000003839 salts Chemical group 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010828 elution Methods 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000843 powder Substances 0.000 description 30
- 239000012298 atmosphere Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000003860 storage Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 229910018084 Al-Fe Inorganic materials 0.000 description 11
- 229910018192 Al—Fe Inorganic materials 0.000 description 11
- 239000005022 packaging material Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000012423 maintenance Methods 0.000 description 7
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 7
- 239000001433 sodium tartrate Substances 0.000 description 7
- 229960002167 sodium tartrate Drugs 0.000 description 7
- 235000011004 sodium tartrates Nutrition 0.000 description 7
- 235000013305 food Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229940123973 Oxygen scavenger Drugs 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 description 5
- 150000004692 metal hydroxides Chemical class 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- -1 aluminum ions Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229940120146 EDTMP Drugs 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 235000013402 health food Nutrition 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 235000019685 rice crackers Nutrition 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 229960001790 sodium citrate Drugs 0.000 description 2
- 235000011083 sodium citrates Nutrition 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QENMPTUFXWVPQZ-UHFFFAOYSA-N (2-hydroxyethylazaniumyl)formate Chemical class OCCNC(O)=O QENMPTUFXWVPQZ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- KWMLJOLKUYYJFJ-UHFFFAOYSA-N 2,3,4,5,6,7-Hexahydroxyheptanoic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)=O KWMLJOLKUYYJFJ-UHFFFAOYSA-N 0.000 description 1
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000533293 Sesbania emerus Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical class OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- OUDSFQBUEBFSPS-UHFFFAOYSA-N ethylenediaminetriacetic acid Chemical compound OC(=O)CNCCN(CC(O)=O)CC(O)=O OUDSFQBUEBFSPS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000003761 preservation solution Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- UPMFZISCCZSDND-JJKGCWMISA-M sodium gluconate Chemical compound [Na+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UPMFZISCCZSDND-JJKGCWMISA-M 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- OESFSXYRSCBAQJ-UHFFFAOYSA-M sodium;3-carboxy-3,5-dihydroxy-5-oxopentanoate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC([O-])=O OESFSXYRSCBAQJ-UHFFFAOYSA-M 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
- A23L3/3418—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor in a controlled atmosphere, e.g. partial vacuum, comprising only CO2, N2, O2 or H2O
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Definitions
- the present invention relates to a method for storing an oxygen absorbent, and more particularly to a method for storing an oxygen absorbent that can absorb and remove oxygen even in a low humidity atmosphere.
- oxygen absorbers deoxygenating agents
- an oxygen scavenger that removes oxygen in the atmosphere is placed inside the sealed package together with the object, and the inside of the sealed package is made oxygen-free, thereby causing oxidative degradation, mold, This technology suppresses discoloration and the like.
- oxygen absorbers that remove oxygen in the atmosphere have been proposed from various inorganic materials and organic materials. Among them, there is no moisture that is 30% RH (25 ° C.) or less using a metal obtained by removing aluminum from an alloy composed of aluminum and iron, or an alloy composed of aluminum and nickel using an aqueous sodium hydroxide solution.
- An oxygen absorbent that can absorb and remove oxygen in the atmosphere at a level equivalent to that of a conventional oxygen scavenger has been developed (for example, International Publication No. 2012/105457).
- an oxygen absorbent comprising a metal obtained as described above is stored by being immersed in an acid or an aqueous solution having a buffer function. It is also disclosed that the oxygen absorbent can be stored stably for a long period of time while maintaining the oxygen absorption activity.
- oxygen absorbers described in the above patent documents react sensitively to acidic aqueous solutions, so immerse the oxygen absorbent in an aqueous solution having an acid or buffer function. Even in such a case, the oxygen absorbent cannot be stored while maintaining sufficient oxygen absorption performance.
- the present invention solves the above-mentioned problems in the prior art, and as a method for storing an oxygen absorbent having an ability to absorb oxygen in the atmosphere even in an atmosphere with little or no moisture, the safety is high and low.
- An object of the present invention is to provide a method capable of stably storing an oxygen absorbent for a long time while maintaining sufficient oxygen absorption performance at a low price.
- the present inventors perform elution treatment of the component (B) with a base such as sodium hydroxide when producing the oxygen absorbent, and therefore, in the micropores formed in the metal by the elution treatment of the component (B).
- metal hydroxide such as aluminum hydroxide remains, and this residue cannot be completely removed even after the water washing step, and this residue gradually elutes into the water when the oxygen absorbent is stored in water. I noticed going.
- the metal oxide such as aluminum hydroxide eluted in the aqueous solution is deposited on the surface of the oxygen absorbent over time. I suspected that it has declined.
- the present invention provides the following [1] to [4].
- [1] (A) at least one transition metal selected from the group consisting of iron, cobalt, nickel, and copper; (B) aluminum; Is an oxygen absorbent made of a metal obtained by subjecting an alloy containing a metal to a basic aqueous solution treatment to elute and remove at least a part of the aluminum (B), and has a specific surface area of 10 m 2 measured by the BET method.
- An oxygen absorbent that is greater than / g The oxygen absorbent is stored by being immersed in an aqueous solution containing a chelating agent.
- a method for preserving an oxygen absorbent comprising: [2] The method for storing an oxygen absorbent according to [1], wherein the chelating agent is a hydroxycarboxylic acid salt. [3] The method for storing an oxygen absorbent according to [1] or [2], wherein the content of the chelating agent in the aqueous solution is 0.1 to 20 parts by mass with respect to 100 parts by mass of the oxygen absorbent. . [4] The method for storing an oxygen absorbent according to any one of [1] to [3], wherein the pH of the aqueous solution is 7 to 12.
- an oxygen absorbent of the present invention after the production of the oxygen absorbent, it can be stably stored, and even after long-term storage, the oxygen absorption activity equivalent to that immediately after the production can be maintained, Even in an atmosphere where there is no or almost no oxygen, oxygen in the atmosphere can be absorbed and removed at a level equivalent to the conventional deoxygenation ratio.
- the method for storing an oxygen absorbent according to the present invention includes a step of preparing an oxygen absorbent and a step of storing the prepared oxygen absorbent by immersing it in an aqueous solution containing a chelating agent.
- the oxygen absorbent according to this embodiment includes the following two components (A) and (B): (A) at least one transition metal selected from the group consisting of iron, cobalt, nickel, and copper; B) A metal obtained by bringing an alloy containing aluminum into contact with a basic aqueous solution and eluting and removing at least a part of the component (B) from the alloy.
- the “oxygen absorber” refers to an agent that can selectively absorb oxygen from the ambient atmosphere in which the agent is installed.
- the transition metal that can be used as the component (A) is selected from iron, cobalt, nickel, and copper.
- the transition metals described above may be used alone or in combination of two or more.
- an Fe—Ni alloy may be used as component (A).
- the component (A) is preferably iron or nickel, and more preferably iron. Among these, iron is preferable because it is safe and inexpensive.
- aluminum is used as a component (B) which comprises an oxygen absorber.
- the alloy used in the present embodiment includes the component (A) and the component (B) described above, but the alloy may further contain molybdenum, chromium, titanium, vanadium, tungsten, or the like as an additive metal. Good. Additional components such as cyanic acids may be further included.
- the alloy containing the component (A) and the component (B) as described above can be prepared by a melting method.
- the composition ratio of the component (A) and the component (B) is preferably 20 to 80% by mass when the component (A) is 20 to 80% by mass, and more Preferably, when component (A) is 30 to 70% by mass, component (B) is 30 to 70% by mass.
- the component (A) is iron or nickel
- the ratio of iron or nickel is preferably 30 to 55% by mass
- the ratio of aluminum is preferably 45 to 70% by mass. .
- alloy may be subjected to a basic aqueous solution treatment as it is, but it is usually subjected to a basic aqueous solution treatment after being finely pulverized.
- alloy includes not only a single composition having a specific crystal structure but also a mixture thereof and a mixture of metals themselves.
- the alloy As a method for finely pulverizing the alloy, a conventional method for crushing and pulverizing metals can be used as appropriate.
- the alloy is pulverized with a jaw crusher, a roll crusher, a hammer mill, etc. Accordingly, it can be finely pulverized with a ball mill.
- the molten alloy may be pulverized by a rapid solidification method such as an atomizing method.
- the atomizing method when used, it is preferably performed in an inert gas such as an argon gas.
- a method described in JP-A-5-23597 can be used.
- the particle size of the obtained alloy powder is preferably in the range of 5 to 200 ⁇ m, and the particle size distribution is preferably as narrow as possible. From the viewpoint of eliminating particles having a large particle size or aligning the particle size distribution, sieving (classification) may be appropriately performed using a commercially available sieve (for example, 200 mesh). In the case of the atomizing method, the powder tends to be nearly spherical and the particle size distribution tends to be narrow.
- the particle size of the alloy powder can be measured using a particle size-shape distribution measuring device or the like.
- the alloy or alloy powder obtained as described above is subjected to a basic aqueous solution treatment to elute and remove at least part of the component (B) from the alloy. That is, as the oxygen absorbent used in the storage method according to the present invention, a metal obtained after eluting and removing at least a part of the component (B) from the alloy is used.
- the basic aqueous solution the component (A) does not dissolve or hardly dissolves, while the component (B) can be dissolved and removed, that is, the component (B) is leached (eluted) from the alloy. Any one can be used as long as it can be used.
- Examples of the base in the basic aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; sodium carbonate and potassium carbonate. Alkali metal carbonates such as ammonia can be used. About these basic aqueous solution, you may use it in combination of 2 or more types as needed.
- an aqueous solution of an alkali metal or alkaline earth metal hydroxide as the basic aqueous solution, and more preferably an aqueous sodium hydroxide solution.
- sodium hydroxide when sodium hydroxide is used as the basic aqueous solution, it is easy to remove excess sodium hydroxide by washing with water and to remove the eluted aluminum. Therefore, the effect of reducing the number of washings is expected. it can.
- the alloy powder In the basic aqueous solution treatment, usually, if an alloy powder, the alloy powder is gradually added to the basic aqueous solution while stirring, but the alloy powder is put in water and a more concentrated basic aqueous solution is added here. It may be dripped.
- the concentration of the basic aqueous solution used is, for example, 5 to 60% by mass, and more specifically, for example, in the case of sodium hydroxide, 10 to 40% by mass is preferable.
- the aqueous solution treatment it is preferable to use the aqueous solution at a temperature of about 20 to 120 ° C., for example.
- the temperature of the basic aqueous solution is 25 to 100 ° C.
- the treatment time for which the alloy or alloy powder is subjected to the basic aqueous solution treatment may vary depending on the shape, state, and amount of the alloy used, the concentration of the basic aqueous solution, the temperature at the time of treatment, etc. It may be about 30 to 300 minutes.
- the elution amount of the component (B) from the alloy can be adjusted by the treatment time.
- At least a part of the component (B) is eluted and removed from the alloy by a basic aqueous solution treatment.
- “leaving and removing at least a part of the component (B)” means to elute and remove a part of the component (B) from the alloy containing the component (A) and the component (B), It is meant to include the case where all of component (B) is eluted and removed from the alloy.
- the possibility that a part of component (A) dissolves as a result cannot be denied, so only “component (B)” is included in “at least a part of component (B)”. It is not necessary to interpret the present invention only when it is eluted by a basic aqueous solution treatment.
- the rate of elution of the component (B) from the alloy can be represented by the content (residual rate based on mass) of the component (B) in the metal obtained by elution removal.
- the content of the component (B) is preferably 0.1 to 60% by mass, more preferably 1 to 40%. % By mass. More specifically, for example, when the alloy is an Al—Fe alloy, the aluminum content in the metal obtained by elution removal of aluminum by the basic aqueous solution treatment is preferably 0.1 to 50% by mass. More preferably, it is 1 to 40% by mass, and further preferably 1 to 5% by mass.
- content of the component (B) in the metal used for an oxygen absorber can be measured by IPC method, for example.
- the metal hydroxide of component (A) and / or component (B) may be formed on the alloy surface by the basic aqueous solution treatment.
- the metal hydroxide can be removed from the alloy. That is, after the component (B) is eluted from the alloy, the metal hydroxide can be removed by washing with a basic aqueous solution having a higher concentration.
- the metal obtained as described above has a porous shape (or a porous body).
- the multi-milky shape means a state having a large number of pores on the surface and inside that can be confirmed with an electron microscope.
- the degree of the porous shape of the metal can be expressed by its specific surface area.
- the specific surface area of the metal used in the oxygen absorbent of the present invention by the BET method is 10 m 2 / g or more, preferably 20 m 2 / g or more, more preferably 40 m 2 / g or more, and still more preferably. 80 m 2 / g or more.
- the specific surface area of the resulting porous metal is about 10 to 120 m 2 / g
- the specific surface area is about 0.07 to 0.13 m 2 / g, and it is clear whether it is a porous shape.
- the degree of the multi-milky shape possessed by the metal can also be expressed by bulk density.
- the bulk density of the oxygen absorbent (metal) obtained as described above is 2 g / cm 3 or less, and preferably 1.5 g / cm 3 or less. In the case of ordinary iron powder (reduced iron powder or atomized iron powder) that is not porous, the bulk density is about 2 to 3 g / cm 3 .
- the bulk density can be measured according to JIS Z2504.
- the porous metal used as the oxygen absorbent has a high oxygen absorption activity, and therefore has a low humidity condition (for example, a condition of 30% RH (relative humidity) (25 ° C.) or lower). Even under an atmosphere, it can be suitably used as an oxygen absorbent. Needless to say, it can be suitably used as an oxygen absorbent even in an atmosphere of high humidity conditions (for example, conditions of 100% RH (relative humidity) (25 ° C.)).
- the metal obtained as described above is at least 5 mL / g oxygen, more preferably 10 mL / g oxygen in a low humidity atmosphere of 30% RH (relative humidity) (25 ° C.) or less. Can be absorbed. Further, when the metal is used as an oxygen absorbent, the oxygen absorption amount is, for example, 5 to 150 mL / g in a low humidity atmosphere of 30% RH (relative humidity) (25 ° C.) or less.
- the present invention by immersing and storing a metal oxygen absorbent in an aqueous solution containing a chelating agent, it becomes possible to stably store after production, even after long-term storage, immediately after production.
- the oxygen absorption activity equivalent to the above can be maintained, and even in an atmosphere with little or no moisture, oxygen in the atmosphere can be absorbed and removed at a level equivalent to that of a conventional oxygen scavenger.
- the oxygen absorbing activity of the oxygen absorbent can be maintained by using an aqueous solution containing a chelating agent, but the following mechanism is assumed. That is, when the oxygen absorbent is produced as described above, the elution treatment of the component (B) is performed with a base such as sodium hydroxide, and therefore, in the micropores formed in the metal by the elution treatment of the component (B). Remains aluminum hydroxide or the like. Even after the water washing step, aluminum hydroxide and the like cannot be completely removed, and when the oxygen absorbent is stored in water, aluminum hydroxide and the like are gradually eluted in the water.
- a base such as sodium hydroxide
- an aqueous solution containing a chelating agent is used as the aqueous solution for immersing the oxygen absorbent.
- the pH of the aqueous solution is preferably 7 to 12, more preferably 8 to 12, and further preferably 10 to 11.
- the pH of the aqueous solution is within the above range, dissolution of the iron (Fe) component in the oxygen absorbent can be further suppressed.
- the substance that can be used as the chelating agent is not particularly limited, and specifically, hydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, darconic acid, heptonic acid, and the like.
- Salts of dicarboxylic acids such as succinic acid, malonic acid, oxalic acid and phthalic acid; salts of polycarboxylic acids such as polyacrylic acid and polymaleic acid: glycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethyl Aminocarboxylic acids and salts thereof such as ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid, polyaminopolycarboxylic acid; etidronic acid (HEDP), nitrilotris (methylenephosphonic acid) (ATMP), ethylenediaminetetramethylenephosphonic acid (EDTMP), etc.
- dicarboxylic acids such as succinic acid, malonic acid, oxalic acid and phthalic acid
- salts of polycarboxylic acids such as polyacrylic acid and polymaleic acid: glycine, nitrilo
- Phosphite chelate And salts thereof ethylenediamine, diethylenetriamine, at least one selected from an amine type chelating agents such as triethylene tetramine or a combination of two or more thereof may be used.
- a salt of hydroxycarboxylic acid is preferable, an alkali metal salt of hydroxycarboxylic acid is more preferable, sodium lactate, sodium malate, sodium tartrate, sodium citrate, gluconic acid Sodium is more preferable, and sodium tartrate, sodium citrate, and sodium gluconate are particularly preferable.
- a chelating resin can also be suitably used as the chelating agent used in the present invention.
- substances that can be used as the chelating resin include Amberlite IRC748 (manufactured by Organo Corporation), Diaion CR11 (manufactured by Mitsubishi Chemical Corporation), and the like.
- the content of the chelating agent in the aqueous solution is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the oxygen absorbent, more The amount is preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.
- the oxygen absorbent is immersed in an aqueous solution having a mass twice or more the mass of the oxygen absorbent and stored at room temperature or lower.
- the oxygen absorbent can be sufficiently immersed in the aqueous solution.
- the oxygen absorbent When using an oxygen absorbent stored in an aqueous solution containing a chelating agent, the oxygen absorbent may be taken out from the aqueous solution and dried. However, since the oxygen absorbent is easily oxidized and deteriorated in the air as described above, the influence of oxygen is eliminated as much as possible by means such as vacuum drying in order not to impair the oxygen absorption activity. It is desirable to use after drying under conditions.
- the oxygen absorbent according to the present invention is easily oxidized and deteriorated in the air, the oxygen absorbent is mixed (kneaded) with the resin when used, and the obtained oxygen absorbent resin Can be used in form.
- thermoplastic resins such as polyolefin resins, polyester resins, polyamide resins, polyvinyl alcohol resins, and chlorine resins can be used.
- polyethylene, polypropylene, ethylene-vinyl acetate copolymer, elastomer, or a mixture thereof can be suitably used.
- the relative humidity (RH) of the atmosphere in which the low moisture content articles are stored is preferably 20-70%, more preferably 20-50%. It is.
- the moisture content of the low moisture content article is preferably 50% by weight or less, more preferably 30% by weight or less, and particularly preferably 10% by weight or less.
- low moisture content articles packaged products that require low humidity storage conditions
- powders for example, powders, granular foods (powder soups, powdered beverages, powdered confectionery, seasonings, cereal flour, nutritional foods, health foods, coloring
- fragrances, flavorings, spices powders, granule drugs (powdered powders, powdered soaps, toothpastes, industrial chemicals), and molded articles (tablet type), etc.
- granular foods powders, granular foods (powder soups, powdered beverages, powdered confectionery, seasonings, cereal flour, nutritional foods, health foods, coloring
- fragrances, flavorings, spices powders
- granule drugs poowdered powders, powdered soaps, toothpastes, industrial chemicals
- molded articles tablette type
- a certain food, medicine, etc. can be illustrated.
- oxygen in the atmosphere is at a level equivalent to that of a conventional oxygen scavenger, even in an atmosphere with little or no moisture. It can be absorbed and removed.
- it can be suitably used for applications such as deoxidizing the atmosphere of dry foods, pharmaceuticals, and electronic material packages that are difficult to apply conventional oxygen scavengers.
- dry foods such as powder seasonings, powdered coffee, coffee beans, rice, tea, beans, rice crackers, rice crackers, and health foods such as pharmaceuticals and vitamins.
- An oxygen-absorbing package is obtained by packaging the above-described oxygen absorbent or oxygen-absorbing resin composition with a packaging material using a breathable packaging material in whole or in part.
- a packaging material two breathable packaging materials are bonded together to form a bag, or one breathable packaging material and one non-breathable packaging material are bonded together to form a bag. Or a bag made by folding one breathable packaging material and sealing the green parts excluding the bent part.
- a packaging material that transmits oxygen and carbon dioxide can be used as the breathable packaging material. Examples of such a breathable packaging material include those obtained by imparting breathability to a conventionally known plastic film in addition to paper and non-woven fabric.
- Al (aluminum) powder and Fe (iron) powder were mixed at a ratio of 50% by mass and dissolved in nitrogen to obtain an Al—Fe alloy.
- the obtained Al—Fe alloy was pulverized using a jaw crusher, a roll crusher and a pole mill, and the pulverized product was classified using a node having an opening of 200 mesh (0.075 mm), and the particle size was 200 mesh or less.
- Al-Fe alloy powder was obtained. 150 g of the Al—Fe alloy powder obtained in this way was stirred and mixed in a 30% by mass aqueous sodium hydroxide solution at 50 ° C.
- the porous alloy powder was prepared by a reaction in an aqueous solution in order to avoid contact with oxygen.
- the obtained porous alloy powder was vacuum dried at 200 Pa or less and 80 ° C. for 2 hours to obtain a dried product of Al—Fe porous alloy powder.
- the bulk density of the obtained alloy powder was 0.9 g / cm 3 (measured according to JIS Z2504).
- 0.5g of the obtained alloy powder is packed in a breathable sachet, put in a gas barrier bag (Al foil laminated plastic bag) together with a desiccant, and filled with 50 mL of air (oxygen concentration 20.9% by volume) and sealed.
- the oxygen concentration after storage at 25 ° C. for 7 days was 9.1% by volume.
- the oxygen absorption amount was 130 mL / g.
- the average particle size of the obtained Al—Fe porous alloy powder was measured using a particle size-shape distribution measuring device (“PITA-2” manufactured by Seishin Enterprise Co., Ltd.), the average particle size was 31 ⁇ m. there were. Furthermore, when the specific surface area of the obtained Al—Fe porous alloy powder was measured using an automatic specific surface area measuring device (“Gemini VII2390” manufactured by Shimadzu Corporation), the specific surface area was 100 m 2 / g. It was.
- Example 2 The same measurement as in Example 1 was performed except that the amount of sodium tartrate used in Example 1 was changed to 5 g, and the oxygen absorption performance maintenance rate was calculated. The results were as shown in Table 1 below.
- Example 3 The same measurement as in Example 1 was performed except that the sodium tartrate used in Example 1 was changed to sodium gluconate, and the oxygen absorption performance maintenance rate was calculated. The results were as shown in Table 1 below.
- Example 1 Comparative Example 1 In Example 1, except that sodium tartrate was not added to the water slurry, the same measurement as in Example 1 was performed, and the oxygen absorption performance maintenance rate was calculated. The results were as shown in Table 1 below.
- Comparative Example 2 The same measurement as in Example 1 was performed except that sodium tartrate used in Example 1 was changed to citric acid, and the oxygen absorption performance maintenance rate was calculated. The results were as shown in Table 1 below.
- Comparative Example 3 100 g of a pH 6 citrate-sodium citrate buffer solution prepared to have a concentration of 0.2 M was added to 200 g of an aqueous slurry containing 100 g of an oxygen absorbent composed of an Al—Fe porous alloy powder used in Example 1. Except for the addition and storage, the same measurement as in Example 1 was performed, and the oxygen absorption performance maintenance ratio was calculated. The results were as shown in Table 1 below.
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Abstract
Description
[1](A)鉄、コバルト、ニッケル、および銅からなる群より選択される少なくとも1種の遷移金属と、
(B)アルミニウムと、
を含む合金を、塩基性水溶液処理に供して、前記アルミニウム(B)の少なくとも一部を溶出除去して得られる金属からなる酸素吸収剤であって、BET法により測定される比表面積が10m2/g以上である酸素吸収剤を準備し、
前記酸素吸収剤を、キレート剤を含有する水溶液に浸潰して保存する、
ことを含んでなる、酸素吸収剤の保存方法。
[2]前記キレート剤が、ヒドロキシカルボン酸の塩である、[1]に記載の酸素吸収剤の保存方法。
[3]前記水溶液中のキレート剤の含有量が、前記酸素吸収剤100質量部に対して0.1~20質量部である、[1]または[2]に記載の酸素吸収剤の保存方法。
[4]前記水溶液のpHが、7~12である、[1]~[3]のいずれかに記載の酸素吸収剤の保存方法。
<酸素吸収剤の準備工程>
本実施態様による酸素吸収剤は、下記の(A)および(B)の2成分、即ち、(A)鉄、コバルト、ニッケル、銅からなる群より選択される少なくとも1種の遷移金属と、(B)アルミニウムとを含む合金を、塩基性水溶液に接触させて、前記合金から成分(B)の少なくとも一部を溶出除去して得られる金属を含んでなるものである。なお、本明細書において、「酸素吸収剤」とは、かかる剤を設置した周囲の雰囲気中から酸素を選択的に吸収することができるものをいう。
上記した金属は、成分(B)の溶出除去処理を行った後、通常は水洗が行われる。このようにして得られた金属または金属粉末は、大気中では直ちに酸化し、酸素吸収活性を失ってしまう。したがって、成分(A)と成分(B)とを含む合金を塩基性水溶液処理した後は、合金を酸素に極力触れさせないように配慮する必要がある。そのため、上記した一連の処理を水溶液中および水中で行ってそのまま保存したり、無酸素雰囲気、または不活性ガス雰囲気で保存することが考えられる。しかしながら、水中で当該金属を保存した場合、酸素吸収活性の急激な低下は防げるものの、経時的に酸素吸収活性が低下してしまうことが判明した。また、無酸素雰囲気、または不活性雰囲気で保存を行うには、装置等が必要になるためコスト増加を招く。
キレート剤を含有する水溶液中に保存した酸素吸収剤を使用するに際しては、当該水溶液から酸素吸収剤を取り出して乾燥させればよい。但し、酸素吸収剤は、上記したように大気中では酸化し劣化し易いものであることから、酸素吸収活性を損なわないために、例えば、真空乾燥などの手段により、酸素による影響をできるだけ排除した条件にて、乾燥を行い、使用することが望ましい。
Al(アルミニウム)粉とFe(鉄)粉とを、それぞれ50質量%の割合で混合し、窒素中で溶解して、Al-Fe合金を得た。次いで、得られたAl-Fe合金を、ジョークラッシャー、ロールクラッシャーおよびポールミルを用いて粉砕し、粉砕物を目開き200メッシュ(0.075mm)の節を用いて分級し、粒径が200メッシュ以下のAl-Fe合金粉を得た。このようにして得られたAl-Fe合金粉150gを、30質量%の水酸化ナトリウム水溶液中に50℃で1時間撹拌混合した後、濾別を行い、更に40質量% 水酸化ナトリウム水溶液中で50℃で1時間攪拌混合を行った。続いて、混合溶液を静置し、上層液を取り除いた。残った沈殿物をpHが11以下になるまで蒸留水で洗浄し、Al-Fe多孔質合金粉を得た。このように、多孔質合金粉は、酸素に接触させることを回避すべく水溶液中での反応により作製した。
上記のようにして得られたAl-Fe多孔質合金粉からなる酸素吸収剤100gを含む水スラリー300gに、キレート剤として酒石酸ナトリウムを2g添加して保存した。保存開始から14日後、28日後および56日後に酸素吸収剤の一部をサンプリングし、200Pa以下、80℃で水分量1質量%以下になるまで真空乾燥を行った。その後、上記と同様にして酸素濃度の測定を行い、酸素吸収剤の酸素吸収量を算出した。得られた酸素吸収量から、下記式を用いて酸素吸収性能維持率(%)を算出した。
酸素吸収性能維持率(%)
=(保存後の酸素吸収量)/(調製直後の酸素吸収量=130)×100
結果は下記の表1に示される通りであった。
実施例1において用いた酒石酸ナトリウムの添加量を、5gに変更した以外は実施例1と同様の測定を行い、酸素吸収性能維持率を算出した。結果は下記の表1に示される通りであった。
実施例1おいて用いた酒石酸ナトリウムを、グルコン酸ナトリウムに変更した以外は実施例1と同様の測定を行い、酸素吸収性能維持率を算出した。結果は下記の表1に示される通りであった。
実施例1において、水スラリーに酒石酸ナトリウムの添加しなかった以外は、実施例1と同様の測定を行い、酸素吸収性能維持率を算出した。結果は下記の表1に示される通りであった。
実施例1 において用いた酒石酸ナトリウムをクエン酸に変更した以外は実施例1と同様の測定を行い、酸素吸収性能維持率を算出した。結果は下記の表1に示される通りであった。
実施例1において用いたAl-Fe多孔質合金粉からなる酸素吸収剤100gを含む水スラリー200gに、濃度が0.2Mとなるように調製されたpH6のクエン酸-クエン酸ナトリウム緩衝液を100g添加して保存したこと以外は実施例1と同様の測定を行い、酸素吸収性能維持率を算出した。結果は下記の表1に示される通りであった。
Claims (4)
- (A)鉄、コバルト、ニッケル、および銅からなる群より選択される少なくとも1種の遷移金属と、
(B)アルミニウムと、
を含む合金を、塩基性水溶液処理に供して、前記アルミニウム(B)の少なくとも一部を溶出除去して得られる金属からなる酸素吸収剤であって、BET法により測定される比表面積が10m2/g以上である酸素吸収剤を準備し、
前記酸素吸収剤を、キレート剤を含有する水溶液に浸潰して保存する、
ことを含んでなる、酸素吸収剤の保存方法。 - 前記キレート剤が、ヒドロキシカルボン酸の塩である、請求項1に記載の酸素吸収剤の保存方法。
- 前記水溶液中のキレート剤の含有量が、前記酸素吸収剤100質量部に対して0.1~20質量部である、請求項1または2に記載の酸素吸収剤の保存方法。
- 前記水溶液のpHが、7~12である、請求項1~3のいずれか一項に記載の酸素吸収剤の保存方法。
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KR1020167004957A KR20160074452A (ko) | 2013-10-22 | 2014-10-22 | 산소 흡수제의 보존 방법 |
JP2015543888A JP6578947B2 (ja) | 2013-10-22 | 2014-10-22 | 酸素吸収剤の保存方法 |
EP14856142.6A EP3061523A4 (en) | 2013-10-22 | 2014-10-22 | Method for storing oxygen absorber |
US15/028,827 US20160250617A1 (en) | 2013-10-22 | 2014-10-22 | Method for storing oxygen absorbing agent |
CN201480057761.9A CN105658320A (zh) | 2013-10-22 | 2014-10-22 | 吸氧剂的保存方法 |
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Citations (7)
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JPS5499092A (en) * | 1978-01-23 | 1979-08-04 | Fujishima Daishiro | Oxygen scavenger primarily made of reformed iron powder |
JPS562845A (en) * | 1980-01-21 | 1981-01-13 | Mitsubishi Gas Chem Co Inc | Oxygen absorbent |
JPS62244443A (ja) * | 1986-04-16 | 1987-10-24 | Shimadaya Honten:Kk | 脱酸素剤 |
JPH0523597A (ja) | 1991-07-23 | 1993-02-02 | Nikko Rika Kk | 触媒用球状ラネ−合金の製造方法 |
JPH09253481A (ja) * | 1996-03-22 | 1997-09-30 | Sony Corp | 脱酸素剤及びその製造方法 |
WO2012105457A1 (ja) | 2011-01-31 | 2012-08-09 | 三菱瓦斯化学株式会社 | 酸素吸収剤およびその保存方法 |
WO2014021430A1 (ja) * | 2012-08-02 | 2014-02-06 | 三菱瓦斯化学株式会社 | 酸素吸収剤の製造方法 |
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DE1156769B (de) * | 1961-02-07 | 1963-11-07 | Varta Ag | Verfahren zur Herstellung aktivierter Katalysatoren aus Raney-Legierungen |
AU471081B2 (en) * | 1973-10-12 | 1976-04-08 | Method of producing olefinic amides with a raney copper catalyst | |
US7375053B2 (en) * | 2003-04-07 | 2008-05-20 | W. R. Grace & Co.- Conn. | Nickel and cobalt plated sponge catalysts |
EP2749604B1 (en) * | 2011-11-15 | 2016-10-05 | Mitsubishi Gas Chemical Company, Inc. | Oxygen-absorbing resin composition, oxygen-absorbing multilayer laminate, and oxygen-absorbing hollow container |
-
2014
- 2014-10-22 CN CN201480057761.9A patent/CN105658320A/zh active Pending
- 2014-10-22 US US15/028,827 patent/US20160250617A1/en not_active Abandoned
- 2014-10-22 KR KR1020167004957A patent/KR20160074452A/ko not_active Application Discontinuation
- 2014-10-22 EP EP14856142.6A patent/EP3061523A4/en not_active Withdrawn
- 2014-10-22 TW TW103136453A patent/TWI666051B/zh active
- 2014-10-22 WO PCT/JP2014/078132 patent/WO2015060356A1/ja active Application Filing
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS5499092A (en) * | 1978-01-23 | 1979-08-04 | Fujishima Daishiro | Oxygen scavenger primarily made of reformed iron powder |
JPS562845A (en) * | 1980-01-21 | 1981-01-13 | Mitsubishi Gas Chem Co Inc | Oxygen absorbent |
JPS62244443A (ja) * | 1986-04-16 | 1987-10-24 | Shimadaya Honten:Kk | 脱酸素剤 |
JPH0523597A (ja) | 1991-07-23 | 1993-02-02 | Nikko Rika Kk | 触媒用球状ラネ−合金の製造方法 |
JPH09253481A (ja) * | 1996-03-22 | 1997-09-30 | Sony Corp | 脱酸素剤及びその製造方法 |
WO2012105457A1 (ja) | 2011-01-31 | 2012-08-09 | 三菱瓦斯化学株式会社 | 酸素吸収剤およびその保存方法 |
WO2014021430A1 (ja) * | 2012-08-02 | 2014-02-06 | 三菱瓦斯化学株式会社 | 酸素吸収剤の製造方法 |
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Title |
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EP3061523A4 (en) | 2017-06-21 |
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CN105658320A (zh) | 2016-06-08 |
TW201529151A (zh) | 2015-08-01 |
KR20160074452A (ko) | 2016-06-28 |
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