JPH0735253B2 - Zirconia or zirconia-based spherical particles and method for producing metal-supported zirconia or zirconia-based spherical particles - Google Patents
Zirconia or zirconia-based spherical particles and method for producing metal-supported zirconia or zirconia-based spherical particlesInfo
- Publication number
- JPH0735253B2 JPH0735253B2 JP2028538A JP2853890A JPH0735253B2 JP H0735253 B2 JPH0735253 B2 JP H0735253B2 JP 2028538 A JP2028538 A JP 2028538A JP 2853890 A JP2853890 A JP 2853890A JP H0735253 B2 JPH0735253 B2 JP H0735253B2
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- spherical
- sol
- spherical particles
- metal
- 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
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 178
- 239000012798 spherical particle Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims description 47
- 239000000839 emulsion Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 24
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 19
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- -1 compound compound Chemical class 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920001515 polyalkylene glycol Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000007863 gel particle Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000004279 alanine Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 229940024606 amino acid Drugs 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical class CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HXUIDZOMTRMIOE-UHFFFAOYSA-N 3-oxo-3-phenylpropionic acid Chemical compound OC(=O)CC(=O)C1=CC=CC=C1 HXUIDZOMTRMIOE-UHFFFAOYSA-N 0.000 description 1
- FHSUFDYFOHSYHI-UHFFFAOYSA-N 3-oxopentanoic acid Chemical compound CCC(=O)CC(O)=O FHSUFDYFOHSYHI-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/066—Treatment or coating resulting in a free metal containing surface-region
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 [産業上の利用分野] 本発明はジルコニア球状粒子およびその製造方法に関す
る。詳しくは、本発明はサブミクロン(約1μm以下)
から数十ミクロンに至るまで粒径制御が可能で、かつそ
の粒径分布が狭い単分散ジルコニア球状粒子およびその
製造方法に関する。さらに詳しくは該球状粒子はその形
状特性から高充填性、滑り性を持ち、セラミックス成形
体の原料として最適であるばかりでなく、コーティング
剤、研磨剤等として有用である。TECHNICAL FIELD The present invention relates to zirconia spherical particles and a method for producing the same. Specifically, the present invention is submicron (about 1 μm or less)
TECHNICAL FIELD The present invention relates to monodisperse zirconia spherical particles having a narrow particle size distribution and capable of controlling the particle size from 10 to several tens of microns, and a method for producing the same. More specifically, the spherical particles have a high filling property and a slip property due to their shape characteristics, and are not only optimal as a raw material for a ceramic molded body but also useful as a coating agent, an abrasive or the like.
また、本発明ではジルコニウム以外の金属成分を含有し
たジルコニア系球状粒子の製造も可能であり、さらに
は、球状粒子のもつ高分散性のゆえに、粒子表面を他の
金属で被覆することによって粒子としての機能を高める
ことが容易であり、このように組成が複合化されたジル
コニア球状粒子や金属被覆あるいは担持ジルコニア球状
粒子は触媒、ペーストのフィラー、導電性材料、分散メ
ッキ用フィラー、装飾材料等の幅広い分野での利用が可
能である。Further, in the present invention, it is possible to produce zirconia-based spherical particles containing a metal component other than zirconium, and further, because of the high dispersibility of the spherical particles, as a particle by coating the particle surface with another metal. It is easy to enhance the function of zirconia spherical particles or metal-coated or supported zirconia spherical particles having a composite composition as described above, such as catalyst, paste filler, conductive material, dispersion plating filler, and decorative material. It can be used in a wide range of fields.
[従来の技術] ジルコニア球状粒子あるいは無機球状微粒子の製造方法
が本発明者らによって、特願昭62−40085号、特願昭62
−170868号、特願昭63−40839号に開示されている。こ
れらの製造方法では無機金属塩の水溶液からジルコニア
等の金属酸化物ゾルを調製し、該ゾルと有機溶媒及び界
面活性剤とを混合してw/o型エマルジョンを形成させ、
このゾルエマルジョンをゲルエマルジョンとなし、該ゲ
ルエマルジョンを乾燥後焼成することによってジルコニ
ア等の無機球状微粒子を調製するものである。[Prior Art] A method for producing spherical particles of zirconia or inorganic spherical particles has been disclosed by the present inventors in Japanese Patent Application Nos. 62-40085 and 62-62.
-170868 and Japanese Patent Application No. 63-40839. In these production methods, a metal oxide sol such as zirconia is prepared from an aqueous solution of an inorganic metal salt, and the sol is mixed with an organic solvent and a surfactant to form a w / o type emulsion,
This sol emulsion is formed into a gel emulsion, and the gel emulsion is dried and then baked to prepare inorganic spherical fine particles such as zirconia.
[発明が解決しようとする課題] 上記の製造方法ではゾルの出発原料として無機金属の塩
化物や硝酸塩を使用しているため、得られたゾル中に塩
素イオンや硝酸イオンが存在する。そのために、装置の
腐食や後の工程において有機溶媒及び界面活性剤との反
応による低温発火性物質を生成しやすくなり取扱が煩雑
になるなどの問題がある。従って、ゾルを限外濾過等に
よって充分洗浄し、ゾル中の塩素イオンや硝酸イオンを
除去する必要があり、この高純度化のためにジルコニア
等の無機球状微粒子を工業的に製造する場合は生産性に
劣る問題を有していた。[Problems to be Solved by the Invention] In the above production method, since chlorides and nitrates of inorganic metals are used as starting materials for the sol, chlorine ions and nitrate ions are present in the obtained sol. Therefore, there is a problem that corrosion of the apparatus or a low temperature ignitable substance due to a reaction with an organic solvent and a surfactant is likely to be generated in a subsequent step, and handling becomes complicated. Therefore, it is necessary to sufficiently wash the sol by ultrafiltration or the like to remove chlorine ions and nitrate ions in the sol. In the case of industrially producing inorganic spherical fine particles such as zirconia for high purification, production It had a problem of poor sex.
[課題を解決するための手段] 本発明者らは上記の課題を解決するため鋭意検討した結
果、特許請求の範囲において特定された製造方法によっ
て製造されるジルコニウム水和物含有ゾル(以下「ジル
コニアゾル」と記す)を使用することにより、高生産性
でジルコニア球状粒子が得られ、しかも得られたジルコ
ニア球状粒子が優れた特性を有していることが判明し本
発明に至ったものである。[Means for Solving the Problems] As a result of intensive studies for solving the above problems, the present inventors have found that zirconium hydrate-containing sol (hereinafter, “zirconia”) manufactured by the manufacturing method specified in the claims. It is found that zirconia spherical particles can be obtained with high productivity, and that the obtained zirconia spherical particles have excellent characteristics by using (sol)). .
従って、本発明の目的は実質的に球形を有し単分散性に
優れたジルコニア球状粒子、およびジルコニウム以外の
金属成分を含有したジルコニア系球状粒子、並びにそれ
らの工業的生産性に優れ経済的に有利な製造方法を提供
するものである。なお、以下においては特に断わらない
限りジルコニア系球状粒子をジルコニア球状粒子と総称
する。Therefore, the object of the present invention is to have substantially spherical zirconia spherical particles having excellent monodispersibility, and zirconia-based spherical particles containing a metal component other than zirconium, and their excellent industrial productivity economically. The present invention provides an advantageous manufacturing method. In the following, zirconia-based spherical particles are collectively referred to as zirconia spherical particles unless otherwise specified.
また、本発明の他の目的は高機能化されたジルコニア球
状粒子およびその製造方法を提供するものである。Another object of the present invention is to provide highly functionalized zirconia spherical particles and a method for producing the same.
以下本発明を詳細に説明する。The present invention will be described in detail below.
本発明は、炭酸ジルコニルアンモニウムとキレート剤と
の反応生成物を60℃以上で加熱・加水分解して調製され
る、酸化ジルコニウムとしての含有率が5〜40重量%で
あり、pHが5〜10の範囲であるジルコニウム水和物含有
ゾルを、界面活性剤0.05〜30重量%および水不溶性ない
し水難溶性の有機溶媒5〜80重量%と撹拌混合して、W/
O型エマルジョンを形成させ、次いで該エマルジョンを
加熱してエマルジョンの水相を形成する球状ゾル中の水
分を該有機溶媒との混合物として系外に除去することに
より、球状ゾルを球状ゲル化し、さらに、該球状ゲルを
300℃以上で焼成することにより界面活性剤等の有機物
を除去することよりなる平均粒子径が0.05〜50μmの範
囲でその標準偏差値が1〜1.5の範囲、比表面積が5〜2
00m2/gであるジルコニア球状粒子の製造方法である。The present invention is prepared by heating and hydrolyzing a reaction product of zirconyl ammonium carbonate and a chelating agent at 60 ° C. or higher, the content of zirconium oxide is 5 to 40% by weight, and the pH is 5 to 10%. Zirconium hydrate-containing sol in the range of 0.05 to 30% by weight of a surfactant and 5 to 80% by weight of a water-insoluble or sparingly water-soluble organic solvent by stirring and mixing,
Forming an O-type emulsion, and then heating the emulsion to remove water in the spherical sol forming the aqueous phase of the emulsion as a mixture with the organic solvent to the outside of the system to form a spherical gel in the spherical sol, , The spherical gel
By removing organic substances such as surfactants by baking at 300 ° C or higher, the average particle size is in the range of 0.05 to 50 μm, the standard deviation is in the range of 1 to 1.5, and the specific surface area is 5 to 2
A method for producing spherical particles of zirconia having a particle size of 00 m 2 / g.
また、本発明は、上記方法において、ジルコニウム水和
物含有ゾルにマグネシウム、カルシウム、アルミニウ
ム、ケイ素、チタニウム、スズ、イットリウム、ランタ
ンおよびセリウムの各々を含む化合物の少なくとも1種
またはこれら金属元素の2種以上を含む複合化合物の少
なくとも1種を添加することを特徴とする平均粒子径が
0.05〜50μmの範囲でその標準偏差値が1〜1.5の範
囲、比表面積が5〜200m2/gであるジルコニア系球状粒
子の製造方法である。The present invention also provides, in the above method, at least one compound selected from the group consisting of magnesium, calcium, aluminum, silicon, titanium, tin, yttrium, lanthanum, and cerium in the zirconium hydrate-containing sol, or two of these metal elements. The average particle diameter characterized by adding at least one kind of the composite compound containing the above
It is a method for producing zirconia-based spherical particles having a standard deviation value of 1 to 1.5 and a specific surface area of 5 to 200 m 2 / g in the range of 0.05 to 50 μm.
さらに、本発明は、上記方法で得られる平均粒子径が0.
05〜50μmの範囲でその標準偏差値が1〜1.5の範囲、
比表面積が5〜200m2/gであるジルコニア球状粒子また
はジルコニア系球状粒子にルテニウム、ロジウム、パラ
ジウム、銀、インジウム、白金および金からなる群から
選ばれた少なくとも1種の金属および/またはバナジウ
ム、クロム、マンガン、鉄、コバルト、ニッケル、銅、
モリブデン、タングステンおよびビスマスからなる群か
ら選ばれた少なくとも1種の金属またはそれらの金属酸
化物を担持することを特徴とする金属担持ジルコニア球
状粒子またはジルコニア系球状粒子の製造方法である。Further, the present invention, the average particle size obtained by the above method is 0.
In the range of 05 to 50 μm, the standard deviation value is in the range of 1 to 1.5,
Zirconia spherical particles or zirconia-based spherical particles having a specific surface area of 5 to 200 m 2 / g, at least one metal selected from the group consisting of ruthenium, rhodium, palladium, silver, indium, platinum and gold, and / or vanadium, Chromium, manganese, iron, cobalt, nickel, copper,
A method for producing metal-supported zirconia spherical particles or zirconia-based spherical particles, which comprises supporting at least one metal selected from the group consisting of molybdenum, tungsten and bismuth, or a metal oxide thereof.
特に、本発明の特徴はジルコニアゾルの調製法として、
炭酸ジルコニルアンモニウムとキレート化剤との反応生
成物を加水分解してpHが5〜10の範囲である高濃度なジ
ルコニアゾルを得、さらにこのジルコニアゾルをジルコ
ニア球状粒子原料に使用することにある。In particular, the feature of the present invention is as a method for preparing a zirconia sol,
The reaction product of zirconyl ammonium carbonate and a chelating agent is hydrolyzed to obtain a high-concentration zirconia sol having a pH in the range of 5 to 10, and this zirconia sol is used as a raw material for zirconia spherical particles.
以下該ゾルの製法等に次いてついて示す。The method for producing the sol and the like will be described below.
即ち、撹拌槽型反応器に炭酸ジルコニルアンモニウム水
溶液を入れ、撹拌下、キレート化剤を添加して炭酸ジル
コニルアンモニウムとキレート化剤とを室温での反応せ
しめ生成物を得る。次いで、該生成物を含む水溶液をさ
らに60℃以上に加熱して炭酸ジルコニルアンモニウムと
キレート化剤との反応生成物を加水分解せしめる。この
場合、二酸化炭素とアンモニアを主体とするガスが発生
するが、該生成物を含む水溶液は増粘することもなく透
明性を保持したまま加水分解が完了する。反応後の液の
pHは弱アルカリ性から中性および弱酸性であり、この反
応液が本発明に係わるのジルコニアゾルとして好適に使
用される。That is, a zirconyl ammonium carbonate aqueous solution is put into a stirred tank reactor, and a chelating agent is added under stirring to obtain a reaction product of the zirconyl ammonium carbonate and the chelating agent at room temperature. Then, the aqueous solution containing the product is further heated to 60 ° C. or higher to hydrolyze the reaction product of zirconyl ammonium carbonate and the chelating agent. In this case, a gas mainly containing carbon dioxide and ammonia is generated, but the aqueous solution containing the product does not thicken and hydrolysis is completed while maintaining transparency. Of the liquid after the reaction
The pH is weakly alkaline to neutral and weakly acidic, and this reaction solution is preferably used as the zirconia sol of the present invention.
上記ゾル調製法を採用することにより、加水分解反応中
にゾルとしては不純物となるアンモニウムイオンや炭酸
イオンがアンモニアや二酸化炭素として系外に排出され
るため、炭酸ジルコニルアンモニウムとキレート化剤と
の反応生成物の加水分解反応後の反応液を特に洗浄する
必要がなく、そのまま本発明のジルコニアゾルとして使
用される。さらに、通常の加熱濃縮によって高濃度化も
可能であり、工業的生産性に優れ経済的に有利なジルコ
ニア球状粒子の製造方法に関わる。By adopting the above sol preparation method, ammonium ions and carbonate ions, which are impurities as a sol during the hydrolysis reaction, are discharged out of the system as ammonia and carbon dioxide, and thus the reaction between zirconyl ammonium carbonate and the chelating agent It is not necessary to wash the reaction liquid after the hydrolysis reaction of the product, and it can be used as it is as the zirconia sol of the present invention. Further, it is possible to increase the concentration by ordinary heating concentration, and it relates to a method for producing spherical particles of zirconia which is excellent in industrial productivity and economically advantageous.
また、当然ながら該反応液中に残存する微量の未反応
物、アンモニウムイオンや炭酸イオン等を限外濾過膜に
よる洗浄によって高純度のジルコニアゾルとして本発明
のジルコニア球状粒子の製造に使用することも可能であ
る。Further, of course, a trace amount of unreacted material remaining in the reaction solution, ammonium ion, carbonate ion, etc. can be used for the production of the zirconia spherical particles of the present invention as a high-purity zirconia sol by washing with an ultrafiltration membrane. It is possible.
本発明に使用されるジルコニアゾルの調製時に使用され
るキレート化剤としてはカテコール、ピロガロール等の
オキシフェノール類、ジエタノールアミン、トリエタノ
ールアミン等のアミノアルコール類、グリコール酸、ク
エン酸、酒石酸、乳酸、マンデル酸、リンゴ酸、ヒドロ
キシアクリル酸等のオキシ酸類およびそれらのメチル、
エチル、ヒドロキシエチル等のエステル類、グリコール
アルデヒド等のオキシアルデヒド類、シュウ酸、マロン
酸等のポリカルボン酸類、グリシン、アラニン等のアミ
ノ酸類、アセチルアセトン、ベンゾイルアセトン、ステ
アロイルアセトン、ステアロイルベンゾイルメタン、ジ
ベンゾイルメタン等のβ−ジケトン類ならびにアセト酢
酸、プロピオニル酢酸、ベンゾイル酢酸等のβ−ケトン
酸類およびそれらのメチル、エチル、n−プロピル、イ
ソプロピル、n−ブチル、t−ブチル等のエステル類の
1種または2種以上を組み合わせて使用することができ
る。これらの中でグリコール酸、クエン酸、酒石酸、乳
酸、マンデル酸、リンゴ酸、ヒドロキシアクリル酸等の
オキシ酸類またはアセチルアセトン等のβ−ジケトン類
が好ましく使用される。さらに好ましくはα−、β−お
よびγ−オキシ酸類でそれぞれのα、β、γの炭素上の
酸素原子を有する官能基をもつα−、β−およびγ−ケ
トン酸類あるいはそれらのエステル類である。As the chelating agent used in the preparation of the zirconia sol used in the present invention, catechol, oxyphenols such as pyrogallol, amino alcohols such as diethanolamine and triethanolamine, glycolic acid, citric acid, tartaric acid, lactic acid, and mandel Oxy acids such as acid, malic acid, hydroxyacrylic acid and their methyl,
Esters such as ethyl and hydroxyethyl, oxyaldehydes such as glycolaldehyde, polycarboxylic acids such as oxalic acid and malonic acid, amino acids such as glycine and alanine, acetylacetone, benzoylacetone, stearoylacetone, stearoylbenzoylmethane, dibenzoyl One of β-diketones such as methane and β-ketone acids such as acetoacetic acid, propionylacetic acid, benzoylacetic acid and their esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl, or Two or more kinds can be used in combination. Of these, oxyacids such as glycolic acid, citric acid, tartaric acid, lactic acid, mandelic acid, malic acid and hydroxyacrylic acid or β-diketones such as acetylacetone are preferably used. More preferably, α-, β- and γ-oxy acids are α-, β- and γ-ketonic acids or their esters each having a functional group having an oxygen atom on the α, β and γ carbon atoms. .
また、キレート化剤の使用量は用いるキレート化剤の種
類により異なるが炭酸ジルコニルアンモニウム中のジル
コニウムに対し0.02〜4当量(モル比)、好ましくは0.
1〜3当量(モル比)、より好ましく0.5〜2当量(モル
比)の範囲になるように選択される。キレート化剤の使
用量が0.02当量を下回る場合は、炭酸ジルコニルアンモ
ニウムとキレート化剤との反応成生物の加水分解反応が
不十分でジルコニアゾルが充分生成せず、4当量(モル
比)を上回る場合は特別の効果は認められない。The amount of chelating agent used varies depending on the type of chelating agent used, but is 0.02 to 4 equivalents (molar ratio) to zirconium in zirconyl ammonium carbonate, preferably 0.
It is selected to be in the range of 1 to 3 equivalents (molar ratio), more preferably 0.5 to 2 equivalents (molar ratio). When the amount of the chelating agent used is less than 0.02 equivalent, the hydrolysis reaction of the reaction product between zirconyl ammonium carbonate and the chelating agent is insufficient and the zirconia sol is not sufficiently formed, so that it exceeds 4 equivalents (molar ratio). If no special effect is observed.
さらに、上記方法における加水分解反応は40℃以上に加
熱すればよく、反応を促進するために加圧雰囲気下で反
応せしめることも好ましい。実際的な反応温度は60〜20
0℃である。Furthermore, the hydrolysis reaction in the above method may be carried out by heating at 40 ° C. or higher, and it is also preferable to react in a pressurized atmosphere in order to accelerate the reaction. Practical reaction temperature is 60 ~ 20
It is 0 ° C.
上記の方法により酸化ジルコニウムとしての含有率が5
〜40重量%であり、pHが5〜10であるジルコニアゾルを
得ることができるが、ゾル濃度は球状粒子径に影響し、
ジルコニア球状粒子の製造には5〜30重量%の濃度のジ
ルコニアゾルを用いることが好ましい。According to the above method, the content of zirconium oxide is 5
It is possible to obtain a zirconia sol having a pH of ˜40% by weight and a pH of 5 to 10, but the sol concentration affects the spherical particle size,
For the production of spherical zirconia particles, it is preferable to use a zirconia sol having a concentration of 5 to 30% by weight.
ジルコニウム以外の金属成分を含有したジルコニア系球
状粒子も上記と同様に製造できるが、この場合、ジルコ
ニウム以外の金属成分はその添加物の形態としてはゾル
である必要はなく、酢酸塩、炭酸塩、水酸化物等の水溶
液やスラリーの形態でもよい。含有する金属成分として
はマグネシウム、カルシウム、アルミニウム、珪素、チ
タニウム、スズおよびイットリウム、ランタンやセリウ
ム等の稀土類元素が好適である。Zirconia-based spherical particles containing a metal component other than zirconium can also be produced in the same manner as above, but in this case, the metal component other than zirconium need not be a sol as the form of the additive, but an acetate salt, a carbonate salt, It may be in the form of an aqueous solution such as a hydroxide or a slurry. As the metal component contained, magnesium, calcium, aluminum, silicon, titanium, tin and yttrium, and rare earth elements such as lanthanum and cerium are suitable.
以下、ジルコニア球状粒子の製造方法について述べる。Hereinafter, a method for producing the zirconia spherical particles will be described.
上記の製造方法にしたがって得られたゾル濃度が5〜40
重量%のジルコニアゾルに水不溶性ないし水難溶性の有
機溶媒、界面活性剤を添加したのち、通常の撹拌羽根や
ホモジナイザー、コロイドミル、超音波分散機等を使用
して撹拌混合して乳化せしめw/o型エマルジョンを形成
させる。The sol concentration obtained according to the above manufacturing method is 5-40
After adding a water-insoluble or sparingly water-soluble organic solvent and a surfactant to the zirconia sol by weight%, emulsify by stirring and mixing using a normal stirring blade, a homogenizer, a colloid mill, an ultrasonic disperser, etc. Form an o-type emulsion.
この場合、用いる有機溶媒としてはベンゼン、トルエ
ン、キシレン等の芳香族炭化水素類、クロルベンゼン、
ジクロルベンゼン、四塩化炭素、ジクロルメタン、トリ
クロルエチレン等のハロゲン化炭化水素類、ヘプタン、
オクタン、デカン、ドデカン等の脂肪族炭化水素類、シ
クロヘキサン、シクロドデカン等の脂環式炭化水素類、
ヘキサノール類、ヘプタノール類、オクタノール類等の
高級脂肪族アルコール類、シクロペンタノール、シクロ
ヘキサノール等の脂環式アルコール類等が好適に使用さ
れる。なお、w/o型エマルジョンの形成に不都合が生じ
ない程度の量の水溶性有機溶媒も混合することができ
る。In this case, the organic solvent used is benzene, toluene, aromatic hydrocarbons such as xylene, chlorobenzene,
Halogenated hydrocarbons such as dichlorobenzene, carbon tetrachloride, dichloromethane, trichloroethylene, heptane,
Aliphatic hydrocarbons such as octane, decane and dodecane, alicyclic hydrocarbons such as cyclohexane and cyclododecane,
Higher aliphatic alcohols such as hexanols, heptanols and octanols, and alicyclic alcohols such as cyclopentanol and cyclohexanol are preferably used. In addition, an amount of the water-soluble organic solvent that does not cause any inconvenience in the formation of the w / o type emulsion can be mixed.
また、使用される界面活性剤としてはw/o型の乳化を起
こせしめるものであれば公知のものを使用できるが、界
面活性剤に含まれる金属イオン等の混入を避けるためノ
ニオン型界面活性剤を用いることが好ましい。ノニオン
型界面活性剤としては例えば、ポリオキシエチレンアル
キルエーテル型、ポリオキシエチレンアルキルアリール
エーテル型、ポリオキシエチレンアルキルアミン型、ポ
リオキシエチレンアルキルアミド型、ポリオキシエチレ
ンソルビタン脂肪酸エステル型、プルロニック型、テト
ロニック型等のポリアルキレングリコール型あるいは多
価アルコール型がある。また、この時、乳化安定剤とし
てグリシン、アラニン、フエニルアラニン、バリン、ロ
イシン、イソロイシン、リシン、セリン、アスパラギン
酸、グルタミン酸、メチオニン、アルギニン等のアミノ
酸類またはそれらの塩類、ソルビトール、グリセリンの
ような多価アルコール類を用いることにより安定なエマ
ルジョンを得ることができる。その使用量は用いるゾル
に対して0.05〜30重量%、好ましくは0.1〜5重量%で
ある。Further, as the surfactant used, known ones can be used as long as they can cause w / o emulsification, but in order to avoid mixing of metal ions contained in the surfactant, nonionic surfactants Is preferably used. Examples of nonionic surfactants include polyoxyethylene alkyl ether type, polyoxyethylene alkylaryl ether type, polyoxyethylene alkylamine type, polyoxyethylene alkylamide type, polyoxyethylene sorbitan fatty acid ester type, pluronic type, and TE type. There are polyalkylene glycol type such as tronic type and polyhydric alcohol type. Further, at this time, as an emulsion stabilizer, amino acids such as glycine, alanine, phenylalanine, valine, leucine, isoleucine, lysine, serine, aspartic acid, glutamic acid, methionine, arginine or salts thereof, sorbitol, glycerin and the like. A stable emulsion can be obtained by using polyhydric alcohols. The amount used is 0.05 to 30% by weight, preferably 0.1 to 5% by weight, based on the sol used.
使用される原料ゾル濃度、有機溶媒の種類及び水層との
量比、界面活性剤の種類及び濃度、さらにw/o型エマル
ジョン調製時の機械的乳化の方法、乳化時の温度等々に
よりエマルジョンの粒子径及び安定性が異なってくるの
は通常の乳化方法の場合と同様である。そして、エマル
ジョンの粒子径と得られる球状粒子の粒径との間には直
接的な相関性があり、このエマルジョンの粒子径と原料
ゾル濃度により球状粒子の粒径が決定される。Depending on the raw material sol concentration used, the type of organic solvent and the amount ratio with the aqueous layer, the type and concentration of the surfactant, the method of mechanical emulsification when preparing the w / o type emulsion, the temperature during emulsification, etc. The difference in particle size and stability is the same as in the case of a usual emulsification method. There is a direct correlation between the particle size of the emulsion and the particle size of the obtained spherical particles, and the particle size of the spherical particles is determined by the particle size of this emulsion and the concentration of the raw material sol.
したがって、粒子径の分布の狭いw/o型エマルジョンを
調製することが、粒径分布が狭い単分散ジルコニア球状
粒子を製造することになる。このためには水不溶性ない
し水難溶性の有機溶媒を5〜80重量%、好ましくは10〜
60重量%、より好ましくは30〜50重量%の範囲、ゾル濃
度(ゾル中の酸化ジルコニウムとしての含有率)が5〜
40重量%であるジルコニアゾルを20〜95重量%、好まし
くは40〜90重量%、より好ましくは50〜70重量%の範
囲、界面活性剤を0.1〜30重量%、好ましくは1〜10重
量%、より好ましくは1〜5重量%の範囲で撹拌混合
し、10〜90℃、好ましくは40〜80℃の範囲で乳化せしめ
ることにより、粒子径分布の狭いw/o型エマルジョンが
製造される。Therefore, preparing a w / o type emulsion having a narrow particle size distribution produces monodispersed zirconia spherical particles having a narrow particle size distribution. For this purpose, a water-insoluble or poorly water-soluble organic solvent is contained in an amount of 5 to 80% by weight, preferably 10 to
60 wt%, more preferably in the range of 30 to 50 wt%, the sol concentration (content as zirconium oxide in the sol) is 5 to
20% to 95% by weight of zirconia sol, which is 40% by weight, preferably 40 to 90% by weight, more preferably 50 to 70% by weight, and 0.1 to 30% by weight, preferably 1 to 10% by weight of a surfactant. More preferably, the mixture is stirred and mixed in the range of 1 to 5% by weight and emulsified in the range of 10 to 90 ° C, preferably 40 to 80 ° C to produce a w / o type emulsion having a narrow particle size distribution.
次いで、該w/o型エマルジョンを加熱して該エマルジョ
ンの水層を形成する球状ゾル中の水分を該有機溶媒との
混合物として系外に除去し、同時に該球状ゾルを球状ゲ
ルとする。エマルジョンの加熱は常圧下10〜120℃の範
囲でもよいが、球状ゾル中の水分をすみやかに脱水し、
同時に該球状ゾルをゲル化するために減圧下での加熱が
好ましく、この時の温度は0〜100℃、好ましくは10〜7
0℃の範囲である。Then, the w / o type emulsion is heated to remove the water in the spherical sol forming the aqueous layer of the emulsion as a mixture with the organic solvent out of the system, and at the same time, the spherical sol is made into a spherical gel. The heating of the emulsion may be in the range of 10 to 120 ° C. under normal pressure, but the water in the spherical sol is immediately dehydrated,
At the same time, heating under reduced pressure is preferable for gelling the spherical sol, and the temperature at this time is 0 to 100 ° C., preferably 10 to 7
It is in the range of 0 ° C.
かくして得られた球状ゲル粒子は界面活性剤等の有機物
を含んでおり、これを焼成することにより、ゲルの脱
水、結晶化および界面活性剤等の有機物を燃焼せしめ
る。この場合球状を保持したままゲルの脱水、結晶化が
おこっており、0.05〜50μmの範囲でかつその粒径分布
が狭い、特にその標準偏差が1〜1.5の単分散ジルコニ
ア球状粒子が製造される。The spherical gel particles thus obtained contain an organic substance such as a surfactant, and by firing this, dehydration and crystallization of the gel and burning of the organic substance such as a surfactant are carried out. In this case, the gel is dehydrated and crystallized while maintaining the spherical shape, and monodispersed zirconia spherical particles having a narrow particle size distribution in the range of 0.05 to 50 μm, especially the standard deviation of 1 to 1.5 are produced. .
焼成は界面活性剤が分解する300℃以上で行えばよい
が、600℃以上で焼成することにより高強度なジルコニ
ア球状粒子を得ることができる。界面活性剤が焼成分解
する時に悪臭を伴うガスが発生するので、連続焼成式の
ゾーン加熱が可能な炉壁の回転する管状焼成炉ロータリ
ーキルンで行うことが好ましい。The firing may be performed at 300 ° C. or higher at which the surfactant decomposes, but by firing at 600 ° C. or higher, high-strength zirconia spherical particles can be obtained. Since a gas accompanied by a foul odor is generated when the surfactant is decomposed by firing, it is preferable to perform the heating in a tubular kiln rotary kiln with a rotating furnace wall capable of continuous firing type zone heating.
かくして得られたジルコニア球状粒子および、マグネシ
ウム、カルシウム、アルミニウム、珪素、チタニウム、
スズおよびイットリウム、ランタンやセリウム等の稀土
類元素等のジルコニウム以外の金属成分を含有したジル
コニア系球状粒子は平均粒子径が0.05〜50μmの範囲、
その標準偏差が1〜1.5の範囲、比表面積が5〜200m2/g
なる特性を有している。また、それぞれの粒子の真密度
は添加元素の種類、焼成温度等により異なるが4g/cm3以
上である。Zirconia spherical particles thus obtained and magnesium, calcium, aluminum, silicon, titanium,
The zirconia-based spherical particles containing a metal component other than zirconium such as tin and yttrium, rare earth elements such as lanthanum and cerium, have an average particle size in the range of 0.05 to 50 μm.
Its standard deviation is in the range of 1-1.5, specific surface area is 5-200 m 2 / g
It has the following characteristics. Further, the true density of each particle is 4 g / cm 3 or more, although it varies depending on the type of additive element, firing temperature and the like.
なお、本発明でいう平均粒子径および標準偏差値は下記
の方法により求めた。The average particle diameter and standard deviation value referred to in the present invention were determined by the following methods.
10万倍の電子顕微鏡撮影像の任意の粒子100個の粒子径
を実測して求め、平均粒子径および標準偏差値を下記の
式により求めた。The particle diameter of 100 arbitrary particles in an electron micrograph image of 100,000 times was measured and determined, and the average particle diameter and standard deviation were calculated by the following formulas.
(但し、Xiはi個目の粒子径を示し、nは100であ
る。) このような分散性に優れ、高比表面積を有するジルコニ
ア球状微粒子およびジルコニア系球状粒子は、その粒子
表面や内部に金属あるいは金属酸化物あるいは両者を担
持し、粒子としての機能を高めることができる。担持さ
れる金属や金属酸化物はルテニウム、ロジウム、パラジ
ウム、銀、インジウム、白金および金からなる群から選
ばれた少なくとも1種の金属および/またはバナジウ
ム、クロム、マンガン、鉄、コバルト、ニッケル、銅、
モリブデン、タングステンおよびビスマスからなる群か
ら選ばれた少なくとも1種の金属またはそれらの金属酸
化物が選択され、その担持方法は用途により、上記金属
化合物の水溶液等の含浸、上記金属や金属化合物の蒸
着、スパッタリング、イオンプレーティングやプラズマ
溶射、上記金属のメッキ、特に無電解メッキ等の方法が
適宜選択される。 (However, Xi represents the i-th particle diameter and n is 100.) Such zirconia spherical fine particles and zirconia-based spherical particles having excellent dispersibility and a high specific surface area can be formed on the surface or inside of the particles. By supporting a metal or a metal oxide or both, the function as particles can be enhanced. The supported metal or metal oxide is at least one metal selected from the group consisting of ruthenium, rhodium, palladium, silver, indium, platinum and gold and / or vanadium, chromium, manganese, iron, cobalt, nickel, copper. ,
At least one metal selected from the group consisting of molybdenum, tungsten, and bismuth or a metal oxide thereof is selected, and the supporting method depends on the application, impregnation with an aqueous solution of the above metal compound, vapor deposition of the above metal or metal compound. A method such as sputtering, ion plating, plasma spraying, plating of the above-mentioned metals, particularly electroless plating is appropriately selected.
これらの金属あるいは金属酸化物あるいはそれらの混合
物を担持したジルコニア球状微粒子は触媒用、装飾用、
粒子分散強化複合材料用および導電ペースト用などの導
電性材料として好適に使用される。特に触媒用としては 1)メタン、エタン、プロパン、ブタン、灯油、有機溶
剤等の炭化水素や一酸化炭素の燃焼用触媒、 2)窒素酸化物(NOx)、硫黄酸化物(SOx)オゾン
(O3)などの燃焼あるいは分解用触媒、 3)フタル酸、マレイン酸、アクリル酸、メタクリル酸
等の有機酸合成プロセス用触媒、 4)炭化水素と水蒸気を400〜1500℃の温度で接触させ
て水素および一酸化炭素からなるガスを製造する水蒸気
改質用触媒、 等に好適に使用される。Zirconia spherical fine particles carrying these metals or metal oxides or mixtures thereof are for catalysts, for decoration,
It is preferably used as a conductive material for a particle dispersion-reinforced composite material, a conductive paste, and the like. Especially for catalysts, 1) catalysts for combustion of hydrocarbons and carbon monoxide such as methane, ethane, propane, butane, kerosene, and organic solvents, 2) nitrogen oxides (NOx), sulfur oxides (SOx) ozone (O) 3 ) Combustion or decomposition catalysts such as 3 ) Catalysts for organic acid synthesis processes such as phthalic acid, maleic acid, acrylic acid, methacrylic acid, etc. 4) Hydrocarbons are contacted with steam at a temperature of 400-1500 ° C to produce hydrogen. And a steam reforming catalyst for producing a gas composed of carbon monoxide, and the like.
[実施例] 以下、本発明を実施例、参考例、比較例により更に詳し
く説明するが、これら実施例等に限定されるものではな
い。[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples, and Comparative Examples, but is not limited to these Examples and the like.
参考例1 容量10リットルの撹拌槽型反応器に酸化ジルコニウムと
して13重量%含有する炭酸ジルコニルアンモニウム水溶
液を13Kg入れ、撹拌しながらグリコール酸1Kgを徐々に
添加した。この際に無臭性のガスが発生する。次いで、
マントルヒーターにより該反応器を加熱しながら加水分
解反応を行った。反応液の温度が50〜60℃になるとアン
モニア臭のガスが発生し始め、さらに昇温するにつれ激
しく発泡し二酸化炭素とアンモニアを主体とするガスが
発生する。これらガスを系外に排出しながら100℃まで
昇温したのち3時間保持し、該反応器中に適宜純水を添
加しながらさらに100℃で12時間保持し加水分解反応を
完了せしめた。反応液を室温まで下げた後純水を添加し
ながら濃度調整し、酸化ジルコニウムとして35重量%を
含有し、pHが7の透明なジルコニアゾルを得た。該ゾル
は長期間安定であった。Reference Example 1 13 kg of an aqueous zirconyl ammonium carbonate solution containing 13% by weight of zirconium oxide was placed in a stirred tank reactor having a capacity of 10 liters, and 1 kg of glycolic acid was gradually added with stirring. At this time, odorless gas is generated. Then
The hydrolysis reaction was performed while heating the reactor with a mantle heater. When the temperature of the reaction solution reaches 50 to 60 ° C., a gas with an ammonia odor begins to be generated, and as the temperature further rises, it foams violently, and a gas mainly containing carbon dioxide and ammonia is generated. After discharging these gases to the outside of the system, the temperature was raised to 100 ° C. and maintained for 3 hours. While adding pure water into the reactor, the temperature was further maintained at 100 ° C. for 12 hours to complete the hydrolysis reaction. After cooling the reaction solution to room temperature, the concentration was adjusted while adding pure water to obtain a transparent zirconia sol containing 35% by weight of zirconium oxide and having a pH of 7. The sol was stable for a long period of time.
参考例2 参考例1と同様方法によって調製された酸化ジルコニウ
ムとして30重量%を含有し、pHが7の透明なジルコニア
ゾルに酢酸イットリウムを該ゾル中の酸化ジルコニウム
に対して酸化イットリウムが5.3重量%になるように添
加し、さらに加熱濃縮して酸化ジルコニウムとして30重
量%、酸化イットリウムとして5.3重量%を含有するpH
が6の透明なジルコニア系ゾルを得た。該ゾルは長期間
安定であった。Reference Example 2 Yttrium acetate was added to a transparent zirconia sol containing 30% by weight of zirconium oxide prepared by the same method as in Reference Example 1 and having a pH of 7, and 5.3% by weight of yttrium oxide was used with respect to zirconium oxide in the sol. To 30% by weight as zirconium oxide and 5.3% by weight as yttrium oxide.
A transparent zirconia sol of No. 6 was obtained. The sol was stable for a long period of time.
参考例3 参考例1と同様方法によって調製された酸化ジルコニウ
ムとして30重量%を含有し、pHが7の透明なジルコニア
ゾルに酢酸イットリウムを該ゾル中の酸化ジルコニウム
に対して酸化イットリウムが14.2重量%になるように添
加し、さらに加熱濃縮した酸化ジルコニウムとして30重
量%、酸化イットリウムとして14.2重量%を含有するpH
が5.5の透明なジルコニア系ゾルを得た。該ゾルは長期
間安定であった。Reference Example 3 Yttrium acetate was contained in a transparent zirconia sol containing 30% by weight of zirconium oxide prepared by the same method as in Reference Example 1 and having a pH of 7.2% by weight of yttrium oxide based on zirconium oxide in the sol. PH that contains 30% by weight of zirconium oxide and 14.2% by weight of yttrium oxide, which have been added to
A transparent zirconia-based sol of 5.5 was obtained. The sol was stable for a long period of time.
参考例4 参考例1と同様方法によって調製された酸化ジルコニウ
ムとして30重量%を含有し、pHが7の透明なジルコニア
ゾルに酢酸セリウムを該ゾル中の酸化ジルコニウムに対
して酸化セリウムが5.3重量%になるように添加し、さ
らに加熱濃縮して酸化ジルコニウムとして30重量%、酸
化セリウムとして5.3重量%を含有するpHが8の透明な
ジルコニア系ゾルを得た。該ゲルは長期間安定であっ
た。Reference Example 4 As a zirconium oxide prepared by the same method as in Reference Example 1, containing 30% by weight, transparent zirconia sol having a pH of 7 and cerium acetate 5.3% by weight of cerium oxide to zirconium oxide in the sol. To give a transparent zirconia-based sol having a pH of 8 and containing 30% by weight of zirconium oxide and 5.3% by weight of cerium oxide. The gel was stable for a long time.
実施例1 界面活性剤であるHLB約5のポリアルキレングリコール
0.9Kgを溶解したオクタノール30Kgをコロイドミル中に
循環させながら、参考例1で得たジルコニアゾルを1Kg/
minの割合でコロイドミル中に投入しゾルエマルジョン
を形成せしめた。Example 1 Polyalkylene glycol having a HLB of about 5 as a surfactant
While circulating 30 kg of octanol in which 0.9 kg was dissolved in a colloid mill, 1 kg of the zirconia sol obtained in Reference Example 1 was added.
It was put into a colloid mill at a ratio of min to form a sol emulsion.
次いで、該ゾルエマルジョンをウォタージャケットを備
えた撹拌式振動流動乾燥器に移送し、水流ポンプにて乾
燥器内を減圧にした後、ジャケットに水蒸気を投入して
該ゾルエマルジョンを撹拌しながら加熱した。該ゾルエ
マルジョンがほとんど流動性を示さなくなったとき、乾
燥器を振動させて乾燥し次いで水蒸気を投入を停止して
加熱をやめ、乾燥器内が60℃以下になれば器内を大気圧
に戻し有機物含有球状ゲル粒子を得た。Next, the sol emulsion was transferred to an agitated vibrating fluidized dryer equipped with a water jacket, the interior of the dryer was depressurized by a water flow pump, and then steam was introduced into the jacket to heat the sol emulsion while stirring. . When the sol emulsion shows almost no fluidity, the dryer is vibrated to dry, then steam is stopped and heating is stopped, and when the temperature inside the dryer becomes 60 ° C or lower, the inside pressure is returned to atmospheric pressure. Spherical gel particles containing an organic substance were obtained.
次いで、該有機物含有球状ゲル粒子を600℃に昇温した
ロータリーキルンに投入して球状ゲル粒子に付着してい
る界面活性剤等の有機物を焼成除去し、平均粒子径が0.
3μm、比表面積が50m2/gであるジルコニア球状粒子を
得た。その標準偏差は1.18であった。Next, the organic substance-containing spherical gel particles are put into a rotary kiln heated to 600 ° C. to remove organic substances such as surfactants adhering to the spherical gel particles by firing, and the average particle size is 0.
Spherical zirconia particles having a particle size of 3 μm and a specific surface area of 50 m 2 / g were obtained. Its standard deviation was 1.18.
実施例2 界面活性剤としてHLB約11のポリアルキレングリコール
を使用した以外は実施例1と同様にして、平均粒子径が
2μm、比表面積が25m2/gであるジルコニア球状粒子を
得た。その標準偏差は1.32であった。Example 2 Zirconia spherical particles having an average particle size of 2 μm and a specific surface area of 25 m 2 / g were obtained in the same manner as in Example 1 except that polyalkylene glycol having an HLB of about 11 was used as the surfactant. Its standard deviation was 1.32.
実施例3 界面活性剤であるHLB約5のポリアルキレングリコール
0.6KgとHLB約11のポリアルキレングリコール0.6Kgとを
溶解したオクタノール30Kgをコロイドミル中に循環させ
ながら、参考例2で得たジルコニアゾルを1Kg/minの割
合でコロイドミル中に投入しゾルエマルジョンを形成せ
しめた。以下、実施例1と同様にして、平均粒子径が0.
5μm、比表面積が100m2/gである酸化イットリウム3mol
%添加ジルコニア球状粒子を得た。その標準偏差は1.12
であった。Example 3 HLB about 5 polyalkylene glycol as a surfactant
While circulating 30 kg of octanol in which 0.6 kg of polyalkylene glycol (0.6 kg of HLB is about 11) was circulated in the colloid mill, the zirconia sol obtained in Reference Example 2 was charged into the colloid mill at a rate of 1 kg / min to obtain a sol emulsion. Was formed. Thereafter, in the same manner as in Example 1, the average particle size was 0.
3 mol of yttrium oxide with 5 μm and specific surface area of 100 m 2 / g
% Zirconia spherical particles were obtained. Its standard deviation is 1.12
Met.
実施例4 界面活性剤であるHLB約5のポリアルキレングリコール
0.8KgとHLB約11のポリアルキレングリコール0.3Kgとを
使用した以外は実施例1と同様にして、平均粒子径が2.
5μm、比表面積が70m2/gである酸化イットリウム3mol
%添加ジルコニア球状粒子を得た。その標準偏差は1.28
であった。Example 4 Polyalkylene glycol having a HLB of about 5 as a surfactant
An average particle size of 2. was obtained in the same manner as in Example 1 except that 0.8 kg and 0.3 kg of polyalkylene glycol having an HLB of about 11 were used.
3 mol of yttrium oxide with 5 μm and specific surface area of 70 m 2 / g
% Zirconia spherical particles were obtained. Its standard deviation is 1.28
Met.
実施例5 界面活性剤であるHLB約5のポリアルキレングリコール
0.9KgとHLB約11のポリアルキレングリコール0.9Kgとを
使用した以外は実施例1と同様にして、平均粒子径が2.
0μm、比表面積が120m2/gである酸化イットリウム8mol
%添加ジルコニア球状粒子を得た。その標準偏差は1.2
であった。Example 5 HLB about 5 polyalkylene glycol which is a surfactant
An average particle size of 2. was obtained in the same manner as in Example 1 except that 0.9 kg and 0.9 kg of polyalkylene glycol having an HLB of about 11 were used.
8 mol of yttrium oxide with 0 μm and specific surface area of 120 m 2 / g
% Zirconia spherical particles were obtained. Its standard deviation is 1.2
Met.
実施例6 界面活性剤であるHLB約5のポリアルキレングリコール
0.6KgとHLB約11のポリアルキレングリコール0.6Kgとを
溶解したオクタノール30Kgをコロイドミル中に循環させ
ながら、参考例4で得たジルコニアゾルを1Kg/minの割
合でコロイドミル中に投入しゾルエマルジョンを形成せ
しめた。以下、実施例1と同様にして、平均粒子径が0.
5μm、比表面積が70m2/gである酸化セリウム3mol%添
加ジルコニア球状粒子を得た。その標準偏差は1.27であ
った。Example 6 Surfactant HLB about 5 polyalkylene glycol
While circulating 30 kg of octanol in which 0.6 kg of polyalkylene glycol 0.6 kg of HLB about 11 was circulated in the colloid mill, the zirconia sol obtained in Reference Example 4 was charged into the colloid mill at a rate of 1 kg / min to obtain a sol emulsion. Was formed. Thereafter, in the same manner as in Example 1, the average particle size was 0.
Spherical particles of zirconia containing 3 mol% of cerium oxide having a particle size of 5 μm and a specific surface area of 70 m 2 / g were obtained. Its standard deviation was 1.27.
実施例7 実施例5で得た平均粒子径が2.0μm、比表面積が120m2
/gである酸化イットリウム8mol%添加ジルコニア球状粒
子を塩化第1スズ溶液(SnCl2・2H2O158g/l)を用いて
室温で2分間センシタイジングを行い、水洗後塩化パラ
ジウム溶液(PdCl20.2g/l)中で40℃3分間アクチベー
ションを行い水洗した。上記のセンシタイジングとアク
チベーションを再度繰り返した後、パラジウムメッキ液
(上村工業(株)A−10X)に該酸化イットリウム8mol
%添加ジルコニア球状粒子を添加し室温で5分間撹拌し
たの後、マイクロフィルターで水洗し、これを還元剤
(上村工業(株)BEL−801R)に添加し室温で5分間撹
拌し、さらにマイクロフィルターで水洗したのち乾燥し
てパラジウム被覆ジルコニア球状粒子を得た。Example 7 The average particle size obtained in Example 5 was 2.0 μm and the specific surface area was 120 m 2.
/ g yttrium oxide 8mol% added zirconia spherical particles were sensitized at room temperature for 2 minutes using stannous chloride solution (SnCl 2 · 2H 2 O 158g / l), washed with water and then palladium chloride solution (PdCl 2 0.2 g / l), and activated at 40 ° C. for 3 minutes and washed with water. After repeating the above sensitizing and activation again, 8 mol of the yttrium oxide was added to a palladium plating solution (A-10X, Uemura Kogyo Co., Ltd.).
% Zirconia spherical particles were added and stirred at room temperature for 5 minutes, then washed with a microfilter, added to a reducing agent (BEL-801R, Uemura Kogyo Co., Ltd.), stirred at room temperature for 5 minutes, and further microfiltered. It was washed with water and dried to obtain spherical zirconia particles coated with palladium.
実施例8 実施例7で得たパラジウム被覆ジルコニア球状粒子を80
℃のロジウムメッキ液(奥野製薬(株)Rh−1)に添加
し同温で5分間撹拌したの後加温を停止し室温まで冷却
する。マイクロフィルターで水洗したのち乾燥してロジ
ウム被覆ジルコニア球状粒子を得た。Example 8 Palladium-coated zirconia spherical particles obtained in Example 7 were mixed with 80
The mixture is added to a rhodium plating solution (Rh-1 of Okuno Seiyaku Co., Ltd.) at ℃ and stirred for 5 minutes at the same temperature, and then heating is stopped and cooled to room temperature. It was washed with a microfilter and dried to obtain rhodium-coated zirconia spherical particles.
実施例9 実施例1で得た平均粒子径が0.3μm、比表面積が50m2/
gであるジルコニア球状粒子パラジウム300gに塩化白金
酸溶液を添加浸漬せしめた後150℃で乾燥した。これを
乳鉢で粉砕した後、950℃で5時間焼成して担持量が酸
化ジルコニウム100gに対して白金として1gを担持した白
金担持ジルコニア球状粒子を得た。Example 9 The average particle size obtained in Example 1 is 0.3 μm, and the specific surface area is 50 m 2 /
A chloroplatinic acid solution was added to 300 g of spherical zirconia spherical particles (g) and immersed therein, and then dried at 150 ° C. This was crushed in a mortar and then baked at 950 ° C. for 5 hours to obtain platinum-supported zirconia spherical particles in which 1 g of platinum was supported on 100 g of zirconium oxide.
実施例10 実施例6で得た平均粒子径が0.5μm、比表面積70m2/g
である酸化セリウム30mol%添加ジルコニア球状粒子300
gにに硝酸コバルト、硝酸ランタン、硝酸ストロンチウ
ムの混合溶液コバルトを添加浸積せしめた後150℃で乾
燥した。これを乳鉢で粉砕した後、920℃で3時間焼成
して酸化ジルコニウム100gに対してLa0.8Sr0.2O3なるペ
ロブスカイト型複合酸化物としてSgを担持したLa0.8S
r0.2O3担持ジルコニア球状粒子を得た。Example 10 The average particle size obtained in Example 6 was 0.5 μm, and the specific surface area was 70 m 2 / g.
Zirconia Spherical Particles with Addition of Cerium Oxide 30mol% 300
Cobalt nitrate, lanthanum nitrate, and strontium nitrate mixed solution cobalt was added to g, and the mixture was dipped and dried at 150 ° C. This was ground in a mortar, La 0 against the zirconium oxide 100g and calcined 3 hours at 920 ℃. 8 Sr 0. La 0 carrying Sg as 2 O 3 becomes a perovskite-type composite oxide. 8 S
It was obtained r 0. 2 O 3 supported zirconia spherical particles.
試験例1 実施例7で得たパラジウム被覆ジルコニア球状粒子をペ
ースト化し、アルミナ基板上にスクリーン印刷後900℃
で30分間焼成してPd厚膜回路を形成した。この回路を使
用してはんだ割れテストを行った結果、はんだ浸積テス
トを10回行った後のはんだくわれはほとんど認められず
導電ペーストとして有効に使用されるものであった。Test Example 1 Palladium-coated zirconia spherical particles obtained in Example 7 were made into a paste and screen-printed on an alumina substrate, and then 900 ° C.
The Pd thick film circuit was formed by firing for 30 minutes. As a result of performing a solder crack test using this circuit, solder nicks after the solder immersion test was performed 10 times were hardly observed, and it was effectively used as a conductive paste.
試験例2 実施例8で得たロジウム被覆ジルコニア球状粒子20gと
白金1gを含有する比表面積が100m2/gの活性アルミナ80g
とをボールミルで20時間湿式粉砕することによりコーテ
ィング用スラリーを調製した。このスラリーに横断面積
が1インチ平方当り約400個のガス流通セルを有する外
径25.4mmφ、長さ500mlのコージェライト質モノリス担
体を浸積し、取り出した後セル内の過剰スラリーを圧縮
空気でブローしてセル内の目詰まりを除去した。次いで
130℃で3時間乾燥して完成触媒を得た。該触媒を空気
中900℃で10時間電気炉エージングをした後、電子制御
式のエンジン(4気筒1800cc)を使用し空燃比をA/F=1
4.6に固定して一酸化炭素、炭化水素および一酸化窒素
の浄化性能を測定した。浄化率が50%を示す触媒入口ガ
ス温度を求めて触媒性能を評価した結果、一酸化炭素浄
化温度は390℃、炭化水素浄化温度は396℃、および一酸
化窒素浄化温度は388℃と良好な結果を示し、排気ガス
浄化用触媒として有効に使用されるものであった。Test Example 2 80 g of activated alumina having a specific surface area of 100 m 2 / g and containing 20 g of rhodium-coated zirconia spherical particles obtained in Example 8 and 1 g of platinum
A slurry for coating was prepared by wet-milling and with a ball mill for 20 hours. A cordierite monolith carrier with an outer diameter of 25.4 mmφ and a length of 500 ml having a cross-sectional area of about 400 gas flow cells per square inch was immersed in this slurry, and the excess slurry in the cell was extracted with compressed air after removal. It was blown to remove the clogging in the cell. Then
It was dried at 130 ° C. for 3 hours to obtain a finished catalyst. The catalyst was aged in air at 900 ° C for 10 hours in an electric furnace, and then an air-fuel ratio was set to A / F = 1 using an electronically controlled engine (four-cylinder 1800cc).
It was fixed at 4.6 and the purification performance of carbon monoxide, hydrocarbons and nitric oxide was measured. As a result of evaluating the catalyst performance by obtaining the catalyst inlet gas temperature showing a purification rate of 50%, the carbon monoxide purification temperature was 390 ° C, the hydrocarbon purification temperature was 396 ° C, and the nitric oxide purification temperature was 388 ° C. The results are shown and it was effectively used as an exhaust gas purifying catalyst.
試験例3 実施例9で得た白金担持ジルコニア球状粒子と比表面積
が100m2/gの活性アルミナ80gとをボールミルで20時間湿
式粉砕することによりコーティング用スラリーを調製し
た。次いで、試験例2と同様にして完成触媒を得た。Test Example 3 A platinum-supported zirconia spherical particle obtained in Example 9 and 80 g of activated alumina having a specific surface area of 100 m 2 / g were wet-milled for 20 hours with a ball mill to prepare a coating slurry. Then, a completed catalyst was obtained in the same manner as in Test Example 2.
この触媒を流通式反応装置に装着し、一酸化炭素200ppm
(空気バランス)のガスを反応ガス(SV=20000Hr-1)
として、触媒入口ガス温度300℃での触媒入口側のCO濃
度と触媒出口側のCO濃度を測定し触媒性能を評価した。
さらに、該触媒を空気中900℃で10時間電気炉エージン
グをした後も同様の測定をした。This catalyst was installed in a flow reactor and carbon monoxide was 200ppm.
(Air balance) gas as reaction gas (SV = 20000Hr -1 )
As a result, the catalyst performance was evaluated by measuring the CO concentration on the catalyst inlet side and the CO concentration on the catalyst outlet side at a catalyst inlet gas temperature of 300 ° C.
Furthermore, the same measurement was performed after the catalyst was aged in an electric furnace at 900 ° C. for 10 hours in the air.
その結果、フレッシュ触媒でCO転化率が99%、エージン
グ後でCO転化率が87%と良好な結果を示した。As a result, the CO conversion was 99% with the fresh catalyst, and the CO conversion was 87% after aging, which was a good result.
試験例4 実施例10で得たLa0.8Sr0.2O3担持ジルコニア球状粒子60
gを酸化ジルコニウム5重量%、pH7なるジルコニアゾル
300gに分散せしめ、平均繊維径約3μmを有し、比表面
積が135m2/gかつ平均細孔径20Aでシリカ5重量%アルミ
ナ95重量%からなるγ−アルミナ型アルミナ繊維の積層
体(縦10cm、横12.5cm、厚さ2cm)を該ゾルに浸積した
後、120℃で乾燥600℃で焼成して完成触媒体を得た。La 0 obtained in Test Example 4 Example 10. 8 Sr 0. 2 O 3 supported zirconia spherical particles 60
Zirconia sol with g of 5% by weight zirconium oxide and pH 7
It is dispersed in 300 g, has an average fiber diameter of about 3 μm, a specific surface area of 135 m 2 / g, an average pore size of 20 A, and a γ-alumina type alumina fiber laminate consisting of 5% by weight of silica and 95% by weight of alumina (10 cm in length, After immersing 12.5 cm in width and 2 cm in thickness) into the sol, it was dried at 120 ° C. and calcined at 600 ° C. to obtain a completed catalyst body.
これを表面拡散式触媒燃焼器に装着して1.5Kcal/cm2・H
rに相当するプロパンガスを該触媒体に供給してヒータ
ーにて着火せしめた。1.5Kcal / cm 2 · H by mounting this on a surface diffusion type catalytic combustor
Propane gas corresponding to r was supplied to the catalyst body and ignited by a heater.
その結果、触媒表面温度が中央部で440〜520℃、周辺部
で240〜350℃に維持され、排ガス組成も一酸化炭素で〜
4ppm、未燃焼プロパンが30〜500ppm、燃焼効率99.5%と
良好な値を示した。As a result, the catalyst surface temperature is maintained at 440 to 520 ℃ in the central part and 240 to 350 ℃ in the peripheral part, and the exhaust gas composition is also carbon monoxide ~
4ppm, unburned propane was 30-500ppm, and combustion efficiency was 99.5%.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 B01J 2/08 23/40 ZAB A 8017−4G 23/54 ZAB A 8017−4G (72)発明者 本 輝之 兵庫県姫路市網干区興浜字西沖992番地の 1 日本触媒化学工業株式会社触媒研究所 内 審査官 中田 とし子 (56)参考文献 特開 平1−126229(JP,A)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location B01J 2/08 23/40 ZAB A 8017-4G 23/54 ZAB A 8017-4G (72) Inventor Teruyuki Moto 1 992 Nishi-oki, Okihama, Aboshi-ku, Himeji-shi, Hyogo Pref. Toshiko Nakata, Inspector, Catalysis Laboratory, Nippon Catalysis Chemical Co., Ltd. (56) Reference JP-A-1-126229 (JP, A)
Claims (4)
との反応生成物を60℃以上で加熱・加水分解して調製さ
れる、酸化ジルコニウムとしての含有率が5〜40重量%
であり、pHが5〜10の範囲であるジルコニウム水和物含
有ゾルを、界面活性剤0.05〜30重量%および水不溶性な
いし水難溶性の有機溶媒5〜80重量%と撹拌混合して、
W/O型エマルジョンを形成させ、次いで該エマルジョン
を加熱してエマルジョンの水相を形成する球状ゾル中の
水分を該有機溶媒との混合物として系外に除去すること
により、球状ゾルを球状ゲル化し、さらに、該球状ゲル
を300℃以上で焼成することにより界面活性剤等の有機
物を除去することよりなる平均粒子径が0.05〜50μmの
範囲でその標準偏差値が1〜1.5の範囲、比表面積が5
〜200m2/gであるジルコニア球状粒子の製造方法。1. The content of zirconium oxide prepared by heating and hydrolyzing a reaction product of zirconyl ammonium carbonate and a chelating agent at 60 ° C. or higher is 5 to 40% by weight.
And a zirconium hydrate-containing sol having a pH in the range of 5 to 10 by stirring and mixing with a surfactant of 0.05 to 30% by weight and a water-insoluble or poorly water-soluble organic solvent of 5 to 80% by weight,
A spherical sol is formed into a spherical gel by forming a W / O type emulsion and then heating the emulsion to remove the water in the spherical sol forming the aqueous phase of the emulsion as a mixture with the organic solvent out of the system. Furthermore, the average particle size of the spherical gel is obtained by removing organic substances such as a surfactant by baking the spherical gel at 300 ° C. or higher, and the standard deviation value is in the range of 1 to 1.5 and the specific surface area is in the range of 0.05 to 50 μm. Is 5
A method for producing spherical particles of zirconia having a particle size of about 200 m 2 / g.
との反応生成物を60℃以上で加熱・加水分解して調製さ
れる、酸化ジルコニウムとしての含有率が5〜40重量%
であり、pHが5〜10の範囲であるジルコニウム水和物含
有ゾルにマグネシウム、カルシウム、アルミニウム、ケ
イ素、チタニウム、スズ、イットリウム、ランタンおよ
びセリウムの各々を含む化合物の少なくとも1種または
これら金属元素の2種以上を含む複合化合物の少なくと
も1種を添加した後、界面活性剤0.05〜30重量%および
水不溶性ないし水難溶性の有機溶媒5〜80重量%と撹拌
混合して、W/O型エマルジョンを形成させ、次いで該エ
マルジョンを加熱してエマルジョンの水相を形成する球
状ゾル中の水分を該有機溶媒との混合物として系外に除
去することにより、球状ゾルを球状ゲル化し、さらに、
該球状ゲルを300℃以上で焼成することにより界面活性
剤等の有機物を除去することよりなる平均粒子径が0.05
〜50μmの範囲でその標準偏差値が1〜1.5の範囲、比
表面積が5〜20m2/gであるジルコニア系球状粒子の製造
方法。2. The content of zirconium oxide prepared by heating and hydrolyzing a reaction product of zirconyl ammonium carbonate and a chelating agent at 60 ° C. or higher is 5 to 40% by weight.
And a zirconium hydrate-containing sol having a pH in the range of 5 to 10 at least one compound containing magnesium, calcium, aluminum, silicon, titanium, tin, yttrium, lanthanum, and cerium, or a metal element of these. After adding at least one compound compound containing two or more kinds, the mixture is stirred and mixed with 0.05 to 30% by weight of a surfactant and 5 to 80% by weight of a water-insoluble or sparingly water-soluble organic solvent to form a W / O type emulsion. The spherical sol is formed into a spherical gel by removing the water in the spherical sol that forms the aqueous phase of the emulsion from the system as a mixture with the organic solvent to form a spherical gel.
The average particle diameter obtained by removing organic substances such as a surfactant by baking the spherical gel at 300 ° C. or higher is 0.05.
A method for producing zirconia-based spherical particles having a standard deviation value of 1 to 1.5 and a specific surface area of 5 to 20 m 2 / g in the range of ˜50 μm.
が0.05〜50μmの範囲でその標準偏差値が1〜1.5の範
囲、比表面積が5〜200m2/gであるジルコニア球状粒子
にルテニウム、ロジウム、パラジウム、銀、インジウ
ム、白金および金からなる群から選ばれた少なくとも1
種の金属および/またはバナジウム、クロム、マンガ
ン、鉄、コバルト、ニッケル、銅、モリブデン、タング
ステンおよびビスマスからなる群から選ばれた少なくと
も1種の金属またはそれらの金属酸化物を担持すること
を特徴とする金属担持ジルコニア球状粒子の製造方法。3. A zirconia spherical particle obtained by the method according to claim 1, which has an average particle size of 0.05 to 50 μm, a standard deviation value of 1 to 1.5 and a specific surface area of 5 to 200 m 2 / g. At least one selected from the group consisting of ruthenium, rhodium, palladium, silver, indium, platinum and gold
One metal and / or at least one metal selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, tungsten and bismuth, or a metal oxide thereof. A method for producing metal-supported zirconia spherical particles.
が0.05〜50μmの範囲でその標準偏差値が1〜1.5の範
囲、比表面積が5〜200m2/gであるジルコニア系球状粒
子にルテニウム、ロジウム、パラジウム、銀、インジウ
ム、白金および金からなる群から選ばれた少なくとも1
種の金属および/またはバナジウム、クロム、マンガ
ン、鉄、コバルト、ニッケル、銅、モリブデン、タング
ステンおよびビスマスからなる群から選ばれた少なくと
も1種の金属またはそれらの金属酸化物を担持すること
を特徴とする金属担持ジルコニア系球状粒子の製造方
法。4. A zirconia-based spherical particle having an average particle size of 0.05 to 50 μm, a standard deviation value of 1 to 1.5, and a specific surface area of 5 to 200 m 2 / g, which is obtained by the method according to claim 2. At least one selected from the group consisting of ruthenium, rhodium, palladium, silver, indium, platinum and gold.
One metal and / or at least one metal selected from the group consisting of vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, tungsten and bismuth, or a metal oxide thereof. A method for producing spherical zirconia particles supported on a metal.
Priority Applications (1)
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JP2028538A JPH0735253B2 (en) | 1990-02-09 | 1990-02-09 | Zirconia or zirconia-based spherical particles and method for producing metal-supported zirconia or zirconia-based spherical particles |
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JP2028538A JPH0735253B2 (en) | 1990-02-09 | 1990-02-09 | Zirconia or zirconia-based spherical particles and method for producing metal-supported zirconia or zirconia-based spherical particles |
Publications (2)
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JPH03232724A JPH03232724A (en) | 1991-10-16 |
JPH0735253B2 true JPH0735253B2 (en) | 1995-04-19 |
Family
ID=12251447
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GB9322358D0 (en) * | 1993-10-29 | 1993-12-15 | Johnson Matthey Plc | Pigmentary material |
US6524548B1 (en) | 1994-12-17 | 2003-02-25 | Degussa Ag | Zirconium dioxide powder, method of its production and use |
JP4564645B2 (en) * | 2000-11-27 | 2010-10-20 | 株式会社キャタラー | Exhaust gas purification catalyst |
JP4901072B2 (en) * | 2004-03-17 | 2012-03-21 | 大阪瓦斯株式会社 | Hydrocarbon removal catalyst and hydrocarbon removal method thereof |
MY143356A (en) * | 2004-06-25 | 2011-04-29 | Very Small Particle Company Pty Ltd | Method for producing fine-grained particles |
JP5035545B2 (en) * | 2005-06-29 | 2012-09-26 | 日産化学工業株式会社 | Method for producing alkaline zirconia sol |
JP5081830B2 (en) * | 2005-10-13 | 2012-11-28 | ヴェロシス インコーポレイテッド | Electroless plating in microchannels |
JP5034314B2 (en) * | 2006-05-19 | 2012-09-26 | 住友大阪セメント株式会社 | High refractive index transparent particle manufacturing method, high refractive index transparent particle, high refractive index transparent composite, and light emitting device |
US7910514B2 (en) * | 2007-08-09 | 2011-03-22 | Nissan Motor Co., Ltd. | Inorganic fiber catalyst, production method thereof and catalyst structure |
JP5460969B2 (en) * | 2008-03-03 | 2014-04-02 | 国立大学法人 岡山大学 | Catalyst production method and catalyst |
JP5303483B2 (en) * | 2010-01-27 | 2013-10-02 | 株式会社豊田中央研究所 | Ozone decomposition removal catalyst, method for producing the same, and ozone decomposition removal method using the same |
JP6460090B2 (en) * | 2014-02-27 | 2019-01-30 | 堺化学工業株式会社 | Method for producing composite metal oxide polishing material and composite metal oxide polishing material |
JP6985913B2 (en) * | 2017-12-11 | 2021-12-22 | エヌ・イーケムキャット株式会社 | Exhaust gas purification catalyst, its manufacturing method, and integrated structure exhaust gas purification catalyst |
JP7030305B2 (en) * | 2018-01-11 | 2022-03-07 | 株式会社豊田中央研究所 | Core-shell type oxide material, its manufacturing method, exhaust gas purification catalyst using it, and exhaust gas purification method |
CN112237917B (en) * | 2019-07-18 | 2023-04-07 | 中国石油化工股份有限公司 | Low-carbon alkane dry reforming catalyst carrier and catalyst thereof |
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