KR100968102B1 - Low uranium (U) content hydrotalcite compounds and methods for their preparation - Google Patents
Low uranium (U) content hydrotalcite compounds and methods for their preparation Download PDFInfo
- Publication number
- KR100968102B1 KR100968102B1 KR1019990040714A KR19990040714A KR100968102B1 KR 100968102 B1 KR100968102 B1 KR 100968102B1 KR 1019990040714 A KR1019990040714 A KR 1019990040714A KR 19990040714 A KR19990040714 A KR 19990040714A KR 100968102 B1 KR100968102 B1 KR 100968102B1
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- water
- hydrotalcite
- hours
- product
- 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.)
- Expired - Fee Related
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- 229910052770 Uranium Inorganic materials 0.000 title claims abstract description 49
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title description 2
- -1 hydrotalcite compound Chemical class 0.000 claims abstract description 62
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 52
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 8
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 8
- 239000000057 synthetic resin Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 57
- 239000000725 suspension Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000011777 magnesium Substances 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000000975 co-precipitation Methods 0.000 claims description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 18
- 239000001099 ammonium carbonate Substances 0.000 claims description 18
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000011282 treatment Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- 150000003752 zinc compounds Chemical class 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 239000012756 surface treatment agent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 2
- 239000011163 secondary particle Substances 0.000 abstract description 20
- 239000003822 epoxy resin Substances 0.000 abstract description 11
- 229920000647 polyepoxide Polymers 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 6
- 239000000565 sealant Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 21
- 238000005259 measurement Methods 0.000 description 15
- 238000000634 powder X-ray diffraction Methods 0.000 description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 description 12
- 235000017550 sodium carbonate Nutrition 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 5
- 229910052776 Thorium Inorganic materials 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000012857 radioactive material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- KPUBIZJWWGSWGQ-UHFFFAOYSA-N azane;carbonic acid Chemical compound N.N.N.OC(O)=O.OC(O)=O KPUBIZJWWGSWGQ-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IFHHXXQUVQTCGV-UHFFFAOYSA-M dimagnesium acetate nitrate Chemical compound C(C)(=O)[O-].[Mg+2].[N+](=O)([O-])[O-].[Mg+2] IFHHXXQUVQTCGV-UHFFFAOYSA-M 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- MASNVFNHVJIXLL-UHFFFAOYSA-N ethenyl(ethoxy)silicon Chemical compound CCO[Si]C=C MASNVFNHVJIXLL-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
특히, 트랜지스터, IC, LSI 등과 같은 반도체 디바이스용 밀봉제로 사용되는 에폭시 수지와 같은 합성 수지에의 첨가제로 유용한 히드로탈사이트 화합물로서, 이 화합물은 하기 화학식 1 로 표시되는 조성을 갖는 것과,In particular, a hydrotalcite compound useful as an additive to a synthetic resin such as an epoxy resin used as a sealant for semiconductor devices such as transistors, ICs, LSIs, etc., the compound having a composition represented by
[식 중, M2+는 Mg2+ 및 Zn2+ 중 하나 이상이고,[ Wherein M 2+ is at least one of Mg 2+ and Zn 2+ ,
x 는 0.2 ≤x ≤0.5 범위 내의 양수이며,x is a positive number in the range 0.2 ≤ x ≤ 0.5,
A2-는 CO3 2- 및 SO4 2- 중 하나 이상이고,A 2- is at least one of CO 3 2- and SO 4 2- ,
m 은 0 - 2 범위 내의 수이다]m is a number in the range 0-2]
10 ppb 이하의 우라늄(U) 함량, 약 3 ㎛ 이하의 평균 이차 입자 크기 및 30 m2/g 이하의 BET 비표면적을 갖는 것을 특징으로 한다.It has a uranium (U) content of 10 ppb or less, an average secondary particle size of about 3 μm or less and a BET specific surface area of 30 m 2 / g or less.
Description
본 발명은 낮은 우라늄(U) 함량의 히드로탈사이트 화합물 및 그것의 제조 방법에 관한 것이다. 더욱 특별하게는, 본 발명은, 소프트 오류에 대한 디바이스의 신뢰도의 악화 없이, 큰 용량, 높은 집적화의 메모리 반도체 디바이스를 밀봉하는데 사용되는 에폭시 수지용 각종 안정화제 또는 이온 제거제로 유용한 히드로탈사이트 화합물에 관한 것이다. The present invention relates to a low uranium (U) content hydrotalcite compound and a process for its preparation. More particularly, the present invention relates to hydrotalcite compounds useful as various stabilizers or ion removers for epoxy resins used to seal large capacity, high integration memory semiconductor devices without degrading the reliability of the device against soft errors. It is about.
수지용 무기 분말 첨가제에 요구되는 각종 특성, 예컨대 생성물의 외관에 대해 저해 효과가 없고 양호한 분산성 및 가공성을 동시에 갖는 히드로탈사이트가 일본 특허 공개 제 80447/80A 에 기재되었다. 이 공보에 나타난 히드로탈사이트는 실제적으로 PVC의 열안정화제, 폴리올레핀용 안정화제 등으로 많은 합성 수지에서 사용되고 있다.Hydrotalcite having no inhibitory effect on the various properties required for the inorganic powder additive for resin, such as the appearance of the product, and having good dispersibility and processability simultaneously, has been described in Japanese Patent Laid-Open No. 80447 / 80A. The hydrotalcites shown in this publication are actually used in many synthetic resins as thermal stabilizers for PVC, stabilizers for polyolefins, and the like.
반면에, 트랜지스터, IC, LSI 등과 같은 반도체 디바이스들은 외부로부터의 접촉, 오염 및 습기로부터의 차단 및 보호를 위해 밀봉될 필요가 있다. 현재, 수지 밀봉 방법은 생산성 및 경제의 관점에서 유리하고, 널리 실행된다. 특히, 에폭시 수지는 바람직한 전기적 특성, 내습성 및 접착성으로 인해, 반도체 디바이스의 밀봉에 사용된다. 히드로탈사이트 화합물은 반도체 디바이스용 에폭시 수지 밀봉 재료에서 이온 제거제 등으로서 사용되어 배선의 내습성 향상 및 부식 방지의 작용 및 역할을 수행한다. On the other hand, semiconductor devices such as transistors, ICs, LSIs, etc., need to be sealed for protection and protection from external contact, contamination and moisture. At present, the resin sealing method is advantageous in terms of productivity and economy, and is widely implemented. In particular, epoxy resins are used for sealing semiconductor devices because of their desirable electrical properties, moisture resistance and adhesion. The hydrotalcite compound is used as an ion remover or the like in an epoxy resin sealing material for semiconductor devices, and serves to improve the moisture resistance of the wiring and to prevent corrosion.
최근의 반도체 메모리가 용량이 더욱 커지고 집적화가 고도화되면서, 밀봉 수지 조성물에 함유되는 우라늄, 토륨과 같은 방사성 물질의 붕괘에서 방출되는 알파 광선에 기인하는 소프트 에러의 발생이 문제를 일으키기 시작한다. 예를 들어, 우라늄 및 토륨의 함량은, 소프트 에러에 대한 신뢰도를 확보하기 위해, 4M 비트 메모리에 대해서는 1 ppb(ng/g)을 초과하지 않고, 4 - 16M 비트 메모리에 대해서는 0.1 ppb(ng/g)를 초과하지 않도록 요구된다. 그 결과, 에폭시 수지 밀봉제에 이 수지의 수 백분율 이하 정도로 작은 양으로 섞인 히드로탈사이트 화합물 또한 마이크로 수준 이하의 방사성 물질을 함유하도록 요구된다. As the recent semiconductor memory becomes larger in capacity and higher in integration, the generation of soft errors due to alpha rays emitted from the borax of radioactive materials such as uranium and thorium contained in the sealing resin composition starts to cause problems. For example, the contents of uranium and thorium do not exceed 1 ppb (ng / g) for 4M bit memory and 0.1 ppb (ng / g) for 4-16M bit memory to ensure reliability for soft errors. g) is not required to exceed. As a result, hydrotalcite compounds mixed in epoxy resin sealants in amounts as small as a few percent or less of these resins are also required to contain submicron radioactive materials.
본 발명의 목적은 용량이 증가하고 집적화 수준의 승급이 매우 향상되었으며, 소프트 에러에 대해 높은 신뢰도를 갖는 메모리 반도체 디바이스용 밀봉제로 작용하는 에폭시 수지 조성물을 위한 이온 제거제로서 유용한 히드로탈사이트 화합물을 제공하는 것이다. 이 목적은 방사성 물질 함량, 예를 들어 우라늄 및 토륨의 함량이 매우 낮은 높은 순도의 히드로탈사이트 화합물을 제공함으로써 실현된다. 따라서, 본 발명의 주제는 수지에의 첨가제를 위해 요구되는 성질을 갖고 매우 낮은 우라늄 함량을 갖는 히드로탈사이트 화합물 및 그것의 제조 방법을 제공하는 것이다.It is an object of the present invention to provide a hydrotalcite compound useful as an ion scavenger for epoxy resin compositions which increases capacity, greatly improves the level of integration, and acts as a sealant for memory semiconductor devices with high reliability against soft errors. will be. This object is achieved by providing a high purity hydrotalcite compound with a very low content of radioactive substances, for example uranium and thorium. Accordingly, the subject of the present invention is to provide a hydrotalcite compound having a property required for an additive to a resin and having a very low uranium content and a process for producing the same.
본 발명의 히드로탈사이트 화합물은 하기 화학식 1로 표현되는 조성을 갖고, 10 ppb 이하의 우라늄(U) 함량, 약 3 ㎛ 이하의 평균 2 차 입자 크기 및 30 m2/g 이하의 BET 비표면적을 갖는다는 것을 특징으로 한다:The hydrotalcite compound of the present invention has a composition represented by the following Chemical Formula 1, and has a uranium (U) content of 10 ppb or less, an average secondary particle size of about 3 μm or less, and a BET specific surface area of 30 m 2 / g or less It is characterized by:
[화학식 1][Formula 1]
[식 중, M2+는 M2+는 Mg2+ 및 Zn2+ 중 하나 이상이고,[ Wherein M 2+ is M 2+ is at least one of Mg 2+ and Zn 2+ ,
x 는 0.2 ≤x ≤0.5 범위 내의 양수이며,x is a positive number in the range 0.2 ≤ x ≤ 0.5,
A2-는 CO3 2- 및 SO4 2- 중 하나 이상이고,A 2- is at least one of CO 3 2- and SO 4 2- ,
m 은 0 -2 범위 내의 수이다].m is a number in the range 0-2.
본 발명의 히드로탈사이트 화합물은, 바람직하게는, 고급 지방산, 음이온 계면 활성제, 실란 함유 커플링제, 티탄산염 함유 커플링제, 알루미늄 함유 커플링제 및 고급 알콜의 인산 에스테르로 구성되는 군에서 선택된 하나 이상의 표면 처리제로 표면 처리된 것들이다.The hydrotalcite compound of the present invention is preferably at least one surface selected from the group consisting of higher fatty acids, anionic surfactants, silane-containing coupling agents, titanate-containing coupling agents, aluminum-containing coupling agents and phosphate esters of higher alcohols Surface treated with a treatment agent.
이들 중에서, 화합물의 3 중량 % 이하의 실란 함유 커플링제로 표면 처리된 히드로탈사이트 화합물이 특히 바람직하다.Among them, hydrotalcite compounds surface-treated with 3% by weight or less of silane-containing coupling agent of the compounds are particularly preferred.
본 발명의 히드로탈사이트 화합물은 합성 수지용 충전제 또는 첨가제로서 편리하게 사용된다.The hydrotalcite compound of this invention is conveniently used as a filler or additive for synthetic resins.
본 발명의 상기 화학식 1 의 히드로탈사이트 화합물 중, 특히 A2- 가 CO3 2- 인 것들이 바람직하다. 반면에, CO3 2- 의 일부가 다른 음이온으로 대체된 것, 예를 들어, Al의 1/5 몰 이하(-CO3 2-의 40 몰% 이하), 특히 Al의 1/10 몰 이하(-CO3 2-의 20 몰% 이하)의 SO4 2-을 함유하는 것들도 바람직하다. Of the hydrotalcite compounds of the general formula (1) of the present invention, those in particular A 2- is CO 3 2- are preferred. On the other hand, a portion of CO 3 2- is replaced by another anion, for example, 1/5 mol or less of Al (40 mol% or less of -CO 3 2- ), in particular 1/10 mol or less of Al ( Preference is also given to those containing SO 4 2- ) up to 20 mol% of —CO 3 2- .
본 발명에 따른, 낮은 우라늄 함량의 히드로탈사이트 화합물은 하기와 같은 단계를 통해 제조될 수 있다:According to the present invention, a low uranium content hydrotalcite compound may be prepared by the following steps:
(1) 알칼리성 조건 하, 10 - 50 ℃ 범위의 온도 하 및 교반 하에서, 하기 수학식 1a 에 의해 정의되는 범위 내의 몰비를 만족하는 출발 물질의 조성으로, 수용성 알루미늄 화합물의 수용액과 수용성 마그네슘 화합물 및/또는 수용성 아연 화합물 수용액을 공침 반응시킴[이후부터 단계 (1)로 가리킬 수 있음), 및:(1) A composition of a starting material that satisfies the molar ratio within the range defined by the following formula (1a) under alkaline conditions, under a temperature in the range of 10-50 ° C., and under stirring, an aqueous solution of a water-soluble aluminum compound and a water-soluble magnesium compound, and / Or coprecipitation reaction with an aqueous solution of water-soluble zinc compound (which may be referred to as step (1) thereafter), and:
[식 중, M2+ 는 Mg2+ 및 Zn2+ 중의 하나 이상을 나타낸다][ Wherein M 2+ represents one or more of Mg 2+ and Zn 2+ ]
(2) 90 -200 ℃ 범위의 온도에서 0.5 시간 이상 동안, 단계 (1) 반응에서 생 성된 현탁액 형태의 수득된 공침 반응 생성물을 수열 반응시킴[이하부터 단계 (2)로 가리킬 수 있음], 이 경우,(2) hydrothermal reaction of the obtained coprecipitation reaction product in the form of a suspension produced in step (1) reaction, for a temperature of 90-200 ° C. for at least 0.5 hours, which can be referred to as step (2) from Occation,
(3) 수열 반응 후 반응 현탁액의 pH가 7.0 내지 13.5 범위가 되도록 반응 조건을 조절함.(3) Adjust the reaction conditions so that the pH of the reaction suspension after the hydrothermal reaction is in the range of 7.0 to 13.5.
본 발명에 따른 제조 방법에서, 알칼리성 조건 하, 10 - 50 ℃ 범위의 온도 하 및 교반 하에서, 하기 수학식 1b 에 의해 정의되는 범위 내의 몰비를 만족하는 출발 물질의 조성으로, 수용성 알루미늄 화합물의 수용액과 수용성 마그네슘 화합물 및/또는 수용성 아연 화합물의 수용액의 공침 반응(1)을 수행하는 것이 특히 바람직하다.In the production method according to the present invention, the composition of the starting material satisfies the molar ratio within the range defined by Equation 1b under alkaline conditions, under a temperature in the range of 10-50 ° C., and with stirring, It is particularly preferable to carry out coprecipitation reaction (1) of an aqueous solution of a water-soluble magnesium compound and / or a water-soluble zinc compound.
[식 중, M2+ 는 Mg2+ 및 Zn2+ 중의 하나 이상을 나타낸다].[ Wherein , M 2+ represents one or more of Mg 2+ and Zn 2+ .
또한, 본 발명에서, 상기 단계 (1)에서 수득된 공침 반응 생성물을 반응의 모액 내의 현탁액 상태에 방치하고, 그 생성물의 수열 반응을 90 - 200 ℃ 의 온도에서 0.5 시간 이상, 바람직하게는 0.5 - 24 시간 동안 수행하고, 수열 반응 후 반응 현탁액의 pH 가 7.0 - 13.5 범위가 되도록 반응 조건을 조절하는 것도 바람직하다[단계 (2)]], 이어서Further, in the present invention, the coprecipitation reaction product obtained in the step (1) is left in a suspension state in the mother liquor of the reaction, and the hydrothermal reaction of the product is carried out at a temperature of 90-200 ° C for at least 0.5 hours, preferably 0.5- It is also preferable to carry out for 24 hours and to adjust the reaction conditions after the hydrothermal reaction so that the pH of the reaction suspension is in the range of 7.0-13.5 [step (2)], then
(4) 물로 세척한 수열 반응 생성물을 탄산 암모늄 및/또는 탄산(수소) 알칼리의 수용액에 현탁시키고, 10 - 100 ℃ 의 온도에서 1 - 24 시간 동안 현탁액을 교반하는 것(용리 처리). (4) The hydrothermal reaction product washed with water is suspended in an aqueous solution of ammonium carbonate and / or an alkali of carbonate (hydrogen), and the suspension is stirred at a temperature of 10-100 ° C. for 1 to 24 hours (elution treatment).
상기 (4)에서 사용된 수용액 내의 탄산 암모늄 및/또는 탄산 또는 탄산수소 알칼리의 바람직한 농도는 0.1 내지 3.0 몰/L 이다.The preferred concentration of ammonium carbonate and / or carbonic acid or hydrogen carbonate alkali in the aqueous solution used in the above (4) is 0.1 to 3.0 mol / L.
본 발명의 제조 방법 중 단계 (2)의 수열 반응 후 현탁액의 pH 값은, 우라늄의 제거 비율을 조절하는 중요한 조건인데, 기본적으로 수용액에서 UO2 2+ 이온이 UO2(OH)3 -, UO2(CO3)2 2-, UO2(CO3)3 4- 등과 같은 착이온 형태를 취하는 것, 즉 7.0 이상은 충분한 것일 수 있다. 과도하게 높은 pH 영역에서는, 히드로탈사이트 화합물의 표면 전하가 네가티브 수준으로 뒤바뀌고, 우라늄의 착이온과 전기적으로 반발하여 우라늄의 흡수 등을 방지해서, 더 양호한 우라늄 제거가 가능하게 되고, 탄산, 알칼리 탄산(수소) 암모늄 등을 사용하는 용리 단계 (4) 없이도 목적한 우라늄 함량 수준이 달성될 수 있다. 용리 처리 단계 (4)를 포함하는 본 발명의 제조 방법에 따르면, 수열 반응 후 현탁액의 적합한 pH 범위는 7.0 - 13.5, 바람직하게는 9.0 -13.0 이다. 우라늄 제거를 위한 메카니즘은 아직 명확하지는 않지만, 이 수열 반응 중에, 히드로탈사이트 화합물이 결정 성장을 하여 감소된 BET 비표면적을 갖는데, 이로써 입자의 분산성이 증가되고 수지 첨가제에 바람직한 분말성이 증가될 뿐만 아니라, 결정 성장 과정에 동반하는 물질의 세정 작용으로 인해 일종의 불순물인 우라늄 이온도 결정 밖으로 축출된다고 가정한다. 따라서 축출된 우라늄 이온은 용액 내에 남아 있거나 또는, 재흡수되면 결정의 표면 부분에 남아, 탄산염 수용액 등으로 이것을 쉽게 용리할 수 있다. 높은 pH를 갖고 리간드로 작용할 수 있는 음이온을 함유하는 반응의 모액은, 축출된 우라늄 이온을 그 안에 용해해서 보유하기 위해 이들의 착이온 등을 형성하여 용액의 용량을 증가시키는데 기여할 수 있다고 추정된다. PH value after the hydrothermal reaction of step (2) of the manufacturing method of the present invention suspensions, is an important condition to control the removal ratio of uranium, basically the UO 2 2+ ion UO 2 (OH) 3 in aqueous solution -, UO Taking a complex ion form such as 2 (CO 3 ) 2 2- , UO 2 (CO 3 ) 3 4-, etc., ie, 7.0 or more may be sufficient. In the excessively high pH region, the surface charge of the hydrotalcite compound is reversed to the negative level, and electrically repels with the ions of uranium to prevent the absorption of uranium and the like, thereby allowing for better uranium removal, carbonate, alkali The desired uranium content level can be achieved without the elution step (4) using ammonium carbonate (hydrogen) carbonate or the like. According to the production process of the present invention comprising the eluting step (4), the suitable pH range of the suspension after hydrothermal reaction is 7.0-13.5, preferably 9.0-13.0. The mechanism for uranium removal is not yet clear, but during this hydrothermal reaction, the hydrotalcite compound undergoes crystal growth and has a reduced BET specific surface area, thereby increasing the dispersibility of the particles and the desired powderiness of the resin additive. In addition, it is assumed that uranium ions, which are a kind of impurity, are also removed from the crystal due to the cleaning action of materials accompanying the crystal growth process. The uranium ions thus removed remain in solution or, upon reabsorption, remain in the surface portion of the crystal and can be easily eluted with an aqueous solution of carbonate or the like. It is presumed that the mother liquor of the reaction having an anion capable of acting as a ligand having a high pH may contribute to increasing the capacity of the solution by forming their complex ions or the like to dissolve and retain the extracted uranium ions therein.
수열 반응은 90 - 200 ℃ 범위 내의 온도에서 0.5 내지 24 시간 동안, 바람직하게는 100 - 170 ℃에서 1 - 10 시간 동안 편리하게 수행될 수 있다. 시간-온도 조건이 명기된 범위보다 더 낮으면, 히드로탈사이트 화합물의 결정 성장이 불충분하고, 이것은 화합물의 분산성을 불완전하게 하는 경향이 있고, 우라늄 제거 효율을 악화시킨다. 따라서 이 같은 조건은 본 발명의 생성물을 수득하기에 불편하다. 다시 말해, 명기된 범위보다 더 높거나 더 낮은 시간 및 온도의 채택은, 제조가를 쓸데 없이 증가시키는 반면에, 우라늄 제거 효율이 주목할만하게 증가하지는 않는다.The hydrothermal reaction can be conveniently carried out at temperatures in the range of 90-200 ° C for 0.5 to 24 hours, preferably at 100-170 ° C for 1-10 hours. If the time-temperature condition is lower than the stated range, the crystal growth of the hydrotalcite compound is insufficient, which tends to incomplete dispersibility of the compound and worsens the uranium removal efficiency. Such conditions are therefore inconvenient to obtain the product of the present invention. In other words, the adoption of time and temperature higher or lower than the stated range adds to the manufacturing cost, while the uranium removal efficiency does not significantly increase.
용리 처리에서 사용되는 용리액으로는, 0.1 내지 3.0 몰/L 범위의 농도의 탄산 암모늄 수용액, 탄산수소 나트륨 수용액, 탄산나트륨 수용액, 탄산 암모늄/탄산수소 나트륨의 혼합 수용액, 탄산 암모늄/탄산나트륨의 혼합 수용액 등이 편리하게 사용되고, 이 수용액들의 바람직한 농도는 0.5 - 2.5 몰/L이다.Examples of the eluent used in the elution treatment include an aqueous ammonium carbonate solution, an aqueous sodium bicarbonate solution, an aqueous sodium carbonate solution, an aqueous mixed solution of ammonium carbonate / sodium carbonate, and an aqueous mixed solution of ammonium carbonate / sodium carbonate. Conveniently used, the preferred concentration of these aqueous solutions is 0.5-2.5 mol / L.
본 발명의 낮은 우라늄 함량의 히드로탈사이트 화합물의 상기 제조 방법에서 단계 (1) 공침 반응에서 사용되는 마그네슘, 아연 및 알루미늄의 염 또는 수용성 화합물로는, 마그네슘 화합물, 예컨대 염화 마그네슘, 황산 마그네슘, 질산 마그네슘, 아세트산 마그네슘, 수산화 마그네슘, 간수, 염수 등; 아연 화합물, 예컨대 염화 아연, 질산 아연, 황산 아연, 아세트산 아연 등; 알루미늄 화합물, 예컨대 염화 알루미늄, 황산 알루미늄, 질산 알루미늄, 알루미늄산 나트륨 등을 예로서 들 수 있다. 또한, 공침 반응 및 수열 반응을 통해 생성된 현탁액의 pH를 7.0 내지 13.5 범위 (실온에서) 내의 값으로 조절하기 위해 사용되는 알칼리성 화합물의 예로는 수산화 나트륨, 수산화 칼륨, 탄산 나트륨, 탄산 칼륨, 수용성 암모니아 및 암모니아 기체가 포함된다. As the salt or water-soluble compound of magnesium, zinc and aluminum used in the step (1) coprecipitation reaction in the above method for producing a low uranium content hydrotalcite compound of the present invention, a magnesium compound such as magnesium chloride, magnesium sulfate, magnesium nitrate Magnesium acetate, magnesium hydroxide, brine, brine and the like; Zinc compounds such as zinc chloride, zinc nitrate, zinc sulfate, zinc acetate and the like; Aluminum compounds, such as aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate, etc. are mentioned as an example. In addition, examples of the alkaline compounds used to adjust the pH of the suspension produced through the coprecipitation reaction and the hydrothermal reaction to values within the range of 7.0 to 13.5 (at room temperature) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and water-soluble ammonia. And ammonia gas.
단계 (4) 용리 처리에서 사용되는 탄산염의 예로는, 탄산 암모늄, 탄산나트륨, 탄산수소 나트륨, 탄산 칼륨 및 탄산수소 칼륨이 포함된다. 또한 탄산 암모늄/탄산나트륨, 탄산 암모늄/탄산수소 나트륨 등과 같이 상기 농도 범위(0.1 - 3.0 몰/L) 내의 임의의 혼합비에서 이들을 혼합하여 사용하는 것도 허용될 수 있다. Examples of the carbonate used in the step (4) eluting treatment include ammonium carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium hydrogen carbonate. It is also acceptable to use them in any mixing ratio within the above concentration range (0.1-3.0 mol / L) such as ammonium carbonate / sodium carbonate, ammonium carbonate / sodium carbonate and the like.
본 발명의 낮은 우라늄 함량의 히드로탈사이트 화합물을 합성 수지에 혼입하는 경우, 화합물은 고급 지방산, 음이온성 계면 활성제, 실란 함유 커플링제, 티탄산염 함유 커플링제, 알루미늄 함유 커플링제 및 고급 알콜의 인산 에스테르로 구성되는 군에서 선택된 하나 이상의 표면 처리제로 표면 처리되어서 개선된 적합성 및 가공성과 함께 제공될 수 있다. 본 발명에 따른 바람직한 표면 처리제의 예로는; 고급 지방산 예컨대 라우르산, 팔미트산, 스테아르산, 아라키드산, 올레산, 에루크산 등, 및 이 고급 지방산들의 알칼리 금속 염; 음이온성 계면 활성제 예컨대 스테아릴 알콜, 올레일 알콜 등과 같은 고급 알콜의 황산 에스테르 염, 아미드 결합 황산 에스테르 염, 에테르 결합 알킬알릴 술폰산 염 등; 인산 에스테르 예컨대 오르토인산 및 올레일 알콜, 스테아릴 알콜 등 간의 모노- 또는 디-에스테르인, 산 또는 알칼리 금속 염 또는 아민 염, 또는 이 에스테르들의 혼합물; 실란 함유 커플링제 예컨대 비닐에톡시실란, γ-메타크릴옥시프로필트리메톡시실란, γ-글리시독시프로필트리메톡시실란, 비닐-트리스(2-메톡시에톡시)실란, γ-아미노프로필트리메톡시실란 및 N-페닐-γ-아미노-프로필트리메톡시실렌; 티탄산염 함유 커플링제, 예컨대 이소프로필 트리이소스테아로일 티탄산염, 이소프로필 트리스(디옥틸피로포스페이트) 티탄산염 및 이소프로필 트리데실벤젠술포닐 티탄산염; 및 알루미늄 함유 커플링제 예컨대 아세트알콕시알루미늄 디이소프로필레이트 등이 포함된다.When incorporating the low uranium content hydrotalcite compound of the present invention into a synthetic resin, the compound may be a higher fatty acid, anionic surfactant, silane-containing coupling agent, titanate-containing coupling agent, aluminum-containing coupling agent and phosphoric acid ester of higher alcohol. Surface treatment with one or more surface treatment agents selected from the group consisting of can be provided with improved suitability and processability. Examples of preferred surface treating agents according to the present invention include; Higher fatty acids such as lauric acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid and the like, and alkali metal salts of these higher fatty acids; Anionic surfactants such as sulfuric acid ester salts of higher alcohols such as stearyl alcohol, oleyl alcohol and the like, amide bond sulfuric acid ester salts, ether bond alkylallyl sulfonic acid salts, and the like; Acid or alkali metal salts or amine salts, or mixtures of these esters, which are mono- or di-esters between phosphoric acid esters such as orthophosphoric acid and oleyl alcohol, stearyl alcohol and the like; Silane-containing coupling agents such as vinylethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyl-tris (2-methoxyethoxy) silane, γ-aminopropyltri Methoxysilane and N-phenyl-γ-amino-propyltrimethoxysilane; Titanate-containing coupling agents such as isopropyl triisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate and isopropyl tridecylbenzenesulfonyl titanate; And aluminum-containing coupling agents such as acetalkoxyaluminum diisopropylate and the like.
표면 처리의 방법으로는, 습식법 및 건식법이 있다. 습식법에서는, 액체 또는 유탁액 상태의 위에서 언급된 표면 처리제를 히드로탈사이트 화합물의 슬러리에 첨가하고, 약 10 - 100 ℃ 의 온도에서 교반 하여 충분히 혼합한다. 건식법에서는, 히드로탈사이트의 분말을 헨쉘(Henschel) 믹서와 같은 믹서에 넣어 여기에 액체, 분산액 또는 고체 상태의 표면 처리제를 첨가하고, 가열하면서 또는 가열없이 충분히 혼합한다. 바람직하게는, 표면 처리제는 히드로탈사이트의 약 0.05 - 약 10 중량 %의 양으로 사용된다.As a method of surface treatment, there are a wet method and a dry method. In the wet method, the above-mentioned surface treating agent in the liquid or emulsion state is added to the slurry of the hydrotalcite compound, and stirred and mixed sufficiently at a temperature of about 10-100 ° C. In the dry method, the powder of hydrotalcite is placed in a mixer such as a Henschel mixer, and the liquid, dispersion or solid surface treatment agent is added thereto and mixed sufficiently with or without heating. Preferably, the surface treating agent is used in an amount of about 0.05 to about 10 weight percent of hydrotalcite.
본 발명의 낮은 우라늄 함량의 히드로탈사이트 화합물이 편리하게 사용되는 합성 수지의 예로는 하기의 것들이 포함된다:Examples of synthetic resins in which the low uranium content hydrotalcite compound of the present invention is conveniently used include the followings:
폴리올레핀 수지 예컨대 에틸렌 단일 중합체, 에틸렌/α-올레핀 공중합체; 에틸렌/비닐 아세테이트 또는 에틸 아크릴레이트 또는 메틸 메타트릴레이트 공중합 체, 프로필렌 단일 중합체, 프로필렌/α-올레핀 공중합체, α-올레핀 단일 중합체 또는 공중합체; 및 이들의 할로겐화 수지;Polyolefin resins such as ethylene homopolymers, ethylene / α-olefin copolymers; Ethylene / vinyl acetate or ethyl acrylate or methyl methacrylate copolymers, propylene homopolymers, propylene / α-olefin copolymers, α-olefin homopolymers or copolymers; And halogenated resins thereof;
폴리아미드 수지 예컨대 에틸렌/프로필렌 열가소성 탄성체, 나일론 6, 6.6, 1.1, 1.2, 4.6, 6.10, 6.12 등;Polyamide resins such as ethylene / propylene thermoplastic elastomers, nylon 6, 6.6, 1.1, 1.2, 4.6, 6.10, 6.12 and the like;
에폭시 수지 예컨대 비스페놀 A 에폭시 수지, 노볼락 에폭시 수지, 지환족 에폭시 수지, 글리시딜 에폭시 수지, 비페닐 에폭시 수지, 나프탈렌 고리 함유 에폭시 수지, 시틀로펜타디엔 함유 에폭시 수지; 및 폴리에스테르 수지 예컨대 PET, PBT 등, 및Epoxy resins such as bisphenol A epoxy resins, novolac epoxy resins, cycloaliphatic epoxy resins, glycidyl epoxy resins, biphenyl epoxy resins, naphthalene ring-containing epoxy resins, and cyclopentadiene-containing epoxy resins; And polyester resins such as PET, PBT, and the like, and
유기 디이소시아네이트와 같은 폴리이소시아네이트, 디올과 같은 폴리올, 및 디아민과 같은 폴리아민의 반응 생성물인 폴리우레탄 수지.Polyurethane resins which are reaction products of polyisocyanates such as organic diisocyanates, polyols such as diols, and polyamines such as diamines.
히드로탈사이트 화합물을 가열할 때, 결정수 해리는 약 180 - 230 ℃ 근처에서 일어나기 시작한다. 거품 형성, 은색 줄무늬 및 결정 수분의 해리에 기인하는 기타의 불편과 같은 문제가, 공정(또는 가교와 같은 처리) 온도가 비교적 높은, 예를 들어 200 ℃ 이상인 합성 수지에 적용시 예상된다면, 본 발명의 히드로탈사이트 화합물을 미리 200 - 350 ℃ 에서 0.5 - 24 시간 동안 가열하여 탈수형[화학식 1을 가리키는데, 여기서 m 은 대략 0.05 - 0, 즉, 0 에 가깝다]으로 만들 수 있다. 이와 같은 탈수형 히드로탈사이트 화합물은 결정수를 함유하는 원래의 화합물과 비교하여 비교적 더 높은 우라늄 함량을 갖지만, 대략 동일한 수준의 화학적 성질 예켠대 산 중화력 및 이온 교환성 및 물리적 성질 예컨대 이차 입자 크기, 비표면적 등을 갖고, 동일한 사용에서 사용될 때 변화되지 않은 성능을 나타낸다.When heating the hydrotalcite compound, crystal water dissociation starts to occur around about 180-230 ° C. If problems such as foaming, silver streaks and other inconveniences due to dissociation of crystalline moisture are expected when applied to a synthetic resin having a relatively high process (or treatment such as crosslinking) temperature, for example 200 ° C. or more, the present invention The hydrotalcite compound of can be preheated at 200-350 ° C. for 0.5-24 hours to make it dehydrated (wherein m is approximately 0.05-0, ie close to zero). Such dehydrated hydrotalcite compounds have a relatively higher uranium content compared to the original compound containing crystalline water, but have approximately the same chemical properties such as acid neutralization and ion exchange and physical properties such as secondary particle size. , Specific surface area, etc., and exhibit unchanged performance when used in the same use.
물리적으로, 탈수형 히드로탈사이트 화합물은, 결정층 사이에 존재하는 결정수는 제거되지만, 음이온들은 층 사이에 있었던 대로 남아 있는 것이다. 이들의 분말 X-선 회절 (XRD) 도표는 결정수를 함유하는 원래의 화합물의 것에서 변화한다. 즉, 층 사이의 결정수를 손실하였기 때문에, 층사이의 거리가 수축되고 좁아진다. 그 결과, XRD 도포에서, (001) 평면의 회절선이 더 높은 각 변(더 작은 층간 거리의 방향)으로 이동한다.Physically, dehydrated hydrotalcite compounds are those in which the crystal water present between the crystal layers is removed, but the anions remain as they were between the layers. Their powder X-ray diffraction (XRD) plots vary from that of the original compound containing crystal water. That is, since the number of crystals between layers is lost, the distance between the layers shrinks and narrows. As a result, in the XRD application, the diffraction lines of the (001) plane move to the higher angular sides (the direction of the smaller interlayer distance).
이후부터 본 발명은 실시예 및 비교예를 참고로, 보다 자세하게 설명된다. 히드로탈사이트 화합물 내의 우라늄의 정량적인 분석은, 각각의 시료를 염산 및 과염소산에 용해시킴, 묽은 질산으로 용액을 희석함 및 ICP 질량 분광광도법으로 액체 중의 우라늄을 측정함의 단계를 통해 처리된다. 평균 입자 크기는, 각 시료에 대하여 물 또는 유기 용매에 첨가되고 초음파 처리로 분산될 때, 레이저 회절 산란 방법으로, 소위 평균 이차 입차 크기로서 측정되었다. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Quantitative analysis of uranium in the hydrotalcite compound is handled through the steps of dissolving each sample in hydrochloric and perchloric acid, diluting the solution with dilute nitric acid, and measuring uranium in the liquid by ICP mass spectrophotometry. The average particle size was measured as the so-called average secondary particle size by the laser diffraction scattering method when added to water or an organic solvent and dispersed by sonication for each sample.
비표면적은 질소 기체 흡수의 양을 기재로 즉, BET 방법을 사용하여 결정하였다. The specific surface area was determined based on the amount of nitrogen gas uptake, ie using the BET method.
참고예Reference Example
시판용 합성 히드로탈사이트이고 합성 수지에의 첨가제로서 현재 가장 광범위하게 사용되는, Kyowa Chemical Industries, Co., LTD.에서 제조되는 DHT-4A(상표명) 내의 우라늄 및 토륨을 분석한 결과가 하기에 나타난다. The results of the analysis of uranium and thorium in DHT-4A (trade name) manufactured by Kyowa Chemical Industries, Co., LTD., Which are commercially available synthetic hydrotalcites and which are currently most widely used as additives to synthetic resins, are shown below.
단위: ng/g(ppb)Units: ng / g (ppb)
상기 자료로부터, 예를 들어, 시판되는 합성 히드로탈사이트의 5 중량 %의 혼합으로 약 10 ppb 우라늄 함량의 수지 조성물이 생기고, 현재 판매되는 생성물의 이같은 2 자리수의 우라늄 함량은 감소되어야 한다는 것이 이해될 수 있을 것이다. 또한, 통상적인 출발 물질을 사용하여 히드로탈사이트가 합성될 때, 토륨은 항상 검출 한계의 수준보다 더 낮고, 우라늄 함량에서의 축소가 본 발명의 목적을 만족시키기 위해 극복해야할 장애라는 것도 이해된다. From the above data it will be understood that a resin composition of about 10 ppb uranium content, for example, is produced by mixing 5 wt% of commercially available synthetic hydrotalcite, and this double-digit uranium content of the currently marketed product should be reduced. Could be. In addition, when hydrotalcite is synthesized using conventional starting materials, it is also understood that thorium is always below the level of detection limit, and that a reduction in uranium content is an obstacle to overcome to meet the object of the present invention.
실시예 1Example 1
Mg 농도 1.5 몰/L 의 간수[Mg(OH)2 당 전환값으로 50 ng/g(ppb)의 우라늄을 함유함] 361 ㎖ 및 Al 농도 1.03 몰/L 의 공업용 등급 황산 알루미늄 수용액[Al(OH)3 당 전환값으로 576ng/g(ppb)의 우라늄을 함유함] 117㎖ 을 혼합하였다. 이 혼합된 수용액을 2 리터 비이커에 넣고, 여기에 3.4 N의 수산화 나트륨 수용액 585 ㎖ 및 0.8 몰/L의 탄산나트륨 수용액 226 ㎖를 실온에서 격렬한 교반 하에 주입하였다. 약 30 분 동안 교반을 계속하여, 공침 생성물을 제공하였다.Industrial grade aluminum sulphate aqueous solution [Al (OH) with 361 mL of Mg concentration of 1.5 mol / L [contains 50 ng / g (ppb) of uranium as conversion value per Mg (OH) 2 ] and 1.03 mol / L of Al concentration. ) converted to a value per 3 by containing uranium of 576ng / g (ppb)] it was mixed 117㎖. This mixed aqueous solution was placed in a 2 liter beaker, to which 585 ml of an aqueous 3.4 N sodium hydroxide solution and 226 ml of an aqueous 0.8 mol / L sodium carbonate solution were injected under vigorous stirring at room temperature. Stirring was continued for about 30 minutes, giving a coprecipitation product.
침강 분리에 의해 700 ㎖의 부피로 농축된 공침 생성물의 현탁액을 0.98 리터 오토클레이브로 옮기고, 170 ℃에서 6 시간동안 수열 반응시켰다. 연속하여 냉각 후, 현탁액의 pH는 13.17(30.1 ℃)였다. 생성물을 여과에 의해 회수하고, 물로 세척하고 95 ℃에서 18 시간 동안 건조시키고, 건조 생성물을 100-메시 체로 체질했다.A suspension of coprecipitation product concentrated to a volume of 700 ml by sedimentation separation was transferred to a 0.98 liter autoclave and subjected to hydrothermal reaction at 170 ° C. for 6 hours. After continuous cooling, the pH of the suspension was 13.17 (30.1 ° C.). The product was recovered by filtration, washed with water and dried at 95 ° C. for 18 hours, and the dried product was sieved with 100-mesh sieve.
생성물은 분말 X-선 회절 측정에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 8 ppb[ng/g (건조 분말)]이고, 평균 이차 입자 크기는 1.0 ㎛ 이며, BET 비표면적은 11.2 ㎡/g 이었다.The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement. Its uranium (U) content was 8 ppb [ng / g (dry powder)], the average secondary particle size was 1.0 μm, and the BET specific surface area was 11.2 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.72Al0.27(OH)2(CO3)0.13
실시예 2-1Example 2-1
3.4 N 수산화 나트륨 수용액 및 0.8 몰/L 탄산나트륨 수용액의 양을 각각 478 ㎖ 및 226 ㎖ 로 변화시킨 것 이외에는, 실시예 1 의 것들과 동일한 출발 물질을 사용하여, 실시예 1의 조작을 반복하였다. 170 ℃에서 6 시간 동안의 수열 반응 후의 현탁액은 12.08 (28.6℃)의 pH를 갖는다.The procedure of Example 1 was repeated using the same starting materials as those of Example 1, except that the amounts of 3.4 N aqueous sodium hydroxide solution and 0.8 mol / L aqueous sodium carbonate solution were changed to 478 ml and 226 ml, respectively. The suspension after hydrothermal reaction at 170 ° C. for 6 hours has a pH of 12.08 (28.6 ° C.).
생성물은 분말 X-선 회절 측정에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 17 ppb[ng/g (건조 분말)]이고, 평균 이차 입자 크기는 0.59 ㎛ 이며, BET 비표면적은 13.4 ㎡/g 이었다.The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement. Its uranium (U) content was 17 ppb [ng / g (dry powder)], the average secondary particle size was 0.59 μm, and the BET specific surface area was 13.4 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.70Al0.30(OH)2(CO3)0.15
실시예 2-2Example 2-2
1 등급 탄산 암모늄 47 g을 이온제거수에 용해하고 용액의 총부피를 700 ㎖로 조절하고, 이것을 1 리터 비이커에 넣었다. 교반 하에, 실시예 2-1 에서 수득된 히드로탈사이트 화합물 27 g을 용액에 첨가하고 20 시간 동안 실온에서 교반 하였다. 생성물을 여과로 회수하고, 물로 세척하고 95 ℃에서 18 시간동안 건조시켰다. 건조 생성물을 100-메시 체로 체질했다.47 g of first grade ammonium carbonate was dissolved in deionized water and the total volume of the solution was adjusted to 700 ml, which was placed in a 1 liter beaker. Under stirring, 27 g of the hydrotalcite compound obtained in Example 2-1 were added to the solution and stirred at room temperature for 20 hours. The product was recovered by filtration, washed with water and dried at 95 ° C. for 18 hours. The dry product was sieved with 100-mesh sieve.
생성물은 분말 X-선 회절 측정에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 5 ppb(ng/g)이하이고, 평균 이차 입자 크기는 0.59 ㎛ 이며, BET 비표면적은 13.0 ㎡/g 이었다. 생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다: The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement. Its uranium (U) content was less than 5 ppb (ng / g), the average secondary particle size was 0.59 μm, and the BET specific surface area was 13.0 m 2 / g. The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.30(OH)2(CO3)0.15
실시예 2-3Example 2-3
0.5 몰/L 의 공업용 등급 탄산나트륨 수용액 700 ㎖를 1 리터 비이커에 넣고, 여기에 실시예 2-1 에서 수득된 히드로탈사이트 화합물 27 g을 교반 하에 첨가한 후, 20 시간 동안 실온에서 교반하였다. 생성물을 여과로 회수하고, 물로 세척하고 95 ℃ 에서 18 시간 동안 건조시켰다. 건조 생성물을 100-메시 체로 체질했다. 상기 생성물은 분말 X-선 회절 측정에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 5 ppb(ng/g)이고, 평균 이차 입자 크기는 0.59 ㎛ 이며, BET 비표면적은 13.3 ㎡/g 이었다. 생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:700 ml of an aqueous 0.5 mol / L industrial grade sodium carbonate solution was placed in a 1 liter beaker, and 27 g of the hydrotalcite compound obtained in Example 2-1 was added under stirring, followed by stirring at room temperature for 20 hours. The product was recovered by filtration, washed with water and dried at 95 ° C. for 18 hours. The dry product was sieved with 100-mesh sieve. The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement. Its uranium (U) content was 5 ppb (ng / g), the average secondary particle size was 0.59 μm, and the BET specific surface area was 13.3 m 2 / g. The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.70Al0.30(OH)2(CO3)0.15
실시예 3Example 3
3.4 N 수산화 나트륨 수용액 및 0.8 몰/L 탄산나트륨 수용액의 양을 각각 461 ㎖ 및 226 ㎖ 로 변화시킨 것 이외에는, 실시예 1 의 것들과 동일한 출발 물질을 사용하여, 실시예 1의 조작을 반복하였다. 수열 반응의 생성된 현탁액은 11.05 (28.2℃)의 pH를 갖는다.The operation of Example 1 was repeated using the same starting materials as those of Example 1, except that the amounts of 3.4 N aqueous sodium hydroxide solution and 0.8 mol / L aqueous sodium carbonate solution were changed to 461 mL and 226 mL, respectively. The resulting suspension of hydrothermal reaction has a pH of 11.05 (28.2 ° C.).
여과 및 물로 세척하여 수득된 케이크를 1.0 몰/L의 1등급 탄산 암모늄 수용액 700 ㎖에 넣고 교반 하에서 현탁시킨 후, 20 시간 동안 실온에서 교반했다. 여과 및 물로 세척해서 수득된 케이크를 2 리터 비이커에 넣고, 여기에 800 ㎖의 이온제거수를 교반 하에 첨가하여 현탁액을 얻고 80 ℃로 가열하였다. 200 ㎖ 비이커에 1.2 g의 스테아르산나트륨(순도: 86%) 및 150 ㎖의 이온제거수를 넣고 약 80 ℃ 로 가열하여 용액을 생성시켰다. 용액을 교반 하에 현탁액에 주입하고, 계를 80 ℃에서 30 분 동안 유지시켰다. 여과에 의해 반응 생성물을 회수하고, 물로 세척하고 95 ℃에서 18 시간 동안 건조시킨 후, 100-메시 체로 체질했다. 생성물은 분말 X-선 회절 측정에 의해 히드로탈사이트 화합물로 밝혀졌다. 생성물의 우라늄(U) 함량은 5 ppb(ng/g)이하이고, 평균 이차 입자 크기는 0.59 ㎛ 이며, BET 비표면적은 13.0 ㎡/g 이었다. 생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The cake obtained by filtration and washing with water was placed in 700 ml of a 1.0 mol / L first-grade ammonium carbonate aqueous solution and suspended under stirring, followed by stirring at room temperature for 20 hours. The cake obtained by filtration and washing with water was placed in a 2 liter beaker, to which 800 ml of deionized water was added under stirring to obtain a suspension and heated to 80 ° C. 1.2 g of sodium stearate (purity: 86%) and 150 ml of deionized water were added to a 200 ml beaker, and the solution was heated to about 80 ° C. The solution was injected into the suspension under stirring and the system was held at 80 ° C. for 30 minutes. The reaction product was recovered by filtration, washed with water and dried at 95 ° C. for 18 hours and then sieved with 100-mesh sieve. The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement. The uranium (U) content of the product was 5 ppb (ng / g) or less, the average secondary particle size was 0.59 μm, and the BET specific surface area was 13.0 m 2 / g. The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.31(OH)2(CO3)0.15
실시예 4Example 4
1.2 몰/L의 염화 아연 수용액 300 ㎖을 0.4 몰/L 의 공업용 등급 황산 알루미늄 수용액 225 ㎖과 혼합하였다. 혼합물을 2 리터 비이커에 넣고, 여기에 318 ㎖의 공업용 등급 3.4 N NaOH 용액 및 135 ㎖의 공업용 등급 0.8 몰/L Na2CO3 용액을 실온에서 격렬한 교반 하에 주입한 후, 30분 동안 교반하였다.300 ml of 1.2 mol / L aqueous zinc chloride solution was mixed with 225 ml of 0.4 mol / L industrial grade aqueous aluminum sulfate solution. The mixture was placed in a 2 liter beaker, where 318 ml of industrial grade 3.4 N NaOH solution and 135 ml of industrial grade 0.8 mol / L Na 2 CO 3 solution were injected under vigorous stirring at room temperature and then stirred for 30 minutes.
수득된 공침 생성물의 현탁액의 총부피를 침강 분리 농축에 의해 700 ㎖로 감소시켰다. 현탁액을 0.98 리터 오토클레이브로 옮기고, 110 ℃에서 15 시간 동안 수열 반응시켰다.The total volume of the suspension of coprecipitation product obtained was reduced to 700 ml by sedimentation separation concentration. The suspension was transferred to a 0.98 liter autoclave and hydrothermally reacted at 110 ° C. for 15 hours.
냉각 후의 수득된 현탁액은 10.51의 pH (29.2 ℃)를 가졌다. 여과에 의해 회수된 케이크를 물로 세척하고 700 ㎖의 0.5 몰/L 1등급 탄산 암모늄수용액에 넣고, 교반기로 균일하게 현탁시킨 후 20 시간 동안 실온에서 교반시켰다. 현탁액을 여과하여, 회수된 케이크를 물로 세척하고 95 ℃에서 18 시간 동안 건조시켰다. 건조 생성물을 100-메시 체로 체를 쳤는데, 이것은 분말 X-선 회절 측정 및 화학적 분석에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 5 ppb[ng/g (건조 분말)] 이하이고, 평균 이차 입자 크기는 1.2 ㎛ 이며, BET 비표면적은 9.9 ㎡/g 이었다.The obtained suspension after cooling had a pH of 10.51 (29.2 ° C.). The cake recovered by filtration was washed with water and placed in 700 mL of 0.5 mol / L first grade ammonium carbonate solution, uniformly suspended with a stirrer and stirred at room temperature for 20 hours. The suspension was filtered, the recovered cake was washed with water and dried at 95 ° C. for 18 hours. The dry product was sieved with a 100-mesh sieve, which was found to be a hydrotalcite compound by powder X-ray diffraction measurements and chemical analysis. Its uranium (U) content was below 5 ppb [ng / g (dry powder)], the average secondary particle size was 1.2 μm, and the BET specific surface area was 9.9 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Zn0.67Al0.33(OH)2(CO3)0.17
실시예 5Example 5
실시예 1 과 동일한 방식으로, Mg 농도 1.5 몰/L 의 간수 1,363 ㎖ 를 Al 농도 1.03 몰/L 의 공업용 등급 황산 알루미늄 수용액[Al(OH)3 117㎖ 과 혼합하고, 이 혼합물을 2 리터 비이커에 넣고, 여기에 3.4 N 수산화 나트륨 용액 463 ㎖ 및 0.8 몰/L 공업용 등급 Na2CO3 용액 303 ㎖를 실온에서 격렬한 교반 하에 주입한 후, 약 30 분 동안 교반하였다.In the same manner as in Example 1, 1,363 mL of Mg concentration of 1.5 mol / L of brine was mixed with 117 mL of industrial grade aluminum sulfate aqueous solution [Al (OH) 3 , of Al concentration of 1.03 mol / L, and the mixture was added to a 2 liter beaker. It was charged with 463 mL of 3.4 N sodium hydroxide solution and 303 mL of 0.8 mol / L industrial grade Na 2 CO 3 solution at room temperature under vigorous stirring, followed by stirring for about 30 minutes.
수득된 공침물의 현탁액으로부터, 600 ㎖를 0.98 리터 오토클레이브로 옮기고, 170 ℃에서 6 시간동안 수열반응을 시켰다. 연속하여 냉각 후에, 현탁액의 pH는 10.56(25.0 ℃)이었다. 생성물을 여과에 의해 회수하고, 물로 세척하고 95 ℃에서 18 시간 동안 건조하고, 건조 생성물을 100-메시 체로 체질했다.From the suspension of the obtained coprecipitate, 600 ml were transferred to a 0.98 liter autoclave and subjected to hydrothermal reaction at 170 ° C. for 6 hours. After continuous cooling, the pH of the suspension was 10.56 (25.0 ° C). The product was recovered by filtration, washed with water and dried at 95 ° C. for 18 hours, and the dried product was sieved with 100-mesh sieve.
생성물은 분말 X-선 회절 측정에 의해 히드로탈사이트 화합물로 밝혀졌다.The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement.
그것의 우라늄(U) 함량은 13 ppb이고, 평균 이차 입자 크기는 0.60 ㎛ 이며, BET 비표면적은 14 ㎡/g 이었다.Its uranium (U) content was 13 ppb, the average secondary particle size was 0.60 μm, and the BET specific surface area was 14 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.31(OH)2(CO3)0.15
따라서 수득된 히드로탈사이트 화합물을 700 ㎖의 1.0 몰/L 1등급 탄산 암모늄 수용액에 교반 하에 첨가하고 현탁시킨 후, 20 시간 동안 실온에서 교반시켰다. 생성물을 여과에 의해 회수하고, 물로 세척하고 95 ℃에서 18 시간 동안 건조시켰다. 건조 생성물을 100-메시 체로 체질했다. 생성물은 분말 X-선 회절 측정에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 5 ppb(ng/g)이하이고, 평균 이차 입자 크기는 0.60 ㎛ 이며, BET 비표면적은 14 ㎡/g 이었다. 생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The hydrotalcite compound thus obtained was added to 700 ml of 1.0 mol / L grade 1 ammonium carbonate aqueous solution under stirring and suspended, followed by stirring at room temperature for 20 hours. The product was recovered by filtration, washed with water and dried at 95 ° C. for 18 hours. The dry product was sieved with 100-mesh sieve. The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement. Its uranium (U) content was less than 5 ppb (ng / g), the average secondary particle size was 0.60 μm and the BET specific surface area was 14 m 2 / g. The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.31(OH)2(CO3)0.15
비교예 1Comparative Example 1
실시예 5에서 수득된 공침물의 현탁액으로부터, 5,600 ㎖을 취해서 여과하였다. 필터 케이크를 물로 세척하고 1 리터 비이커에 넣었다. 케이크를 이온제거수에 현탁시키고 현탁액의 총량을 600 ㎖로 조절하였다. 현탁액을 0.98 리터 오토클레이브로 옮기고 170 ℃에서 15 시간 동안 수열 반응시켰다. 연속하여 냉각 후에, 현탁액은 9.94의 pH(24.1 ℃)를 갖는다. 여과에 의해 생성물을 회수하고, 물로 세척하고 95 ℃에서 18 시간 동안 건조시킨다. 건조 생성물을 100-메시 체로 체질했다.From the suspension of the coprecipitation obtained in Example 5, 5,600 mL was taken and filtered. The filter cake was washed with water and placed in a 1 liter beaker. The cake was suspended in deionized water and the total amount of suspension was adjusted to 600 ml. The suspension was transferred to a 0.98 liter autoclave and hydrothermally reacted at 170 ° C. for 15 hours. After subsequent cooling, the suspension has a pH of 9.94 (24.1 ° C). The product is recovered by filtration, washed with water and dried at 95 ° C. for 18 hours. The dry product was sieved with 100-mesh sieve.
상기 생성물은 분말 X-선 회절 측정 및 화학적 분석에 의해 히드로탈사이트 화합물로 밝혀졌다.The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement and chemical analysis.
이것의 우라늄(U) 함량은 190 ppb(ng/g)이고, 평균 이차 입자 크기는 0.6 ㎛ 이며, BET 비표면적은 19 ㎡/g 이었다.Its uranium (U) content was 190 ppb (ng / g), the average secondary particle size was 0.6 μm, and the BET specific surface area was 19 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.31(OH)2(CO3)0.15
실시예 6Example 6
실시예 1에서의 것들과 동일한 출발 액체 재료를 사용하여, 공침 반응을 연속적인 반응 방법에 의해 처리하였다. 즉, 교반 하에 각각 12.1 ㎖/분, 3.92 ㎖/분, 및 5.5 ㎖/분의 유동 속도로, 1.5 몰/L의 Mg 농도를 갖는 간수, 1.03 몰/L 농도의 황산 암모늄 수용액 및 0.8 몰/L 탄산나트륨 수용액을, 반응 현탁액이 연속 적으로 배출될 수 있는 대략 1 리터 반응 용기에 주입하였다. 동시에, 반응 현탁액의 pH를 10 ±0.2에서 유지하도록 조절되는 유동 속도에서, 유동 속도를 조절할 수 있는 공급 펌프로 3.4 N 수산화 나트륨 수용액을 계에 첨가하였다. 공침 반응을 3 시간 동안 계속하였다.Using the same starting liquid material as those in Example 1, the coprecipitation reaction was processed by a continuous reaction method. I.e., brine with a Mg concentration of 1.5 mol / L, an aqueous ammonium sulfate solution of 1.03 mol / L and 0.8 mol / L, respectively, at a flow rate of 12.1 ml / min, 3.92 ml / min, and 5.5 ml / min under stirring Aqueous sodium carbonate solution was injected into the approximately 1 liter reaction vessel into which the reaction suspension can be continuously discharged. At the same time, at a flow rate controlled to maintain the pH of the reaction suspension at 10 ± 0.2, 3.4 N aqueous sodium hydroxide solution was added to the system with a feed pump with adjustable flow rate. The coprecipitation reaction was continued for 3 hours.
수득된 반응 현탁액을 침전 분리에 의해 약 1.5 배의 농도로 응축하고, 여기에서 700 ㎖를 0.98 리터 오토클레이브로 옮기고 170 ℃에서 6 시간 동안 수열 반응시킨 후, 냉각, 여과하고, 물로 세척하였다. 1 리터 비이커에서, 101 g 의 탄산 암모늄을 이온제거수에 용해시키고, 용액의 부피를 700 ㎖로 조절하고, 여기에 상기 물로 세척한 후의 케이크를 교반 하에 첨가하고 현탁시킨 후, 20 시간 동안 실온에서 교반하였다. 이어서 현탁액을 여과하고 회수한 케이크를 물로 세척하고, 2 리터 비이커로 옮기고, 교반 하에 1 리터의 이온제거수에 현탁시켰다. 현탁액에 3 g의 γ-글리시독시프로필트리메톡시실란(A-187, Nippon Unicar)을 교반 하에 주입한 후, 30분 동안 교반하였다. 수득된 현탁액을 분무 건조기로 보내서 건조하여, 백색의 건조 분말을 제공하였다. 따라서 수득된 히드로탈사이트 화합물은 5 ppb(ng/g)이하의 우라늄(U) 함량, 0.62 ㎛의 평균 이차 입자 크기, 13 ㎡/g의 BET 비표면적을 갖는다.The resulting reaction suspension was condensed to a concentration of about 1.5 times by precipitation separation, where 700 ml were transferred to a 0.98 liter autoclave and hydrothermally reacted at 170 ° C. for 6 hours, then cooled, filtered and washed with water. In a 1 liter beaker, 101 g of ammonium carbonate was dissolved in deionized water, the volume of the solution was adjusted to 700 mL, and the cake after washing with the water was added under stirring and suspended, followed by 20 hours at room temperature. Stirred. The suspension was then filtered and the recovered cake was washed with water, transferred to a 2 liter beaker and suspended in 1 liter of deionized water under stirring. 3 g of γ-glycidoxypropyltrimethoxysilane (A-187, Nippon Unicar) was injected into the suspension under stirring, followed by stirring for 30 minutes. The suspension obtained was sent to a spray drier to dry, giving a white dry powder. The hydrotalcite compound thus obtained has a uranium (U) content of less than 5 ppb (ng / g), an average secondary particle size of 0.62 μm and a BET specific surface area of 13 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.31(OH)2(CO3)0.15
비교예 2Comparative Example 2
실시예 6의 연속적인 공침 반응에서 수득된 반응 현탁액으로부터, 6,700 ㎖을 취하고, 여과하고 물로 세척하였다. 따라서 회수된 공침 생성물의 케이크를 이온제거수에 현탁시키고, 현탁액의 부피를 700 ㎖로 조절하였다. 현탁액을 0.98 리터 오토클레이브로 옮기고 170 ℃에서 20 시간 동안 수열 반응을 시킨 후, 냉각, 여과하고, 물로 세척하고 95 ℃에서 18 시간 동안 건조시켰다. 건조 후, 생성물을 100-메시 체로 체질했다. 생성물은 분말 X-선 회절 측정 및 화학적 분석에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 200 ppb(ng/g)이고, 평균 이차 입자 크기는 0.5 ㎛ 이며, BET 비표면적은 13.5 ㎡/g 이었다.From the reaction suspension obtained in the continuous coprecipitation reaction of Example 6, 6700 mL was taken, filtered and washed with water. The cake of recovered coprecipitation product was therefore suspended in deionized water and the volume of the suspension was adjusted to 700 ml. The suspension was transferred to a 0.98 liter autoclave and subjected to hydrothermal reaction at 170 ° C. for 20 hours, then cooled, filtered, washed with water and dried at 95 ° C. for 18 hours. After drying, the product was sieved with a 100-mesh sieve. The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement and chemical analysis. Its uranium (U) content was 200 ppb (ng / g), the average secondary particle size was 0.5 μm, and the BET specific surface area was 13.5 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.31(OH)2(CO3)0.15
1등급의 탄산 암모늄 101 g을 이온제거수에 용해시키고, 용액의 부피를 700 ㎖로 조절하고, 이것을 1 리터 비이커에 넣었다. 교반기로 교반하면서, 비교예 1에서 수득된 히드로탈사이트 화합물 38 g을 용액에 첨가한 후, 20 시간 동안 실온에서 교반하였다. 생성된 현탁액을 여과하여, 회수된 케이크를 물로 세척하고 95 ℃에서 18 시간 동안 건조시켰다. 건조 생성물을 100-메시 체로 체질했다.101 g of first grade ammonium carbonate was dissolved in deionized water and the volume of the solution was adjusted to 700 ml and placed in a 1 liter beaker. While stirring with a stirrer, 38 g of the hydrotalcite compound obtained in Comparative Example 1 were added to the solution, followed by stirring at room temperature for 20 hours. The resulting suspension was filtered, the recovered cake was washed with water and dried at 95 ° C. for 18 hours. The dry product was sieved with 100-mesh sieve.
생성물은 분말 X-선 회절 측정 및 화학적 분석에 의해 히드로탈사이트 화합물로 밝혀졌다. 그것의 우라늄(U) 함량은 110 ppb(ng/g)이고, 평균 이차 입자 크기는 0.54 ㎛ 이며, BET 비표면적은 13 ㎡/g 이었다.The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement and chemical analysis. Its uranium (U) content was 110 ppb (ng / g), the average secondary particle size was 0.54 μm, and the BET specific surface area was 13 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.69Al0.31(OH)2(CO3)0.15
실시예 7Example 7
실시예 1에서 사용된 대로 1.5 몰/L의 Mg 농도를 갖는 동일한 간수 133 ㎖, 0.2 몰/L의 황산 아연 수용액 143 ㎖ 및 0.4 몰/L의 공업용 등급 황산 알루미늄 수용액 143 ㎖를 혼합하여 혼합물을 생성시키고, 이것을 1 리터 비이커에 넣었다. 격렬한 교반 하에, 202 ㎖의 공업용 등급 3.4 NaOH 용액 및 143 ㎖의 공업용 등급 0.8 몰/L Na2CO3 용액을 상기 비이커에 주입한 후, 약 30 분 동안 교반하였다. 생성된 공침물의 현탁액(침전 분리 농축에 의해 총부피가 700 ㎖로 감소됨)을 0.98 리터 오토클레이브에 옮기고 150 ℃에서 10 시간 동안 수열 반응시켰다. 냉각 후의 수득된 현탁액은 9.71의 pH(32.4 ℃)를 가졌다. 현탁액을 여과하고, 필터 케이크를 물로 세척하고 700 ㎖의 0.6 몰/L 1등급 탄산수소 나트륨 수용액에 넣고 교반기로 균일하게 현탁시킨 후, 50 ℃로 가열하고, 2 시간 동안 방치하였다. 이어서 현탁액을 여과하고, 필터 케이크를 물로 세척하고, 95 ℃에서 18 시간 동안 건조시켰다. 건조 생성물을 100-메시 체로 체질했다.A mixture was formed by mixing 133 ml of the same brine with a Mg concentration of 1.5 mol / L, 143 ml of 0.2 mol / L aqueous zinc sulfate solution and 143 ml of 0.4 mol / L industrial grade aqueous aluminum sulfate solution as used in Example 1 And put it into a 1 liter beaker. Under vigorous stirring, 202 ml of industrial grade 3.4 NaOH solution and 143 ml of industrial grade 0.8 mol / L Na 2 CO 3 solution were injected into the beaker and then stirred for about 30 minutes. The resulting suspension of coprecipitate (total volume reduced to 700 ml by sedimentation separation concentration) was transferred to a 0.98 liter autoclave and subjected to hydrothermal reaction at 150 ° C. for 10 hours. The obtained suspension after cooling had a pH of 9.71 (32.4 ° C.). The suspension was filtered, the filter cake was washed with water and placed in 700 ml of 0.6 mol / L first grade sodium hydrogen carbonate aqueous solution, uniformly suspended with a stirrer, heated to 50 ° C. and left for 2 hours. The suspension was then filtered, the filter cake was washed with water and dried at 95 ° C. for 18 hours. The dry product was sieved with 100-mesh sieve.
생성물은 분말 X-선 회절 측정 및 화학적 분석에 의해 히드로탈사이트 화합물로 밝혀졌다. The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement and chemical analysis.
그것의 우라늄(U) 함량은 5 ppb[ng/g (건조 분말)]이고, 평균 이차 입자 크기는 0.6 ㎛ 이며, BET 비표면적은 8.0 ㎡/g 이었다.Its uranium (U) content was 5 ppb [ng / g (dry powder)], the average secondary particle size was 0.6 μm, and the BET specific surface area was 8.0 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.58Zn0.08Al0.33(OH)2(CO3)0.16
실시예 8Example 8
실시예 1에서 사용된 대로 1.5 몰/L의 Mg 농도를 갖는 동일한 간수 213 ㎖, 0.2 몰/L의 공업용 등급 황산 알루미늄 수용액 1,266 ㎖ 및 1 등급 Na2SO4 15 g을 혼합하여 혼합물을 생성시키고, 이것을 1 리터 비이커에 넣었다. 격렬한 교반 하에, 251 ㎖의 공업용 등급 3.4 N NaOH 용액을 혼합물에 실온에서 주입한 후, 30 분 동안 교반하였다. 수득된 공침물 현탁액을 0.98 리터 오토클레이브에 옮기고 170 ℃에서 12 시간 동안 수열 반응시켰다. 냉각 후 생성된 현탁액은 11.08의 pH(29 ℃)를 가졌다.A mixture was prepared by mixing 213 ml of the same brine having a Mg concentration of 1.5 mol / L, 1,266 ml of 0.2 mol / L of industrial grade aqueous aluminum sulfate solution and 15 g of Grade 1 Na 2 SO 4 as used in Example 1, Put this in a 1 liter beaker. Under vigorous stirring, 251 mL of industrial grade 3.4 N NaOH solution was injected into the mixture at room temperature and then stirred for 30 minutes. The obtained coprecipitation suspension was transferred to a 0.98 liter autoclave and subjected to hydrothermal reaction at 170 ° C. for 12 hours. The resulting suspension, after cooling, had a pH of 11.08 (29 ° C.).
현탁액을 여과하고, 필터 케이크를 물로 세척하고 700 ㎖의 공업용 등급 0.5 몰/L Na2CO3 수용액에 넣고 교반기로 균일하게 현탁시킨 후, 실온에서 10시간 동안 교반하였다. 이어서 현탁액을 여과하고, 필터 케이크를 물로 세척하고 95 ℃에서 18 시간 동안 건조시켰다.The suspension was filtered, the filter cake was washed with water and placed in 700 ml of industrial grade 0.5 mol / L Na 2 CO 3 aqueous solution and uniformly suspended with a stirrer, followed by stirring at room temperature for 10 hours. The suspension was then filtered, the filter cake was washed with water and dried at 95 ° C. for 18 hours.
건조 생성물을 100-메시 체로 체질했다.The dry product was sieved with 100-mesh sieve.
생성물은 분말 X-선 회절 측정 및 화학적 분석에 의해 히드로탈사이트 화합물로 밝혀졌다. The product was found to be a hydrotalcite compound by powder X-ray diffraction measurement and chemical analysis.
생성물의 우라늄 함량은 8 ppb[ng/g (건조 분말)]이고, 평균 이차 입자 크기는 1.5 ㎛이며, BET 비표면적은 10.9 ㎡/g 이다.The uranium content of the product is 8 ppb [ng / g (dry powder)], the average secondary particle size is 1.5 μm and the BET specific surface area is 10.9 m 2 / g.
생성물의 화학적 분석 결과로부터 결정된 화학식은 다음과 같았다:The chemical formula determined from the chemical analysis of the product was as follows:
Mg0.75Al0.25(OH)2(CO3)0.113(SO4)0.012
실시예 9Example 9
실시예 5에서 수득된 수성 탄산 암모늄 처리 후의 히드로탈사이트 화합물의 건조 분말을 실험실용 기어 오븐 내에서 270 ℃에서 8 시간 동안 건조 처리하여, 탈수형 히드로탈사이트 화합물로 전환시켰는데, 이것의 우라늄(U) 함량은 6 ppb[ng/g]이고, 평균 이차 입자 크기는 0.6 ㎛ 이며, BET 비표면적은 15 ㎡/g 이었다. 250 ℃에서 1 시간 동안의 가열로 인한 중량 증가는 0.5 %였다.The dried powder of the hydrotalcite compound after aqueous ammonium carbonate treatment obtained in Example 5 was dried for 8 hours at 270 ° C. in a laboratory gear oven to convert to a dehydrated hydrotalcite compound. U) content was 6 ppb [ng / g], average secondary particle size was 0.6 μm, and BET specific surface area was 15 m 2 / g. The weight gain due to heating at 250 ° C. for 1 hour was 0.5%.
실시예 10Example 10
실시예 6에서과 같이 공침 반응, 수열 반응, 탄산 암모늄 수용액으로의 처리, 여과 및 물로의 세척 단계를 거쳐 수득된 케이크를 이온제거수에 현탁시켰다. 현탁액을 80 ℃로 가열하고, 여기에 상기 양의 5 중량 %의 스테아르산나트륨 용액을 교반 하에 주입한 후, 30 분 동안 교반하였다. 이어서 현탁액을 여과하고, 여과케이크를 물로 세척하고 95 ℃에서 18 시간 동안 건조시켰다. 건조 생성물을 분쇄하여 표면 처리된 건조 분말을 제공하였는데, 이것을 추가적으로 열풍 건조기 내에서 230 ℃에서 20 시간 동안 건조시켰다. 수득된 탈수형 히드로탈사이트 화합물의 우라늄(U) 함량은 8 ppb[ng/g]이고, 평균 이차 입자 크기는 0.65 ㎛ 이며, BET 비표면적은 14 ㎡/g 이었다. 250 ℃ 에서 1 시간 동안의 가열로 인한 중량 감소는 0.8 %였다.The cake obtained through the coprecipitation reaction, hydrothermal reaction, treatment with aqueous ammonium carbonate solution, filtration and washing with water as in Example 6 was suspended in deionized water. The suspension is heated to 80 ° C., to which 5% by weight of a sodium stearate solution is injected under stirring, followed by stirring for 30 minutes. The suspension was then filtered, the filter cake was washed with water and dried at 95 ° C. for 18 hours. The dry product was ground to give a surface treated dry powder which was further dried at 230 ° C. for 20 hours in a hot air dryer. The uranium (U) content of the obtained dehydrated hydrotalcite compound was 8 ppb [ng / g], the average secondary particle size was 0.65 m, and the BET specific surface area was 14 m 2 / g. The weight loss due to heating at 250 ° C. for 1 hour was 0.8%.
실시예 9 및 실시예 10 에서 수득된 탈수형 히드로탈사이트 화합물의, XRD 측정에 의해 결정된 (003) 평면 위의 회절 사이트[2θ값] 및 간격[d(003) 값] 이 하기에 나타나 있다.The diffraction sites [2θ value] and spacing [d (003) value] on the (003) plane, determined by XRD measurement, of the dehydrated hydrotalcite compound obtained in Examples 9 and 10 are shown below.
2θ [도]
d(003) [Å]
13.60
6.65
11.60
7.62
2θ[도]
d(003) [Å]
13.10
6.75
11.60
7.62
(CuKα 선에 의한 XRD 측정)
2θ [degrees]
d (003) [iii]
13.60
6.65
11.60
7.62
2θ [degrees]
d (003) [iii]
13.10
6.75
11.60
7.62
(XRD measurement by CuKα line)
앞에서 설명한 바와 같이, 본 발명에 따르면 높은 순도(10 ppb 이하의 우라늄 함량)의 히드로탈사이트 화합물이 용이하게 및 공업적으로 제조될 수 있다. 따라서, 높은 집적화 수준의 반도체 메모리 디바이스 밀봉 수지에의 첨가제로서 적합한 히드로탈사이트 화합물이 제공될 수 있다. As described above, according to the present invention, high purity (uranium content of 10 ppb or less) hydrotalcite compounds can be easily and industrially produced. Thus, a hydrotalcite compound suitable as an additive to a high integration level semiconductor memory device sealing resin can be provided.
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| JPH01245039A (en) * | 1988-03-28 | 1989-09-29 | Ube Kagaku Kogyo Kk | Flame retardant and flame retardant resin composition using said flame retardant |
| JPH04202555A (en) * | 1990-11-30 | 1992-07-23 | Toray Ind Inc | Epoxy resin composition for sealing semiconductor |
| JPH08337638A (en) * | 1996-07-22 | 1996-12-24 | Nitto Denko Corp | Semiconductor device |
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| US4683253A (en) * | 1985-02-12 | 1987-07-28 | Risho Kogyo Co., Ltd. | Resin molding compound for sealing electronic parts |
| JPH01245039A (en) * | 1988-03-28 | 1989-09-29 | Ube Kagaku Kogyo Kk | Flame retardant and flame retardant resin composition using said flame retardant |
| JPH04202555A (en) * | 1990-11-30 | 1992-07-23 | Toray Ind Inc | Epoxy resin composition for sealing semiconductor |
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