JP4220495B2 - Titanium oxide dried product - Google Patents
Titanium oxide dried product Download PDFInfo
- Publication number
- JP4220495B2 JP4220495B2 JP2005177206A JP2005177206A JP4220495B2 JP 4220495 B2 JP4220495 B2 JP 4220495B2 JP 2005177206 A JP2005177206 A JP 2005177206A JP 2005177206 A JP2005177206 A JP 2005177206A JP 4220495 B2 JP4220495 B2 JP 4220495B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- metal
- catalyst
- hydrosol
- dried product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 179
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 50
- 239000002184 metal Substances 0.000 claims description 50
- 239000002245 particle Substances 0.000 claims description 42
- 239000003966 growth inhibitor Substances 0.000 claims description 40
- 150000001768 cations Chemical class 0.000 claims description 20
- 239000000017 hydrogel Substances 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 17
- -1 carbonyl anion Chemical class 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 100
- 239000011148 porous material Substances 0.000 description 40
- 230000000704 physical effect Effects 0.000 description 32
- 238000000034 method Methods 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 22
- 229910044991 metal oxide Inorganic materials 0.000 description 19
- 150000004706 metal oxides Chemical class 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 12
- 239000011733 molybdenum Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000004898 kneading 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
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910000347 yttrium sulfate Inorganic materials 0.000 description 2
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 241001168730 Simo Species 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FLVFLHZPYDNHJE-UHFFFAOYSA-N chloro hypochlorite;hafnium Chemical compound [Hf].ClOCl FLVFLHZPYDNHJE-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 description 1
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- AKEKKCGPLHMFCI-UHFFFAOYSA-L potassium sodium hydrogen carbonate Chemical compound [Na+].[K+].OC([O-])=O.OC([O-])=O AKEKKCGPLHMFCI-UHFFFAOYSA-L 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Images
Description
（発明の属する技術分野）
本発明は、触媒担体、触媒、乾燥剤、吸着剤、充填剤等の用途に有用な多孔質チタニアを製造するための酸化チタン乾燥物に係るもので、特に、高比表面積でかつ熱安定性にも優れた多孔質チタニアの製造に好適な酸化チタン乾燥物に関する。
(Technical field to which the invention belongs)
The present invention relates to a dried titanium oxide for producing porous titania useful for applications such as a catalyst carrier, a catalyst, a desiccant, an adsorbent, and a filler, and in particular, has a high specific surface area and thermal stability. Further, the present invention relates to a dried titanium oxide suitable for production of excellent porous titania .
（従来の技術）
従来、多孔質４族金属酸化物は、例えば、液相における水酸化チタンの一般的な合成方法である硫酸チタン(硫酸チタニル)溶液を加水分解する方法、四塩化チタンあるいは硫酸チタン(硫酸チタニル)等の水溶液をアルカリで中和する方法、チタンアルコキシドを加水分解するゾル・ゲル化方法等で生成させた４族金属含水酸化物を乾燥・焼成して製造されている。
(Conventional technology)
Conventionally, the porous Group 4 metal oxide is, for example, a method of hydrolyzing a titanium sulfate (titanyl sulfate) solution, which is a general method for synthesizing titanium hydroxide in a liquid phase, titanium tetrachloride or titanium sulfate (titanyl sulfate). It is manufactured by drying and firing a Group 4 metal hydroxide produced by a method of neutralizing an aqueous solution such as alkali with a sol / gelation method of hydrolyzing titanium alkoxide.
しかしながら、このような従来法で製造されるチタニアについては、熱安定性が悪く、図１の比表面積と焼成温度の関係に示す如く、焼成温度が高くなるにつれて、その比表面積が急激に低下し、高比表面積を維持することが困難であった。これは、この高温焼成の過程で、いわゆるシンタリングや脱水縮合により粒子の成長が起こるためである。例えば、含水酸化チタンの場合は、シンタリングや脱水縮合により無定形からアナタース、ルチル等への結晶化や結晶転移が起こり、図１のように比表面積が激減してしまう。 However, the titania produced by such a conventional method has poor thermal stability, and as the firing temperature increases, as shown in the relationship between the specific surface area and the firing temperature in FIG. It was difficult to maintain a high specific surface area. This is because particle growth occurs by so-called sintering or dehydration condensation during the high-temperature firing. For example, in the case of hydrous titanium oxide, crystallization or crystal transition from amorphous to anatase or rutile occurs due to sintering or dehydration condensation, and the specific surface area is drastically reduced as shown in FIG.
このため、例えば、従来技術によって製造されるチタニア担体あるいはチタニア触媒は、炭化水素の水素化処理用触媒として単位比表面積当たりの水素化処理活性が非常に優れているにも拘わらず、アルミナやシリカ系の触媒担体或いは触媒のようには工業的に利用されることがなかった。また、例えば、アルキレーション用触媒として用いる場合には、超強酸としての酸性質を発現させるために高温処理する必要があるが、従来の担体では熱安定性が悪く低比表面積になるため、その酸の絶対量が少なくなり触媒としての必要性能を確保することができなかった。また、排煙脱硝用触媒として用いる場合にも、単位比表面積当たりの脱硝活性が非常に優れているにも拘わらず、熱安定性の問題から通常４０〜５０ｍ2／ｇの低比表面積でしか使用できないため、多量の触媒を必要としているのが現状である。更に、この熱安定性の問題のため適用の温度範囲が狭いという問題もあった。また、チタニアについては、その摩耗強度が高いにもかかわらず、フィシャー・トロプシュ（ＦＴ）反応用触媒として用いる場合は、低比表面積のものしか得られないため性能的に満足の行く触媒が得られていないのが現状である。そのため、従来技術によって製造されるチタニア担体及び触媒は、その使用目的や使用条件等によって要求される性能を十分満足させることができない。すなわち、熱安定性が悪いために高温において高比表面積が維持できず性能が悪いものとなっているという問題があった。 For this reason, for example, a titania support or a titania catalyst produced by a conventional technique is excellent in hydrotreating activity per unit specific surface area as a hydrocarbon hydrotreating catalyst, but is not limited to alumina or silica. It was not used industrially like the catalyst support or catalyst of the system. In addition, for example, when used as an alkylation catalyst, it is necessary to perform a high temperature treatment in order to develop the acidity as a super strong acid, but the conventional support has poor thermal stability and a low specific surface area. The absolute amount of the acid was reduced, and the required performance as a catalyst could not be ensured. Also, when used as a flue gas denitration catalyst, it has a low specific surface area of usually 40 to 50 m 2 / g due to the problem of thermal stability, despite its excellent denitration activity per unit specific surface area. Since it cannot be used, a large amount of catalyst is currently required. Further, there is a problem that the temperature range of application is narrow due to the problem of thermal stability. In addition, titania has a high wear strength, but when used as a Fischer-Tropsch (FT) reaction catalyst, only a low specific surface area can be obtained. The current situation is not. For this reason, the titania carrier and catalyst produced by the prior art cannot sufficiently satisfy the performance required depending on the purpose of use and conditions of use. That is, since the thermal stability is poor, a high specific surface area cannot be maintained at a high temperature, resulting in poor performance.
また、上述した従来法ではシャープな細孔径分布を有するチタニアを製造することは困難であった。一般的に、高性能を有する触媒の細孔径の範囲は、対象とする反応物質に適した細孔径に制御することが必要である。すなわち反応物質の拡散抵抗がなく、かつ反応に有効でない小さなあるいは大きすぎる無駄な細孔を持たないことが重要である。このため、反応の目的に合わせて細孔径が制御された触媒であることが理想的である。例えば、反応に有効な触媒細孔径は、軽油の脱硫を目的とした場合には６〜１０ｎｍであり、重質油の脱硫を目的とした場合には８〜１５ｎｍであり、脱メタルを目的とした場合には１５〜３０ｎｍであり、脱アスファルテンを目的とした場合には２０〜４０ｎｍの範囲にある。しかし、従来法によって製造されるチタニア触媒については、反応に最適な触媒細孔径が少ないために、反応の選択性や活性及び触媒寿命の点で十分な性能が得られないという問題等もあった。 In addition, it has been difficult to produce titania having a sharp pore size distribution by the conventional method described above. In general, it is necessary to control the pore diameter range of a catalyst having high performance to a pore diameter suitable for the target reactant. That is, it is important that there is no diffusion resistance of the reactants and that there are no small or too large useless pores that are not effective for the reaction. For this reason, it is ideal that the pore diameter is controlled in accordance with the purpose of the reaction. For example, the effective catalyst pore diameter for the reaction is 6 to 10 nm for the purpose of desulfurization of light oil, and 8 to 15 nm for the purpose of desulfurization of heavy oil. In the case of deasphaltening, it is in the range of 20 to 40 nm. However, the titania catalyst produced by the conventional method has a problem that sufficient performance cannot be obtained in terms of reaction selectivity, activity, and catalyst life because the catalyst pore diameter optimum for the reaction is small. .
そこで、このような問題を解決し、細孔径分布をシャープにし細孔径の範囲を制御するための方法として、例えば特公昭６０−５０,７２１号公報において、種子となるヒドロゾルを得る工程と、このヒドロゾルのｐＨを、ヒドロゾル溶解領域とヒドロゾル沈殿領域との間で交互に変動させ、これによって結晶を成長させて疎凝集体を形成したヒドロゾルを得る工程と、この疎凝集体を形成したヒドロゾルを乾燥し、焼成して金属酸化物を得る工程とを有する多孔質無機酸化物の製造方法が提案されている。 Therefore, as a method for solving such problems and sharpening the pore size distribution and controlling the range of the pore size, for example, in Japanese Patent Publication No. 60-50,721, a process for obtaining a seed hydrosol, The step of alternately changing the pH of the hydrosol between the hydrosol dissolution region and the hydrosol precipitation region to obtain a hydrosol in which crystals are grown to form loose aggregates, and the hydrosol that has formed the loose aggregates is dried. And the manufacturing method of the porous inorganic oxide which has the process of baking and obtaining a metal oxide is proposed.
しかしながら、単にこの方法のみでは、例えば、チタニアについて制御されたシャープな細孔径分布を有することはできるが、触媒の焼成や反応系での反応熱等による熱履歴に対しても活性低下を起こさないようなチタニア触媒を製造することは困難であった。 However, this method alone can, for example, have a sharp pore size distribution controlled for titania, but does not cause a decrease in activity even with respect to thermal history due to catalyst firing or reaction heat in the reaction system. It has been difficult to produce such a titania catalyst.
そこで、本発明者らは、熱安定性にも優れ比表面積が大きい、多孔質４族金属酸化物とそれを製造する方法について鋭意検討した結果、一般式ＭＯ2・ｎＨ2Ｏ（但し、Ｍは４族金属を示し、ｎは０．０２以上である）で表される４族金属含水酸化物のヒドロゾル又はヒドロゲル若しくはそれらの乾燥物に、粒子成長抑制剤として１種又は２種以上のアニオン、又はカチオン、若しくはこれらアニオン及びカチオンを添加したのち、乾燥、焼成することにより、熱安定性に優れ、８０ｍ2／ｇ以上の高い比表面積を有し、かつ触媒金属が高分散している多孔質４族金属酸化物が得られることを見出し、本発明を完成した。 Therefore, as a result of intensive studies on the porous group 4 metal oxide having a high thermal stability and a large specific surface area and a method for producing the same, the present inventors have found that the general formula MO 2 · nH 2 O (however, M Represents a group 4 metal, and n is 0.02 or more), a hydrosol or hydrogel of a group 4 metal-containing oxide or a dried product thereof, and one or more anions as a particle growth inhibitor Or by adding a cation or these anions and cations, followed by drying and baking, and having excellent thermal stability, a high specific surface area of 80 m 2 / g or more, and a highly dispersed catalyst metal The present inventors have found that a quaternary Group 4 metal oxide can be obtained.
従って、本発明の目的は、熱安定性に優れ比表面積が大きく、触媒金属が高分散されている多孔質チタニアの製造に好適な酸化チタン乾燥物を提供することにある。 Accordingly, an object of the present invention is to provide a dried titanium oxide suitable for production of porous titania having excellent thermal stability, a large specific surface area, and a highly dispersed catalyst metal.
また、本発明の他の目的は、熱安定性に優れ比表面積が大きく、かつ触媒金属の高分散に加え、制御されたシャープな細孔径分布を持ち優れた反応選択性を有する触媒又は触媒担体として有用な多孔質チタニアの製造に好適な酸化チタン乾燥物を提供することにある。 Another object of the present invention is a catalyst or catalyst support having excellent thermal selectivity, a large specific surface area, high dispersion of catalyst metal, controlled sharp pore size distribution, and excellent reaction selectivity. It is to provide a dried titanium oxide suitable for the production of porous titania useful as the above.
すなわち、本発明は、一般式ＭＯ2・ｎＨ2Ｏ（但し、Ｍは４族金属であるチタン（Ti）を示し、ｎは０．０２以上である）で表される含水酸化チタンのヒドロゾル又はヒドロゲル若しくはそれらの乾燥物に、焼成時の粒子成長を抑制する粒子成長抑制剤としてＰ、Ｓ、Ｍｏ、Ｗ、Ｖ、Ｂ、Ａｌ、及びＳｉから選ばれた１種又は２種以上の金属を含むオキシアニオン及び／又は金属カルボニルアニオン、又は、Ｆｅ、Ｎｉ、Ｃｏ、Ｍｇ、Ｍｎ、Ｐｔ、Ｐｄ、Ｒｈ、及びＲｕから選ばれた１種又は２種以上の金属カチオン、若しくは、これらオキシアニオン及び／又は金属カルボニルアニオンと金属カチオンとを添加してイオン交換させ、次いで乾燥して得られた焼成前の酸化チタン乾燥物であり、５００℃、３時間の条件で焼成して得られた多孔質チタニアの比表面積が８０m2/g以上であることを特徴とする酸化チタン乾燥物。 That is, the present invention provides a hydrosol of hydrous titanium oxide represented by the general formula MO 2 · nH 2 O (wherein M represents titanium (Ti) which is a group 4 metal and n is 0.02 or more), One or more metals selected from P, S, Mo, W, V, B, Al, and Si as a particle growth inhibitor that suppresses particle growth during firing are added to the hydrogel or a dried product thereof. Containing oxyanions and / or metal carbonyl anions, or one or more metal cations selected from Fe, Ni, Co, Mg, Mn, Pt, Pd, Rh, and Ru, or these oxyanions and / or the metal carbonyl anions and metal cations is added for ion exchange, then a titanium oxide dried product before calcination obtained by drying, 500 ° C., obtained by sintering under the conditions of 3 hours Titanium oxide dried product having a specific surface area of the porous titania characterized in that at 80 m 2 / g or more.
本発明の多孔質チタニアにおいて、アニオンの添加はアナターゼの等電点未満のｐＨで、カチオンの添加はアナターゼの等電点以上のｐＨで、アニオン及びカチオンを同時に添加する場合はアナターゼの等電点未満のｐＨで行われることが好ましく、含水酸化チタンのヒドロゾル又はヒドロゲルは、含水酸化チタンの沈殿領域ｐＨと溶解領域ｐＨとの間を交互に複数回以上スイングすることにより製造されることが好ましい。 In the porous titania of the present invention, the anion is added at a pH lower than the isoelectric point of anatase, the cation is added at a pH higher than the isoelectric point of anatase, and when an anion and a cation are added simultaneously, the isoelectric point of anatase is added. The hydrous titanium hydrosol or hydrogel is preferably produced by swinging alternately between the precipitation region pH and the dissolution region pH of the hydrous titanium oxide more than once.
本発明方法において、４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物は、ＭＯ2・ｎＨ2Ｏとして表される当該４族金属含水酸化物のｎが０．０２以上のものであればよい。ここで規定するｎが０．０２以上である意味は、４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物がもつＯＨ基の下限値を規定するものである。４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物が有するＯＨ基が熱履歴ではずれていくことでシンタリングや脱水縮合による粒子成長が起こる。この際、置換可能なＯＨ基を他の官能基等と置換することによって、熱安定性を増し、高比表面積を得ることができる。従って、従来より汎用されている加水分解法、中和反応法、ゾルゲル法等の方法で製造したものを用いることができる。また、制御されたシャープな細孔径分布を持ち、優れた反応活性・選択性を有する触媒を製造するのに好適な多孔質４族金属酸化物を得るために、４族金属含水酸化物のヒドロゾルあるいはヒドロゲル又はその乾燥物の製造を、ヒドロゾルのｐＨをその沈殿領域と溶解領域に交互に複数回以上スイングすることによって行うことができる。 In the method of the present invention, the hydrosol or hydrogel of a Group 4 metal hydrated oxide or a dried product thereof, if n of the Group 4 metal hydrated oxide expressed as MO 2 · nH 2 O is 0.02 or more. Good. The meaning that n defined here is 0.02 or more defines the lower limit value of the OH group possessed by the hydrosol or hydrogel of the Group 4 metal-containing oxide or its dried product. When the OH group of the hydrosol or hydrogel of the Group 4 metal hydrated oxide or the dried product thereof is deviated by the thermal history, particle growth occurs due to sintering or dehydration condensation. At this time, by substituting the substitutable OH group with another functional group or the like, the thermal stability can be increased and a high specific surface area can be obtained. Therefore, what was manufactured by methods, such as a conventionally used hydrolysis method, neutralization reaction method, sol gel method, can be used. In addition, in order to obtain a porous Group 4 metal oxide suitable for producing a catalyst having a controlled and sharp pore size distribution and having excellent reaction activity and selectivity, a hydrosol of Group 4 metal hydrous oxide is obtained. Alternatively, the production of the hydrogel or dried product thereof can be carried out by swinging the pH of the hydrosol alternately several times or more between the precipitation region and the dissolution region.
ここで、４族金属含水酸化物のヒドロゾル又はヒドロゲル又はその乾燥物を製造するために用いる４族金属化合物としては、具体的には、チタン（Ti）、ジルコニウム（Zr）又はハフニウム（Hf）の塩化物、硝酸塩、硫酸塩、炭酸塩、酢酸塩、燐酸塩、ホウ酸塩、蓚酸塩、フッ酸塩、珪酸塩、ヨウ素酸塩等の４族金属塩や、チタン酸、ジルコニウム酸、ハフニウム酸等の４族金属オキソ酸塩等及び４族金属のアルコキシド類であり、これらの１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。これらの４族金属化合物のうち、チタンの場合に特に好ましいものとしては、例えば、四塩化チタン、硫酸チタン、硫酸チタニル、三塩化チタン、チタンメトキシド、チタンエトキシド、チタンプロポキシド、チタンイソプロポキシド、チタンブトキシド等を挙げることができる。また、ジルコニウムの場合に特に好ましいものとしては、例えば、四塩化ジルコニウム、オキシ塩化ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウム、酢酸ジルコニウム、ジルコニウムアセチルアセナート、ジルコニウムプロポキシド、ジルコニウム t-ブトキシド等を挙げることができる。又はフニウムの場合に特に好ましいものとしては、例えば、塩化ハフニウム、硫酸ハフニウム、オキシ塩化ハフニウム等を挙げることができる。 Here, as a Group 4 metal compound used for producing a hydrosol or hydrogel of a Group 4 metal-containing oxide or a dried product thereof, specifically, titanium (Ti), zirconium (Zr) or hafnium (Hf) is used. Group 4 metal salts such as chloride, nitrate, sulfate, carbonate, acetate, phosphate, borate, oxalate, hydrofluorate, silicate, iodate, titanic acid, zirconium acid, hafnium acid Group 4 metal oxoacid salts and the like and Group 4 metal alkoxides, and only one of them can be used alone, or a mixture of two or more can also be used. Among these group 4 metal compounds, particularly preferred in the case of titanium are, for example, titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium trichloride, titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxy. And titanium butoxide. Particularly preferable examples of zirconium include zirconium tetrachloride, zirconium oxychloride, zirconium sulfate, zirconium nitrate, zirconium acetate, zirconium acetyl acetonate, zirconium propoxide, zirconium t-butoxide and the like. . In the case of funium, particularly preferable examples include hafnium chloride, hafnium sulfate, hafnium oxychloride and the like.
また、本発明に用いる粒子成長抑制剤は、Ｐ、Ｓ、Ｍｏ、Ｗ、Ｖ、Ｂ、Ａｌ、Ｓｉ等から選択されるオキシアニオン、金属カルボニルアニオン、及びＦｅ、Ｎｉ、Ｃｏ、Ｍｇ、Ｍｎ、Ｐｔ、Ｐｄ、Ｒｈ、Ｒｕ等の金属カチオンを用いることができる。更に詳しくは、ＰＯ4 3-、ＮｂＯ4 3-、ＳＯ4 2-、ＭｏＯ4 2-、ＷＯ4 2-、ＣｒＯ4 2-、ＢＯ3 3-、ＡｌＯ3 3-、ＳｉＯ4 4-、ＧｅＯ4 4-等のイオンの形を有するオキシアニオン、金属カルボニルアニオンＦｅ2+、Ｆｅ3+、Ｎｉ2+、Ｃｏ2+、Ｃａ2+、Ｍｇ2+、Ｍｎ2+、Ｙ3+、Ｐｔ2+、Ｐｄ2+、Ｒｈ3+、Ｒｕ3+等の金属カチオンである。 Further, the particle growth inhibitor used in the present invention is an oxyanion selected from P, S, Mo, W, V, B, Al, Si and the like, a metal carbonyl anion, and Fe, Ni, Co, Mg, Mn, Metal cations such as Pt, Pd, Rh, and Ru can be used. More specifically, PO 4 3− , NbO 4 3− , SO 4 2− , MoO 4 2− , WO 4 2− , CrO 4 2− , BO 3 3− , AlO 3 3− , SiO 4 4− , GeO 4 Oxy anions having the form of ions such as 4- , metal carbonyl anions Fe 2+ , Fe 3+ , Ni 2+ , Co 2+ , Ca 2+ , Mg 2+ , Mn 2+ , Y 3+ , Pt 2 Metal cations such as + , Pd 2+ , Rh 3+ and Ru 3+ .
特に好適なオキシアニオンを提供する化合物としては、モリブデン酸アンモニウム｛(NH4)6Mo7O24・4H2O、（NH4）2MoO4、(NH4)Mo2O7｝、モリブデン酸ソーダ(Na2MoO4・2H2O)、モリブデン酸（H2MoO4、H2MoO3・H2O）、五塩化モリブデン(MoCl5)、ケイモリブデン酸(H4SiMo12O40・nH2O)、タングステン酸（H2WO4）、タングステン酸アンモニウム｛5(NH4)2O・12WO3・H2O、3(NH4)2O・12WO3・nH2O｝、タングステン酸ナトリウム（Na2ＷO4・2H2O）、メタバナジン酸（HVO3）、オルトバナジン酸（H3VO4）、ピロバナジン酸（H2V2O7）、ペルオキソバナジン酸（HVO4）、ポリバナジウム酸、H2CrO4、クロム酸アンモニウム｛(NH4)2CrO4｝、H3PO4、HPO3、H4P2O7、P2O5、NH4H2PO4、(NH4)2HPO4、(NH4)3PO4・H2O、Nb2O5・nH2O、Ca3NbO4、Ca4Nb2O7、H3BO3、NH4B5O8、H2SO4、(NH4)2SO4、更にH3[PO4W12O36]・5H2OやMo、W、Vをポリ酸とするヘテロポリ酸塩等を挙げることができる。これらは、その１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。
As a compound that provides a particularly suitable oxyanion, ammonium molybdate {(NH 4 ) 6 Mo 7 O 24 · 4H 2 O, (NH 4 ) 2 MoO 4 , (NH 4 ) Mo 2 O 7 }, sodium molybdate (Na 2 MoO 4 · 2H 2 O), molybdic acid (H 2 MoO 4 , H 2 MoO 3 · H 2 O), molybdenum pentachloride (MoCl 5 ), silicomolybdic acid (H 4 SiMo 12 O 40 · nH 2 O), tungstic acid (H 2 WO 4 ), ammonium tungstate {5 (NH 4 ) 2 O · 12WO 3 · H 2 O, 3 (NH 4 ) 2 O · 12WO 3 · nH 2 O}, sodium tungstate (Na 2 WO 4 · 2H 2 O), metavanadate (HVO 3), orthovanadate (H 3 VO 4), pyrovanadates (H 2 V 2 O 7) , peroxovanadate (HVO 4), poly vanadate , H 2 CrO 4 , ammonium chromate {(NH 4 ) 2 CrO 4 }, H 3 PO 4 , HPO 3 , H 4 P 2 O 7 , P 2 O 5 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4, (NH 4) 3 PO 4 · H 2 O, Nb 2 O 5 · nH 2 O, Ca 3 NbO 4 Ca 4 Nb 2 O 7, H 3 BO 3, NH 4 B 5
また、金属カルボニルアニオンを供給する多価金属塩の好適な化合物としては、例えば(NEt4)[Mo(CO)5(OOCCH3)]、Mo(CO)6-NEt3-EtSH、Ru3(CO)12-NEt3-EtSH、(η-C5H4Me)2Mo2Co2S3(CO)4、W(CO)6、W(CO)6-NEt3-EtSH、Cr(CO)6-NEt3-EtSH等で表される金属カルボニルアニオンである。 Moreover, as a suitable compound of the polyvalent metal salt which supplies a metal carbonyl anion, for example, (NEt 4 ) [Mo (CO) 5 (OOCCH 3 )], Mo (CO) 6 -NEt 3 -EtSH, Ru 3 ( CO) 12 -NEt 3 -EtSH, (η-C 5 H 4 Me) 2 Mo 2 Co 2 S 3 (CO) 4 , W (CO) 6 , W (CO) 6 -NEt 3 -EtSH, Cr (CO It is a metal carbonyl anion represented by 6- NEt 3 -EtSH and the like.
また、多価金属カチオンを供給する多価金属塩の好適な化合物としては、二価以上の金属の塩をいい、例えば、硫酸第１鉄（FeSO4・H2O）、硫酸第２鉄｛４｛Fe2(SO4)3｝、塩化第１鉄、塩化第２鉄（FeCl3）、硝酸第１鉄、硝酸第２鉄｛Fe(NO3)3・9H2O｝、硝酸ニッケル｛Ni(NO3)2・6H2O｝、硫酸ニッケル（NiSO4・6H2O）、塩化ニッケル（NiCl2）、酢酸ニッケル｛Ni(CH3CO2)2・4H2O｝、酢酸コバルト｛Co(CH3CO2)2・4H2O｝、硝酸コバルト｛Co(NO3)2・6H2O｝、硫酸コバルト（CoSO4・7H2O）、塩化コバルト（CoCl2・6H2O）、硝酸カルシウム、硫酸カルシウム、塩化カルシウム、硝酸マグネシウム（Mg(NO3)2・6H2O）、硫酸マグネシウム（MgSO4・7H2O）、塩化マグネシウム（MgCl2・H2O）、炭酸マグネシウム（MgCO3）硝酸マンガン｛Mn(NO3)2｝、硫酸マンガン（MnSO4・7H2O）、塩化マンガン、燐酸マンガン（MnPO4）、炭酸マンガン（MnCO3）、硼酸マンガン（MnB4O7・8H2O）、硝酸イットリウム｛Y(NO3)3・6H2O｝、硫酸イットリウム｛Y(SO4)3・8H2O｝、炭酸イットリウム｛Y(CO3)3・3H2O｝、塩化イットリウム（YCl3・6H2O）、燐酸イットリウム（YPO4）、硝酸パラジウム（Pd(NO3)2）、硫酸パラジウム（PdSO4）、塩化パラジウム（PdCl2）、パラジウム塩化カルボニル｛Pd(CO)Cl｝等である。 Further, suitable compounds of a polyvalent metal salt for supplying a polyvalent metal cation, refers to a divalent or more metal salts, e.g., ferrous sulfate (FeSO 4 · H 2 O) , ferric sulfate { 4 {Fe 2 (SO 4 ) 3 }, ferrous chloride, ferric chloride (FeCl 3 ), ferrous nitrate, ferric nitrate {Fe (NO 3 ) 3 · 9H 2 O}, nickel nitrate { Ni (NO 3 ) 2 · 6H 2 O}, nickel sulfate (NiSO 4 · 6H 2 O), nickel chloride (NiCl 2 ), nickel acetate {Ni (CH 3 CO 2 ) 2 · 4H 2 O}, cobalt acetate { Co (CH 3 CO 2 ) 2 · 4H 2 O}, cobalt nitrate {Co (NO 3 ) 2 · 6H 2 O}, cobalt sulfate (CoSO 4 · 7H 2 O), cobalt chloride (CoCl 2 · 6H 2 O) , Calcium nitrate, calcium sulfate, calcium chloride, magnesium nitrate (Mg (NO 3 ) 2 · 6H 2 O), magnesium sulfate (MgSO 4 · 7H 2 O), magnesium chloride (MgCl 2 · H 2 O), magnesium carbonate ( MgCO 3) manganese nitrate {Mn (NO 3) 2} , Manganese (MnSO 4 · 7H 2 O) , manganese chloride, manganese phosphate (MnPO 4), manganese carbonate (MnCO 3), boric acid, manganese (MnB 4 O 7 · 8H 2 O), yttrium nitrate {Y (NO 3) 3・ 6H 2 O}, yttrium sulfate {Y (SO 4 ) 3 · 8H 2 O}, yttrium carbonate {Y (CO 3 ) 3 · 3H 2 O}, yttrium chloride (YCl 3 · 6H 2 O), yttrium phosphate ( YPO 4 ), palladium nitrate (Pd (NO 3 ) 2 ), palladium sulfate (PdSO 4 ), palladium chloride (PdCl 2 ), palladium carbonyl chloride {Pd (CO) Cl}, and the like.
本発明に用いる前記粒子成長抑制剤はその１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。 The particle growth inhibitor used in the present invention can be used alone or in a mixture of two or more.
また、これら粒子成長抑制剤で水素化処理触媒活性を有するものとしては、Ｍｏ、Ｗ、Ｎｉ、Ｃｏ、Ｆｅ、Ｐ、Ｂ、Ｐｔ、Ｐｄ、Ｒｈ、Ｒｕが挙げられる。 Examples of these particle growth inhibitors having hydrotreating catalytic activity include Mo, W, Ni, Co, Fe, P, B, Pt, Pd, Rh, and Ru.
また、ヒドロゾルのｐＨを沈殿領域と溶解領域の間を交互に複数回変動させるｐＨ調整剤として好適な化合物は、原料となる四塩化チタン、硫酸チタン、硫酸チタニル、四塩化チタン、三塩化チタン、硫酸第１鉄、硫酸第２鉄、塩化第１鉄、塩化第２鉄、硝酸第１鉄、硝酸第２鉄、硝酸ニッケル、硫酸ニッケル、塩化ニッケル、硝酸コバルト、硫酸コバルト、塩化コバルト、硝酸マンガン、硫酸マンガン、塩化マンガン、硝酸イットリウム、硫酸イットリウム、塩化イットリウムのほか硝酸（HNO3）、塩酸（HCl）、硫酸（H2SO4）、炭酸（H2CO3）、蟻酸（HCOOH）、酢酸（CH3COOH）等の酸と、アンモニア（NH3）、水酸化ナトリウム（NaOH）、水酸化カリウム（KOH）、炭酸ナトリウム（Na2CO3）、炭酸カリウム（K2CO3）、炭酸水素ナトリウム（NaHCO3）、炭酸水素カリウム（KHCO3）、炭酸水素ナトリウムカリウム（KNaCO3）等のアルカリを挙げることができる。また、これらはその１種のみを単独で使用できるほか、２種以上の混合物として使用することもできる。 In addition, a compound suitable as a pH adjuster that alternately changes the pH of the hydrosol between the precipitation region and the dissolution region multiple times is titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride as raw materials. Ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, ferrous nitrate, ferric nitrate, nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt sulfate, cobalt chloride, manganese nitrate , Manganese sulfate, manganese chloride, yttrium nitrate, yttrium sulfate, yttrium chloride, nitric acid (HNO 3 ), hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), carbonic acid (H 2 CO 3 ), formic acid (HCOOH), acetic acid Acids such as (CH 3 COOH), ammonia (NH 3 ), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), hydrogen carbonate sodium NaHCO 3), potassium bicarbonate (KHCO 3), and alkali such as sodium bicarbonate potassium (KNaCO 3). In addition, these can be used alone or in a mixture of two or more.
［多孔質４族金属酸化物の製造方法］
（４族金属含水酸化物の製造）
４族金属含水酸化物のヒドロゾル、ヒドロゲル又はそれらの乾燥物で、ＭＯ2・ｎＨ2Ｏとして表される当該４族金属含水酸化物のｎが０．０２以上のものを製造する条件は、該多孔質４族金属酸化物（ＭＯ2）濃度は１〜２０重量％、好ましくは３〜１５重量％、反応温度は常温から３００℃、好ましくは常温から１８０℃、更に好ましくは常温から１００℃、反応圧力は常圧から３．０ＭＰａで、好ましくは常圧から０．９ＭＰａで、更に好ましくは常圧から０．１ＭＰａ、ｐＨは０．５〜１１、好ましくは１．０〜１０の範囲でアルカリによる中和反応あるいは加水分解反応によって４族金属含水酸化物を生成する。
[Method for Producing Porous Group 4 Metal Oxide]
(Production of Group 4 metal hydrated oxide)
The conditions for producing a Group 4 metal hydrated hydrosol, hydrogel or dried product thereof, wherein the Group 4 metal hydrated oxide represented by MO 2 · nH 2 O is 0.02 or more, The concentration of the porous group 4 metal oxide (MO 2 ) is 1 to 20% by weight, preferably 3 to 15% by weight, the reaction temperature is from room temperature to 300 ° C., preferably from room temperature to 180 ° C., more preferably from room temperature to 100 ° C. The reaction pressure is from normal pressure to 3.0 MPa, preferably from normal pressure to 0.9 MPa, more preferably from normal pressure to 0.1 MPa, pH is from 0.5 to 11, preferably from 1.0 to 10 A Group 4 metal hydroxide is produced by a neutralization reaction or hydrolysis reaction.
（粒子成長抑制剤の添加）
上記一般式ＭＯ2・ｎＨ2Ｏ（但し、Ｍは４族金属を示し、ｎは０．０２以上である）で表される４族金属含水酸化物のヒドロゾル又はヒドロゲル若しくはそれらの乾燥物に、粒子成長抑制剤として１種又は２種以上のアニオン、又はカチオン、若しくはこれらアニオン及びカチオンを添加するが、この際に、粒子成長抑制剤がアニオンの場合には好ましくは４族金属酸化物の等電点未満のｐＨで添加するのがよく、また、粒子成長抑制剤がカチオンの場合には好ましくは４族金属酸化物の等電点以上のｐＨで添加するのがよく、更に、粒子成長抑制剤がアニオン及びカチオンの場合には好ましくは４族金属酸化物の等電点未満のｐＨで同時に添加するのがよい。これは、イオン交換等による置換がより効果的に進むことによる。そして、これら粒子成長抑制剤の添加量については、４族金属酸化物１００ｇ当たり０．０６〜６ｇ当量、好ましくは０．１〜５ｇ当量添加し、温度常温から１００℃で、熟成時間０．１〜５時間、好ましくは０．２〜３時間保持する。
なお、上記ヒドロゾルはその生成段階のもの、ヒドロゲルはその生成後のものに粒子成長抑制剤を添加するのが効果的である。
(Addition of particle growth inhibitor)
In a hydrosol or hydrogel of a Group 4 metal-containing oxide represented by the above general formula MO 2 · nH 2 O (where M represents a Group 4 metal and n is 0.02 or more), or a dried product thereof, As the particle growth inhibitor, one kind or two or more kinds of anions, or cations, or these anions and cations are added. When the particle growth inhibitor is an anion, a group 4 metal oxide or the like is preferable. It is preferable to add at a pH lower than the electric point. When the particle growth inhibitor is a cation, it is preferably added at a pH higher than the isoelectric point of the group 4 metal oxide. When the agent is an anion or cation, it is preferable to add them simultaneously at a pH lower than the isoelectric point of the group 4 metal oxide. This is because substitution by ion exchange or the like proceeds more effectively. And about the addition amount of these particle growth inhibitors, 0.06-6g equivalent with respect to 100g of group 4 metal oxides, Preferably 0.1-5g equivalent is added, and the aging time is 0.1 to 100 degreeC. Hold for -5 hours, preferably 0.2-3 hours.
In addition, it is effective to add a particle growth inhibitor to the hydrosol in the production stage and the hydrogel in the production stage.
例えば、酸化チタンの場合は、含水酸化チタンを洗浄し、粒子成長抑制剤として酸化チタンのアナターゼの等電点である６．１未満でのｐＨで一種類以上のアニオンを添加あるいは等電点以上のｐＨで一種類以上のカチオンを添加、アニオンとカチオンを同時に添加する場合は等電点未満のｐＨで、酸化チタン１００g当たり０．０６〜６ｇ当量、好ましくは０．１〜５ｇ当量添加し、常温から１００℃で、熟成時間０．１〜５時間、好ましくは０．２〜３時間保持する。 For example, in the case of titanium oxide, the hydrous titanium oxide is washed, and one or more kinds of anions are added at a pH of less than 6.1, which is the isoelectric point of anatase of titanium oxide as a particle growth inhibitor, or the isoelectric point is exceeded. In the case of adding one or more kinds of cations at the same pH, and simultaneously adding anions and cations, 0.06 to 6 g equivalents, preferably 0.1 to 5 g equivalents per 100 g of titanium oxide, at a pH lower than the isoelectric point, The aging time is 0.1 to 5 hours, preferably 0.2 to 3 hours at room temperature to 100 ° C.
また、粒子成長抑制剤の添加法としては、直接混練法も使用することができる。この方法においては、粒子成長抑制剤をゲルあるいは乾燥物に４族金属酸化物１００g当たり０．０５〜５ｇ当量、好ましくは０．１〜４ｇ当量粒子成長抑制剤を直接添加し、常温から１００℃の温度範囲で、熟成時間０．１〜５時間、好ましくは０．２〜３時間混練する。 As a method for adding the particle growth inhibitor, a direct kneading method can also be used. In this method, a particle growth inhibitor is added directly to a gel or a dried product in an amount of 0.05 to 5 g equivalent, preferably 0.1 to 4 g equivalent, per 100 g of Group 4 metal oxide. In the temperature range of 0.1 to 5 hours, preferably 0.2 to 3 hours.
（乾燥・焼成条件）
４族金属酸化物基準での含水量を３０〜９００重量％、好ましくは５０〜７００重量％にろ過・脱水し、所要の形状に成型し、乾燥温度４０〜350℃、好ましくは８０〜２００℃で、乾燥時間０．５〜２４時間、好ましくは８０〜２００℃で乾燥し、温度３５０〜１２００℃、好ましくは４００〜７００℃で焼成する。
(Drying and firing conditions)
The water content on the basis of the Group 4 metal oxide is 30 to 900% by weight, preferably 50 to 700% by weight, filtered and dehydrated, molded into a required shape, and a drying temperature of 40 to 350 ° C., preferably 80 to 200 ° C. The drying time is 0.5 to 24 hours, preferably 80 to 200 ° C., and the temperature is 350 to 1200 ° C., preferably 400 to 700 ° C.
また、種子生成工程とヒドロゾル合成工程とを有する４族金属含水酸化物のヒドロゾルの製造方法については、具体的には特公昭６０−５０,７２１号公報に記載された方法を例示することができる。
すなわち、種子生成工程については、不均一沈殿法、均一沈殿法、共沈法、イオン交換法、加水分解法、及び金属溶解法等の慣用の方法を採用することができる。また、ヒドロゾル合成工程については、上記種子生成工程で得られた４族金属含水酸化物のヒドロゾルに４族金属化合物の水溶液、及び／又はｐＨ調整剤とを交互に添加し、ヒドロゾル溶解ｐＨ領域とヒドロゾル析出ｐＨ領域との間を交互に複数回変動させるものであり、ヒドロゾル溶解ｐＨ領域とは微細粒子のヒドロゾルを可溶化し得るｐＨ領域をいい、また、ヒドロゾル析出ｐＨ領域とはヒドロゾル粒子の成長及び凝集を生起させるｐＨ領域をいう。更に、このヒドロゾル合成工程においては、必要により、熟成、洗浄、固形分含量調節等の処理が行われ、所望の性状を有する４族金属含水酸化物のヒドロゾルあるいはヒドロゲルとされる。
In addition, as for the method for producing a hydrosol of a Group 4 metal-containing oxide having a seed generation step and a hydrosol synthesis step, the method described in JP-B-60-50,721 can be specifically exemplified. .
That is, for the seed production step, conventional methods such as a heterogeneous precipitation method, a uniform precipitation method, a coprecipitation method, an ion exchange method, a hydrolysis method, and a metal dissolution method can be employed. For the hydrosol synthesis step, an aqueous solution of a Group 4 metal compound and / or a pH adjuster are alternately added to the hydrosol of the Group 4 metal-containing oxide obtained in the seed generation step, The hydrosol precipitation pH region refers to a pH region that can solubilize a fine particle hydrosol, and the hydrosol deposition pH region is a growth of hydrosol particles. And the pH range where aggregation occurs. Further, in this hydrosol synthesis step, treatments such as aging, washing, and solid content adjustment are performed as necessary to obtain a hydrosol or hydrogel of a Group 4 metal hydrated oxide having desired properties.
上記４族金属酸化物の製造において、該４族金属含水酸化物の製造条件は、ｐＨをスイングする各段階の沈殿領域のｐＨを０．５〜１１、濃度を０．１〜２０重量％、温度を常温から３００℃、保持時間を０．０１〜０．5時間、好ましくは０．０２〜０．３時間とする。また、４族金属含水酸化物の溶解領域のｐＨは０〜３、濃度は０．１〜２０重量％、温度は常温から３００℃、保持時間は０．０２〜５時間の範囲が好適である。また、沈殿領域と溶解領域に交互に保持する回数は２回から２０回の範囲が好適である。 In the production of the Group 4 metal oxide, the production conditions of the Group 4 metal hydrated oxide are as follows: the pH of the precipitation region in each stage swinging the pH is 0.5 to 11, the concentration is 0.1 to 20% by weight, The temperature is from room temperature to 300 ° C., and the holding time is 0.01 to 0.5 hours, preferably 0.02 to 0.3 hours. Further, the pH of the dissolution region of the Group 4 metal-containing oxide is preferably from 0 to 3, the concentration is from 0.1 to 20% by weight, the temperature is from room temperature to 300 ° C., and the holding time is from 0.02 to 5 hours. . In addition, the number of times of holding alternately in the precipitation region and the dissolution region is preferably in the range of 2 to 20 times.
例えば、酸化チタンの場合は、該含水酸化チタンのｐＨをスイングする各段階の製造条件は、沈殿領域のｐＨを１．０〜１０、濃度を０．１〜１５重量％、温度を常温から１８０℃、保持時間を０．０１〜０．5時間、好ましくは０．０２〜０．３時間、溶解領域のｐＨを０〜２、濃度を０．１〜１５重量％、温度を常温から１８０℃、保持時間を０．０２〜５時間の範囲が好適である。また、沈殿領域と溶解領域に交互に保持する回数は２回から１０回の範囲が好適である。 For example, in the case of titanium oxide, the production conditions at each stage of swinging the pH of the hydrous titanium oxide are as follows: the pH of the precipitation region is 1.0 to 10; the concentration is 0.1 to 15% by weight; ℃, holding time is 0.01 to 0.5 hours, preferably 0.02 to 0.3 hours, pH of dissolution region is 0 to 2, concentration is 0.1 to 15% by weight, temperature is from normal temperature to 180 ° C The holding time is preferably in the range of 0.02 to 5 hours. In addition, the number of times of alternately holding in the precipitation region and the dissolution region is preferably in the range of 2 to 10 times.
本発明方法により得られた多孔質４族金属酸化物は、触媒担体、触媒、乾燥剤、吸着剤、充填剤等の用途に有用であるが、特に、本発明方法により得られた多孔質４族金属酸化物は、８０ｍ2／ｇ以上の高比表面積を持ち、細孔シャープネス度（定義を後述）が３０％以上等の特徴を持つため水素化処理（脱硫、脱窒素、脱メタル、アスファルテン分解、芳香族の水素化）、水素化分解、アルキレーション、フィッシャートロプシュ、排煙脱硝、光反応等の高性能触媒担体又は触媒として使用することができる。なお、８０ｍ2／ｇ以下の高比表面積では、所望の反応活性を発揮しにくくなる。また、細孔シャープネス度が３０％以下であると反応の選択性が低下することになる。 The porous group 4 metal oxide obtained by the method of the present invention is useful for applications such as a catalyst carrier, a catalyst, a desiccant, an adsorbent, and a filler, but in particular, the porous 4 obtained by the method of the present invention. Group metal oxides have a high specific surface area of 80 m 2 / g or more and a degree of pore sharpness (definition will be described later) of 30% or more, etc., so hydrotreatment (desulfurization, denitrification, demetalization, asphaltenes) Decomposition, aromatic hydrogenation), hydrocracking, alkylation, Fischer-Tropsch, flue gas denitration, photoreaction, etc., and can be used as a high-performance catalyst carrier or catalyst. In addition, it becomes difficult to exhibit desired reaction activity in the high specific surface area of 80 m < 2 > / g or less. Moreover, the selectivity of reaction will fall that a pore sharpness degree is 30% or less.
［物理性状の測定について］
（細孔シャープネス度）
水銀ポロシメータにより測定された累積細孔分布曲線に関し、先ず累積細孔容積を示す縦軸と細孔直径（Å）を表す横軸において、全細孔容積（PVT）の（１／２）ＰＶにおける細孔径（メデアン直径）を求める。次に、メディアン直径の対数値における±５％の細孔径範囲内に有する細孔容積（PVM）を求め、その細孔容積（PVM）と全細孔容積（PVT）から以下の式により、細孔分布のシャープ度を表わす細孔シャープネス度を求める。
細孔シャープネス度＝｛細孔容積（PVM）／全細孔容積（PVT）｝*１００
ここで定義する細孔シャープネス度は、全細孔容積に対する反応に最適な細孔の度合いを評価するための因子であり、細孔シャープネス度が大きい程、シャープな細孔分布を有することになり、好ましいものとなる。
[Measurement of physical properties]
(Pore sharpness)
Regarding the cumulative pore distribution curve measured by the mercury porosimeter, first, the vertical axis indicating the cumulative pore volume and the horizontal axis indicating the pore diameter (Å), at (1/2) PV of the total pore volume (PVT) The pore diameter (median diameter) is determined. Next, the pore volume (PVM) within a pore diameter range of ± 5% in the logarithmic value of the median diameter is obtained, and the fine volume is calculated from the pore volume (PVM) and the total pore volume (PVT) by the following formula. The degree of pore sharpness representing the degree of sharpness of the pore distribution is obtained.
Pore sharpness = {pore volume (PVM) / total pore volume (PVT)} * 100
The pore sharpness degree defined here is a factor for evaluating the optimum degree of pores for the reaction with respect to the total pore volume. The larger the pore sharpness degree, the sharper the pore distribution. This is preferable.
（比表面積の測定法）
触媒及び担体の比表面積は、ＢＥＴの三点法により測定し、測定機器にはマウンテック社製Macsorb Model-1201を使用した。
(Measurement method of specific surface area)
The specific surface areas of the catalyst and the carrier were measured by the BET three-point method, and Macsorb Model-1201 manufactured by Mountec Co., Ltd. was used.
（細孔分布の測定法）
触媒及び担体の細孔容積と細孔分布は、測定圧力４１４ＭＰａで水銀圧入法により測定し、測定機器には島津製作所製オートポア9200形を使用した。
(Measurement method of pore distribution)
The pore volume and pore distribution of the catalyst and the carrier were measured by a mercury intrusion method at a measurement pressure of 414 MPa, and Autopore 9200 model manufactured by Shimadzu Corporation was used as the measurement instrument.
（結晶構造の測定法）
触媒及び担体の結晶構造はX線回折法により測定し、測定機器にはPHILIPS社製PW3710を使用した。
(Measurement method of crystal structure)
The crystal structure of the catalyst and the support was measured by X-ray diffraction, and PW3710 manufactured by PHILIPS was used as a measuring instrument.
本発明の酸化チタン乾燥物は、これを焼成することにより、単に比表面積が大きいだけでなく、同時に熱安定性にも優れ、しかも、制御されたシャープな細孔径分布を有する多孔質チタニアを製造することができるので、優れた反応選択性を有し、しかも、比表面積が大きくて触媒活性に優れているだけでなく、同時に熱安定性にも優れた触媒又は触媒担体として用いることができる多孔質チタニアの中間体として極めて有用である。 Titanium oxide dried product of the present invention is prepared by calcining this, not only a large specific surface area, excellent in the same time the thermal stability, moreover, the porous titania having controlled sharp pore size distribution Therefore, the porous material can be used as a catalyst or a catalyst carrier that has excellent reaction selectivity, has a large specific surface area and excellent catalytic activity, and at the same time has excellent thermal stability. It is extremely useful as an intermediate for quality titania.
以下、実施例及び比較例に基づいて、本発明の好適な実施の形態を具体的に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail based on examples and comparative examples.
［ヒドロゾルの調製］
（四塩化チタン水溶液の調製）
氷を加えた純水に冷却した四塩化チタン（TiCl4）１ｋｇを徐々に添加し酸化チタン換算濃度２１０ｇ／リットルの四塩化チタン水溶液を調製した。
（14wt%ＮＨ4ＯＨ水溶液の調製）
28wt%ＮＨ4ＯＨを２倍に希釈し、14wt%ＮＨ4ＯＨ水溶液を調製した。
[Preparation of hydrosol]
(Preparation of titanium tetrachloride aqueous solution)
1 kg of cooled titanium tetrachloride (TiCl 4 ) was gradually added to pure water to which ice was added to prepare a titanium tetrachloride aqueous solution having a titanium oxide equivalent concentration of 210 g / liter.
(Preparation of 14wt% NH 4 OH aqueous solution)
28 wt% NH 4 OH was diluted 2 times to prepare a 14 wt% NH 4 OH aqueous solution.
（ヒドロゾル合成工程）
次に、３０リットルの撹拌機付きベッセルに純水１０リットルを入れ、攪拌しながら前記四塩化チタン水溶液１．５リットルを添加し、ｐＨを０．５以下まで低下させた。
この溶液に上記14wt%ＮＨ4ＯＨ水溶液２．３リットルを添加し、ｐＨを７まで上昇させ、約５分間放置した。
(Hydrosol synthesis process)
Next, 10 liters of pure water was placed in a 30 liter vessel equipped with a stirrer, and 1.5 liters of the titanium tetrachloride aqueous solution was added while stirring to lower the pH to 0.5 or lower.
To this solution, 2.3 liters of the above 14 wt% NH 4 OH aqueous solution was added, the pH was raised to 7, and left for about 5 minutes.
（濾過、洗浄）
上記ヒドロゾル合成工程終了後、濾過し、得られたケーキを純水にて洗浄し、硝酸銀滴定により濾液中に塩素（Cl-）が確認されなくなるまで洗浄操作を繰り返し、含水酸化チタンのヒドロゾルを得た。
(Filtering and washing)
After completion of the hydrosol synthesis step, filtration is performed, and the resulting cake is washed with pure water, and the washing operation is repeated until no chlorine (Cl-) is confirmed in the filtrate by silver nitrate titration to obtain hydrous titanium oxide hydrosol. It was.
（乾燥物の調製）
以上のようにして得られた含水酸化チタンのヒドロゾルを吸引濾過し、含水量約５０重量％になるまで脱水し、次いで穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃にて３時間乾燥し、含水酸化チタンの乾燥成形物を得た。
(Preparation of dried product)
The hydrous titanium hydrosol obtained as described above was filtered by suction, dehydrated until the water content was about 50% by weight, and then molded using a die having a hole diameter of 1.5 mmφ. It dried at 120 degreeC for 3 hours, and obtained the dry molding of the hydrous titanium oxide .
（粒子成長抑制剤添加工程）
上記で得られた含水酸化チタンの乾燥成形物を、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを含有する水溶液に浸漬し、室温下に２時間放置したのち、５Ｃの濾紙で濾過し、モリブデン担持物を得た。
(Particle growth inhibitor addition process)
The dry molded product of hydrous titanium oxide obtained above was immersed in an aqueous solution containing 16.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide, and left at room temperature for 2 hours. Filtration through a filter paper gave a molybdenum support.
（乾燥焼成工程）
得られたモリブデン担持物を１２０℃で３時間乾燥した後、５００℃で３時間焼成し、モリブデン担持チタニア触媒を得た。
得られたモリブデン担持チタニア触媒の物性を表１に示す。
(Dry firing process)
The obtained molybdenum-supported product was dried at 120 ° C. for 3 hours and then calcined at 500 ° C. for 3 hours to obtain a molybdenum-supported titania catalyst.
Table 1 shows the physical properties of the obtained molybdenum-supporting titania catalyst.
実施例１と同じ方法でヒドロゾルを合成し、更に撹拌しながら前記四塩化チタン水溶液１．５リットルを添加してｐＨを再び０．５まで低下させ、次いで５分間放置した後、14wt%ＮＨ4ＯＨ水溶液２．８リットルを添加して再びｐＨを７まで上昇させ、更に５分間放置した。
これらの操作を更に３回繰り返し、ヒドロゾル溶解ｐＨ領域（ｐＨ０．５）とヒドロゾル析出ｐＨ領域（ｐＨ７）との間を交互に合計５回変動させた。
これ以降の洗浄・濾過・成形・乾燥・粒子成長抑制剤添加工程・乾燥焼成工程は実施例１と同様とした。
得られたモリブデン担持チタニア触媒の物性を表１に示す。
A hydrosol was synthesized in the same manner as in Example 1, 1.5 liters of the above aqueous titanium tetrachloride solution was added with stirring, the pH was lowered to 0.5 again, and then allowed to stand for 5 minutes, then 14 wt% NH 4 2.8 liters of OH aqueous solution was added to raise the pH to 7 again and left for another 5 minutes.
These operations were repeated three more times, and the hydrosol dissolution pH range (pH 0.5) and the hydrosol deposition pH range (pH 7) were alternately changed 5 times in total.
The subsequent washing, filtration, molding, drying, particle growth inhibitor addition step, and drying and firing step were the same as in Example 1.
Table 1 shows the physical properties of the obtained molybdenum-supporting titania catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で８重量％の燐酸を用いた以外は、実施例２と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表１に示す。
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 2 except that 8% by weight of phosphoric acid on an oxide basis per titanium oxide was used as the particle growth inhibitor.
The physical properties of the obtained catalyst are shown in Table 1.
実施例２の洗浄後のヒドロゾルを、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを含有する水溶液に浸漬し、室温下に２時間放置した後、吸引濾過し、含水量５０重量％になるまで脱水した。次いで、穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃で３時間乾燥した後、５００℃で３時間焼成してモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表２に示す。
The washed hydrosol of Example 2 was immersed in an aqueous solution containing 16.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide, allowed to stand at room temperature for 2 hours, filtered with suction, and contained in water. It dehydrated until it became 50 weight%. Subsequently, it shape | molded using the die | dye with a hole diameter of 1.5 mm (phi), and after drying the obtained molded object at 120 degreeC for 3 hours, it baked at 500 degreeC for 3 hours, and obtained the molybdenum carrying | support titania catalyst.
Table 2 shows the physical properties of the obtained catalyst.
実施例２の濾過後のヒドロゲルを、酸化チタン当たり酸化物基準で８重量％の燐酸を含有する水溶液に浸漬し、室温下に２時間放置した後、吸引濾過し、含水量５０重量％になるまで脱水した。次いで、穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃で３時間乾燥した後、５００℃で３時間焼成してリン担持チタニア触媒を得た。
得られた触媒の物性を表２に示す。
The filtered hydrogel of Example 2 was immersed in an aqueous solution containing 8% by weight of phosphoric acid on an oxide basis per titanium oxide, left at room temperature for 2 hours, and then suction filtered to a water content of 50% by weight. Until dehydrated. Subsequently, it shape | molded using the die | dye of hole diameter 1.5mm (phi), and after drying the obtained molded object at 120 degreeC for 3 hours, it baked at 500 degreeC for 3 hours, and obtained the phosphorus carrying | support titania catalyst.
Table 2 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２０．６重量％のメタタングステン酸アンモニウムを用いた以外は、実施例４と同様にしてタングステン担持チタニア触媒を得た。
得られた触媒の物性を表２に示す。
A tungsten-supported titania catalyst was obtained in the same manner as in Example 4 except that 20.6 wt% ammonium metatungstate based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 2 shows the physical properties of the obtained catalyst.
実施例５と同様の方法で原料を硫酸チタンにした濾過後のヒドロゲルに、粒子成長抑制剤として硫酸を、酸化チタン当たりＳＯ3基準で９重量％加えた以外は、実施例５と同様にして硫酸担持チタニア触媒を得た。
得られた触媒の物性を表３に示す。
In the same manner as in Example 5, except that 9% by weight of sulfuric acid as a particle growth inhibitor was added to the hydrogel after filtration using titanium sulfate as a raw material in the same manner as in Example 5 on a SO 3 basis per titanium oxide. A sulfuric acid-supported titania catalyst was obtained.
Table 3 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．９重量％の硼酸を用いた以外は、実施例４と同様にしてボリア担持チタニア触媒を得た。
得られた触媒の物性を表３に示す。
A boria-supported titania catalyst was obtained in the same manner as in Example 4 except that 3.9% by weight of boric acid based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 3 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり金属酸化物基準で９．０重量％の硫酸第１鉄を用いた以外は、実施例５と同様にして鉄担持チタニア触媒を得た。
得られた触媒の物性を表３に示す。
An iron-supported titania catalyst was obtained in the same manner as in Example 5 except that 9.0% by weight of ferrous sulfate was used as the particle growth inhibitor based on the metal oxide per titanium oxide.
Table 3 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で８．４重量％の硝酸ニッケルを用いた以外は、実施例５と同様にしてニッケル担持チタニア触媒を得た。
得られた触媒の物性を表４に示す。
A nickel-supported titania catalyst was obtained in the same manner as in Example 5 except that 8.4% by weight of nickel nitrate based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 4 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．０重量％の燐酸と１０．０重量％のパラモリブデン酸アンモニウムを同時に用いた以外は、実施例５と同様にしてリン・モリブデン担持チタニア触媒を得た。
得られた触媒の物性を表４に示す。
Phosphorus / molybdenum-containing titania as in Example 5 except that 3.0% by weight phosphoric acid and 10.0% by weight ammonium paramolybdate on a titanium oxide basis were simultaneously used as the particle growth inhibitor. A catalyst was obtained.
Table 4 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．０重量％の硝酸コバルトと１０．０重量％のパラモリブデン酸アンモニウムを同時に用いた以外は、実施例４と同様にしてコバルト・モリブデン担持チタニア触媒を得た。
得られた触媒の物性を表４に示す。
Cobalt / molybdenum supported in the same manner as in Example 4 except that 3.0% by weight of cobalt nitrate and 10.0% by weight of ammonium paramolybdate were simultaneously used as particle growth inhibitors based on oxides per titanium oxide. A titania catalyst was obtained.
Table 4 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３．０重量％の硝酸ニッケルと１０．０重量％のパラモリブデン酸アンモニウムを同時に用いた以外は、実施例４と同様にしてニッケル・モリブデン担持チタニア触媒を得た。
得られた触媒の物性を表５に示す。
Nickel / molybdenum supported in the same manner as in Example 4 except that 3.0% by weight of nickel nitrate and 10.0% by weight of ammonium paramolybdate were simultaneously used as the particle growth inhibitor on an oxide basis per titanium oxide. A titania catalyst was obtained.
Table 5 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の燐酸と８．０重量％のパラモリブデン酸アンモニウムと２．０重量％の硝酸コバルトを同時に用いた以外は、実施例５と同様にしてリン・モリブデン・コバルト担持チタニア触媒を得た。
得られた触媒の物性を表５に示す。
Example 5 except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium paramolybdate and 2.0% by weight cobalt nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as above, a phosphorus / molybdenum / cobalt-supported titania catalyst was obtained.
Table 5 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の燐酸と８．０重量％のパラモリブデン酸アンモニウムと２．０重量％の硝酸ニッケルとを同時に用いた以外は、実施例５と同様にしてリン・モリブデン・ニッケル担持チタニア触媒を得た。
得られた触媒の物性を表５に示す。
Examples were used, except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium paramolybdate and 2.0% by weight nickel nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as in Example 5, a phosphorus / molybdenum / nickel-supported titania catalyst was obtained.
Table 5 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の硝酸ニッケルと８．０重量％のパラモリブデン酸アンモニウムと２．０重量％の硝酸コバルトとを同時に用いた以外は、実施例５と同様にしてニッケル・モリブデン・コバルト担持チタニア触媒を得た。
得られた触媒の物性を表６に示す。
Implemented except that 2.0 wt.% Nickel nitrate, 8.0 wt.% Ammonium paramolybdate and 2.0 wt.% Cobalt nitrate were simultaneously used as particle growth inhibitors on an oxide basis per titanium oxide. In the same manner as in Example 5, a nickel / molybdenum / cobalt-supported titania catalyst was obtained.
Table 6 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たりＳＯ3基準で５重量％の硫酸と金属酸化物基準で８．０重量％のパラモリブデン酸アンモニウムと金属酸化物基準で２．０重量％の硝酸ニッケルとを用いた以外は、実施例７と同様にして硫酸・モリブデン・ニッケル担持チタニア触媒を得た。
得られた触媒の物性を表６に示す。
As a particle growth inhibitor, and 2.0 wt% of nickel nitrate in 8.0% by weight of ammonium paramolybdate and metal oxide basis at 5% by weight of sulfuric acid and the metal oxide basis in SO 3 basis per titanium oxide A sulfuric acid / molybdenum / nickel-supported titania catalyst was obtained in the same manner as in Example 7 except that it was used.
Table 6 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で２．０重量％の燐酸と８．０重量％のメタタングステン酸アンモニウムと２．０重量％の硝酸ニッケルとを同時に用いた以外は、実施例４と同様にしてリン・タングステン・ニッケル担持チタニア触媒を得た。
得られた触媒の物性を表６に示す。
Examples were used, except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium metatungstate and 2.0% by weight nickel nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as in Example 4, a phosphorus / tungsten / nickel-supported titania catalyst was obtained.
Table 6 shows the physical properties of the obtained catalyst.
粒子成長抑制剤の添加方法を浸漬からポアフィリング法による含浸に変えた以外は、実施例３と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表７に示す。
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 3 except that the method for adding the particle growth inhibitor was changed from immersion to impregnation by the pore filling method.
Table 7 shows the physical properties of the obtained catalyst.
粒子成長抑制剤の添加方法を浸漬から直接混練に変えた以外は、実施例５と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表７に示す。
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 5 except that the method for adding the particle growth inhibitor was changed from immersion to direct kneading.
Table 7 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で８重量％の燐酸を用いた以外は、実施例４と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表７に示す。
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 4 except that 8% by weight of phosphoric acid based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 7 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で３０．３重量％のパラモリブデン酸アンモニウムを用いた以外は、実施例４と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表８に示す。
A molybdenum-supported titania catalyst was obtained in the same manner as in Example 4 except that 30.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide was used as a particle growth inhibitor.
Table 8 shows the physical properties of the obtained catalyst.
焼成温度を３５０℃に変えた以外は、実施例５と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表８に示す。
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 5 except that the calcination temperature was changed to 350 ° C.
Table 8 shows the physical properties of the obtained catalyst.
粒子成長抑制剤として、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを用いて、焼成温度を６００℃に変えた以外は、実施例５と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表８に示す。
A molybdenum-supported titania catalyst was prepared in the same manner as in Example 5 except that 16.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide was used as the particle growth inhibitor and the calcination temperature was changed to 600 ° C. Obtained.
Table 8 shows the physical properties of the obtained catalyst.
焼成温度を２００℃に変えた以外は、実施例５と同様にしてリン担持チタニア触媒を得た。
得られた触媒の物性を表９に示す。
A phosphorus-supported titania catalyst was obtained in the same manner as in Example 5 except that the calcination temperature was changed to 200 ° C.
Table 9 shows the physical properties of the obtained catalyst.
実施例２４のゾル合成温度条件を９５℃に変えた以外は、実施例２４と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表９に示す。
A molybdenum-supported titania catalyst was obtained in the same manner as in Example 24 except that the sol synthesis temperature condition in Example 24 was changed to 95 ° C.
Table 9 shows the physical properties of the obtained catalyst.
実施例２４のゾル合成温度条件を２００℃に変えた以外は、実施例２４と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表９に示す。
［参考例２８］
A molybdenum-supported titania catalyst was obtained in the same manner as in Example 24 except that the sol synthesis temperature condition in Example 24 was changed to 200 ° C.
Table 9 shows the physical properties of the obtained catalyst.
[Reference Example 28]
実施例２と同様の方法で原料をオキシ塩化ジルコニウムにした濾過後のジルコニアヒドロゲルを、酸化ジルコニウム当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを含有する水溶液に浸漬し、室温下に２時間放置した後、吸引濾過し、含水量５０重量％になるまで脱水した。次いで、穴径１．５ｍｍφのダイスを用いて成形し、得られた成形物を１２０℃で３時間乾燥した後、５００℃で３時間焼成してモリブデン担持ジルコニア触媒を得た。
得られた触媒の物性を表９に示す。
A zirconia hydrogel after filtration in which the raw material was zirconium oxychloride in the same manner as in Example 2 was immersed in an aqueous solution containing 16.3% by weight ammonium paramolybdate on the oxide basis per zirconium oxide, and at room temperature. After standing for 2 hours, the solution was filtered by suction and dehydrated until the water content reached 50% by weight. Subsequently, it shape | molded using the die | dye with a hole diameter of 1.5 mm (phi), and after drying the obtained molded object at 120 degreeC for 3 hours, it baked at 500 degreeC for 3 hours, and obtained the molybdenum carrying | support zirconia catalyst.
Table 9 shows the physical properties of the obtained catalyst.
（比較例１）
四塩化チタン水溶液と14wt%ＮＨ4ＯＨ水溶液を９５℃の合成温度条件にて連続で混合し、含水酸化チタンのヒドロゾルを得た。得られた含水酸化チタンのヒドロゾルを濾過し、水で３回洗浄し、次いで成形した後、５００℃で３時間焼成してチタニア担体を製造した。
得られたチタニア担体の物性を表１０に示す。
(Comparative Example 1)
A titanium tetrachloride aqueous solution and a 14 wt% NH 4 OH aqueous solution were continuously mixed under a synthesis temperature condition of 95 ° C. to obtain a hydrous titanium oxide hydrosol. The obtained hydrous titanium oxide hydrosol was filtered, washed three times with water, then molded, and then calcined at 500 ° C. for 3 hours to produce a titania carrier.
Table 10 shows the physical properties of the obtained titania carrier.
（比較例２）
実施例２で得られた粒子成長抑制剤添加前の含水酸化チタンの乾燥成形物を５００℃で焼成し、チタニア担体を製造した。
得られたチタニア担体の物性を表１０に示す。
(Comparative Example 2)
The dried hydrous titanium oxide product obtained in Example 2 before addition of the particle growth inhibitor was fired at 500 ° C. to produce a titania carrier.
Table 10 shows the physical properties of the obtained titania carrier.
（比較例３）
実施例２で得られた粒子成長抑制剤添加前の含水酸化チタンの乾燥成形物を３７０℃で乾燥し、含水酸化物水分量（ｎ）を０．０１に調整したのち、粒子成長抑制剤として、酸化チタン当たり酸化物基準で１６．３重量％のパラモリブデン酸アンモニウムを加えた以外は実施例２と同様にしてモリブデン担持チタニア触媒を得た。
得られた触媒の物性を表１０に示す。
(Comparative Example 3)
The dried product of hydrous titanium oxide before addition of the particle growth inhibitor obtained in Example 2 was dried at 370 ° C. and the moisture content (n) of the hydrous oxide was adjusted to 0.01. A molybdenum-supported titania catalyst was obtained in the same manner as in Example 2 except that 16.3% by weight of ammonium paramolybdate based on oxide per titanium oxide was added.
Table 10 shows the physical properties of the obtained catalyst.
小型の流通式反応装置を用いて、減圧軽油（窒素濃度０．２重量％）を原料とし、反応温度３７０℃、反応圧力（水素分圧）８．０ＭＰａ、ＬＨＳＶ２-1、Ｈ2／oil比５００Ｎｍ3／Ｋｌの反応条件で、触媒として実施例１５のリン・モリブデン・ニッケル担持チタニア触媒（ＢＥＴ比表面積は１６７ｍ2／ｇ）を用いて水素化処理を行った。得られた生成油の窒素濃度は０．０２２重量％であった。 Using a small flow reactor, starting from vacuum gas oil (nitrogen concentration 0.2 wt%), reaction temperature 370 ° C, reaction pressure (hydrogen partial pressure) 8.0 MPa, LHSV2 -1 , H 2 / oil ratio Hydrogenation was performed using the phosphorus / molybdenum / nickel-supported titania catalyst of Example 15 (BET specific surface area of 167 m 2 / g) as a catalyst under the reaction conditions of 500 Nm 3 / Kl. The nitrogen concentration of the resulting oil was 0.022% by weight.
（比較例４）
触媒として市販のチタニアを触媒化し、ＢＥＴ比表面積４２ｍ2／ｇのＮｉ／Ｍｏ担持チタニア触媒（Ｎｉ:2.4wt%／Ｍｏ:16.7wt%）を用いた以外は、上記実施例２９と同様にして水素化処理を行った。この水素化処理の結果、生成油の窒素濃度は０．１０重量％となった。
脱窒素反応を１次反応として脱窒素反応速度を求めると、実施例１５の触媒は、比較例４の触媒と比較して、約３．５倍の脱窒素活性を示した。
(Comparative Example 4)
Except that a commercially available titania was catalyzed as a catalyst and a Ni / Mo supported titania catalyst having a BET specific surface area of 42 m 2 / g (Ni: 2.4 wt% / Mo: 16.7 wt%) was used, the same as in Example 29 above. Hydrogenation treatment was performed. As a result of this hydrogenation treatment, the nitrogen concentration of the product oil was 0.10% by weight.
When the denitrification reaction rate was determined using the denitrification reaction as the primary reaction, the catalyst of Example 15 showed about 3.5 times as much denitrification activity as the catalyst of Comparative Example 4.
小型の流通式反応装置を用いて、常圧軽油（硫黄濃度１．３重量％）を原料とし、反応温度３５０℃、反応圧力（水素分圧）５．０ＭＰａ、ＬＨＳＶ２-1、Ｈ2／oil比２００Ｎｍ3／Ｋｌの反応条件で、触媒として実施例１４のリン・モリブデン・コバルト担持チタニア触媒（ＢＥＴ比表面積は１４９ｍ2／ｇ）を用いて水素化処理を行った。得られた生成油の硫黄濃度は８０ｐｐｍであった。
Using a small flow-type reaction apparatus, starting from atmospheric pressure light oil (sulfur concentration 1.3% by weight),
（比較例５）
触媒として、市販のチタニアを触媒化し、ＢＥＴ比表面積４０ｍ2／ｇのＣｏ・Ｍｏ担持チタニア触媒（Ｃｏ:3.9wt%／Ｍｏ:13.3wt%）を用いた以外は、上記実施例３０と同様にして水素化処理を行った。この水素化処理の結果、生成油の硫黄濃度は４５０ｐｐｍとなった。脱硫反応を１．５次反応として脱硫反応速度を求めると、実施例１４の触媒は、比較例５の触媒と比較して、約３．８倍の脱硫活性を示した。
(Comparative Example 5)
The same procedure as in Example 30 except that commercially available titania was catalyzed and a Co / Mo-supported titania catalyst having a BET specific surface area of 40 m 2 / g (Co: 3.9 wt% / Mo: 13.3 wt%) was used. The hydrogenation treatment was performed. As a result of this hydrogenation treatment, the sulfur concentration of the product oil was 450 ppm. When the desulfurization reaction rate was determined using the desulfurization reaction as the 1.5th order reaction, the catalyst of Example 14 showed a desulfurization activity about 3.8 times that of the catalyst of Comparative Example 5.
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