TWI666051B - 氧吸收劑的保存方法 - Google Patents
氧吸收劑的保存方法 Download PDFInfo
- Publication number
- TWI666051B TWI666051B TW103136453A TW103136453A TWI666051B TW I666051 B TWI666051 B TW I666051B TW 103136453 A TW103136453 A TW 103136453A TW 103136453 A TW103136453 A TW 103136453A TW I666051 B TWI666051 B TW I666051B
- Authority
- TW
- Taiwan
- Prior art keywords
- oxygen
- oxygen absorbent
- aqueous solution
- component
- alloy
- 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
- 239000002250 absorbent Substances 0.000 title claims abstract description 81
- 230000002745 absorbent Effects 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000003860 storage Methods 0.000 title claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 53
- 239000000956 alloy Substances 0.000 claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002738 chelating agent Substances 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000006096 absorbing agent Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 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
- 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 4
- 229910052751 metal Inorganic materials 0.000 abstract description 30
- 239000002184 metal Substances 0.000 abstract description 30
- 238000011282 treatment Methods 0.000 abstract description 18
- 239000000843 powder Substances 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000010521 absorption reaction Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000005022 packaging material Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 229910018084 Al-Fe Inorganic materials 0.000 description 10
- 229910018192 Al—Fe Inorganic materials 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
- 230000000694 effects Effects 0.000 description 9
- 238000012423 maintenance Methods 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- -1 aluminum compound Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 description 5
- 150000004692 metal hydroxides Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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 3
- 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
- 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
- 229940079593 drug Drugs 0.000 description 3
- 235000011194 food seasoning agent Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000176 sodium gluconate Substances 0.000 description 3
- 235000012207 sodium gluconate Nutrition 0.000 description 3
- 229940005574 sodium gluconate Drugs 0.000 description 3
- 229910000838 Al alloy Inorganic materials 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
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-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
- 229910000640 Fe alloy Inorganic materials 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
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 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
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect 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
- 235000013402 health food Nutrition 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000004679 hydroxides Chemical class 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
- 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
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 235000009566 rice 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
- 238000001291 vacuum drying Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- HHZAHYUACNWGAQ-UHFFFAOYSA-N 3,4-diaminobutan-2-ol Chemical compound CC(O)C(N)CN HHZAHYUACNWGAQ-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
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-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
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 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
- 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
- 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
- 239000004411 aluminium Substances 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
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 235000012970 cakes Nutrition 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 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
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives 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
- 239000012153 distilled water Substances 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008187 granular material 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
- 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
- 239000000463 material Substances 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
- 150000002739 metals 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
- 235000008935 nutritious Nutrition 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
- 235000012771 pancakes Nutrition 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-K pentetate(3-) Chemical compound OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QPCDCPDFJACHGM-UHFFFAOYSA-K 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003761 preservation solution Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000011888 snacks Nutrition 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
- 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
- 235000014347 soups Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 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
- A23L3/3427—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 in which an absorbent is placed or used
- A23L3/3436—Oxygen absorbent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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Abstract
藉由本發明之氧吸收劑的保存方法係包括下列步驟進行;準備藉由BET法所測定之比表面積為10m2/g以上之氧吸收劑,以及將前述氧吸收劑浸漬於含螯合劑的水溶液中保存,其中,前述氧吸收劑係由含(A)選自由鐵、鈷、鎳及銅所成之群的至少一種過渡金屬,與(B)鋁所得之合金供給至鹼性水溶液處理,且將前述鋁(B)之至少一部分溶出去除而得到之金屬所構成。
Description
本發明係關於氧吸收劑的保存方法,更詳細而言,係關於即使低濕度的環境中亦能吸收氧,去除氧之氧吸收劑的保存方法。
作為一個食品或醫藥品等的保存技術,有經由氧吸收劑(脫氧劑)的保存技術。具體而言,藉由將去除環境中的氧之脫氧劑與對象物一起裝進密封包裝體裏後,將密封包裝體裏設為無氧狀態,而抑制對象物的氧化劣化、霉、變色等技術。
迄今為止作為去除環境中的氧之脫氧劑,提案有由各種無機系材料構成者及有機系材料構成者。其中,開發有下列氧吸收劑,即,利用氫氧化鈉水溶液,使用從由鋁與鐵構成的合金,或由鋁與鎳構成的合金去除鋁之金屬,即使沒有如30%RH(25℃)以下之水分,或幾乎沒有水分的環境中,在與以往為同等水平的脫氧劑之下,能吸收,亦能去除環境中的氧之氧吸收劑(例如國際公開第2012/105457號等)。
又,在國際公開第2012/105457號亦揭示,經由於持有酸或緩衝功能的水溶液中浸漬如上述所得到由金屬構成之氧吸收劑保存,一邊能維持氧吸收劑的氧吸收活性,一邊能長期穩定地保存氧吸收劑。
[專利文獻1]國際公開第2012/105457號
然而,記載在上述專利文獻的氧吸收劑,特別是氧吸收性能高之氧吸收劑會對酸性水溶液敏感地反應,故即使於持有酸或緩衝功能的水溶液中浸漬氧吸收劑,有不能一邊維持充分之氧吸收性能,一邊保存氧吸收劑之情形。
本發明係解決以往技術產生的上述問題,其目的在於提供一種作為即使沒有水分或幾乎沒有水分的環境下亦能具有吸收環境中之氧的功能之氧吸收劑的保存方法,其安全性高、且低價格,能一邊維持充分之氧吸收性能,一邊長期穩定地保存氧吸收劑之方法。
本發明人等發現,製造氧吸收劑之際,經由
氫氧化鈉等的鹼進行成分(B)的溶出處理,因而成分(B)的溶出處理,於金屬形成之微細孔中殘餘氫氧化鋁等的金屬氫氧化物,即使經由水洗步驟此殘餘物不能完全去除,於水中保管氧吸收劑之際,此殘餘物漸漸地溶出至水中。接著,推測於水溶液中保存氧吸收劑時,藉由溶出至水溶液中之氫氧化鋁等的金屬氧化物經時地析出至氧吸收劑表面,而可能降低氧吸收劑的氧活性吸收。進一步檢討的結果,即使於水溶液中浸漬金屬氫氧化物,藉由於水溶液添加螯合劑,而得到能一邊維持氧吸收劑的氧吸收活性,一邊保存之見解。本發明係根據此見解者。
亦即,本發明提供下列[1]~[4]。
[1]一種氧吸收劑的保存方法,其係包括準備藉由BET法所測定之比表面積為10m2/g以上的氧吸收劑,以及將前述氧吸收劑浸漬於含螯合劑的水溶液中保存,其中,前述氧吸收劑係由含(A)選自由鐵、鈷、鎳及銅所成之群的至少一種過渡金屬,與(B)鋁所得之合金供給至鹼性水溶液處理,且將前述鋁(B)之至少一部份溶出去除而得到之金屬所構成。
[2]如[1]之氧吸收劑的保存方法,其中,前述螯合劑為羥基羧酸的鹽。
[3]如[1]或[2]之氧吸收劑的保存方法,其中前述水溶液中之螯合劑的含量對於前述氧吸收劑100質量份,為0.1~
20質量份。
[4]如[1]~[3]中任一項之氧吸收劑的保存方法,其中前述水溶液的pH為7~12。
根據本發明之氧吸收劑的保存方法,氧吸收劑的製造後,成為可能穩定地保存,即使長期保存後亦能維持與製造後即刻為同等的氧收吸收活性,即使沒有水分或幾乎沒有水分的環境中,將環境中的氧與以往的脫氧劑同等的水平能吸收、去除。
以下說明有關本發明之實施形態。另外,以下之實施形態係為了說明本發明的例示,本發明並非僅限定該實施形態。
根據本發明之氧吸收劑的保存方法,係包括準備氧吸收劑的步驟,以及將準備之氧吸收劑浸漬於含螯合劑的水溶液中保存的步驟。以下詳述有關各步驟。
根據本實施態樣之氧吸收劑係包含下列(A)與(B)的2成分,亦即,使包含由(A)選自由鐵、鈷、鎳及銅所成群組之至少1種的過渡金屬,與(B)鋁所得之合金與鹼性水
溶液接觸,由前述合金將成分(B)之至少一部份溶出去除而得到之金屬所成者。另外,本說明書中「氧吸收劑」意指從設置了此劑之周圍的環境中能選擇地吸收氧者。
可能用於作為成分(A)之過渡金屬選自鐵、鈷、鎳、銅者。上述過渡金屬能單獨或組合2種以上使用即可。例如選擇鐵與鎳時,作為成分(A)亦能使用Fe-Ni合金。作為成分(A)佳為鐵或鎳,更佳為鐵。該等之中,鐵由於安全性高且廉價而較佳。又,作為構成氧吸收劑的成分(B),使用鋁。
用於本實施形態之合金係包含上述成分(A)與成分(B),合金中作為添加金屬進而能包含鉬、鉻、鈦、釩、鎢等。亦能進而包含氰酸類等添加成分。
包含上述成分(A)與成分(B)之合金係能藉由熔融法調製。此時,成分(A)與成分(B)之組成的比例佳為成分(A)是20~80質量%時,成分(B)是20~80質量%,更佳為成分(A)是30~70質量%時,成分(B)是30~70質量%。列舉更具體例時,成分(A)是鐵或鎳時,鐵或鎳的比例係30~55質量%,鋁的比例係45~70質量%為佳。
雖所得到的合金亦能直接供給至鹼性水溶液處理,通常微粉碎後供給至鹼性水溶液處理。另外,本說明書中「合金」意指不僅具有特定結晶構造之單一組成者,亦包含該混合物及金屬本身的混合物。
作為微粉碎合金的方法,能適宜使用為了慣例之金屬的解碎及粉碎之方法,例如以顎式破碎機、輥式
破碎機、錘磨機等粉碎合金,進而能視需要以球磨機進行微粉碎。或,亦能經由霧化法等的驟冷凝固法將前述合金的熔融微粉化。此處藉由霧化法時,於氬氣等的非活性氣體中進行為佳。作為霧化法,例如能使用特開平5-23597號公報中記載的方法。
所得到的合金粉末之粒徑成為在於5~200μm的範圍內為佳,另外,該粒徑分布儘量狹窄為佳。從排除粒徑大者或使粒徑分布一致的觀點考量,亦能使用市售的網篩(例如200目篩等)適宜進行篩分(分級)。另外,利用霧化法時,粉末存在接近球狀的傾向,另外,存在能使粒徑分布狹窄的傾向。另外,能使用粒度-形狀分布測定器等測定合金粉末的粒徑。
接著,將如上述所得到的合金或合金粉末供給至鹼性水溶液處理,從合金使成分(B)的至少一部份溶出去除。亦即,作為經由本發明的保存方法使用之氧吸收劑,使用從上述合金使成分(B)的至少一部份溶出去除後所得到的金屬。作為鹼性水溶液,為不溶解或幾乎不溶解成分(A)者。另一方面,若使成分(B)溶解並能去除者,亦即,若從合金能使成分(B)浸出(溶出)者,則能沒有特別限制地使用,能使用任一者。作為鹼性水溶液中的鹼,例如能使用氫氧化鈉、氫氧化鉀等鹼性金屬的氫氧化物;氫氧化鈣、氫氧化鎂等之鹼土類金屬的氫氧化物;碳酸鈉、碳酸鉀等鹼性金屬的碳酸鹽;氨等。對於鹼性水溶液而言,能視需要適宜組合兩種以上使用。
根據本實施形態,作為鹼性水溶液使用鹼金屬或鹼土類金屬之氫氧化物的水溶液為佳,更佳為氫氧化鈉水溶液。例如作為鹼性水溶液使用氫氧化鈉時,容易藉由水洗去除過剩量的氫氧化鈉,或容易去除溶出的鋁,因此,能期待能削減水洗次數的效果。
鹼性水溶液處理中,通常若合金粉末,則於鹼性水溶液中邊攪拌邊少量地投入合金粉末,亦能於水中置入合金粉末,於此進而滴下濃厚的鹼性水溶液。
鹼性水溶液處理中,所使用之鹼性水溶液的濃度係例如5~60質量%,更具體而言,例如氫氧化鈉時,10~40質量%為佳。
鹼性水溶液處理中,例如將水溶液的溫度加溫至20~120℃左右使用為佳。佳為鹼性水溶液的溫度是25~100℃。
將合金或合金粉末供給至鹼性水溶液處理的處理時間係因所使用之合金的形狀、狀態、及其量、鹼性水溶液濃度、處理之際的溫度等可能會有所不同,通常為30~300分鐘左右即可。藉由處理時間,亦能調整從合金之成分(B)的溶出量。
本實施形態中,藉由鹼性水溶液處理,從合金溶出去除成分(B)的至少一部份。此處,溶出去除「成分(B)的至少一部份」意指從包含成分(A)與成分(B)所得的合金使成分(B)的一部份溶出去除以外,亦意味著包含從合金使成分(B)的全部溶出去除之情形。另外,於成分(B)的
溶出過程中,亦不能否定其結果作為成分(A)之一部份會溶解的可能性,不需要解釋為限定在「成分(B)的至少一部份」中僅成分(B)藉由鹼性水溶液處理溶出的情形。
藉由鹼性水溶液處理,成分(B)的至少一部份佳為其大部份從合金溶出。從合金成分(B)的溶出比例,係藉由溶出去除所得到之金屬中能以成分(B)的含有率(質量基準的殘餘率)表示。
溶出作為用於氧吸收劑的金屬(亦即溶出成分(B)後的金屬)中,成分(B)的含有率係佳為0.1~60質量%,更佳為1~40質量%。更具體而言,例如合金係Al-Fe合金時,藉由經由鹼性水溶液處理之鋁的溶出去除所得到之金屬中鋁的含有率係佳為0.1~50質量%,更佳為1~40質量%,特佳為1~5質量%。另外,用於氧吸收劑之金屬中成分(B)的含量係能利用例如IPC法測定。
藉由鹼性水溶液處理,有於合金表面形成成分(A)及/或成分(B)的金屬氫氧化物之情形。為了提升氧吸收劑的氧吸收性能,能從合金去除金屬氫氧化物。亦即,從合金溶出成分(B)後,進而藉由以高濃度的鹼性水溶液洗淨,能去除金屬氫氧化物。
如上述得到的金屬係具有多孔質形狀(或多孔體)。此處,多孔質形狀意指以電子顯微鏡能確認程度之於表面及內部具有多數的細孔之狀態。本發明中,金屬具有之多孔質形狀的程度係能以其比表面積表示。具體而言,藉由BET法用於本發明的氧吸收劑之金屬的比表面
積為10m2/g以上,佳為20m2/g以上,更佳為40m2/g以上,特佳為80m2/g以上。
例如本實施形態中作為成分(A)使用鐵時,所得到之多孔質形狀的金屬之比表面積(藉由BET法者)係10~120m2/g左右,另一方面,並非多孔質之通常的鐵粉(還元鐵粉或霧化鐵粉)時,其比表面積為0.07~0.13m2/g左右,能很明顯地瞭解是否為多孔質形狀。
又,金屬所具有之多孔質形狀的程度係能以體積密度表示。如上述所得到的氧吸收劑(金屬)的體積密度係2g/cm3以下,佳為1.5g/cm3以下。另外,並非多孔質之通常的鐵粉(還元鐵粉或霧化鐵粉)時,其體積密度係2~3g/cm3左右。另外,體積密度係能依JIS Z2504測定。
本實施形態中,因用於作為氧吸收劑之多孔質的金屬具有高氧吸收活性,即使低濕度條件(例如30%RH(相對濕度)(25℃)以下的條件)的環境下,能作為氧吸收劑適宜地使用。當然即使高濕度條件(例如100%RH(相對濕度)(25℃)之條件)的環境下,亦能作為氧吸收劑適宜地使用是不言而喻的。
因此,如上述所得到的金屬係30%RH(相對濕度)(25℃)以下之低濕度環境中,能吸收至少5mL/g以上的氧,更佳為10mL/g以上的氧。又,用於作為氧吸收劑之該金屬時的氧吸收量係例如30%RH(相對濕度)(25℃)以下的低濕度環境中成為5~150mL/g。
上述金屬係進行成分(B)的溶出去除處理之後,通常實施水洗。如此所得到的金屬或金屬粉末係於大氣中立即氧化,失去氧吸收活性。因此,鹼性水溶液處理包含成分(A)與成分(B)所得的合金之後,有必要考慮極力使合金不接觸氧。因此,能思及於水溶液中及水中進行上述一連串處理後直接保存,於無氧環境下保存,或於不惰性氣體環境下保存。然而,判別於水中保存該金屬時,雖能防止氧活性吸收之大幅下降,但氧活性吸收會經時下降。又,於無氧環境下,或於不惰性環境下進行保存會成為需要裝置等,而造成增加成本。
本發明中,經由將由金屬所成氧吸收劑浸漬於含螯合劑的水溶液中保存,成為可能製造後穩定地保存,即使長期保存後亦能維持與製造後即刻為同等的氧吸收活性,即使沒有水分或幾乎沒有水分的環境中,將環境中的氧與以往的脫氧劑同等的水平能吸收、去除。
本發明中,關於使用含螯合劑的水溶液,雖能維持氧吸收劑的氧活性吸收之理由並不瞭解,例如能推測以下機構。亦即,能思及如上述製造氧吸收劑之際,藉由氫氧化鈉等的鹼進行成分(B)的溶出處理,經由成分(B)的溶出處理形成於金屬的微細孔中,會殘餘氫氧化鋁等。即使經由水洗步驟亦不能完全去除氫氧化鋁等,於水中保存氧吸收劑時氫氧化鋁等會漸漸地溶出至水中。之後,含
鋁化合物析出至氧吸收劑表面而有堵塞氧吸收之活性點的可能性。然而,使用含螯合劑的水溶液,螯合劑會封鎖鋁離子。能推測藉此防止藉由析出物之活性點的堵塞。
作為使氧吸收劑浸漬之保存介質,就安全性及成本的觀點而言,適宜水。因此,作為使氧吸收劑浸漬之水溶液,使用含螯合劑的水溶液。另外,水溶液的pH係7~12為佳,8~12為更佳,10~11為特佳。將水溶液的pH設為上述範圍內時,更能抑制氧吸收劑中之鐵(Fe)成分的溶解。
作為可能用於上述螯合劑的物質,並沒有特別限制者,具體而言,乙醇酸、乳酸、蘋果酸、酒石酸、檸檬酸、葡糖酸、庚酸等羥基羧酸的鹽;琥珀酸、丙二酸、草酸、鄰苯二甲酸等之二羧酸的鹽;聚丙烯酸、聚馬來酸等之聚羧酸的鹽:甘氨酸、次氮基三乙酸、乙二胺四乙酸(EDTA)、羥乙基乙二胺三乙酸酯(HEDTA)、二乙烯三胺五乙酸酯、聚胺基聚羧酸等的胺基羧酸及其鹽;依替膦酸(HEDP)、次氮基三(亞甲基膦酸)(ATMP)、乙二胺四亞甲基膦酸(EDTMP)等的亞磷酸系螯合劑及其鹽;能使用選自乙二胺、二乙烯三胺、三乙烯四胺等之胺系螯合劑等之中的至少1種,或能組合2種以上使用。該等之中,對生體的安全性、成本面等而言,羥基羧酸的鹽為佳,羥基羧酸的鹼金屬鹽為較佳、乳酸鈉、蘋果酸鈉、酒石酸鈉、檸檬酸鈉、葡糖酸鈉為更佳、酒石酸鈉、檸檬酸鈉、葡糖酸鈉為特佳。
又,作為本發明中使用的螯合劑,亦能適宜地使用螯合樹脂。例示可能用於作為螯合樹脂的物質時,能使用Amberlite RC-748(ORGANO CORPORATION製)、DiaionCR11(Mitsubishi Chemical Corporation製)等。
又,根據本實施形態之氧吸收劑的保存方法中,水溶液中之螯合劑的含量係相對於氧吸收劑100質量份,為0.1~20質量份為佳,更佳為1~10質量份,特佳為2~5質量份。藉由將螯合劑的濃度設定在上述範圍,而能更維持氧吸收劑的製造即刻之氧吸收活性。
本實施形態中,於氧吸收劑之質量的2倍量以上之質量的水溶液中使氧吸收劑浸漬,而以常溫以下的溫度保存為佳。藉由將水溶液的量調製成氧吸收劑之2倍以上的量,而能於水溶液中充分地浸漬氧吸收劑。
使用保存於含螯合劑之水溶液中的氧吸收劑之際,從該水溶液取出氧吸收劑並乾燥其即可。惟,如上述,由於氧吸收劑於大氣中容易氧化並劣化,為了不損及氧吸收活性,藉由例如真空乾燥等的手段,以儘量排除因氧影響的條件進行乾燥後使用為理想。
如上述,由於根據本發明之氧吸收劑,係於大氣中容易氧化並劣化,使用之際能將氧吸收劑混合(混煉)樹脂,而能以所得到的氧吸收性樹脂之形態使用。
作為能使用的樹脂,對其種類沒有特別限
制,能使用聚烯烴樹脂、聚酯樹脂、聚醯胺樹脂、聚乙烯醇樹脂及氯系樹脂等的熱可塑性樹脂。特別是能適宜地使用聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物、彈性體、或該等混合物。
為了保存需要低濕度保存條件的含低水分物品,保存含低水分物品之環境的相對濕度(RH)佳為20~70%,更佳為20~50%。含低水分物品的水分含有率佳為50質量%以下,更佳為30質量%以下,特佳為10質量%以下的物品全部適合。作為需要低濕度保存條件的含低水分物品(被包裝物),能例示出例如粉末、顆粒食品類(湯粉、粉末飲料、粉末點心、調料、穀物粉末、營養食品、健康食品、著色劑、著香劑、香辣調味料),粉末、顆粒藥品(散劑類、肥皂粉、牙粉、工業藥品),該等成型體(片劑型)等需要忌避水分的增加、避免混入異物的食品、藥品等。特別是在後述的氧吸收性包裝體填充該等被包裝物時,即使在沒有水分或幾乎沒有水分的環境中,亦能以與以往的脫氧劑同等的水平能吸收、去除環境中的氧氣。因此,能合適地用於使難以適用以往的脫氧劑之忌避水分的乾燥食品、藥品、電子材料的包裝的環境形成脫氧狀態等用途。例如能合適地用於粉末調料、粉末咖啡、咖啡豆、米、茶、豆、年糕片、煎餅等乾燥食品或藥品、維生素劑等健康食品。
根據本發明之另一形態的氧吸收性包裝體,係以用於全部或一部份之透氣性包裝材料的包裝材料包裝
上述氧吸收劑或氧吸收性樹脂組成物。此處,作為包裝材料,能列舉出將兩片透氣性包裝材料貼合而形成袋狀的包裝材料,將一片透氣性包裝材料與一片非透氣性包裝材料貼合而形成袋狀的包裝材料,或將一片透氣性包裝材料彎曲,並將除了彎曲部的邊緣部之間密封而形成袋狀的包裝材料。另外,作為透氣性包裝材料,能使用透過氧氣和二氧化碳的包裝材料。作為如此透氣性包裝材料,除了紙或無紡布之外,亦能列舉出以往公知的對塑料薄膜賦予了透氣性的包裝材料。
以下藉由實施例對本發明進行更具體的說明,但是本發明並非被以下的實施例限定者。
分別以50質量%的比例將Al(鋁)粉末和Fe(鐵)粉末混合,於氮氣中熔解,得到Al-Fe合金。接著,使用顎式破碎機、輥式破碎機及球磨機將所得到的Al-Fe合金粉碎,使用孔徑200目篩(0.075mm)的網將粉碎物分級,得到粒徑為200目篩以下的Al-Fe合金粉末。將如此所得到的Al-Fe合金粉末150g於50℃的30質量%氫氧化鈉水溶液中攪拌並混合1小時後,進行過濾,進而在50℃的40質量%的氫氧化鈉水溶液中攪拌並混合1小時。接著,靜置混合溶液,去除上層液。用蒸餾水將所殘留的沈澱物洗
淨至pH為11以下,得到Al-Fe多孔質合金粉末。如此,多孔質合金粉末為了應避免與氧氣接觸而經由於水溶液中反應得到。
將所得到的多孔質合金粉末在200Pa以下、80℃下真空乾燥2小時,得到Al-Fe多孔質合金粉末乾燥物。所得到的合金粉末之體積密度為0.9g/cm3(依照JIS Z2504測定)。將所得到的合金粉末0.5g包裝到透氣性小袋內,與乾燥劑一起裝入到阻氣袋(層壓Al箔的塑料袋),填充50mL的空氣(氧氣濃度為20.9容量%)並密封,測定25℃下保存7天後的氧氣濃度時,為9.1容量%。從阻氣袋內之減少的氧氣濃度算出氧吸收量,結果氧吸收量為130mL/g。
另外,使用粒度-形狀分布測定器(SEISHIN ENTERPRISE Co.,Ltd.製“PITA-2”)測定所得到的Al-Fe多孔質合金粉末之平均粒徑,結果平均粒徑為31μm。進而,使用自動比表面積測定裝置(SHIMADZU SEISAKUSHO LTD.製“GEMINI VII2390”)測定所得到的Al-Fe多孔質合金粉末的比表面積,結果比表面積為100m2/g。
如上述,於含由所得到的Al-Fe多孔質合金粉末所成氧吸收劑100g之水漿300g,添加作為螯合劑的酒石酸鈉2g後保存。從保存開始14天後、28天後及56天後採樣氧吸收劑的一部份,200Pa以下、80℃下水分量成為1質
量%以下為止進行真空乾燥。然後,與上述同等地進行氧氣濃度的測定,求出氧吸收劑的氧吸收量。使用下述通式從所得到的氧吸收量求出氧吸收性能維持率(%)。
氧吸收性能維持率(%)=(保存後氧吸收量)/(調製即刻的氧吸收量=130)×100
結果係如示於下列的表1。
除了將用於實施例1之酒石酸鈉的添加量變更為5g以外,與實施例1同等地進行測定,求出氧吸收性能維持率。結果係如示於下列的表1。
除了將用於實施例1之酒石酸鈉變更為葡糖酸鈉以外,與實施例1同等地進行測定,求出氧吸收性能維持率。結果係如示於下列的表1。
除了於實施例1中未將酒石酸鈉添加至水漿以外,與實施例1同等地進行測定,求出氧吸收性能維持率。結果係如示於下列的表1。
除了將用於實施例1之酒石酸鈉變更為檸檬酸以外,與實施例1同等地進行測定,求出氧吸收性能維持率。結果係如示於下列的表1。
除了於含由得到的Al-Fe多孔質合金粉末所成氧吸收劑100g之水漿200g,濃度成為0.20M的方式添加經調製為pH6的檸檬酸-檸檬酸鈉緩衝液100g後保存以外,與實施例1同等地進行測定,求出氧吸收性能維持率。結果係如示於下列的表1。
得知使用於保存液含螯合劑的水溶液之實施例1~5中,28天後的氧吸收性能維持率為76~91%之高值,能抑制氧吸收劑性能的降低。另一方面,明顯地瞭解作為氧吸收劑的保存液使用水或檸檬酸水溶液等之比較例1~3中,28天後的氧吸收性能維持率成為11~66%,不能抑制氧吸收劑性能的降低。
Claims (3)
- 一種氧吸收劑的保存方法,其係包括準備藉由BET法所測定之比表面積為10m2/g以上的氧吸收劑,以及將前述氧吸收劑浸漬於含螯合劑的水溶液中保存,其中,前述氧吸收劑係由含(A)選自由鐵、鈷、鎳及銅所成之群的至少一種過渡金屬,與(B)鋁所得之合金供給至鹼性水溶液處理,且將前述鋁(B)之至少一部份溶出去除而得到之金屬所構成,前述螯合劑為羥基羧酸的鹽。
- 如專利範圍第1項之氧吸收劑的保存方法,其中前述水溶液中之螯合劑的含量對於前述氧吸收劑100質量份,為0.1~20質量份。
- 如專利範圍第1或2項之氧吸收劑的保存方法,其中前述水溶液的pH為7~12。
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US3235513A (en) * | 1961-02-07 | 1966-02-15 | Varta Ag | Process for activating raney alloys and solution useful for such process |
TW201247307A (en) * | 2011-01-31 | 2012-12-01 | Mitsubishi Gas Chemical Co | Oxygen absorber and method for storing same |
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AU471081B2 (en) * | 1973-10-12 | 1976-04-08 | Method of producing olefinic amides with a raney copper catalyst | |
JPS5499092A (en) * | 1978-01-23 | 1979-08-04 | Fujishima Daishiro | Oxygen scavenger primarily made of reformed iron powder |
JPS6041986B2 (ja) * | 1980-01-21 | 1985-09-19 | 三菱瓦斯化学株式会社 | 酸素吸収剤 |
JPS62244443A (ja) * | 1986-04-16 | 1987-10-24 | Shimadaya Honten:Kk | 脱酸素剤 |
JP3293846B2 (ja) | 1991-07-23 | 2002-06-17 | 日興リカ株式会社 | 触媒用球状ラネ−合金の製造方法 |
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US7375053B2 (en) * | 2003-04-07 | 2008-05-20 | W. R. Grace & Co.- Conn. | Nickel and cobalt plated sponge catalysts |
US9199778B2 (en) * | 2011-11-15 | 2015-12-01 | Mitsubishi Gas Chemical Company, Inc. | Oxygen absorbing resin composition, oxygen absorbing multilayered body, and oxygen absorbing hollow container |
JP5626488B2 (ja) * | 2012-08-02 | 2014-11-19 | 三菱瓦斯化学株式会社 | 酸素吸収剤の製造方法 |
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US3235513A (en) * | 1961-02-07 | 1966-02-15 | Varta Ag | Process for activating raney alloys and solution useful for such process |
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