JP4420991B2 - Silica spherical particles and method for producing the same - Google Patents
Silica spherical particles and method for producing the same Download PDFInfo
- Publication number
- JP4420991B2 JP4420991B2 JP26997398A JP26997398A JP4420991B2 JP 4420991 B2 JP4420991 B2 JP 4420991B2 JP 26997398 A JP26997398 A JP 26997398A JP 26997398 A JP26997398 A JP 26997398A JP 4420991 B2 JP4420991 B2 JP 4420991B2
- Authority
- JP
- Japan
- Prior art keywords
- silica
- particles
- slurry
- magnesium
- alumina
- 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 - Lifetime
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 94
- 239000000377 silicon dioxide Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000012798 spherical particle Substances 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims description 95
- 239000002002 slurry Substances 0.000 claims description 51
- 239000011148 porous material Substances 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- -1 aluminum compound Chemical class 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- 150000002681 magnesium compounds Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000005299 abrasion Methods 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 25
- 238000005984 hydrogenation reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000010304 firing Methods 0.000 description 15
- 239000000741 silica gel Substances 0.000 description 13
- 229910002027 silica gel Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910003849 O-Si Inorganic materials 0.000 description 3
- 229910003872 O—Si Inorganic materials 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 150000008365 aromatic ketones Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 231100000344 non-irritating Toxicity 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- FEYJIFXFOHFGCC-UHFFFAOYSA-N 1-nitrohexane Chemical class CCCCCC[N+]([O-])=O FEYJIFXFOHFGCC-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CYZJZTQLSCGDDO-UHFFFAOYSA-K O.O.O.O.O.O.Cl(=O)(=O)(=O)[O-].[Al+3].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] Chemical compound O.O.O.O.O.O.Cl(=O)(=O)(=O)[O-].[Al+3].Cl(=O)(=O)(=O)[O-].Cl(=O)(=O)(=O)[O-] CYZJZTQLSCGDDO-UHFFFAOYSA-K 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 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 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- HQQUTGFAWJNQIP-UHFFFAOYSA-K aluminum;diacetate;hydroxide Chemical compound CC(=O)O[Al](O)OC(C)=O HQQUTGFAWJNQIP-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006264 debenzylation reaction Methods 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 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
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical class NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
機械的強度に優れたアルミニウムとマグネシウムを含有するシリカ球状粒子（以下、球状シリカ−アルミナ−マグネシア粒子という。）及びその製造法に関する。
【０００２】
【従来の技術】
球状シリカ系粒子は様々な用途にその特性を活かした材料として利用されている。その例を示すと液体クロマトグラフィー用充填剤、化粧品基剤、触媒担体、流動調整剤、希釈剤等が挙げられる。これらの用途に要求される要件を満たす為に、高比表面積等の物性を満たそうとすると多孔質になり機械的強度が弱くなる。一方、機械的強度を満たそうとすると、高い温度で焼成したりすることから比表面積が小さくなる。このように機械的強度が強く、比表面積が大きいという相反する物性を満たす球状のシリカ系粒子を得ることは難しく、両者の要求を満足する球状のシリカ系粒子は得られていなかった。さらに、このシリカ系粒子を大量に再現性よく製造する方法も望まれている。
【０００３】
シリカ系の物質の一つである石英は硬く、機械的強度が高いことが知られている。しかしながら機械的強度は優れているが比表面積が低く（１ｍ2 ／ｇ以下）、高い比表面積を必要とする用途には使用することができない。
特開昭６３−１６０４９号公報には、粒径が２０〜５００μｍで比表面積が３０〜８００ｍ2 ／ｇで細孔容積が０．３〜２．０ｃｍ3 ／ｇである球状のシリカゲルよりなる流動床用触媒担体が提案されているが、機械的強度は弱い。
【０００４】
特開平６−６４９１５号公報には、界面活性剤を含む非極性有機ハロゲン化物溶媒中で、アルカリ金属ケイ酸塩水溶液を乳化させ、次いでゲル化剤によりゲル化させて、球状シリカを製造する方法が提案されている。ここで得られる球状シリカは１２０℃で数時間乾燥し、ゲル間水を除去したものでゲル間水由来で細孔容積が大きく、比表面積が大きいものが得られるが、機械的強度は弱い。液体クロマトグラフィー用充填剤、化粧品基剤等に用いるた場合には割れ、欠けが生じてしまう。
【０００５】
特開平８−１１９６２１号公報には、比表面積が５０ｍ2 ／ｇ以下で、かつ細孔容積が０．３ｍｌ／ｇ以下かつ耐摩耗性３．０ｗｔ％／１５ｈｒ以下で嵩密度が０．６〜１．３ｇ／ｍｌで平均粒子径が３０〜１５０μｍであるシリカ−リン−ホウ素からなる組成物の製造法が提案されている。しかし、提案されているものは触媒担体、流動調製剤などに使用するには比表面積が小さい。
【０００６】
特開平９−５２０４４号公報には、強度に優れたカルボン酸エステル製造用触媒の担持体として、アルミニウムの含有量が酸化物として５〜４０ｗｔ％、マグネシウムの含有量が酸化物として３〜３０ｗｔ％、ＳｉＯ2 として５０〜９２ｗｔ％の範囲で含有するシリカ−アルミナ−マグネシアを担持体で用いる提案がなされている。この担持体は通常の使用条件下では機械的強度を満足できる。しかし、粒子同士、粒子と撹拌バネ等などの激しい混合条件での反応、例えば懸濁反応等の過酷な条件で使用すると、割れ、欠けの問題が生じる場合があった。また、工業規模でシリカ−アルミナ−マグネシアの担持体を製造しようとした場合に、割れ、欠け、中空が発生することが時々起こり、さらに機械的強度の強い担体、及び再現性良く製造する方法が望まれていた。
【０００７】
【発明が解決しようとする課題】
本発明は、機械的強度が強く、比表面積が大きく、流動性の良い球状シリカ系粒子を提供すること及びその再現性の良い製造方法を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明者らは、機械的強度を満足し、比表面積が大きく、流動性の良い球状シリカ粒子を製造する為にはシリカ−アルミナ−マグネシア粒子を緻密な構造にすることが重要と考え、シリカ−アルミナ−マグネシア粒子の物性と製造条件の相関について鋭意研究を進めた。その結果、割れ、欠け、中空の原因が主に粒子内の密度と深い関係があることを見出し、特定の割合でシリカ、アルミニウム化合物、マグネシウム化合物を含有するスラリーを調合し、該スラリーをある特定の粘度に高めてから噴霧造粒し、焼成すると、驚くべきことに機械的強度が強く、かつ比表面積の大きい、球状シリカ粒子が製造できることを見いだし、本発明に到達した。
【０００９】
すなわち、本発明は以下のとおりである。
（１） 下記ａ）〜ｇ）の特性を有する、アルミニウムとマグネシウムを含有するシリカ球状粒子。
ａ）比表面積 ； ６０〜５００（ｍ２ ／ｇ），
ｂ）細孔容積 ； ０．１〜０．５（ｃｍ３ ／ｇ），
ｃ）細孔分布 ； 細孔直径１０〜５００Åの範囲に細孔容積の９０％以上がある，
ｄ）嵩密度 ； ０．６〜１．３（ｇ／ｃｍ３ ），
ｅ）耐摩耗性 ； ２．０ｗｔ％／１５ｈｒ以下，
ｆ）平均粒子径 ； ０．５〜３００μｍ，
ｇ）アルミニウムの含有量が酸化物として５〜４０ｗｔ％であり、かつマグネシウムの含有量が酸化物として３〜３０ｗｔ％である。
（２） シリカ、アルミニウム化合物、マグネシウム化合物を、それぞれシリカ、アルミニウム酸化物、マグネシウム酸化物として３０〜９２ｗｔ％、５〜４０ｗｔ％、３〜３０ｗｔ％含有するスラリーを調合し、該スラリーの粘度が１００ｃｐ〜１００００ｃｐの範囲で噴霧乾燥造粒して製造する（１）に記載のシリカ球状粒子の製造方法。
（３） （１）に記載のシリカ球状粒子にパラジウムを含む金属成分を担持してなる貴金属担持物。
【００１０】
以下に本発明を詳細に説明する。
本発明は、シリカ、アルミニウム化合物、マグネシウム化合物を含有するスラリーを調合し、そのスラリーの粘度が１００ｃｐ〜１００００ｃｐの範囲で噴霧乾燥造粒することが重要である。これにより如何なる理由で機械的強度が高まるのか詳細な検討は不十分であるが、本発明者らはこの効果について次の様に推定した。
【００１１】
スラリーを噴霧乾燥して造粒した場合は通常いろいろな形状を示すもので、液滴は液体蒸発により、まず収縮をはじめる。その後、次の３種の状態変化がある。▲１▼液滴表面の固形化により、出口をふさがれて内部の液滴の蒸発が外部に向かってできず、一度収縮した粒径が内部圧の上昇で大きくなり、その結果として破壊（割れ、欠け）、孔開球が生じ、その後温度が常温に戻った時点で、内部圧がなくなる、または負圧になることにより、陥没球ができる。稀にそのまま膨張球になる場合もある。▲２▼一度収縮した粒径が保たれて中空球ができる。▲３▼乾燥温度と収縮が上手くバランスすると内部に気孔のない充実球が得られる。本発明の目的の球状シリカ−アルミナ−マグネシア粒子を得る為には、密度を高くし、機械的強度を高めることができる▲３▼のような充実球を再現性良く製造する必要がある。
【００１２】
本発明においては、噴霧乾燥造粒する前のスラリー中において、シリカゲルの未架橋シリカ（Ｓｉ−ＯＨ）鎖に、Ｓｉ−Ｏ−Ａｌ−Ｏ−Ｓｉ結合が新たに形成されるものと推定できる。該スラリーの粘度が高くなることは、Ｓｉ−Ｏ−Ａｌ−Ｏ−Ｓｉ結合数が増えることを示唆していると考えている。この結合形成によりシリカゲルの未架橋シリカ（Ｓｉ−ＯＨ）鎖が減り、Ｓｉ−Ｏ結合が強化されたと考えられる。その結果、噴霧乾燥造粒する前のスラリー段階で強い結合ができていたので、噴霧乾燥造粒時に起こる破壊、中空などの発生を抑制でき、▲３▼の充実球が製造できたと考えている。また、マグネシウム（Ｍｇ）を共存させることで、Ｓｉ−Ｏ−Ａｌ−Ｏ−Ｓｉ架橋構造の生成によるＳｉ（四価）とＡｌ（三価）の価数の違いにより生じる電荷の違いをマグネシウム（二価）が補償中和し、電荷的バランスがとれるため、構造の安定性が高められると推察される。
【００１３】
本発明の球状シリカ−アルミナ−マグネシア粒子は、
ａ）比表面積 ； ６０〜５００（ｍ２ ／ｇ），
ｂ）細孔容積 ； ０．１〜０．５（ｃｃ／ｇ），
ｃ）細孔分布 ； 細孔直径１０〜５００Åの範囲に細孔容積の９０％以上がある，
ｄ）嵩密度 ； ０．６〜１．３（ｇ／ｃｃ），
ｅ）耐摩耗性 ； ２．０ｗｔ％／１５ｈｒ以上，
ｆ）平均粒子径 ； ０．５〜３００μｍ，
ｇ）アルミニウムの含有量が酸化物として５〜４０ｗｔ％であり、かつマグネシウムの含有量が酸化物として３〜３０ｗｔ％であることが必要である。
【００１４】
ａ）比表面積、ｂ）細孔容積、ｃ）細孔分布、ｄ）嵩密度、ｅ）耐摩耗性、ｆ）平均粒子径、ｇ）アルミニウムとマグネシウムの含量が、この範囲内にあれば、本発明の目的である機械的強度が強く、比表面積が大きく、流動性の良い粒子を得ることができる。これはこの範囲内でマグネシウム、アルミニウム、シリカが特定の安定な結合構造を形成するため、球状シリカ−アルミナ−マグネシア粒子が緻密な構造をとることによると推定される。
【００１５】
本発明の、球状シリカ−アルミナ−マグネシア粒子の比表面積は、窒素吸着法による測定で６０〜５００ｍ2 ／ｇであることが必要であり、好ましくは８０〜４００ｍ2 ／ｇであり、より好ましくは１００〜３００ｍ2 ／ｇである。また、噴霧乾燥造粒後に上記比表面積になるように好適な温度で焼成して使用することが好ましい。焼成温度としては２２０〜８００℃の範囲から選ばれる。８００℃を越える温度で焼成すると比表面積の低下が著しく好ましくない。また、焼成雰囲気は特に限定されないが、空気中あるいは窒素中で焼成するのが一般的である。また、焼成時間は、焼成後の比表面積に応じて決めることができる。
【００１６】
本発明の、球状シリカ−アルミナ−マグネシア粒子の細孔容積は０．１〜０．５（ｃｍ3 ／ｇ）であることが必要であり、好ましくは０．１５〜０．４（ｃｍ3 ／ｇ）であり、より好ましくは０．２〜０．３（ｃｍ3 ／ｇ）である。細孔容積が、０．５（ｃｍ3 ／ｇ）より大きくなると機械的強度が弱くなる。また、細孔容積が０．１（ｃｍ3 ／ｇ）未満であると、比表面積が不充分となる。
【００１７】
細孔分布は、細孔容積の９０％以上が細孔直径１０〜５００Åの範囲にあることが必要である。細孔容積の９０％以上が細孔直径が１０〜５００Åの範囲に集中して分布すれば、クラック（歪み）が少なく機械的強度が高くなる。好ましくは９３％以上である。
嵩密度は０．６〜１．３（ｇ／ｃｍ3 ）であることが必要であり、好ましくは０．８〜１．２（ｇ／ｃｍ3 ）であり、より好ましくは０．８５〜１．１５（ｇ／ｃｍ3 ）である。嵩密度は球状シリカ粒子の球状の度合い又は流動状態の指標になっている。嵩密度が０．６（ｇ／ｃｍ3 ）未満であれば、形状が歪な物や、割れ、欠け、中空のシリカ粒子が多くなる。また、１．３（ｇ／ｃｍ3 ）を越えると、比表面積が低下し、不充分となる。
【００１８】
耐磨耗性は、２．０ｗｔ％／１５ｈｒ以下であることが必要であり、好ましくは１．０ｗｔ％／１５ｈｒ以下であり、より好ましくは０．５ｗｔ％／１５ｈｒ以下である。耐磨耗性が、２．０ｗｔ％／１５ｈｒを越えると粒子の粉化、割れ等が起こり易くなる。
平均粒子径は０．５〜３００μｍであることが必要であり、好ましくは２０〜２００μｍであり、より好ましくは３０〜１５０μｍである。
【００１９】
アルミニウム、マグネシウムの含有量は、アルミニウムの含有量が酸化物として５〜４０ｗｔ％であることが必要であり、好ましくは５〜３０ｗｔ％であり、より好ましくは７〜２０ｗｔ％である。マグネシウムの含有量が酸化物として３〜３０ｗｔ％であることが必要であり、好ましくは３〜２０ｗｔ％であり、より好ましくは５〜１５ｗｔ％である。
【００２０】
本発明の球状シリカ−アルミナ−マグネシア粒子の製造法について説明する。
本発明で用いられるスラリーは以下のようにして調合される。
（１）あらかじめシリカ−アルミナゲルを形成させ、酸化マグネシウムを添加して反応させて得られるもの、（２）シリカゲル等の溶液と、アルミニウム化合物及びマグネシウム化合物の溶液とを反応させて得られるもの、（３）シリカゲルと、水に不溶なアルミニウム化合物及びマグネシウム化合物とを反応させて得られるもの、（４）シリカゲルと、水溶性のアルミニウム化合物及びマグネシウム化合物の水溶液とを反応させて得られるもの。このようにして得られたスラリーを、粘度が１００ｃｐ〜１００００ｃｐの範囲で噴霧乾燥造粒して製造することが本発明においては必要であり、好ましくは５００〜１００００ｃｐ、より好ましくは８００〜１００００ｃｐの範囲で噴霧乾燥造粒する。スラリーの粘度が数ｃｐ〜数十ｃｐでは大きな改善効果が認められない。ところが意外にも１００ｃｐを越えると劇的な効果が現れることを本発明者らは見出した。一方、スラリー粘度が１００００ｃｐ以上でも同様の効果は期待できるが、スラリー粘度上昇に伴い、通常、噴霧乾燥造粒が困難になる。
【００２１】
本発明において、平均粒子径が３０μｍ以上の粒子を調製する場合には、スラリーの粘度は５００ｃｐ〜１００００ｃｐが好ましい。さらに好ましくは１０００ｃｐ〜１００００ｃｐ、特に好ましくは２０００ｃｐ〜１００００ｃｐである。スラリーの粘度が高まるのは、スラリー中でシリカとアルミニウム、マグネシウムとの結合が強くなるためであり、平均粒子径の大きなものを調製しようとする場合には、粘度を高めることが機械的強度の強い、球状シリカ−アルミナ−マグネシア粒子を得るためには重要である。一方、３０μｍ未満の粒子を噴霧乾燥造粒により調製する場合には、粘度を高め過ぎると製造時の収率が悪くなるので、１００〜３０００ｃｐが好ましく、より好ましくは１００〜１０００ｃｐである。
【００２２】
以下に、上記（１）〜（４）の入手法について説明する。シリカ原料としては、シリカゾル、水ガラスあるいはシリカゲルを用いることができる。シリカゾル中のシリカコロイド粒子の平均粒子径は、強度を付与するために、数種類の粒径が異なるシリカコロイドを用いることもできる。シリカゲルとしてはアルミニウムと反応する未架橋シリカ（Ｓｉ−ＯＨ）鎖を有すればよく、該Ｓｉ−Ｏ鎖の長さについては限定されない。
アルミニウム原料としては、アルミン酸ソーダ、塩化アルミニウム六水和物、過塩素酸アルミニウム六水和物、硫酸アルミニウム、硝酸アルミニウム九水和物、二酢酸アルミニウム等の水溶性化合物が好ましいが、水酸化アルミニウム、酸化アルミニウム等の水に不溶な化合物でもシリカゾル、シリカゲル中の未架橋シリカと反応する化合物であればいずれも用いることが可能である。
【００２３】
マグネシウム原料としては、酸化マグネシウム、水酸化マグネシウム、酢酸マグネシウム、硝酸マグネシウム、塩化マグネシウム、硫酸マグネシウム等を用いることができる。
シリカ−アルミナゲルを出発原料にする（１）の具体例を挙げれば、予め、水ガラスに硫酸を加えてｐＨ８〜１０．５のシリカヒドロゲルをつくり、これにＡｌ2(ＳＯ4)3 水溶液を加え（ｐＨ２またはそれ以下）、さらにアルミン酸ソーダを添加し（ｐＨ５〜５．５）生成するシリカ−アルミナヒドロゲルを調製し、水分等を調整した後、ＭｇＯを添加し、スラリーを得ることができる。
【００２４】
シリカゾル等の溶液を出発原料とする（２）及び（３）の場合は、シリカゾル等の溶液とアルミニウム化合物及びマグネシウム化合物を混合してスラリーを得る。この際、アルミニウム化合物及びマグネシウム化合物を溶かすために硝酸、硫酸、塩酸等の酸を用いることができる。
シリカゲルを出発原料として用いる（４）の場合は、シリカゲルと、水溶性のアルミニウム化合物及びマグネシウム化合物の水溶液とを反応させてスラリーを得る。その際にシリカゲルを予め所定の粒径まで粉砕しておくか、又は予備的に粗粉砕しておいても良い。
【００２５】
このようにして得られたスラリーは、必要に応じて加熱して粘度を上げることができる。また、工業的に製造する場合のように、噴霧乾燥造粒の時間が長くなる場合にはスラリーの粘度が安定するようにスラリー温度を下げて粘度が余り変化しない状態にしてから噴霧乾燥造粒することが好ましい。
スラリーを加熱する温度としては、４０〜１００℃が好ましく、より好ましくは４０〜８０℃である。加熱する温度が１００℃を越えると、スラリー粘度が高くなりすぎたり、スラリー中の水等が蒸発して再現性を得るのが困難となる。加熱する温度が４０℃未満では粘度が上がらなかったり、粘度を上げるのに時間がかかり過ぎる。
【００２６】
また、本発明において、噴霧乾燥造粒する時のスラリー濃度は、酸化物としての濃度が５〜５０ｗｔ％であることが好ましく、より好ましくは１０〜４０ｗｔ％、特に好ましくは１５〜３０ｗｔ％である。
本発明の製造方法は、再現性も良く、また得られた球状のシリカ−アルミナ−マグネシア粒子が機械的強度に優れ、且つ流動性も良いことから、該粒子を工業的スケールのような大規模に製造する場合に特に好適である。
【００２７】
本発明の球状シリカ−アルミナ−マグネシア粒子は、顔料、充填剤、研磨剤、化粧品基剤、農薬用担体、触媒担体、吸着剤等の材料に用いることができる。
例えば、顔料の求められる用件としては、水、油、有機溶剤などに不溶性の微細な粉末で、機械的強度が強いことが求められている。本発明の球状シリカ−アルミナ−マグネシア粒子は機械的強度が強く、たやすく割れたり、欠けたりしない優れた特性がある。さらに、本発明の粒子は、耐水性、耐油性、耐有機溶剤性にも優れている。また、顔料としては小さな粒子が一般的に用いられ、平均粒子径が０．５〜１０μｍであることが好ましく、さらに好ましくは０．５〜５μｍであることが好ましい。また、塗料、印刷インキ、合成樹脂、繊維、ゴム等の添加剤としても用いることができる。
【００２８】
また、充填剤として、従来用いられていた合成シリカ充てん剤は嵩密度が０．０４〜０．２（ｇ／ｃｍ3 ）と小さいので、輸送、取り扱いが不便であった。本発明の球状シリカ−アルミナ−マグネシア粒子は、嵩密度が０．６〜１．３（ｇ／ｃｃ）と高く、従来の合成シリカ充てん剤の欠点を解決している。また、機械的強度も強いのでポリマーの強度を増加させる補強剤として有用である。さらに、艶消し剤や塩化ビニルペースト、エポキシ樹脂、ポリエステル樹脂のプレポリマーの粘度調整材としても有用である。
【００２９】
本発明の球状シリカ−アルミナ−マグネシア粒子は、耐磨耗性が２．０ｗｔ％／１５ｈｒ以下であることから、研磨剤としても有用である。研磨剤としては、形状および嵩密度の幾何学的性質が重要である。ケイ砂、浮き石、ケイソウ土などに較べ、本発明の粒子は機械的強度が強く、球状で嵩密度が高いので研磨剤としての特性に優れている。また、研磨する対象によって粒径を揃える必要があるが、機械的強度が強いので、分級しても破損等が起こりにくく、研磨対象に適した粒度の球状粒子物を得ることができる。研磨剤としての平均粒子径は、研磨する対象によって様々な粒径のものが用いられ、一般的には１〜３００μｍが好ましく、用途によって最適粒子径のものが用いられる。本発明の粒子はガラス、木材の研磨や、錆び落とし、汚れ落とし、金属、木材、象牙等の骨細工品の仕上げ、美術工芸品、セラミック、軟質金属の光沢出し等に有用である。
【００３０】
化粧品基剤としては、▲１▼人体に無害、無刺激であること、▲２▼安定性がよいこと、▲３▼使用性が良いことが望まれている。本発明の粒子は、無害、無刺激であり、耐水性、耐油性、耐有機溶剤性に優れているので安定性が良く、球形であるので滑らかな感触を与え、使用性も高いので化粧品基剤として有用である。
農薬用担体として用いられる粒子は、粒度分布が斉一であって、かつ、１０μｍ以下の粒子を除く操作（分級）が行われる。それは、１０μｍ以下の粒子を除くと粉剤の物理性、例えば吐粉性、分散性、飛散性等、および経時的安定性が著しく改善されるためである。本発明の球状シリカ−アルミナ−マグネシア粒子は球状で、機械的強度が強いので、風力分級により１０μｍ以下の粒子を除くことは容易である。また、粘度を３０００ｃｐ以上に高めて噴霧乾燥造粒すると粒径１０μｍ以下粒子の割合を少なくした製造もできる。
【００３１】
本発明の球状シリカ−アルミナ−マグネシア粒子を、触媒担体としての利用例を具体的な例をもとに以下に説明する。流動床用触媒担体として用いる場合は、これに触媒活性成分を担持させるが、これらの成分としては対象になる反応により活性成分が適宜選定され、例えばモリブデン、バナジウム、コバルト、ニッケル、銀、銅、タングステン、アルカリ金属、アルカリ土類金属、及び／又は亜鉛などの成分が挙げられる。これらの成分を本発明の球状シリカ−アルミナ−マグネシア粒子に担持させる方法としては、その成分に応じて通常の含浸法、沈殿法、イオン交換法、溶融含浸法又は蒸着法などが採用される。また、本発明の球状シリカ−アルミナ−マグネシア粒子の適用可能な流動床用反応としては特に限定されず、例えば酸化エチレンからアセトアルデヒドへの異性化反応、エチレンシアンヒドリンの脱水によるアクリロントリルの製造反応、ホルムアルデヒドとアセトアルデヒドよりアクロレインを合成する反応、オレフィンの水和反応、ナフタレン又はｏ−キシレンの酸化により無水フタル酸を得る反応などが挙げられる。
【００３２】
本発明の球状シリカ−アルミナ−マグネシア粒子は、パラジウム金属担持触媒、パラジウム金属化合物担持触媒の担体としても好ましく用いられる。該球状シリカ−アルミナ−マグネシア粒子を担体として用いてパラジウム金属担持触媒、パラジウム金属化合物担持触媒を調製する方法としては、含浸法、沈殿法、イオン交換法等があるが、これら触媒の用いる反応にあった調製法を採用すれば良い。
【００３３】
また、パラジウム金属担持触媒、パラジウム金属化合物担持触媒としては広い触媒反応に利用することが出来る。例えば、アルデヒドとアルコールから酸化的カルボン酸エステル化反応、アセチレン類のオレフィン類への部分水素化反応、パラフィン類への完全水素化反応、ジオレフィン類のモノオレフィン化反応、オレフィンの選択水素化反応、脂肪族脱ハロゲン化反応、芳香族脱ハロゲン化反応、酸クロライドの還元反応、芳香族ニトロ化合物のアミンへの水素化反応、芳香族カルボニルの水素化反応、安息香酸の環水素化反応、フェノールのシクロヘキサンへの水素化、芳香族ケトンのアルコールへの水素化、芳香族ケトンのアルキル芳香族への水素化、芳香族カルボニルの水素化分解、芳香族カルボニルの脱カルボニル、芳香族ニトリルアルデヒドへの水素化、シクロヘキセンの不均化、オレフィンの移動、アニリン類の還元Ｎ−メチル化、芳香族ニトロ化合物のヒドラゾベンゼン化合物への水素化、ニトロヘキサン類のシクロオキサノン類への水素化、ニトロオレフィン類のアルキルアミン類への水素化、オキサム類の第一アミンへの水素化、脱ベンジル反応、エポキサイドのアルコール類への水素化、還元アミノ化、キノン類のハイドロキノン類への水素化、芳香族エステル類の環水素化、フラン環の水素化、ピリジン化合物の環の水素化、硝酸塩のヒドロキシアミンへの水素化、過酸化物の水素化、脂肪族ニトロ化合物の水素化、アセトオキシレーション、カルボニレーション、脱水素反応、液相酸化反応、デオキソ反応、一酸化炭素の酸化、ＮＯＸの還元などの触媒として利用できる。
【００３４】
本発明の球状シリカ−アルミナ−マグネシア粒子は比表面積は６０〜５００ｍ2 ／ｇで、細孔容積は０．１〜０．５（ｃｍ3 ／ｇ）で、嵩密度は０．６〜１．３（ｇ／ｃｍ3 ）であるが、貴金属触媒の担体として用いる場合には、反応特性と強度とのバランスから最適化が行われ、パラジウム金属担持触媒、パラジウム金属化合物担持触媒の担体に用いる場合、好ましくは、比表面積７０〜３５０ｍ2 ／ｇで、細孔容積０．１４〜０．４５（ｃｍ3 ／ｇ）で、嵩密度０．７〜１．２０（ｇ／ｃｍ3 ）、より好ましくは比表面積が８０〜３００ｍ2 ／ｇで、細孔容積が０．１８〜０．４０（ｃｍ3 ／ｇ）で、嵩密度は０．８〜１．１５（ｇ／ｃｍ3 ）である。触媒調製上からは、担体の比表面積が大きいことは特に問題はない。しかしながら、比表面積が大きい場合には機械的強度及び耐食性が低下する傾向が見られる。
【００３５】
このため、最も好ましくは比表面積が１００〜２５０ｍ2 ／ｇで、細孔容積が０．１８〜０．３５（ｃｃ／ｇ）で、嵩密度は０．８５〜１．１０（ｇ／ｃｃ）の範囲から選ばれる。比表面積が６０ｍ2 ／ｇ未満でも、パラジウム成分を担持できるが、担持したパラジウムを有効に働かせるためには比表面積が不十分で、得られる触媒の反応活性も低い。
また、流動層反応や液層反応などで、沈降分離法を用いる場合には、分離の為に粒径の最適化が行われ、平均粒子径は１０〜２００μｍが好ましいが、より好ましくは２０〜１５０μｍ、特に好ましくは３０〜１００μｍで用いられる。
【００３６】
【発明実施の形態】
以下、本発明を実施例を挙げて説明する。
なお、実施例および比較例において用いた評価方法は以下のとおりである。
・Ｍｇ，Ａｌ，Ｓｉの含有量の求め方は、Ｍｇは王水で溶解、Ａｌ、Ｓｉはアルカリ溶融塩で溶解させ、ＩＣＰ（プラズマ発光分光分析器）によって測定し、各元素をＭｇＯ、Ａｌ2 Ｏ3 、ＳｉＯ2の酸化物に換算して求めた。
・スラリーの粘度測定は、Ｂ型粘度計を用いて測定した。
・比表面積は窒素ガス吸着法（（株）島津製作所製 ソープトグラフＡＤＳ−１Ｂ）で測定した。
・細孔容積と細孔分布は、２０〜１５０Å範囲で、窒素ガス吸着法（カルロ・エルバ社製 ソープトマチック１８００）で測定した。１５０Å以上は水銀圧入法（島津製作所製 オートポア９２００）で測定した。
・嵩密度（ＣＢＤ）の測定方法は、前処理として、担体をステンレスルツボに約１２０ｇ採取し、５００℃のマッフル炉で１時間焼成を行う。焼成後、デシケータ（シリカゲル入り）に入れ室温まで冷却する。測定は、前処理した担体を１００．０ｇ採取し、２５０ｍｌのメスシリンダーに移し、メスシリンダーを振とう器で１５分間タッピング充填する。メスシリンダーを取り外し、試料表面を平らにし充填容積を読み取る。嵩密度は担体の重量を充填容積で割った値である。
・粒子の摩耗度は、通常ＦＣＣ触媒の試験方法として行われているように、底部に１／６４インチの３つのオリフィスを有する孔明円板を備えた、内径１．５インチの垂直チューブに粒子約５０ｇを精秤投入し、孔明円板を通して毎時１５ＣＦの速度で空気を激しく粒子を稼動させた。粒子の摩耗度を、５〜２０時間の間に微細化して、垂直チューブの上部から逸散した粒子の、初期投入量に対する割合として求めた。
・粒子が球形であること、及び割れ、欠け、中空の観察は電子顕微鏡（ＳＥＭ）（（株）日立製作所製 Ｓ−２７００）により行った。
【００３７】
【実施例１】
５００リットルのステンレス製容器に、硝酸アルミニウム九水和物３７．６ｋｇ、硝酸マグネシウム六水和物２５．５ｋｇ、６０％硝酸５．４ｋｇ、水４６．７ｋｇを入れ撹拌しておく。ついで、シリカゾル溶液（ＳｉＯ2 ３０重量％）（日産化学（株）製、スノーテックスＮ−３０）２００．０ｋｇを少しずつ加え混合させ、スラリーを１５℃に保ち２時間撹拌する。この時のスラリー粘度は１１ｃｐであった。その後、スラリー温度を５０℃になるように撹拌下に加温し、スラリー温度が５０℃になったらそのまま２４時間保持すると粘度は２５４６ｃｐであった。このスラリーを、１３０℃の温度に設定したスプレードライヤーで噴霧乾燥し固形物を得た。つぎに、得た固形物をマッフル炉で室温から３００℃まで２時間かけ昇温後１時間保持した。さらに６００℃まで２時間で昇温後１時間保持した後徐冷して、球状のシリカ−アルミナ−マグネシア粒子（Ａ）を得た。表１にスラリー調合条件、表２に該球状シリカ−アルミナ−マグネシア粒子（Ａ）組成と焼成時の最高温度、表３に該球状シリカ−アルミナ−マグネシア粒子（Ａ）の性状を示す。
【００３８】
【実施例２】
実施例１と同様にして、スラリー温度を５０℃で、５０時間保持し粘度が２６３７ｃｐになったあと、スラリー温度を撹拌下に降温し１５℃にして３時間保持した。この時のスラリー粘度は１１０３ｃｐであった。このスラリーを実施例１と同様に１３０℃の温度に設定したスプレードライヤーで噴霧乾燥し固形物を得た。つぎに、得た固形物をマッフル炉で室温から３００℃まで２時間かけ昇温後１時間保持した。さらに６００℃まで２時間で昇温後１時間保持した後徐冷し、球状のシリカ−アルミナ−マグネシア粒子（Ｂ）を得た。表１にスラリー調合条件、表２に該球状シリカ−アルミナ−マグネシア粒子（Ｂ）組成と焼成時の最高温度、表３に該球状シリカ−アルミナ−マグネシア粒子（Ｂ）の性状を示す。
【００３９】
【比較例１】
実施例１で、５００リットルのステンレス製容器に、硝酸アルミニウム九水和物３７．６ｋｇ、硝酸マグネシウム六水和物２５．５ｋｇ、６０％硝酸５．４ｋｇ、水４６．７ｋｇを入れ撹拌しておく。ついで、シリカゾル溶液（ＳｉＯ2 ３０重量％）（日産化学（株）製 スノーテックスＮ−３０）２００．０ｋｇを少しずつ加え混合させ、スラリーを１５℃に保ち２時間撹拌する。この時のスラリー粘度は１１ｃｐであった。このスラリーを実施例１と同様に１３０℃の温度に設定したスプレードライヤーで噴霧乾燥し固形物を得た。つぎに、得た固形物をマッフル炉で室温から３００℃まで２時間かけ昇温後１時間保持した。さらに６００℃まで２時間で昇温後１時間保持した後徐冷し、球状のシリカ−アルミナ−マグネシア粒子（Ｃ）を得た。表１にスラリー調合条件、表２に該球状シリカーアルミナーマグネシア粒子Ｃ組成と焼成時の最高温度、表３に該球状シリカ−アルミナ−マグネシア粒子（Ｃ）の性状を示す。
【００４０】
【実施例３〜７、比較例２〜３】
実施例１と同等の調製を行ったが、硝酸アルミニウム九水和物、硝酸マグネシウム六水和物、硝酸量を表１の原料項目に示し、スラリー調合時の温度とスラリーを２４時間かけてコントロールした時のスラリー温度を表１の調合条件項目に示した。また、噴霧乾燥する条件は各実施例とも実施例１と同等条件で行った。噴霧乾燥で得られた固形物を焼成する際には得た固形物をマッフル炉で、室温から３００℃まで２時間かけ昇温後１時間保持する工程までは実施例１と同じ様にした。その後実施例１では、さらに６００℃まで２時間で昇温後１時間保持した後徐冷し、球状シリカ−アルミナ−マグネシア粒子を得ているが、この焼成時の最高温度を各実施例について表２に焼成温度として示した。また、球状シリカ−アルミナ−マグネシア粒子組成を表２に示した。表３に各実施例で得た球状シリカ−アルミナ−マグネシア粒子の性状を示した。
【００４１】
【実施例８】
実施例１で得られた球状シリカ−アルミナ−マグネシア粒子（Ａ）１ｋｇを蒸留水５リットルを入れたガラス容器に加え、６０℃で撹拌しながら、塩化パラジウムの希塩酸溶液、硝酸鉛水溶液をＰｄおよびＰｂとして２．５ｗｔ％（粒子（Ａ）に対して）に相当する量を素早く投入する。その後１時間保持し、ヒドラジンを量論量の１．２倍添加し還元する。還元後上澄みをデカントし、Ｃｌイオンが検出されなくなるまで蒸留水で洗浄し、６０℃で真空乾燥しＰｄ、Ｐｂを２．５ｗｔ％担持した触媒を得た。電磁誘導撹拌器付き３００ｍｌのステンレス製オートクレーブに触媒２０ｇ、原料として、メタクロレイン濃度が２０ｗｔ％のメタノールを１５０ｍｌ加え、滞留時間３時間となる様にメタクロレイン濃度２０ｗｔ％のメタノールを連続的に供給し、温度８０℃、圧力４ｋｇ／ｃｍ2 、回転数１０００ｒｐｍ（撹拌チップ速度：１．２ｍ／ｓ）、ｐＨ７となるようにＮａＯＨ／メタノール溶液を、出口酸素濃度８体積％となる様に、空気および窒素を供給し、連続反応を行った。２００時間反応させ、反応生成物をガスクロマトグラフィーで分析したところメタクロレインの転化率は６３．３％でメチルメタクリレート（ＭＭＡ）の選択率は８９．４％であった。また、１０００時間反応後触媒を抜き出し、電子顕微鏡（ＳＥＭ）で調べたところ触媒に割れ、欠け、中空はほとんど見られなかった。
【００４２】
【比較例４】
比較例１の球状シリカ−アルミナ−マグネシア粒子（Ｃ）を実施例８と同様の方法で触媒を得た。実施例８と同様の操作で連続反応を行った。２００時間反応させ、ガスクロマトグラフィーで分析したところメタクロレインの転化率は５９．２％でメチルメタクリレート（ＭＭＡ）の選択率は８７．４％であった。また、１０００時間反応後触媒を抜き出し、電子顕微鏡（ＳＥＭ）で調べたところ触媒の一部に割れ、欠け、中空が見られた。
【００４３】
【実施例９】
実施例１の球状シリカ−アルミナ−マグネシア粒子（Ａ）１ｋｇを０．１Ｎのアンモニア水を酸点の量の３〜４倍に相当する量でイオン交換した。１リットルの蒸留水を加え、６０℃で撹拌しながら０．０１モルの［Ｐｄ［ＮＨ3］4］Ｃ12水溶液をＰｄが２．５ｗｔ％（粒子（Ａ）に対して）に相当する量をゆっくり滴下する。その後ろ過し、Ｃｌイオンが検出されなくなるまで蒸留水で洗浄し、１１０℃で乾燥する。水素気流中で、３００℃、４時間還元し、さらに、酢酸ビスマスをビスマスとして２．５ｗｔ％相当量を含浸担持した触媒を得た。電磁誘導撹拌器付き３００ｍｌのステンレス製オートクレーブに触媒２０ｇ、原料として、アクロレイン濃度が２０ｗｔ％のメタノールを１５０ｍｌ加え、滞留時間３時間となる様にアクロレイン濃度２０ｗｔ％のメタノールを連続的に供給し、温度８０℃、圧力４ｋｇ／ｃｍ2 、回転数１０００ｒｐｍ（撹拌チップ速度：１．２ｍ／ｓ）、ｐＨ７となるようにＮａＯＨ／メタノール溶液を、出口酸素濃度８体積％となる様に、空気および窒素を供給し、連続反応を行った。反応２００時間反応させガスクロマトグラフィーで分析したところアクロレインの転化率は６４．１％でアクリレートの選択率は８８．６％であった。１０００時間反応後触媒を抜き出し、電子顕微鏡（ＳＥＭ）で調べたところ触媒に割れ、欠け、中空はほとんど見られなかった。
【００４４】
【表１】
【表２】
【表３】
【発明の効果】
本発明の球状シリカ−アルミナ−マグネシア粒子は機械的強度が強く、比表面積が大きく、形状が球状で、環境に優しい材料であることから、顔料、充填剤、研磨剤、化粧品基剤、農業用担体、触媒担体、吸着剤等として有用であり、特に、パラジウム系担持触媒を提供する際に、この球状シリカーアルミナーマグネシア粒子を触媒担持とし用いれば、優れた触媒性能を長期間安定に運転継続することができると共に、触媒寿命が大きく改善されたことにより触媒交換の頻度が少なくなることから操作性も良く、経済的効果が大である。
また、本発明の方法によれば、機械的強度が強く、比表面積が大きく、流動性の良い球状シリカーアルミナーマグネシア粒子を再現性良く製造することできる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silica spherical particle containing aluminum and magnesium having excellent mechanical strength (hereinafter referred to as a spherical silica-alumina-magnesia particle) and a method for producing the same.
[0002]
[Prior art]
Spherical silica-based particles are used as materials that take advantage of their properties in various applications. Examples thereof include liquid chromatography fillers, cosmetic bases, catalyst carriers, flow regulators, diluents and the like. In order to satisfy the requirements required for these applications, if the physical properties such as a high specific surface area are satisfied, the material becomes porous and the mechanical strength becomes weak. On the other hand, if the mechanical strength is to be satisfied, the specific surface area is reduced due to firing at a high temperature. Thus, it is difficult to obtain spherical silica-based particles satisfying the contradicting physical properties of high mechanical strength and large specific surface area, and spherical silica-based particles satisfying both requirements have not been obtained. Furthermore, a method for producing a large amount of the silica-based particles with high reproducibility is also desired.
[0003]
It is known that quartz, which is one of silica-based materials, is hard and has high mechanical strength. However, the mechanical strength is excellent, but the specific surface area is low (1 m2/ G or less) and cannot be used for applications requiring a high specific surface area.
Japanese Patent Application Laid-Open No. 63-16049 discloses a particle size of 20 to 500 μm and a specific surface area of 30 to 800 m.2/ G and pore volume of 0.3-2.0 cmThreeAlthough a fluidized bed catalyst support made of spherical silica gel of / g has been proposed, its mechanical strength is weak.
[0004]
JP-A-6-64915 discloses a method for producing spherical silica by emulsifying an alkali metal silicate aqueous solution in a nonpolar organic halide solvent containing a surfactant and then gelling with a gelling agent. Has been proposed. The spherical silica obtained here is dried at 120 ° C. for several hours to remove intergel water, and can be obtained from intergel water and has a large pore volume and a large specific surface area, but the mechanical strength is weak. When used as a liquid chromatography filler, cosmetic base, etc., cracks and chipping occur.
[0005]
JP-A-8-119621 discloses a specific surface area of 50 m.2/ G or less, a pore volume of 0.3 ml / g or less, an abrasion resistance of 3.0 wt% / 15 hr or less, a bulk density of 0.6 to 1.3 g / ml, and an average particle size of 30 to 150 μm. A method for producing a composition comprising silica-phosphorus-boron has been proposed. However, the proposed one has a small specific surface area for use as a catalyst carrier, a fluid preparation agent and the like.
[0006]
In JP-A-9-52044, as a carrier for a catalyst for producing a carboxylic acid ester having excellent strength, the aluminum content is 5 to 40 wt% as an oxide, and the magnesium content is 3 to 30 wt% as an oxide. , SiO2As a proposal, a silica-alumina-magnesia containing 50 to 92 wt% is used as a support. This carrier can satisfy the mechanical strength under normal use conditions. However, when used under severe conditions such as a reaction between particles, a particle and a stirring spring, for example, a harsh condition such as a suspension reaction, cracking and chipping may occur. Further, when an attempt is made to produce a silica-alumina-magnesia carrier on an industrial scale, cracks, chips, and hollows sometimes occur, and a carrier having a high mechanical strength and a method for producing with good reproducibility. It was desired.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide spherical silica-based particles having high mechanical strength, a large specific surface area, and good fluidity, and a production method with good reproducibility thereof.
[0008]
[Means for Solving the Problems]
The present inventors consider that it is important to make silica-alumina-magnesia particles in a dense structure in order to produce spherical silica particles that satisfy mechanical strength, have a large specific surface area, and good fluidity. -We have conducted extensive research on the correlation between the physical properties of alumina-magnesia particles and the production conditions. As a result, it was found that the cause of cracking, chipping and hollowing was mainly related to the density in the particles, and a slurry containing silica, aluminum compound and magnesium compound was prepared at a specific ratio, and the slurry was specified. It was found that spherical silica particles having surprisingly high mechanical strength and a large specific surface area can be produced by spray granulation and firing after increasing the viscosity of the present invention, and reached the present invention.
[0009]
That is, the present invention is as follows.
(1) a)g)Silica spherical particles containing aluminum and magnesium having the following characteristics:
a) Specific surface area; 60-500 (m2 / G),
b) pore volume; 0.1-0.5 (cm3 / G),
c) Pore distribution; 90% or more of the pore volume is in the range of pore diameters of 10 to 500 mm,
d) Bulk density; 0.6 to 1.3 (g / cm3 ),
e) Abrasion resistance; 2.0 wt% / 15 hr or less,
f) Average particle diameter; 0.5 to 300 μm,
g) The aluminum content is 5 to 40 wt% as an oxide, and the magnesium content is 3 to 30 wt% as an oxide.
(2) A slurry containing 30 to 92 wt%, 5 to 40 wt%, and 3 to 30 wt% of silica, aluminum compound, and magnesium compound as silica, aluminum oxide, and magnesium oxide, respectively, was prepared, and the viscosity of the slurry was 100 cp Manufactured by spray drying granulation in the range of 10000 cp (1)InDescriptionofA method for producing silica spherical particles.
(3) A noble metal-supported product obtained by supporting a metal component containing palladium on the silica spherical particles according to (1).
[0010]
The present invention is described in detail below.
In the present invention, it is important that a slurry containing silica, an aluminum compound, and a magnesium compound is prepared and spray-dried and granulated in the range of viscosity of 100 cp to 10000 cp. Although detailed examination of why the mechanical strength increases due to this is insufficient, the present inventors estimated this effect as follows.
[0011]
When the slurry is granulated by spray drying, it usually shows various shapes, and the liquid droplets first begin to shrink due to liquid evaporation. Thereafter, there are three types of state changes. (1) Due to solidification of the droplet surface, the outlet is blocked and the inner droplet cannot evaporate to the outside, and the once shrunk particle size increases as the internal pressure increases, resulting in destruction (cracking). When the temperature returns to room temperature, the internal pressure disappears or the negative pressure is generated, so that a depressed ball is formed. In rare cases, it may become an expanded sphere as it is. {Circle around (2)} A hollow sphere can be formed while maintaining the contracted particle size. (3) When the drying temperature and shrinkage are well balanced, solid spheres without pores can be obtained. In order to obtain the spherical silica-alumina-magnesia particles of the object of the present invention, it is necessary to produce solid spheres such as (3) with high reproducibility that can increase the density and mechanical strength.
[0012]
In the present invention, it can be estimated that a Si—O—Al—O—Si bond is newly formed in the uncrosslinked silica (Si—OH) chain of the silica gel in the slurry before spray-drying granulation. It is thought that the increase in the viscosity of the slurry suggests that the number of Si—O—Al—O—Si bonds increases. This bond formation is thought to reduce the number of uncrosslinked silica (Si—OH) chains in the silica gel and strengthen the Si—O bond. As a result, strong bonds were formed at the slurry stage before spray-drying granulation, so that it was possible to suppress the occurrence of breakage, hollows, etc. that occurred during spray-drying granulation, and it was considered that solid balls (3) could be produced. . In addition, by coexisting magnesium (Mg), the difference in charge caused by the difference in valence between Si (tetravalent) and Al (trivalent) due to the formation of a Si—O—Al—O—Si crosslinked structure can be reduced to magnesium ( It is presumed that the stability of the structure is improved because the (bivalent) is neutralized by compensation and the charge balance is achieved.
[0013]
The spherical silica-alumina-magnesia particles of the present invention are
a) Specific surface area; 60-500 (m2 / G),
b) pore volume; 0.1 to 0.5 (cc / g),
c) Pore distribution; 90% or more of the pore volume is in the range of pore diameters of 10 to 500 mm,
d) Bulk density; 0.6 to 1.3 (g / cc),
e) Abrasion resistance; 2.0 wt% / 15 hr or more,
f) Average particle diameter; 0.5 to 300 μm,
g) It is necessary that the aluminum content is 5 to 40 wt% as an oxide and the magnesium content is 3 to 30 wt% as an oxide.
[0014]
If the content of a) specific surface area, b) pore volume, c) pore distribution, d) bulk density, e) abrasion resistance, f) average particle diameter, and g) aluminum and magnesium are within this range, Particles having high mechanical strength, a large specific surface area, and good fluidity can be obtained. This is presumably because magnesium, aluminum, and silica form a specific stable bonding structure within this range, and thus the spherical silica-alumina-magnesia particles have a dense structure.
[0015]
The specific surface area of the spherical silica-alumina-magnesia particles of the present invention is 60 to 500 m as measured by the nitrogen adsorption method.2/ G, preferably 80 to 400 m2/ G, more preferably 100 to 300 m2/ G. Moreover, it is preferable to use it after baking at suitable temperature so that it may become the said specific surface area after spray-drying granulation. The firing temperature is selected from the range of 220 to 800 ° C. If the firing is performed at a temperature exceeding 800 ° C., the specific surface area is remarkably lowered. The firing atmosphere is not particularly limited, but firing in air or nitrogen is common. The firing time can be determined according to the specific surface area after firing.
[0016]
The pore volume of the spherical silica-alumina-magnesia particles of the present invention is 0.1 to 0.5 (cmThree/ G), preferably 0.15 to 0.4 (cmThree/ G), more preferably 0.2 to 0.3 (cmThree/ G). The pore volume is 0.5 (cmThree/ G), the mechanical strength becomes weaker. The pore volume is 0.1 (cmThree/ G), the specific surface area becomes insufficient.
[0017]
As for the pore distribution, 90% or more of the pore volume needs to be in the range of the pore diameter of 10 to 500 mm. If 90% or more of the pore volume is concentrated and distributed in the range of the pore diameter of 10 to 500 mm, the crack (strain) is reduced and the mechanical strength is increased. Preferably it is 93% or more.
Bulk density is 0.6 to 1.3 (g / cmThree), Preferably 0.8 to 1.2 (g / cmThreeMore preferably, 0.85 to 1.15 (g / cmThree). The bulk density is an index of the spherical degree or flow state of the spherical silica particles. Bulk density is 0.6 (g / cmThree), The number of distorted shapes, cracks, chips, and hollow silica particles increases. Moreover, 1.3 (g / cmThree) Exceeds the specific surface area, it becomes insufficient.
[0018]
The abrasion resistance needs to be 2.0 wt% / 15 hr or less, preferably 1.0 wt% / 15 hr or less, more preferably 0.5 wt% / 15 hr or less. When the wear resistance exceeds 2.0 wt% / 15 hr, the particles are liable to be pulverized or cracked.
The average particle size needs to be 0.5 to 300 μm, preferably 20 to 200 μm, and more preferably 30 to 150 μm.
[0019]
The content of aluminum and magnesium needs to be 5 to 40 wt% as an oxide, preferably 5 to 30 wt%, and more preferably 7 to 20 wt%. The magnesium content is required to be 3 to 30 wt% as an oxide, preferably 3 to 20 wt%, and more preferably 5 to 15 wt%.
[0020]
A method for producing the spherical silica-alumina-magnesia particles of the present invention will be described.
The slurry used in the present invention is prepared as follows.
(1) A silica-alumina gel formed in advance, obtained by adding magnesium oxide and reacted; (2) obtained by reacting a solution such as silica gel with a solution of an aluminum compound and a magnesium compound; (3) What is obtained by reacting silica gel with water-insoluble aluminum compound and magnesium compound, (4) What is obtained by reacting silica gel with water-soluble aluminum compound and magnesium compound aqueous solution. In the present invention, it is necessary to produce the slurry thus obtained by spray-drying granulation in the range of 100 cp to 10000 cp, preferably 500 to 10000 cp, more preferably 800 to 10000 cp. Granulate by spray drying. When the viscosity of the slurry is several cp to several tens cp, no significant improvement effect is observed. However, the present inventors have surprisingly found that a dramatic effect appears when it exceeds 100 cp. On the other hand, the same effect can be expected even when the slurry viscosity is 10,000 cp or more, but normally, spray drying granulation becomes difficult as the slurry viscosity increases.
[0021]
In the present invention, when preparing particles having an average particle size of 30 μm or more, the viscosity of the slurry is preferably 500 cp to 10,000 cp. More preferably, it is 1000 cp-10000 cp, Most preferably, it is 2000 cp-10000 cp. The viscosity of the slurry is increased because the bond between silica, aluminum, and magnesium becomes stronger in the slurry, and when trying to prepare a slurry having a large average particle size, increasing the viscosity increases the mechanical strength. It is important to obtain strong spherical silica-alumina-magnesia particles. On the other hand, when preparing particles of less than 30 μm by spray-drying granulation, if the viscosity is increased too much, the yield at the time of production deteriorates, so 100 to 3000 cp is preferable, and 100 to 1000 cp is more preferable.
[0022]
Below, the acquisition method of said (1)-(4) is demonstrated. Silica sol, water glass or silica gel can be used as the silica raw material. In order to impart strength to the average particle size of the silica colloid particles in the silica sol, several types of silica colloids having different particle sizes can be used. The silica gel may have an uncrosslinked silica (Si—OH) chain that reacts with aluminum, and the length of the Si—O chain is not limited.
The aluminum raw material is preferably a water-soluble compound such as sodium aluminate, aluminum chloride hexahydrate, aluminum perchlorate hexahydrate, aluminum sulfate, aluminum nitrate nonahydrate, and aluminum diacetate. Any compound that is insoluble in water, such as aluminum oxide, can be used as long as it reacts with silica sol and uncrosslinked silica in silica gel.
[0023]
As the magnesium raw material, magnesium oxide, magnesium hydroxide, magnesium acetate, magnesium nitrate, magnesium chloride, magnesium sulfate, and the like can be used.
To give a specific example of (1) using silica-alumina gel as a starting material, a silica hydrogel having a pH of 8 to 10.5 is prepared in advance by adding sulfuric acid to water glass.2(SOFour)ThreeAdd aqueous solution (pH 2 or lower), add sodium aluminate (pH 5 to 5.5), prepare silica-alumina hydrogel to be formed, adjust moisture, etc., then add MgO to obtain slurry Can do.
[0024]
In the case of (2) and (3) using a solution such as silica sol as a starting material, a slurry is obtained by mixing a solution such as silica sol with an aluminum compound and a magnesium compound. At this time, an acid such as nitric acid, sulfuric acid or hydrochloric acid can be used to dissolve the aluminum compound and the magnesium compound.
In the case of (4) using silica gel as a starting material, a slurry is obtained by reacting silica gel with an aqueous solution of a water-soluble aluminum compound and magnesium compound. At that time, the silica gel may be pulverized to a predetermined particle diameter in advance or coarsely pulverized in advance.
[0025]
The slurry thus obtained can be heated to increase the viscosity as necessary. In addition, when the time for spray drying granulation becomes longer as in the case of industrial production, the slurry temperature is lowered so that the viscosity of the slurry does not change so much that the viscosity of the slurry is stabilized. It is preferable to do.
As temperature which heats a slurry, 40-100 degreeC is preferable, More preferably, it is 40-80 degreeC. If the heating temperature exceeds 100 ° C., the slurry viscosity becomes too high, or water in the slurry evaporates, making it difficult to obtain reproducibility. When the heating temperature is less than 40 ° C., the viscosity does not increase or it takes too much time to increase the viscosity.
[0026]
In the present invention, the slurry concentration when spray drying granulation is preferably 5 to 50 wt%, more preferably 10 to 40 wt%, particularly preferably 15 to 30 wt% as an oxide. .
The production method of the present invention has good reproducibility, and since the obtained spherical silica-alumina-magnesia particles have excellent mechanical strength and good fluidity, the particles are produced on a large scale such as an industrial scale. It is particularly suitable for production.
[0027]
The spherical silica-alumina-magnesia particles of the present invention can be used for materials such as pigments, fillers, abrasives, cosmetic bases, agricultural chemical carriers, catalyst carriers, adsorbents and the like.
For example, as a requirement for pigments, fine powders that are insoluble in water, oil, organic solvents, etc., and high mechanical strength are required. The spherical silica-alumina-magnesia particles of the present invention have high mechanical strength and excellent properties that do not easily crack or chip. Furthermore, the particles of the present invention are excellent in water resistance, oil resistance and organic solvent resistance. As the pigment, small particles are generally used, and the average particle diameter is preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm. It can also be used as an additive for paints, printing inks, synthetic resins, fibers, rubbers and the like.
[0028]
Moreover, the synthetic silica filler conventionally used as a filler has a bulk density of 0.04 to 0.2 (g / cmThree), It was inconvenient to transport and handle. The spherical silica-alumina-magnesia particles of the present invention have a high bulk density of 0.6 to 1.3 (g / cc) and solve the drawbacks of conventional synthetic silica fillers. In addition, since it has high mechanical strength, it is useful as a reinforcing agent for increasing the strength of the polymer. Furthermore, it is useful as a matting agent, vinyl chloride paste, epoxy resin, polyester resin prepolymer viscosity modifier.
[0029]
The spherical silica-alumina-magnesia particles of the present invention are useful as an abrasive because their wear resistance is 2.0 wt% / 15 hr or less. As an abrasive, shape and bulk density geometric properties are important. Compared to silica sand, float stone, diatomaceous earth, and the like, the particles of the present invention have a high mechanical strength, a spherical shape and a high bulk density, and thus have excellent properties as an abrasive. Moreover, although it is necessary to arrange | equalize a particle size with the object to grind | polish, since mechanical strength is strong, even if it classifies, damage etc. do not occur easily and the spherical particle thing of the particle size suitable for grinding | polishing object can be obtained. The average particle size as the abrasive is various in particle size depending on the object to be polished, and generally 1 to 300 μm is preferable, and the average particle size is used depending on the application. The particles of the present invention are useful for polishing glass, wood, rust removal, dirt removal, finishing of bones such as metal, wood, ivory, art crafts, ceramics, soft metal glossing, and the like.
[0030]
As cosmetic bases, (1) harmless and non-irritating to the human body, (2) good stability, and (3) good usability are desired. The particles of the present invention are harmless and non-irritating, have excellent water resistance, oil resistance, and organic solvent resistance, and thus have good stability. Since they are spherical, they provide a smooth feel and high usability. Useful as an agent.
The particles used as the agrochemical carrier have a uniform particle size distribution, and an operation (classification) is performed except for particles of 10 μm or less. This is because when the particles of 10 μm or less are removed, the physical properties of the powder, such as dusting properties, dispersibility, scattering properties, and stability over time, are remarkably improved. Since the spherical silica-alumina-magnesia particles of the present invention are spherical and have high mechanical strength, it is easy to remove particles of 10 μm or less by air classification. Further, when the viscosity is increased to 3000 cp or more and spray-drying granulation is carried out, it is possible to produce with a proportion of particles having a particle size of 10 μm or less.
[0031]
The use example of the spherical silica-alumina-magnesia particles of the present invention as a catalyst carrier will be described below based on specific examples. When used as a fluidized bed catalyst support, a catalytically active component is supported on this, but as these components, an active component is appropriately selected depending on the target reaction, for example, molybdenum, vanadium, cobalt, nickel, silver, copper, Components such as tungsten, alkali metals, alkaline earth metals, and / or zinc can be mentioned. As a method for supporting these components on the spherical silica-alumina-magnesia particles of the present invention, a normal impregnation method, precipitation method, ion exchange method, melt impregnation method, vapor deposition method, or the like is employed depending on the component. In addition, the fluidized bed reaction to which the spherical silica-alumina-magnesia particles of the present invention can be applied is not particularly limited. For example, isomerization reaction from ethylene oxide to acetaldehyde, production of acrylontolyl by dehydration of ethylene cyanohydrin. Reaction, synthesis of acrolein from formaldehyde and acetaldehyde, hydration reaction of olefin, reaction of obtaining phthalic anhydride by oxidation of naphthalene or o-xylene, and the like.
[0032]
The spherical silica-alumina-magnesia particles of the present invention are also preferably used as a carrier for a palladium metal supported catalyst and a palladium metal compound supported catalyst. Examples of methods for preparing palladium metal-supported catalyst and palladium metal compound-supported catalyst using the spherical silica-alumina-magnesia particles as a carrier include impregnation method, precipitation method, ion exchange method, etc. A suitable preparation method may be employed.
[0033]
Moreover, it can utilize for a wide catalytic reaction as a palladium metal carrying catalyst and a palladium metal compound carrying catalyst. For example, oxidative carboxylic esterification reaction from aldehyde and alcohol, partial hydrogenation reaction of acetylenes to olefins, complete hydrogenation reaction to paraffins, monoolefination reaction of diolefins, selective hydrogenation reaction of olefins , Aliphatic dehalogenation reaction, aromatic dehalogenation reaction, acid chloride reduction reaction, aromatic nitro compound hydrogenation reaction to amine, aromatic carbonyl hydrogenation reaction, benzoic acid ring hydrogenation reaction, phenol Hydrogenation to cyclohexane, hydrogenation of aromatic ketones to alcohols, hydrogenation of aromatic ketones to alkylaromatics, hydrogenolysis of aromatic carbonyls, decarbonylation of aromatic carbonyls, to aromatic nitrile aldehydes Hydrogenation, cyclohexene disproportionation, olefin transfer, reduction N-methylation of anilines, aroma Hydrogenation of nitro compounds to hydrazobenzene compounds, hydrogenation of nitrohexanes to cyclooxanones, hydrogenation of nitroolefins to alkylamines, hydrogenation of oxams to primary amines, debenzylation Reaction, hydrogenation of epoxides to alcohols, reductive amination, hydrogenation of quinones to hydroquinones, ring hydrogenation of aromatic esters, hydrogenation of furan rings, hydrogenation of ring of pyridine compounds, nitrate conversion Hydrogenation to hydroxyamine, hydrogenation of peroxide, hydrogenation of aliphatic nitro compounds, acetooxylation, carbonation, dehydrogenation reaction, liquid phase oxidation reaction, deoxo reaction, oxidation of carbon monoxide, NOX It can be used as a catalyst for reduction.
[0034]
The spherical silica-alumina-magnesia particles of the present invention have a specific surface area of 60 to 500 m.2/ G, the pore volume is 0.1 to 0.5 (cmThree/ G) and the bulk density is 0.6 to 1.3 (g / cm).ThreeHowever, when used as a support for a noble metal catalyst, optimization is performed from the balance between reaction characteristics and strength, and when used as a support for a palladium metal supported catalyst or a palladium metal compound supported catalyst, preferably a specific surface area. 70-350m2/ G, pore volume of 0.14 to 0.45 (cmThree/ G) and a bulk density of 0.7 to 1.20 (g / cm).Three), More preferably the specific surface area is 80-300 m2/ G, pore volume is 0.18-0.40 (cmThree/ G) and the bulk density is 0.8 to 1.15 (g / cm).Three). From the viewpoint of catalyst preparation, there is no particular problem that the specific surface area of the support is large. However, when the specific surface area is large, the mechanical strength and the corrosion resistance tend to decrease.
[0035]
For this reason, the specific surface area is most preferably 100 to 250 m.2/ G, the pore volume is 0.18 to 0.35 (cc / g), and the bulk density is selected from the range of 0.85 to 1.10 (g / cc). Specific surface area is 60m2The palladium component can be supported even at less than / g, but the specific surface area is insufficient to make the supported palladium work effectively, and the reaction activity of the resulting catalyst is low.
In addition, when using a sedimentation separation method in a fluidized bed reaction or a liquid bed reaction, the particle size is optimized for separation, and the average particle size is preferably 10 to 200 μm, more preferably 20 to 20 μm. It is used at 150 μm, particularly preferably 30 to 100 μm.
[0036]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described with reference to examples.
The evaluation methods used in the examples and comparative examples are as follows.
-The content of Mg, Al, Si is obtained by dissolving Mg in aqua regia, Al, Si in an alkali molten salt, and measuring with an ICP (plasma emission spectrophotometer).2OThree, SiO2It calculated | required in conversion to the oxide of.
-The viscosity of the slurry was measured using a B-type viscometer.
The specific surface area was measured by a nitrogen gas adsorption method (Sorptograph ADS-1B manufactured by Shimadzu Corporation).
-The pore volume and pore distribution were measured by a nitrogen gas adsorption method (Sorptomatic 1800 manufactured by Carlo Elba) in the range of 20 to 150 mm. 150 mm or more was measured by a mercury intrusion method (Autopore 9200, manufactured by Shimadzu Corporation).
-As a pretreatment, the bulk density (CBD) is measured by collecting about 120 g of a carrier in a stainless crucible and firing in a muffle furnace at 500 ° C for 1 hour. After firing, place in a desiccator (with silica gel) and cool to room temperature. For measurement, 100.0 g of the pretreated carrier is collected, transferred to a 250 ml graduated cylinder, and the graduated cylinder is tapped and filled with a shaker for 15 minutes. Remove the graduated cylinder, flatten the sample surface and read the filling volume. The bulk density is a value obtained by dividing the weight of the carrier by the filling volume.
Particle wear is measured in a 1.5 inch ID vertical tube with a perforated disc with three 1/64 inch orifices at the bottom, as is normally done as a test method for FCC catalysts. About 50 g was precisely weighed, and particles were vigorously operated through the perforated disk with air at a speed of 15 CF / hour. The degree of wear of the particles was refined during 5 to 20 hours, and was determined as the ratio of the particles dissipated from the top of the vertical tube to the initial input amount.
-The observation that the particles were spherical and the cracks, chips and hollows were made with an electron microscope (SEM) (S-2700, manufactured by Hitachi, Ltd.).
[0037]
[Example 1]
In a 500 liter stainless steel container, 37.6 kg of aluminum nitrate nonahydrate, 25.5 kg of magnesium nitrate hexahydrate, 5.4 kg of 60% nitric acid, and 46.7 kg of water are placed and stirred. Next, a silica sol solution (SiO2 30 wt%) (Nissan Chemical Co., Ltd., Snowtex N-30) 200.0 kg was added little by little and mixed, and the slurry was kept at 15 ° C. and stirred for 2 hours. The slurry viscosity at this time was 11 cp. Thereafter, the slurry was heated with stirring so that the slurry temperature became 50 ° C. When the slurry temperature reached 50 ° C. and kept for 24 hours, the viscosity was 2546 cp. This slurry was spray-dried with a spray dryer set at a temperature of 130 ° C. to obtain a solid. Next, the obtained solid was held in a muffle furnace from room temperature to 300 ° C. over 2 hours and then held for 1 hour. Further, the temperature was raised to 600 ° C. in 2 hours, held for 1 hour, and then gradually cooled to obtain spherical silica-alumina-magnesia particles (A). Table 1 shows the slurry preparation conditions, Table 2 shows the composition of the spherical silica-alumina-magnesia particles (A) and the maximum temperature during firing, and Table 3 shows the properties of the spherical silica-alumina-magnesia particles (A).
[0038]
[Example 2]
In the same manner as in Example 1, after the slurry temperature was maintained at 50 ° C. for 50 hours and the viscosity reached 2637 cp, the slurry temperature was lowered with stirring to 15 ° C. and maintained for 3 hours. The slurry viscosity at this time was 1103 cp. This slurry was spray-dried with a spray dryer set at a temperature of 130 ° C. in the same manner as in Example 1 to obtain a solid. Next, the obtained solid was held in a muffle furnace from room temperature to 300 ° C. over 2 hours and then held for 1 hour. Further, the temperature was raised to 600 ° C. in 2 hours, and then kept for 1 hour and then gradually cooled to obtain spherical silica-alumina-magnesia particles (B). Table 1 shows the slurry preparation conditions, Table 2 shows the composition of the spherical silica-alumina-magnesia particles (B) and the maximum temperature during firing, and Table 3 shows the properties of the spherical silica-alumina-magnesia particles (B).
[0039]
[Comparative Example 1]
In Example 1, 37.6 kg of aluminum nitrate nonahydrate, 25.5 kg of magnesium nitrate hexahydrate, 5.4 kg of 60% nitric acid, and 46.7 kg of water were placed in a 500-liter stainless steel container and stirred. . Next, a silica sol solution (SiO2 30 wt%) (Snowtex N-30, manufactured by Nissan Chemical Co., Ltd.) 200.0 kg was added little by little, and the slurry was kept at 15 ° C. and stirred for 2 hours. The slurry viscosity at this time was 11 cp. This slurry was spray-dried with a spray dryer set at a temperature of 130 ° C. in the same manner as in Example 1 to obtain a solid. Next, the obtained solid was held in a muffle furnace from room temperature to 300 ° C. over 2 hours and then held for 1 hour. Further, the temperature was raised to 600 ° C. for 2 hours, and then kept for 1 hour, followed by slow cooling to obtain spherical silica-alumina-magnesia particles (C). Table 1 shows the slurry preparation conditions, Table 2 shows the composition of the spherical silica-alumina-magnesia particles C and the maximum temperature during firing, and Table 3 shows the properties of the spherical silica-alumina-magnesia particles (C).
[0040]
Examples 3-7, Comparative Examples 2-3
The same preparation as in Example 1 was performed, but the aluminum nitrate nonahydrate, magnesium nitrate hexahydrate, and the amount of nitric acid are shown in the raw material items in Table 1, and the temperature and slurry during slurry preparation were controlled over 24 hours. The slurry temperature at the time of the preparation is shown in Table 1. The conditions for spray drying were the same as in Example 1 for each example. When the solid obtained by spray drying was baked, the obtained solid was heated in a muffle furnace from room temperature to 300 ° C. over 2 hours and held for 1 hour and then the same procedure as in Example 1. Thereafter, in Example 1, the temperature was further raised to 600 ° C. for 2 hours and then held for 1 hour, followed by slow cooling to obtain spherical silica-alumina-magnesia particles. The maximum temperature during firing was shown for each example. 2 shows the firing temperature. The composition of spherical silica-alumina-magnesia particles is shown in Table 2. Table 3 shows the properties of the spherical silica-alumina-magnesia particles obtained in each example.
[0041]
[Example 8]
While adding 1 kg of the spherical silica-alumina-magnesia particles (A) obtained in Example 1 to a glass container containing 5 liters of distilled water, stirring at 60 ° C., dilute hydrochloric acid solution of palladium chloride, aqueous lead nitrate solution was added to Pd and An amount corresponding to 2.5 wt% (based on the particles (A)) is rapidly added as Pb. Thereafter, the mixture is held for 1 hour, and hydrazine is added 1.2 times the stoichiometric amount to reduce. After reduction, the supernatant was decanted, washed with distilled water until no Cl ions were detected, and vacuum dried at 60 ° C. to obtain a catalyst carrying 2.5 wt% of Pd and Pb. To a 300 ml stainless steel autoclave with an electromagnetic induction stirrer, add 20 g of catalyst, 150 ml of methanol with a methacrolein concentration of 20 wt% as a raw material, and continuously supply methanol with a methacrolein concentration of 20 wt% so that the residence time is 3 hours. , Temperature 80 ° C, pressure 4kg / cm2A continuous reaction was carried out by supplying NaOH / methanol solution at a rotation speed of 1000 rpm (stirring tip speed: 1.2 m / s), pH 7 and air and nitrogen so that the outlet oxygen concentration was 8% by volume. . The reaction product was reacted for 200 hours, and the reaction product was analyzed by gas chromatography. The conversion of methacrolein was 63.3% and the selectivity of methyl methacrylate (MMA) was 89.4%. Further, after the reaction for 1000 hours, the catalyst was extracted and examined with an electron microscope (SEM). As a result, the catalyst was hardly cracked, chipped or hollow.
[0042]
[Comparative Example 4]
A catalyst was obtained from the spherical silica-alumina-magnesia particles (C) of Comparative Example 1 in the same manner as in Example 8. A continuous reaction was carried out in the same manner as in Example 8. As a result of reaction for 200 hours and analysis by gas chromatography, the conversion of methacrolein was 59.2% and the selectivity of methyl methacrylate (MMA) was 87.4%. Further, after the reaction for 1000 hours, the catalyst was extracted and examined with an electron microscope (SEM). As a result, cracks, chips, and hollows were found in a part of the catalyst.
[0043]
[Example 9]
1 kg of spherical silica-alumina-magnesia particles (A) of Example 1 was ion-exchanged with 0.1N ammonia water in an amount corresponding to 3 to 4 times the amount of acid sites. Add 1 liter of distilled water and stir at 60 ° C. with 0.01 mol of [Pd [NHThree]Four] C12The aqueous solution is slowly added dropwise in an amount corresponding to 2.5 wt% Pd (based on the particles (A)). Thereafter, it is filtered, washed with distilled water until no Cl ions are detected, and dried at 110 ° C. The catalyst was reduced in a hydrogen stream at 300 ° C. for 4 hours, and further, a catalyst impregnated and supported by 2.5 wt% corresponding to bismuth acetate as bismuth was obtained. To a 300 ml stainless steel autoclave with an electromagnetic induction stirrer, add 20 g of catalyst and 150 ml of methanol with an acrolein concentration of 20 wt% as a raw material. 80 ° C, pressure 4kg / cm2A continuous reaction was carried out by supplying NaOH / methanol solution at a rotation speed of 1000 rpm (stirring tip speed: 1.2 m / s), pH 7 and air and nitrogen so that the outlet oxygen concentration was 8% by volume. . The reaction was conducted for 200 hours and analyzed by gas chromatography. The conversion of acrolein was 64.1% and the selectivity for acrylate was 88.6%. After the reaction for 1000 hours, the catalyst was extracted and examined with an electron microscope (SEM). As a result, the catalyst was hardly cracked, chipped or hollow.
[0044]
[Table 1]
[Table 2]
[Table 3]
【The invention's effect】
Since the spherical silica-alumina-magnesia particles of the present invention have a high mechanical strength, a large specific surface area, a spherical shape and are environmentally friendly materials, they are pigments, fillers, abrasives, cosmetic bases, agricultural products. It is useful as a carrier, catalyst carrier, adsorbent, etc. Especially when providing a palladium-based supported catalyst, if this spherical silica-alumina-magnesia particle is used as a catalyst supported, excellent catalytic performance can be stably operated over a long period of time. In addition to being able to continue, the catalyst life is greatly improved, so the frequency of catalyst replacement is reduced, so that the operability is good and the economic effect is great.
Further, according to the method of the present invention, spherical silica-alumina-magnesia particles having high mechanical strength, large specific surface area, and good fluidity can be produced with good reproducibility.
Claims (3)
ａ）比表面積 ； ６０〜５００（ｍ２ ／ｇ），
ｂ）細孔容積 ； ０．１〜０．５（ｃｍ３ ／ｇ），
ｃ）細孔分布 ； 細孔直径１０〜５００Åの範囲に細孔容積の９０％以上がある，
ｄ）嵩密度 ； ０．６〜１．３（ｇ／ｃｍ３ ），
ｅ）耐摩耗性 ； ２．０ｗｔ％／１５ｈｒ以下，
ｆ）平均粒子径 ； ０．５〜３００μｍ，
ｇ）アルミニウムの含有量が酸化物として５〜４０ｗｔ％であり、かつマグネシウムの含有量が酸化物として３〜３０ｗｔ％である。Silica spherical particles containing aluminum and magnesium having the following characteristics a) to g) .
a) Specific surface area; 60 to 500 (m 2) / G) ,
b) pore volume; 0.1-0.5 (cm 3) / G) ,
c) Pore distribution; 90% or more of the pore volume is in the range of pore diameters of 10 to 500 mm ,
d) Bulk density; 0.6 to 1.3 (g / cm 3) ) ,
e) Abrasion resistance; 2.0 wt% / 15 hr or less ,
f) Average particle diameter; 0.5 to 300 μm ,
g) The aluminum content is 5 to 40 wt% as an oxide, and the magnesium content is 3 to 30 wt% as an oxide.
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| US6916891B2 (en) * | 2001-02-28 | 2005-07-12 | The Standard Oil Company | Attrition resistant inorganic microspheroidal particles |
| JP4626931B2 (en) * | 2001-07-16 | 2011-02-09 | 旭化成ケミカルズ株式会社 | Carboxylate production catalyst with excellent activity |
| JP4932321B2 (en) * | 2006-05-12 | 2012-05-16 | 旭化成ケミカルズ株式会社 | Gold-supporting particles containing aluminum and silica and method for producing carboxylic acid ester using the particles |
| JP4993437B2 (en) * | 2006-05-12 | 2012-08-08 | 旭化成ケミカルズ株式会社 | Gold-supporting particles containing aluminum, silica and zirconia, and method for producing carboxylic acid ester using the particles |
| EP3658536A1 (en) * | 2017-07-28 | 2020-06-03 | Rohm and Haas Company | A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
| EP4112165A4 (en) * | 2020-02-28 | 2023-08-16 | Asahi Kasei Kabushiki Kaisha | Catalyst for producing carboxylic acid ester, method for producing catalyst for producing carboxylic acid ester, and method for producing carboxylic acid ester |
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| WO2022201533A1 (en) | 2021-03-26 | 2022-09-29 | 旭化成株式会社 | Catalyst for production of carboxylic acid ester, method for producing carboxylic acid ester, and method for producing catalyst for production of carboxylic acid ester |
| TWI763398B (en) * | 2021-03-29 | 2022-05-01 | 日商旭化成股份有限公司 | Catalyst for producing carboxylate, method for producing carboxylate, and method for producing catalyst for producing carboxylate |
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