CN100503004C - Process for refining nitrogen trifluoride gas using alkali earth metal exchanged and impregnated zeolite - Google Patents
Process for refining nitrogen trifluoride gas using alkali earth metal exchanged and impregnated zeolite Download PDFInfo
- Publication number
- CN100503004C CN100503004C CNB2005800300503A CN200580030050A CN100503004C CN 100503004 C CN100503004 C CN 100503004C CN B2005800300503 A CNB2005800300503 A CN B2005800300503A CN 200580030050 A CN200580030050 A CN 200580030050A CN 100503004 C CN100503004 C CN 100503004C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- earth metal
- alkaline
- exchange
- nitrogen trifluoride
- 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.)
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 142
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000010457 zeolite Substances 0.000 title claims abstract description 142
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000007789 gas Substances 0.000 title claims abstract description 41
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000007670 refining Methods 0.000 title claims description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 35
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003463 adsorbent Substances 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 44
- 238000007598 dipping method Methods 0.000 claims description 35
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 31
- 239000011261 inert gas Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 238000003795 desorption Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 14
- 239000002243 precursor Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006424 Flood reaction Methods 0.000 description 3
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 3
- 229910052790 beryllium Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052754 neon Inorganic materials 0.000 description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229960005069 calcium Drugs 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229960003390 magnesium sulfate Drugs 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- WMFHUUKYIUOHRA-UHFFFAOYSA-N (3-phenoxyphenyl)methanamine;hydrochloride Chemical compound Cl.NCC1=CC=CC(OC=2C=CC=CC=2)=C1 WMFHUUKYIUOHRA-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- LMLSTUCUPVCKEU-UHFFFAOYSA-N O.O.O.O.O.O.[Ca] Chemical compound O.O.O.O.O.O.[Ca] LMLSTUCUPVCKEU-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- SMDYOPXOCHURNS-UHFFFAOYSA-N barium;dihydrate Chemical compound O.O.[Ba] SMDYOPXOCHURNS-UHFFFAOYSA-N 0.000 description 1
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 1
- DIMYTQPLZWDZFE-UHFFFAOYSA-L beryllium sulfate tetrahydrate Chemical compound [Be+2].O.O.O.O.[O-]S([O-])(=O)=O DIMYTQPLZWDZFE-UHFFFAOYSA-L 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- QHFQAJHNDKBRBO-UHFFFAOYSA-L calcium chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ca+2] QHFQAJHNDKBRBO-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- CRZXNIPRLGELRX-UHFFFAOYSA-L calcium sulfate hexahydrate Chemical compound O.O.O.O.O.O.S(=O)(=O)([O-])[O-].[Ca+2] CRZXNIPRLGELRX-UHFFFAOYSA-L 0.000 description 1
- JJIQGEZLLWXYKV-UHFFFAOYSA-N calcium;dinitrate;hydrate Chemical compound O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JJIQGEZLLWXYKV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QXQBHOPAZLTPEL-UHFFFAOYSA-K dimagnesium;carbonate;hydroxide;pentahydrate Chemical compound O.O.O.O.O.[OH-].[Mg+2].[Mg+2].[O-]C([O-])=O QXQBHOPAZLTPEL-UHFFFAOYSA-K 0.000 description 1
- DUQAODNTUBJRGF-ONEGZZNKSA-N dinitrogen difluoride Chemical compound F\N=N\F DUQAODNTUBJRGF-ONEGZZNKSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000574 gas--solid chromatography Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 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
- 229940076230 magnesium sulfate monohydrate Drugs 0.000 description 1
- FBDWCTWJJMORIU-UHFFFAOYSA-N magnesium;hexahydrate Chemical compound O.O.O.O.O.O.[Mg] FBDWCTWJJMORIU-UHFFFAOYSA-N 0.000 description 1
- LFCFXZHKDRJMNS-UHFFFAOYSA-L magnesium;sulfate;hydrate Chemical compound O.[Mg+2].[O-]S([O-])(=O)=O LFCFXZHKDRJMNS-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- ULVJUOMUAAYMKJ-UHFFFAOYSA-L strontium;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Sr+2] ULVJUOMUAAYMKJ-UHFFFAOYSA-L 0.000 description 1
- DDGDWXGKPCHUCI-UHFFFAOYSA-N strontium;hydrate Chemical compound O.[Sr] DDGDWXGKPCHUCI-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0423—Beds in columns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
-
- 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
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
Abstract
Disclosed herein are a process for the refinement of nitrogen trifluoride gas and an adsorbent therefor. A nitrogen trifluoride (NF3) gas including carbon tetrafluoride (CF4) as an impurity is permeated into a bed of zeolite 3 A, 4A or 5 A which undergoes ion exchange and impregnation with alkali earth metal and is thermally treated at 150 to 600 DEG C for 0.5 to 100 hours so as to be able to selectively adsorb nitrogen trifluoride onto the bed, followed by the desorption of the nitrogen trifluoride therefrom.
Description
Technical field
The present invention relates generally to Nitrogen trifluoride (NF
3) gas refining, and relate more specifically to by removing carbon tetrafluoride (CF
4) method of refining nitrogen trifluoride gas.
Background technology
In semi-conductor industry, Nitrogen trifluoride has purposes variously, comprises the fluorine source as plasma etching, the cleaning agent of CVD reactor, and semi-conductive dry ecthing agent.In addition, Nitrogen trifluoride can be used to rocket fuel.Along with the development of semi-conductor industry, gas of nitrogen trifluoride has very big demand.Make demand become geometric progression ground to increase to the growing demand of not having any environmental pollution gas to gas of nitrogen trifluoride.Certainly, gas of nitrogen trifluoride requires to have high purity in these purposes.
Nitrogen trifluoride can be used prepared in various methods, comprises directly fluoridizing of ammonia, makes the reaction of ammonia and fluorine with plasma, and with ammonium fluoride or hydrogen fluoride as raw material electrolysis NH
4The molten-salt electrolysis of xHF (x:1.8～2.1).
In most cases when these methods of use, impurity is as nitrous oxide (N
2O), carbon dioxide (CO
2), carbon tetrafluoride (CF
4), dinitrogen difluoride (N
2F
2), or the like, produce in a large number simultaneously, therefore to obtain to be suitable for the high purity N F of semi-conductor industry
3Gas must carry out purifying.
Especially, use usual way, as distillation, body absorption or the like is from NF
3The middle removal as producing NF
3Impurity and the CF that produces
4Be difficult, since their boiling point, molecular weight, and heat of adsorption is all close.In addition, carbon tetrafluoride even the existence of trace is arranged, because form the solid residue of carbon for example or carborundum, also can give rise to trouble when conductor etching.
U.S. Pat .5,069,887 (obligee Takashi et al) have disclosed a kind of method of removing the carbon tetrafluoride refining nitrogen trifluoride gas with synthetic zeolite.In the method, zeolite 5A, the crystallization water that it comprises 1 to 10% weight is used as adsorbent, and the carbon tetrafluoride content that the Nitrogen trifluoride of generation has is 10ppm or littler, has satisfied the requirement of electronics industry.Yet, the shortcoming of this method be the water content of synthetic zeolite must be adjusted in the preset range and the adsorption temp scope very narrow.
Use the visible U.S. Pat .5 of another kind of process for purification of synthetic zeolite, 069,690, (obligee Philip et al.), this Patent publish the dynamics gas-solid chromatography.In the method, the zeolite with certain porosity of hydrothermal treatment consists is used as adsorbent, and discontinuous admixture of gas pulse absorbs attached dose of bed by this porous, and a kind of gas of this adsorbent dynamics ground absorption is easier than other gas of absorption, causes NF
3The selection of gas separates.Yet the hydrothermal pretreatment of control zeolite pores rate is difficult to carry out.In addition, the term of validity of zeolite, promptly the period of saturation is too short, this zeolite method can not be used for business-like large batch of Nitrogen trifluoride and purify.
Summary of the invention
Technical problem
Undertaken by the present inventor, cause of the present invention, to NF
3Deeply and carefully and comprehensively studying of method for refining obtains finding, that is, when exchange of process alkaline-earth metal ions and dipping, zeolite 3A, 4A or 5A, as molecular sieve, can be effectively from NF
3And CF
4Optionally adsorb NF in the mixture
3
Technical scheme
The present invention relates to use through alkaline-earth metal ions exchange and the refining NF of impregnated zeolite 3A
3The method of gas, and zeolite 3A, 4A or the 5A that wherein adopt through alkaline-earth metal ions exchange and dipping.
Commercially available zeolite 3A, 4A and 5A, itself can not be used for purifying NF
3, because they can not distinguish NF in absorption
3And CF
4Zeolite 3A and 4A have less aperture, so that can not adsorb NF fully
3And CF
4, and the aperture of zeolite 5A is even as big as adsorbing NF simultaneously
3And CF
4Therefore, only at NF
3The selection absorption aperture that requires adsorbent to have compare CF
4Molecular dimension little, but than NF
3Molecular dimension big.
The aperture of change zeolite can be used with the ion-exchange or the dipping of metal cation and be realized.Feature of the present invention is that 4A or 5A are to change the aperture of zeolite with ion-exchange of appropriate bases earth metal and dipping zeolite 3A.That is, zeolite 3A, the aperture of 4A or 5A is adjusted to predetermined size by the ion-exchange with alkaline-earth metal, then by further accurately controlling with metal impregnation.
Usually, be used for ion-exchange of the present invention and be widely used in metal ingredient is loaded into such as silica, silica-alumina is on the carrier of zeolite or the like.Especially, zeolite is useful for the adaptability of cation exchange for loading metal ion.The cation of zeolite can exchange according to the kind of ion and concentration and other cations of solution.Except being used for the separating metal ion, the cation exchange capacity (CEC) of zeolite is a kind of method for the acidity and the introducing metal ion of control zeolite.Typically, zeolite A type is synthetic as cation with sodium ion.Have the effective aperture that has about 0.4nm (4A type) as the zeolite A type of cationic sodium ion.When potassium ion becomes 0.3nm (3A type) and becomes 0.5nm (5A type) during as cation when calcium ion in the effective aperture during as cation.On zeolite, cation can exchange according to concentration and other type of cationic kind and solution.When loading by ion-exchange, active material can be evenly distributed on the carrier very much.
Dipping is by contacting with carrier with the solution that comprises active component, and active material is loaded into a kind of method on the carrier.According to contact technique, absorption is arranged, spraying, evaporation drying and incipient wetness method.In absorption method, carrier is dipped in the solution that comprises active component, so that active component is attracted on the carrier surface.The evaporation drying method is usually evaporated so that the mode that active component is fixed on the carrier is finished by carrier is immersed in the solution that comprises active component and with solution.Must be careful when adopting this method, because the big pickup of active component may block the minute aperture of carrier.As for spray-on process, be a kind of of evaporation drying method, comprise that the solution that will comprise active component is ejected on the carrier that shakes or stir in evaporimeter.By spray-on process, active component is impregnated on the carrier surface more, rather than enters in the micropore of carrier.According to incipient wetness method, in the solvent that has with the micropore equal volume of carrier, there is the solution of active component to be adsorbed on the carrier, then remove solvent through super-dry.
According to the present invention, provide a kind of by optionally removing CF
4The method of refining nitrogen trifluoride, wherein the mixture of carbon tetrafluoride and Nitrogen trifluoride is introduced in the pillar of having filled zeolite, zeolite wherein is through alkaline-earth metal ions exchange and flooded, so Nitrogen trifluoride optionally is adsorbed onto on the zeolite and from the zeolite desorption, and carbon tetrafluoride passes through pillar.
Favourable effect
According to method of the present invention, by removing CF
4, can produce highly purified Nitrogen trifluoride effectively.
Preferred forms
Below, will provide detailed description of the present invention.
Being used for zeolite of the present invention is zeolite 3A, 4A or 5A.For the aperture that makes them is fit to optionally only filter NF
3, zeolite carries out ion-exchange with alkaline-earth metal, floods with alkaline-earth metal then.Here, the alkaline-earth metal of ion-exchange and dipping can be identical or different, and is preferably identical.
The alkaline-earth metal that is fit to zeolite ion-exchange and dipping is beryllium (Be), magnesium (Mg), calcium (Ca), one or more in strontium (Sr) or the barium (Ba).According to the present invention, be used for ion-exchange, in the necessary water soluble of the precursor of alkaline-earth metal, preferably this precursor is the nitrate (NO of alkaline-earth metal
3), carbonate (CO
3), chloride (Cl), hydroxide (OH) and sulfate (SO
4) or their hydrate.
The example of the beryllium precursor that is fit to comprises beryllium nitrate hydrate (Be (NO
3)
2XH
2O), beryllium chloride (BeCl
2), beryllium sulfate tetrahydrate (BeSO
44H
2O), or the like, preferential selective chlorination beryllium (BeCl
2).
The example of the magnesium precursor that is fit to comprises magnesium nitrate hexahydrate (Mg (NO
3)
26H
2O), magnesium carbonate magnesium hydroxide pentahydrate (MgCO
3Mg (OH)
25H
2O), magnesium chloride (MgCl
2), magnesium chloride hexahydrate (MgCl
26H
2O), magnesium hydroxide (Mg (OH)
2), magnesium sulfate (MgSO
4), magnesium sulfate monohydrate (MgSO
4H
2O), magnesium sulfate 7 hydrate (MgSO
47H
2O), or the like, preferential selective chlorination magnesium hexahydrate (MgCl
26H
2O).
The calcium precursor that is fit to can be exemplified as calcium nitrate hydrate (Ca (NO
3)
2XH
2O), calcium carbonate (CaCO
3), calcium chloride (CaCl
2), calcium chloride dihydrate (CaCl
22H
2O), calcium chloride hexahydrate (CaCl
26H
2O), calcium chloride hydrate (CaCl
2XH
2O), calcium hydroxide (Ca (OH)
2), calcium sulfate (CaSO
4), and calcium sulfate hexahydrate (CaSO
46H
2O), preferential selective chlorination calcium hexahydrate (CaCl
26H
2O).
The strontium precursor that is fit to can be exemplified as strontium nitrate (Sr (NO
3)
2), strontium carbonate (SrCO
3), strontium chloride (SrCl
2), strontium chloride hydrate (SrCl
2XH
2O), strontium hydroxide (Sr (OH)
2), strontium hydroxide eight hydrates (Sr (OH)
28H
2And strontium sulfate (SrSO O),
4), preferential selective chlorination strontium hydrate (SrCl
2XH
2O).
The barium precursor that is fit to comprises barium nitrate (Ba (NO
3)
2), brium carbonate (BaCO
3), barium chloride (BaCl
2), barium chloride dihydrate (BaCl
22H
2O), barium hydroxide (Ba (OH)
2), barium hydroxide monohydrate (Ba (OH)
2H
2O), barium hydroxide eight hydrates (Ba (OH)
28H
2O), barium sulfate (BaSO
4), or the like, preferential selective chlorination barium dihydrate (BaCl
22H
2O).
Be used for ion-exchange and dipping prepare zeolite, the aqueous solution contains the precursor of metal that remains ion-exchange, and wherein concentration of metal is 0.01 to 3M, and preferably concentration is 0.5 to 1.5M.For example, when the concentration of aqueous solution that comprises the metal of wanting ion-exchange is lower than 0.01M, can not realize ion-exchange fully.On the other hand, when concentration of aqueous solution surpassed 3M, the ion-exchange capacity of zeolite did not further increase along with the increase of solution concentration.
In the aqueous solution, zeolite and metal preferably carried out ion-exchange 0.5 to 24 hour at 50 to 80 ℃ at 35 to 100 ℃, and preferred 2 to 12 hours, stir simultaneously with 5 to 100rpm rotating speed, preferred rotating speed 10 arrives 50rpm.After ion-exchange, zeolite comprises the amount of alkaline-earth metal preferably based on 20 to 95% of the whole weight metals of zeolite.
Except exchanging with alkaline-earth metal ions, zeolite also floods with alkaline-earth metal.For this reason, the aqueous solution that comprises the alkaline-earth metal that is used to flood of required amount with above-mentioned precursor preparation.Then, will immerse in the above-mentioned aqueous solution through the zeolite of alkaline-earth metal ions exchange and keep at room temperature, then, in evaporimeter, with this Zeolite dehydration 0.5 to 24 hour, preferred 2 to 10 hours.This dipping can be regulated the micropore diameter of zeolite 3A to the size that requires.The amount of alkaline-earth metal dipping is preferably based on 0.1 to 5% magnitude of zeolite gross weight.
It is spherical being used for zeolite of the present invention, particle size range from 4 to 100 orders, preferably from 8 to 40 orders.After exchanging with alkaline-earth metal ions, the zeolite with this particle diameter to be heat-treated, treatment temperature is 150-600 ℃, preferred 200-500 ℃, the processing time is 0.5-100 hour, preferred 2-50 hour, more preferably 4-20 hour.
Make zeolite can be used as adsorbent in this temperature range heat treatment, its adsorption capacity that has is enough to realize purpose of the present invention.For example,, heat treatment carries out if being lower than under 150 ℃ in temperature, zeolite, even the processed long period, the adsorption capacity after operation reduces sharp, therefore has very little Nitrogen trifluoride adsorbance.It is believed that this is that the moisture in the zeolite has occupied the position that major part can be adsorbed the Nitrogen trifluoride molecule, makes the NF of per unit volume zeolite owing to be lower than 150 ℃ of processing down in temperature
3The adsorption capacity variation.Therefore, in order to make zeolite dehydration fully, the temperature that heat treatment is carried out preferably is higher than 150 ℃.
On the other hand, heat treatment temperature is higher than the breaking of micropore of 600 ℃ of aggravation changes of zeolite crystal structures or zeolite, reduces the adsorption capacity of zeolite widely.The result makes zeolite the problem that can not adsorb Nitrogen trifluoride occur, or it is saturated to reach absorption after gas permeation in the short time.
The heat treatment of zeolite is preferably carried out in the presence of not dampish substantially slumpability gas, as nitrogen, and helium, neon, argon, xenon, or the like.Equally, heat treatment can be carried out under suction inert gas minimizing pressure.
At length, a kind of heat treatment method is to place zeolite granular and the heating that skim has the requirement Size Distribution in the drier bottom, makes inert gas flow through the thin layer of zeolite particles simultaneously.Yet the absorption of heat treatment and gas of nitrogen trifluoride and purifying should carry out in same container.Promptly, most preferred method is, have after zeolite granular bed that appropriate size distributes forms in a container or pillar, flowing through inert gas heat-treats, zeolite cools off not taking out under container or the pillar then, and will comprise that the admixture of gas of Nitrogen trifluoride introduces the zeolite granular bed.Container or pillar can be made of common material, as stainless steel, and copper, nickel, iron, or the like.
As mentioned above, after finishing heat treatment, zeolite is cooled off naturally or force cool to room temperature (25 ℃) or low temperature more.During cooling, must avoid moisture to enter zeolite granular.
According to the present invention, use the preliminary treatment synthetic zeolite to carry out Nitrogen trifluoride and make with extra care by following four steps.
At first, Nitrogen trifluoride and carbon tetrafluoride mist are introduced in the pillar, have wherein filled hot pretreated and through alkaline-earth metal ions exchange and impregnated zeolite 3A, 4A or 5A make NF
3Be adsorbed onto on the zeolite molecular sieve.
When the admixture of gas that comprises Nitrogen trifluoride saw through, the temperature range of pillar should be at-100 to 50 ℃, preferred-50 to 30 ℃.More preferably gas permeation temperature is lower, still, because practical operation can not be lower than-129 ℃, NF
3Boiling point, make with extra care under-100 ℃ or higher temperature and carry out.Be higher than 50 ℃, then require unnecessary thermal source.
For the mist that comprises Nitrogen trifluoride is passed through, inert gas can be used as carrier.Any gas, only otherwise and NF
3Or the zeolite reaction, all can use.The example of the inert gas that can together use with the target mist comprises nitrogen, helium, neon, argon, and xenon.Inert gas preferably use amount is based on NF
3, CF
4With 20 to 80vol% of the inert gas cumulative volume of introducing.
As for the zeolite bed, preferred diameter is 1 to 50cm and highly is 5 to 200cm.When admixture of gas passed through the zeolite bed, admixture of gas preferred flow speed was 1 to 25g/cm
2Hr, pressure are 1 to 10kg/cm
2According to the present invention, the NF that obtains through this process for purification
3The CF that gas has
4Content is 0 to 30ppm.
Secondly, use the NF of blowing method to optionally adsorbing
3Collect.Zeolite purges with inert gas.For this reason, inert gas is with 1 to 100g/cm
2The mass velocity of hr is preferably with 30 to 60g/cm
2The mass velocity of hr is by the zeolite bed.Any gas, only otherwise and NF
3React with zeolite, all can be used for NF
3Collection, example has nitrogen, helium, neon, argon, and xenon.Mass velocity is defined as linear velocity and multiply by fluid density (linear velocity X fluid density).Passage with constant cross-section area is favourable, especially when handling gas, because, both having made that linear velocity changes with heating/cooling in purge, the mass velocity maintenance is constant.
In purge, zeolite preferably remains under-30 to 50 ℃ of temperature, is preferably 20 to 30 ℃.If temperature is too low, will the time of costing a lot of money finish purge.On the other hand, too high-temperature can make the impurity desorption during purging that is chemically bound on the adsorbent, and therefore makes the NF that obtains
3The purity of gas reduces.
The 3rd, make adsorbent reactivation by temperature increase and desorption process, therebetween, the impurity that is present in the adsorbent is removed fully in a small amount.If absorption-purge is repeated, and do not have temperature increase and desorption, adsorbent further reduces in each adsorption capacity of taking turns absorption.Therefore, temperature increase and desorption process are necessary.
Temperature increase uses moving air or inert gas to carry out, and promoting speed is 0.1 to 20 ℃/min, and preferably speed is 1 to 5 ℃/min, can rise to 500 ℃, preferably to 200 ℃.
At last, after collection process, if the NF that obtains
3The content of gas through measuring its impurity is higher than predetermined standard, then repeats for first to the 3rd step.
Invention embodiment
Can obtain better understanding to the present invention by following examples.These embodiment are for the present invention is described, rather than as restriction of the present invention.
Preparation embodiment 1
Zeolite 3A (commodity of Aldrich. company, particle diameter 8-12 order, spherical) is slowly added in the distilled water solution of 1M alkaline earth metal precursor and mix.Under slowly stirring, this suspension is 80 ℃ of reactions 6 hours, then by filtered and recycled zeolite 3A.After this, zeolite 3A in baking oven in 130 ℃ dry 6 hours down, 500 ℃ of bakings 12 hours down, obtained the metal of its 50% (weight) and the zeolite 3A that alkaline-earth metal has carried out ion-exchange then.The zeolite of this alkaline-earth metal ions exchange is slowly added in the aqueous solution of same alkaline earth metal precursor, it was at room temperature kept 4 hours.The content of control alkaline earth metal precursor in the aqueous solution, the amount that makes alkaline-earth metal be impregnated in the zeolite is based on 1% of zeolite gross weight.Fall after the remaining solvent by heating evaporation, the zeolite that obtains 130 ℃ dry 6 hours down, then 500 ℃ of bakings 12 hours down.This zeolite 3A through alkaline-earth metal ions exchange and dipping is carried out metal content analysis.The result provides in table 1, and is as follows.
Preparation embodiment 2
Carry out same program among the preparation embodiment 1, the different zeolite 4A that are to use replace 3A.This zeolite 4A through alkaline-earth metal ions exchange and dipping is carried out the analysis of tenor.The result provides in table 2, and is as follows.
Preparation embodiment 3
Zeolite 4A through alkaline-earth metal ions exchange 50% (weight) in preparation embodiment 2 floods with identical alkaline-earth metal.At this, prepare alkaline earth metal precursor solution like this, make that the amount of alkaline-earth metal dipping is based on 0.1,0.5 and 1.5% of zeolite gross weight.By with the dipping of solution, obtain zeolite 4A through alkaline-earth metal ions exchange and dipping.The result provides in table 2, and is as follows.
Preparation embodiment 4
Through the zeolite 4A of alkaline-earth metal ions exchange 80% (weight), with similar method among the preparation embodiment 1, flood with identical alkaline-earth metal, be respectively 0.1,0.5,1 and 1.5% (weight), the result provides in table 3, and is as follows.
Preparation embodiment 5
Carry out same program among the preparation embodiment 1, different is to replace 3A with zeolite 5A, produces the zeolite 5A through alkaline-earth metal ions exchange and dipping thus.The result provides in table 4, and is as follows.
Preparation embodiment 6
With same zeolite 5A among the preparation embodiment 5, itself and alkaline-earth metal ions exchange 50% (weight), flood with identical alkaline-earth metal.At this, prepare alkaline earth metal precursor solution like this, make that the amount of alkaline-earth metal dipping is based on 0.1,0.5 and 1.5% of zeolite gross weight.By with solution impregnation, obtain zeolite 5A through alkaline-earth metal ions exchange and dipping.The result provides in table 4, and is as follows.
Preparation embodiment 7
Through the zeolite 5A of alkaline-earth metal ions exchange 80% (weight), with similar method among the preparation embodiment 1, flood with same alkaline-earth metal, pickup is respectively 0.1,0.5,1 and 1.5% (weight).The characteristic through the zeolite 5A of alkaline-earth metal ions exchange and dipping that obtains thus provides in table 5, and is as follows.
Example I
In preparation embodiment 1 through the zeolite 3A of alkaline-earth metal ions exchange and dipping, in the stainless steel pillar of internal diameter 10mm, be filled into the height of 400mm after, 300 ℃ of following heat treatment is 6 hours in inert gas.Then, the zeolite granular bed is cooled to-20 ℃, and makes inert gas, NF
3And CF
4Admixture of gas (inert gas 50vol%, NF
349.75vol% and CF
40.25vol%) with 22.5 (g/cm
2Hr) weight flow rate is by the zeolite bed, up to NF
3By absorption (about 3 hours) fully.Afterwards, the zeolite bed is cooled to 30 ℃ with the speed of 5 ℃/min, with inert gas it is purged, so that only collect NF
3, carry out quantitative analysis with gas-chromatography then.Refining NF
3The scale of gas is shown cc per g (cubic centimetre/every gram is sorbent used).According to the kind of used zeolite 3A, the result provides in table 1, and is as follows.
Comparative example I
For relatively, use common zeolite 3A (Aldrich. company produces, and particle diameter 8-12 order is spherical) to carry out program same in the example I, this zeolite 3A does not both carry out ion-exchange with alkaline-earth metal and does not also flood with it.The result provides in table 1, and is as follows.
Table 1
According to the kind of the alkaline-earth metal of ion-exchange and dipping (exchange to the alkaline-earth metal of zeolite 3A: 50wt%), the adsorption capacity of zeolite 3A.
Example II
Carry out same program in the example I, different is to use the zeolite 4A that exchanges and flood through alkaline-earth metal ions among the preparation embodiment 2 and 3.The result provides in table 2, and is as follows.
Comparative example II
Use common zeolite 4A (Aldrich. company produces, and particle diameter 8-12 order is spherical), this zeolite 4A both also flooded without it without the alkaline-earth metal ions exchange, repeated same program in the example I.The result provides in table 2, and is as follows.
Table 2
(ion-exchange is to the alkaline-earth metal of zeolite 4A: 50wt%) (I), the adsorption capacity of zeolite 4A according to the kind of the alkaline-earth metal of ion-exchange and dipping and concentration.
EXAMPLE III
Carry out program same in the example I, different is to use the zeolite 4A through alkaline-earth metal ions exchange and dipping among the preparation embodiment 4.The result provides in table 3, and is as follows.
Table 3
According to the kind of the alkaline-earth metal of ion-exchange and dipping and the concentration (alkaline-earth metal of ion-exchange to the zeolite 4A: 80wt%) (II), the adsorption capacity of zeolite 4A.
EXAMPLE IV
Carry out program same in the example I, difference is to use the zeolite 5A through alkaline-earth metal ions exchange and dipping among the preparation embodiment 5 and 6.The result provides in table 4, and is as follows.
Comparative Example III
Use common zeolite 5A (Aldrich company produces, and particle diameter 8-12 order is spherical), this zeolite both also flooded without it without the alkaline-earth metal ions exchange, repeated program same in the example I.The result provides in table 4, and is as follows.
Discovery had both been adsorbed CF without the zeolite 5A of alkaline-earth metal ions exchange and dipping
4Also adsorb NF
3, therefore do not have ability to separate NF
3
Table 4
According to the kind of the alkaline-earth metal of ion-exchange and dipping and the concentration (alkaline-earth metal of ion-exchange to the zeolite 5A: 50wt%) (I), the adsorption capacity of zeolite 5A.
EXAMPLE V
Carry out program same in the example I, different is to use the zeolite 5A through alkaline-earth metal ions exchange and dipping among the preparation embodiment 7.The result provides in table 5, and is as follows.
Table 5
According to the kind of the alkaline-earth metal of ion-exchange and dipping and the concentration (alkaline-earth metal of ion-exchange to the zeolite 5A: 80wt%) (II), the adsorption capacity of zeolite 5A.
Example VI
In order to produce the NF of ultra-high purity
3, make the CF that comprises that obtains in the example II
4NF
3Gas passes through the bed through the zeolite 4A of alkaline-earth metal ions exchange and dipping once more.That is, make through what the example II primary purification produced and contain 226ppm CF
4NF
3Gas is by liquid nitrogen storage tank, comprises trace CF with what collect scheduled volume
4The NF of inert free gas
3Gas.Be in the stainless steel pillar of 10mm at internal diameter in addition, the zeolite 4A that will prepare in preparation embodiment 2 is filled into the height of 400mm and makes it be cooled to-20 ℃.Make and comprise 226ppm CF
4NF
3The mixture of gas in the equal-volume inert gas is by the bed of zeolite 4A, and its weight flow rate is 22.5 (g/cm2hr), and the time (about 3 hours) is enough to make NF
3And CF
4All be adsorbed onto on the bed.Afterwards, the bed of adsorbent is heated to 400 ℃ with the heating rate of 1 ℃/min, to NF from the bed desorption
3Carry out quantitative analysis.Gas-chromatography shows, based on the content before the primary purification, CF
4Clearance up to 99.3%.The result provides in table 6, and is as follows.
Table 6
Result after the two-wheeled absorption (zeolite 4A, 50wt% ion-exchange, 1wt% dipping)
Claims (10)
1, a kind of method of refining nitrogen trifluoride gas comprises:
The admixture of gas of Nitrogen trifluoride and carbon tetrafluoride is introduced zeolite 3A, and the bed of 4A or 5A optionally makes Nitrogen trifluoride be adsorbed onto on the bed, and carbon tetrafluoride is by bed, this zeolite 3A, and 4A or 5A are through the alkaline-earth metal ions exchange and flooded; And
Reclaim Nitrogen trifluoride from bed,
Wherein, use described metal concentration to prepare ion-exchange and dipping zeolite as the aqueous solution of 0.01-3M; The described amount that comprises the alkaline-earth metal of ion-exchange through ion-exchange and impregnated zeolite is the 20-95 weight % of metal gross weight in based on zeolite, and to comprise the amount of flood alkaline-earth metal be 0.1-5 weight % based on the zeolite gross weight; And zeolite is shaped as sphere.
2, according to the defined method of claim 1, wherein alkaline-earth metal is a magnesium.
3, according to the defined method of claim 1, wherein alkaline-earth metal is a calcium.
4, according to the defined method of claim 1, wherein alkaline-earth metal is a strontium.
5, according to the defined method of claim 1, wherein alkaline-earth metal is a barium.
6, according to the defined method of claim 1, wherein NF
3And CF
4Mist under-100 to 50 ℃ of temperature, be introduced into bed.
7, according to the defined method of claim 1, wherein NF
3And CF
4Mist be introduced into bed with inert gas, the amount of this inert gas is based on NF
3, CF
420-80 volume % with the cumulative volume of the inert gas of introducing.
8, according to the defined method of claim 7, wherein inert gas is selected from by argon, the group that helium and nitrogen are formed.
9,, wherein adsorb Nitrogen trifluoride to through alkaline-earth metal ions exchange and impregnated zeolite 3A, the introducing step on 4A or the 5A and sequentially repeated twice or repeatedly from the step of zeolite recovery Nitrogen trifluoride according to the defined method of claim 1.
10, a kind of Nitrogen trifluoride adsorbent, it optionally adsorbs Nitrogen trifluoride from the admixture of gas of carbon tetrafluoride and Nitrogen trifluoride, and comprises the zeolite 3A through alkaline-earth metal ions exchange and dipping, 4A or 5A,
Wherein, use described metal concentration to prepare ion-exchange and dipping zeolite as the aqueous solution of 0.01-3M; The described amount that comprises the alkaline-earth metal of ion-exchange through ion-exchange and impregnated zeolite is the 20-95 weight % of metal gross weight in based on zeolite, and to comprise the amount of flood alkaline-earth metal be 0.1-5 weight % based on the zeolite gross weight; And zeolite is shaped as sphere.
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|---|---|---|---|---|
| US9302214B2 (en) * | 2014-08-22 | 2016-04-05 | Air Products And Chemicals, Inc. | Purification of nitrogen trifluoride by pressure swing absorption |
| CN106276828B (en) * | 2016-07-19 | 2018-07-31 | 浙江博瑞电子科技有限公司 | A method of absorption trifluoride by purifying nitrogen |
| CN110639470B (en) * | 2019-08-20 | 2022-08-05 | 中船(邯郸)派瑞特种气体股份有限公司 | Adsorbent for removing difluorodinitrogen and tetrafluorodinitrogen in nitrogen trifluoride |
| CN110639233B (en) * | 2019-08-20 | 2021-12-07 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for removing difluorodinitrogen and tetrafluorodinitrogen in nitrogen trifluoride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5069887A (en) * | 1990-01-10 | 1991-12-03 | Central Glass Company, Limited | Method of refining nitrogen trifluoride gas |
| US5976222A (en) * | 1998-03-23 | 1999-11-02 | Air Products And Chemicals, Inc. | Recovery of perfluorinated compounds from the exhaust of semiconductor fabs using membrane and adsorption in series |
| US6187077B1 (en) * | 1998-04-17 | 2001-02-13 | American Air Liquide Inc. | Separation of CF4 and C2F6 from a perfluorocompound mixture |
| US20030221556A1 (en) * | 2002-02-26 | 2003-12-04 | Igumnov Sergei Mikhailovich | Method of purifying gaseous nitrogen trifluoride |
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2004
- 2004-07-08 KR KR1020040053044A patent/KR100577952B1/en active IP Right Grant
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2005
- 2005-07-07 CN CNB2005800300503A patent/CN100503004C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5069887A (en) * | 1990-01-10 | 1991-12-03 | Central Glass Company, Limited | Method of refining nitrogen trifluoride gas |
| US5976222A (en) * | 1998-03-23 | 1999-11-02 | Air Products And Chemicals, Inc. | Recovery of perfluorinated compounds from the exhaust of semiconductor fabs using membrane and adsorption in series |
| US6187077B1 (en) * | 1998-04-17 | 2001-02-13 | American Air Liquide Inc. | Separation of CF4 and C2F6 from a perfluorocompound mixture |
| US20030221556A1 (en) * | 2002-02-26 | 2003-12-04 | Igumnov Sergei Mikhailovich | Method of purifying gaseous nitrogen trifluoride |
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| Publication number | Publication date |
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| KR100577952B1 (en) | 2006-05-10 |
| KR20060004067A (en) | 2006-01-12 |
| CN101014399A (en) | 2007-08-08 |
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