JP2690652B2 - Fluidized catalyst for vapor phase catalytic oxidation of aromatic hydrocarbons - Google Patents
Fluidized catalyst for vapor phase catalytic oxidation of aromatic hydrocarbonsInfo
- Publication number
- JP2690652B2 JP2690652B2 JP4035213A JP3521392A JP2690652B2 JP 2690652 B2 JP2690652 B2 JP 2690652B2 JP 4035213 A JP4035213 A JP 4035213A JP 3521392 A JP3521392 A JP 3521392A JP 2690652 B2 JP2690652 B2 JP 2690652B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- weight
- concentration
- oxide
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 83
- 238000007254 oxidation reaction Methods 0.000 title claims description 25
- 230000003647 oxidation Effects 0.000 title claims description 23
- 230000003197 catalytic effect Effects 0.000 title claims description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 9
- 239000012808 vapor phase Substances 0.000 title claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 12
- -1 sulfuric acid compound Chemical class 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 229910052792 caesium Inorganic materials 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 150000003682 vanadium compounds Chemical class 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003298 rubidium compounds Chemical class 0.000 claims description 6
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 40
- 239000000499 gel Substances 0.000 description 31
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 27
- 230000000694 effects Effects 0.000 description 27
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 24
- 239000002002 slurry Substances 0.000 description 23
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 22
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 22
- 229940078552 o-xylene Drugs 0.000 description 21
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 18
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- 239000013078 crystal Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 12
- 235000011130 ammonium sulphate Nutrition 0.000 description 12
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 12
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 229940041260 vanadyl sulfate Drugs 0.000 description 11
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 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 6
- 239000002245 particle Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- ICBXFCBCYDWWKQ-UHFFFAOYSA-J [OH-].[OH-].[OH-].[OH-].O.O.O.P.[Ti+4] Chemical compound [OH-].[OH-].[OH-].[OH-].O.O.O.P.[Ti+4] ICBXFCBCYDWWKQ-UHFFFAOYSA-J 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- IMWCPTKSESEZCL-SPSNFJOYSA-H (e)-but-2-enedioate;iron(3+) Chemical compound [Fe+3].[Fe+3].[O-]C(=O)\C=C\C([O-])=O.[O-]C(=O)\C=C\C([O-])=O.[O-]C(=O)\C=C\C([O-])=O IMWCPTKSESEZCL-SPSNFJOYSA-H 0.000 description 1
- CQNPSIAJXGEDQS-VURMDHGXSA-N (z)-2-phenylbut-2-enedioic acid Chemical compound OC(=O)\C=C(/C(O)=O)C1=CC=CC=C1 CQNPSIAJXGEDQS-VURMDHGXSA-N 0.000 description 1
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- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- JFHFMHPKOSJJTE-UHFFFAOYSA-N 4,5-dimethyl-2-benzofuran-1,3-dione Chemical compound CC1=CC=C2C(=O)OC(=O)C2=C1C JFHFMHPKOSJJTE-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- FZQSLXQPHPOTHG-UHFFFAOYSA-N [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 Chemical compound [K+].[K+].O1B([O-])OB2OB([O-])OB1O2 FZQSLXQPHPOTHG-UHFFFAOYSA-N 0.000 description 1
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- JBXYCUKPDAAYAS-UHFFFAOYSA-N methanol;trifluoroborane Chemical compound OC.FB(F)F JBXYCUKPDAAYAS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-M oxalate(1-) Chemical compound OC(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-M 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PYUBPZNJWXUSID-UHFFFAOYSA-N pentadecapotassium;pentaborate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] PYUBPZNJWXUSID-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- YXPHMGGSLJFAPL-UHFFFAOYSA-J tetrabromotungsten Chemical compound Br[W](Br)(Br)Br YXPHMGGSLJFAPL-UHFFFAOYSA-J 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- MMCXETIAXNXKPE-UHFFFAOYSA-J tetraiodotungsten Chemical compound I[W](I)(I)I MMCXETIAXNXKPE-UHFFFAOYSA-J 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【０００１】[0001]
【産業上の利用分野】本発明は、芳香族カルボン酸無水
物の製造に際して、より詳しくはｏ−キシレン、ナフタ
レンおよびデュレンなどの芳香族炭化水素原料を気相接
触酸化して無水フタル酸および無水ピロメリット酸など
を製造する際に用いる流動触媒に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of aromatic carboxylic acid anhydrides, more specifically, by subjecting aromatic hydrocarbon raw materials such as o-xylene, naphthalene and durene to gas phase catalytic oxidation to produce phthalic anhydride and anhydride. The present invention relates to a fluidized catalyst used when producing pyromellitic acid and the like.
【０００２】[0002]
【従来の技術】芳香族カルボン酸無水物は芳香族炭化水
素原料の気相接触酸化により製造され、例えば、ｏ−キ
シレン、ナフタレンおよびデュレンの気相接触酸化によ
る無水フタル酸および無水ピロメリット酸の製造例を挙
げることができる。ｏ−キシレンを気相酸化して無水フ
タル酸を製造する際に用いる流動触媒としては、ナフタ
レンを原料とする場合と同じく、シリカを担体とし、五
酸化バナジウム、硫酸カリウムを、さらには酸化モリブ
デン、酸化タングステン、酸化リン、酸化ホウ素などを
担持させた触媒が提案されている（例えば、Ｂ．Ｐ．，
９４１，２９３（１９６３）；Ｕ．Ｓ．Ｐ．，３，２３
２，９５５（１９６６））。しかし、シリカを担持とし
た前記触媒を用いると、ＣＯやＣＯ2 を生成する過剰酸
化反応や副反応（高沸点生成物）のために高収率で無水
フタル酸を得ることは困難である。Aromatic carboxylic acid anhydrides are produced by vapor-phase catalytic oxidation of aromatic hydrocarbon raw materials, for example, phthalic anhydride and pyromellitic dianhydride by vapor-phase catalytic oxidation of o-xylene, naphthalene and durene. A production example can be given. As a fluidized catalyst used for producing phthalic anhydride by gas phase oxidation of o-xylene, as in the case of using naphthalene as a raw material, silica is used as a carrier, vanadium pentoxide, potassium sulfate, and further molybdenum oxide, A catalyst supporting tungsten oxide, phosphorus oxide, boron oxide or the like has been proposed (for example, BP,
941, 293 (1963); S. P. , 3,23
2, 955 (1966)). However, it is difficult to obtain phthalic anhydride in a high yield due to an excessive oxidation reaction or a side reaction (high boiling point product) that produces CO or CO 2 when the above-mentioned catalyst supporting silica is used.
【０００３】収率を向上させるために、反応ガス中に臭
素（Ｂｒ2 ）のようなハロゲンガスを混合する試みも行
なわれているが、ハロゲンガスを共存させると、腐蝕に
よる装置トラブルを起こす問題がある（Ｄ．Ｐ．，１，
１４４，７０９（１９６３）；Ｕ．Ｓ．Ｐ．，３４５５
９６２（１９６９））。Attempts have been made to mix a halogen gas such as bromine (Br 2 ) into the reaction gas in order to improve the yield. However, the coexistence of the halogen gas causes a problem in the equipment due to corrosion. (DP, 1,
144, 709 (1963); S. P. , 3455
962 (1969)).
【０００４】酸化チタンを担体として用い、これに五酸
化バナジウムを担持させた触媒もいくつか提案されてい
る（たとえばＢ．Ｐ．，１，０６７，７２６（１９６
７）；Ｆｒ．Ｐ．，１，５３７，３５１（１９６
８））。しかしこれらの方法で得られる触媒は全く流動
触媒としての特性が記載されておらず、流動性、摩耗強
度については不明であり、かつ比表面積、細孔容積が著
しく小さいので、活性が低くなるため、高い反応温度を
必要とし、その結果、過剰酸化や副反応を併発する。し
たがってこの方法で得られる触媒を用い、収率よく無水
フタル酸を得ることは困難である。Several catalysts have been proposed in which titanium oxide is used as a carrier and vanadium pentoxide is supported on the carrier (for example, BP, 1,067,726 (196).
7); Fr. P. , 1,537,351 (196
8)). However, the properties of the catalysts obtained by these methods are not described as fluidized catalysts at all, their fluidity and wear strength are unknown, and their specific surface area and pore volume are extremely small, resulting in low activity. However, it requires a high reaction temperature and, as a result, causes excessive oxidation and side reactions. Therefore, it is difficult to obtain phthalic anhydride in good yield using the catalyst obtained by this method.
【０００５】これらの理由により流動床を用いたｏ−キ
シレンの気相酸化による無水フタル酸の製造は実用化に
至っていない。For these reasons, the production of phthalic anhydride by vapor phase oxidation of o-xylene using a fluidized bed has not been put to practical use.
【０００６】デュレンを気相接触酸化して無水ピロメリ
ット酸を製造する触媒としては、α−アルミナのような
低比表面積・不活性担体に五酸化バナジウムを主成分と
する触媒成分を担持した固定床触媒が従来より提案され
ている（例えば、特開昭６１−２８４５６号、特開平１
−２９４６７９号など）。しかし、無水ピロメリット酸
製造用として流動床触媒の開発例はこれまで報告されて
いない。As a catalyst for producing pyromellitic dianhydride by vapor-phase catalytic oxidation of durene, a catalyst having a low specific surface area / inert carrier such as α-alumina and a catalyst component containing vanadium pentoxide as the main component is immobilized. Bed catalysts have been proposed in the past (for example, JP-A-61-28456, JP-A-1).
-294679). However, no development example of a fluidized bed catalyst for producing pyromellitic dianhydride has been reported so far.
【０００７】本発明者らはこれらの欠点を解決した触媒
として酸化チタンを担体として用い、五酸化バナジウ
ム、アルカリ金属酸化物、および硫酸化合物あるいは周
期律表ＩＩＩＢ族金属酸化物を含有する十分な強度と適
度なかさ比重を有する高活性・高選択性の流動床用触媒
をすでに提案した（特開平２−９４４７号、特開平２−
２６１，５４３号）。しかしこれらの触媒は反応初期に
おいては、活性・選択性に優れ、無水フタル酸を高収率
で得ることができるものの、長期間使用すると、活性・
選択性が徐々に低下するという問題があった。The present inventors have used titanium oxide as a carrier as a catalyst for solving these drawbacks, and have sufficient strength containing vanadium pentoxide, an alkali metal oxide, and a sulfuric acid compound or a Group IIIB metal oxide of the periodic table. And a highly active and highly selective catalyst for a fluidized bed having an appropriate bulk specific gravity has been already proposed (Japanese Patent Laid-Open No. 9447/1990 and Japanese Patent Laid-Open No.
261, 543). However, these catalysts have excellent activity and selectivity in the early stage of the reaction, and although phthalic anhydride can be obtained in a high yield, when they are used for a long period of time,
There was a problem that the selectivity gradually decreased.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、ｏ−キシレ
ン、ナフタレンおよびデュレンなどの芳香族炭化水素原
料を気相酸化して無水フタル酸および無水ピロメリット
酸などを製造する反応において、長期間使用しても活性
低下の無い流動床用触媒の提供を目的とする。DISCLOSURE OF THE INVENTION The present invention is for a long period of time in a reaction for producing phthalic anhydride, pyromellitic dianhydride, etc. by gas phase oxidation of an aromatic hydrocarbon raw material such as o-xylene, naphthalene and durene. The purpose of the present invention is to provide a catalyst for a fluidized bed that does not deteriorate in activity even when used.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、酸化チタ
ンを主成分とする無水フタル酸製造用流動床触媒につい
て鋭意研究の結果、本発明を成すに至った。The present inventors have completed the present invention as a result of intensive research on a fluidized bed catalyst for producing phthalic anhydride containing titanium oxide as a main component.
【００１０】すなわち、本発明は、酸化チタン、バナジ
ウム化合物、セシウムおよび／またはルビジウム化合
物、硫酸化合物を必須成分とし、鉄（Ｆｅ）、リン
（Ｐ）、タングステン（Ｗ）、およびバリウム（Ｂａ）
から選ばれる少なくとも一種の元素を酸化物として０．
３〜１５重量％含有することを特徴とする芳香族炭化水
素の気相接触酸化による芳香族カルボン酸無水物製造用
流動触媒を提供するものである。That is, the present invention is a compound of titanium oxide, vanadium compound, cesium and / or rubidium compound.
Substances and sulfuric acid compounds as essential components, iron (Fe), phosphorus (P), tungsten (W), and barium (Ba)
At least one element selected from the above as an oxide.
The present invention provides a fluidized catalyst for the production of aromatic carboxylic acid anhydrides by vapor phase catalytic oxidation of aromatic hydrocarbons, the content of which is 3 to 15% by weight.
【００１１】[0011]
【作用】以下、本発明について詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１２】本発明の触媒は、酸化物基準で酸化チタン
（ＴｉＯ2 ）として４０〜９０重量％、バナジウム化合
物（Ｖ2 Ｏ5 ）として５〜１３重量％、セシウムおよび
／またはルビジウム化合物（Ｍ2 Ｏ）として２．７〜
４．３重量％、硫酸化合物（ＳＯ3 ）として１．５〜
４．５重量％の範囲であることが望ましく、さらにＦ
ｅ、Ｐ、Ｗ、およびＢａから選ばれる少なくとも一種の
元素を酸化物として０．３〜１５重量％の範囲に含有す
ることが望ましい。The catalyst of the present invention contains 40 to 90% by weight of titanium oxide (TiO 2 ) and 5 to 13% by weight of vanadium compound (V 2 O 5 ), cesium and
/ Or 2.7 as a rubidium compound (M 2 O)
4.3 wt%, as a sulfuric acid compound (SO 3 ) 1.5-
It is preferably in the range of 4.5% by weight, and further F
It is desirable to contain at least one element selected from e, P, W, and Ba in the range of 0.3 to 15% by weight as an oxide.
【００１３】特にＦｅ、Ｐ、Ｗ、およびＢａから選ばれ
る少なくとも一種の元素を酸化物として０．３重量％よ
り少ない場合は、触媒の活性低下の抑制効果が得られ
ず、また１５重量％より多い場合は副反応等の促進によ
り目的物無水フタル酸への選択性が低下するので好まし
くない。Ｆｅ、Ｐ、Ｗ、およびＢａから選ばれる少なく
とも一種の元素の酸化物のより好ましい含有量の範囲は
０．５〜１０重量％である。In particular, when the amount of at least one element selected from Fe, P, W and Ba as an oxide is less than 0.3% by weight, the effect of suppressing the decrease in the activity of the catalyst cannot be obtained, and more than 15% by weight. If the amount is too large, the selectivity to the desired product, phthalic anhydride, is lowered due to the promotion of side reactions, which is not preferable. The more preferable content range of the oxide of at least one element selected from Fe, P, W, and Ba is 0.5 to 10% by weight.
【００１４】Ｆｅ、Ｐ、Ｗ、およびＢａなどの成分は酸
化チタン、バナジウム化合物、セシウムおよび／または
ルビジウム化合物、硫酸化合物の活性成分に作用し、特
に酸化チタンの熱や水熱作用による結晶成長を強く抑制
し、芳香族炭化水素の気相酸化触媒としての長期間反応
使用における熱履歴、水熱作用に対しても触媒は非常に
安定となり、活性低下が抑制される。また、これらの添
加成分は過剰酸化を抑制する効果があり、目的物への選
択性の面でも優れた効果がある。The components such as Fe, P, W and Ba are titanium oxide, vanadium compound, cesium and / or
It acts on the active components of rubidium compounds and sulfuric acid compounds, and strongly suppresses the crystal growth due to the heat and hydrothermal action of titanium oxide. The catalyst becomes very stable against the action, and the decrease in activity is suppressed. Further, these additive components have an effect of suppressing excessive oxidation, and also have an excellent effect in terms of selectivity with respect to a target product.
【００１５】本発明の触媒はたとえば、酸化チタン源と
バナジウム化合物、セシウムおよび／またはルビジウム
化合物、硫酸化合物およびＦｅ、Ｐ、Ｗ、Ｂａから選ば
れた酸化物の少なくとも一種の前駆物質を混合した後、
噴霧乾燥、焼成することにより製造される。各原料の混
合順序は任意でよく、２種以上の原料を同時に溶解する
方法、水酸化チタン分散液に活性成分原料を溶解する方
法等も採用できる。The catalyst of the present invention is, for example, a titanium oxide source and a vanadium compound, cesium and / or rubidium.
After mixing a compound, a sulfuric acid compound and at least one precursor of an oxide selected from Fe, P, W and Ba,
It is manufactured by spray drying and firing. The order of mixing the respective raw materials may be arbitrary, and a method of dissolving two or more raw materials at the same time, a method of dissolving the active ingredient raw material in the titanium hydroxide dispersion, and the like can be adopted.
【００１６】上記のように得られた混合スラリーを必要
に応じて濃縮し、適当な濃度に調製したのち、噴霧乾燥
により球状微小粒子を得ることができる。噴霧乾燥法と
しては、公知の方法が採用可能である。噴霧乾燥に当っ
ては、得られる球状微粒子の重量平均粒子径が４０〜１
５０μｍとなるように噴霧条件を設定することが好まし
い。得られた球状粒子は空気中で、好ましくは３００〜
７００℃、より好ましくは４００〜６００℃の温度で焼
成される。If necessary, the mixed slurry obtained as described above is concentrated to an appropriate concentration and then spray-dried to obtain spherical fine particles. As the spray drying method, a known method can be adopted. In the spray drying, the weight average particle diameter of the obtained spherical fine particles is 40 to 1
It is preferable to set the spraying conditions so as to be 50 μm. The spherical particles obtained are preferably in the range of 300 to 300 in air.
It is fired at a temperature of 700 ° C, more preferably 400 to 600 ° C.
【００１７】本発明の触媒の製造に用いられる酸化チタ
ン源は、３００℃で乾燥した時に結晶子径が３００Å以
下の酸化チタンを生成する水酸化チタンであることが望
ましい。結晶子径はデバイ−シェラー法に基づき、Ｘ線
回折図の２θ＝２５．３°（ＣｕＫα アナターゼ型酸
化チタン）における回折ピークの半値幅を用い、次式に
より求められる；The titanium oxide source used for producing the catalyst of the present invention is preferably titanium hydroxide which produces titanium oxide having a crystallite size of 300 Å or less when dried at 300 ° C. The crystallite diameter is determined by the following formula based on the Debye-Scherrer method, using the half value width of the diffraction peak at 2θ = 25.3 ° (CuKα anatase type titanium oxide) in the X-ray diffraction pattern;
【数１】 (Equation 1)
【００１８】これらの酸化チタン源（水酸化チタン）と
しては、顔料酸化チタンを製造する中間工程で、得られ
る熱加水分解法によるチタン酸や、これに酸を加えて得
られるチタニアゾルなどが挙げられる。その他に硫酸チ
タン、硫酸チタニル、四塩化チタンなどを中和加水分解
したり、イオン交換法により脱酸加水分解して得られる
水酸化チタンやチタニアゾルなども使用できる。特に硫
酸チタニルなどの溶液を４０℃以下の低温で中和加水分
解することによって得られる水酸化チタンは乾燥後、数
１０Åの結晶子径を示し、好適である。Examples of these titanium oxide sources (titanium hydroxide) include titanic acid obtained by a thermal hydrolysis method obtained in an intermediate step of producing pigment titanium oxide, and titania sol obtained by adding an acid thereto. . In addition, titanium hydroxide, titania sol, etc. obtained by neutralizing hydrolysis of titanium sulfate, titanyl sulfate, titanium tetrachloride or the like, or deoxidizing hydrolysis by an ion exchange method can also be used. In particular, titanium hydroxide obtained by neutralizing and hydrolyzing a solution of titanyl sulfate or the like at a low temperature of 40 ° C. or lower is preferable because it shows a crystallite size of several tens of Å after drying.
【００１９】本発明の触媒の製造に用いられるバナジウ
ム化合物は水に可溶であり、空気中焼成により酸化バナ
ジウムを生成するもの、例えば、メタバナジン酸アンモ
ニウム、硫酸バナジル（オキシ硫酸バナジウム）、ギ酸
バナジウム、酢酸バナジウム、シュウ酸バナジル、シュ
ウ酸バナジウムアンモニウム、リン酸バナジル、オキシ
ハロゲン化バナジウムなどである。これらのうちで、硫
酸バナジル、メタバナジン酸アンモニウム、シュウ酸バ
ナジルなどを用いることが好ましい。The vanadium compound used in the production of the catalyst of the present invention is soluble in water and produces vanadium oxide by calcination in air, such as ammonium metavanadate, vanadyl sulfate (vanadium oxysulfate), vanadium formate, Examples thereof include vanadium acetate, vanadyl oxalate, ammonium vanadium oxalate, vanadyl phosphate, and vanadium oxyhalide. Of these, vanadyl sulfate, ammonium metavanadate, vanadyl oxalate and the like are preferably used.
【００２０】またセシウムおよび／またはルビジウム化
合物としては、セシウム、ルビジウムの水酸化物、硫酸
塩、炭酸塩、塩化物、硝酸塩、オキシハロゲン化物、チ
オ硫酸塩、亜硝酸塩、亜硫酸水素塩、硫酸水素塩、シュ
ウ酸塩、シュウ酸水素塩などが挙げられる。これらのう
ちで、水酸化物、硫酸塩、炭酸塩などを用いることが好
ましい。 Cesium and / or rubidium formation
The compounds, cesium, hydroxides of rubidium, sulfates, carbonates, chlorides, nitrates, oxyhalides, thiosulfate, nitrite, sulfite, bisulfate, oxalate, hydrogen oxalate Examples include salt. Of these, hydroxides, sulfates, carbonates and the like are preferably used.
【００２１】硫酸化合物としては、硫酸、硫酸アンモニ
ウム、硫酸水素アンモニウムなどが挙げられる。これら
のうちで、硫酸、硫酸アンモニウムなどを用いることが
好ましい。Examples of the sulfuric acid compound include sulfuric acid, ammonium sulfate, ammonium hydrogensulfate and the like. Of these, sulfuric acid and ammonium sulfate are preferably used.
【００２２】また本発明の触媒の製造に用いられる鉄
（Ｆｅ）、リン（Ｐ）、タングステン（Ｗ）、およびバ
リウム（Ｂａ）などの成分は酸、塩など、水に可溶な化
合物はいずれも使用できる。The components such as iron (Fe), phosphorus (P), tungsten (W), and barium (Ba) used in the production of the catalyst of the present invention are acids, salts, and any water-soluble compound. Can also be used.
【００２３】鉄化合物としては、硫酸鉄、塩化鉄、硝酸
鉄、シュウ酸鉄、クエン酸鉄、これらのアンモニウム
塩、過塩素酸鉄、リン酸鉄、フマル酸鉄、乳酸鉄などが
挙げられる。これらのうちで、特に硝酸鉄、シュウ酸鉄
が好ましい。Examples of iron compounds include iron sulfate, iron chloride, iron nitrate, iron oxalate, iron citrate, ammonium salts thereof, iron perchlorate, iron phosphate, iron fumarate, and iron lactate. Of these, iron nitrate and iron oxalate are particularly preferable.
【００２４】タングステン化合物としては、タングステ
ン酸、パラタングステン酸アンモニウム、塩化タングス
テン、臭化タングステン、ヨウ化タングステン等のハロ
ゲン化物、オキシハロゲン化物、ヘテロポリ酸塩、酸化
タングステンゾル等が挙げられる。これらのうちで、特
にタングステン酸、パラタングステン酸アンモニウムが
好ましい。Examples of the tungsten compound include halides such as tungstic acid, ammonium paratungstate, tungsten chloride, tungsten bromide, and tungsten iodide, oxyhalides, heteropolyacid salts, and tungsten oxide sols. Of these, tungstic acid and ammonium paratungstate are particularly preferable.
【００２５】バリウム化合物としてはフッ化バリウム、
臭化バリウム、ヨウ化バリウム、塩化バリウム等のハロ
ゲン化物、硝酸バリウム、酢酸バリウムなどが挙げら
れ、これらのうちで、特に硝酸バリウム、酢酸バリウム
が好ましい。As the barium compound, barium fluoride,
Examples thereof include barium bromide, barium iodide, barium chloride and other halides, barium nitrate, barium acetate and the like. Of these, barium nitrate and barium acetate are particularly preferable.
【００２６】リン化合物としてはリン酸、リン酸水素ア
ンモニウム、ヘテロポリ酸塩などが好ましい。As the phosphorus compound, phosphoric acid, ammonium hydrogenphosphate, heteropolyacid salt and the like are preferable.
【００２７】本発明の触媒の製造においては、上記Ｆ
ｅ、Ｐ、Ｗ、およびＢａ化合物は併用しても差しつかえ
ない。In the production of the catalyst of the present invention, the above F
The e, P, W, and Ba compounds may be used in combination.
【００２８】本発明の触媒は上記製法に限定されるもの
ではなく、酸化チタン源とバナジウム化合物、セシウム
および／またはルビジウム化合物、および硫酸化合物と
を混合したのち、噴霧乾燥して得られる球状微小粒子
を、Ｆｅ、Ｐ、Ｗ、およびＢａから選ばれる少なくとも
一種の元素を含む水溶液中に浸漬し、次いで乾燥・焼成
することにより、製造することも可能である。The catalyst of the present invention is not limited to the above-mentioned production method, but includes a titanium oxide source, a vanadium compound, and cesium.
And / or a rubidium compound , and a sulfuric acid compound are mixed and then spray-dried to obtain spherical fine particles, which are dipped in an aqueous solution containing at least one element selected from Fe, P, W, and Ba, and then It is also possible to manufacture by drying and baking.
【００２９】なお本発明の触媒は酸化チタン、バナジウ
ム化合物、セシウムおよび／またはルビジウム化合物、
硫酸化合物、ならびにＦｅ、Ｐ、Ｗ、およびＢａから選
ばれる少なくとも一種の元素の他に、シリカ（Ｓｉ
Ｏ2 ）、酸化ホウ素（Ｂ2 Ｏ3 ）、稀土類金属（Ｌａ2
Ｏ3 、Ｃｅ2 Ｏ3 ）などの第３成分を含有することもで
きる。第３成分の添加量は２〜５０重量％の範囲にある
のが望ましい。The catalyst of the present invention comprises titanium oxide, vanadium compound, cesium and / or rubidium compound ,
In addition to the sulfuric acid compound and at least one element selected from Fe, P, W, and Ba, silica (Si
O 2 ), boron oxide (B 2 O 3 ), rare earth metal (La 2
A third component such as O 3 or Ce 2 O 3 ) may be contained. The addition amount of the third component is preferably in the range of 2 to 50% by weight.
【００３０】第３成分としてのシリカは触媒粒子の軽質
化剤（低嵩比重化剤）および造粒バインダーとして作用
する。触媒の製造に用いられるシリカ源としては、溶液
やシリカゾルなどの分散性の良い原料、たとえばケイ酸
ソーダやケイ酸カリウムを中和したり、陽イオン交換し
て得られるケイ酸や、エチルシリケートのような有機ケ
イ酸化合物、およびその酸性加水分解物、第四級アンモ
ニウムシリケートおよびその酸性加水分解物、あるいは
コロイダルシリカなどが望ましい。Silica as the third component acts as a lightening agent (low bulk specific gravity agent) for the catalyst particles and a granulating binder. The silica source used in the production of the catalyst is a solution or a raw material having good dispersibility such as silica sol, for example, sodium silicate or potassium silicate, or silicic acid obtained by cation exchange, or ethyl silicate. Such organic silicic acid compounds, acidic hydrolysates thereof, quaternary ammonium silicates and acidic hydrolysates thereof, colloidal silica and the like are desirable.
【００３１】特に高濃度で長時間安定なコロイダルシリ
カは好適であり、このうち安定化剤としてナトリウム
（Ｎａ）を含むものは、予め陽イオン交換や限外濾過な
どの手段によりＮａを除去して用いることが望ましい。
コロイダルシリカのうち、その粒子径が５０ｎｍ以上の
ものは軽質化には有効であるが、バインダー効果が小さ
いので好ましくない。シリカ源としてゲル状のもの、例
えば、ケイ酸ナトリウムを中和して得られるヒドロゲル
や、ゲル状粉末であるホワイトカーボンやアエロジルな
どは分散性が悪くバインダー効果も小さいので好ましく
ない。Colloidal silica having a high concentration and stable for a long period of time is particularly preferable. Among them, those containing sodium (Na) as a stabilizer are obtained by previously removing Na by means such as cation exchange or ultrafiltration. It is desirable to use.
Among colloidal silicas, those having a particle size of 50 nm or more are effective for lightening, but are not preferable because they have a small binder effect. A silica source such as a gel, for example, a hydrogel obtained by neutralizing sodium silicate, a white powder such as white gel or aerosil which is a gel powder, has poor dispersibility and a small binder effect, which is not preferable.
【００３２】第３成分としての酸化ホウ素は触媒強度
（耐摩耗性）、反応選択性を向上させる効果がある。ま
た触媒の製造に用いられる酸化ホウ素源としては、ホウ
酸、四ホウ酸カリウム、五ホウ酸カリウム、メタホウ酸
カリウム、メタホウ酸アンモニウム、四ホウ酸アンモニ
ウムなどの水溶性化合物が用いられるが、比較的溶解度
の大きいホウ酸、メタホウ酸アンモニウムなどが好適で
ある。Boron oxide as the third component has the effect of improving catalyst strength (wear resistance) and reaction selectivity. Further, as the boron oxide source used in the production of the catalyst, water-soluble compounds such as boric acid, potassium tetraborate, potassium pentaborate, potassium metaborate, ammonium metaborate, ammonium tetraborate are used, Boric acid, ammonium metaborate, and the like, which have high solubility, are suitable.
【００３３】第３成分としての稀土類金属酸化物（Ｌａ
2 Ｏ3、Ｃｅ2 Ｏ3 ）は酸化チタンの結晶化を防止し、
その表面積を増大させ、反応活性を向上させるのに有効
である。触媒の製造に用いられる稀土類金属酸化物源と
しては、塩化物、炭酸塩、硫酸塩、硝酸塩、酢酸塩、シ
ュウ酸塩などが挙げられるが、これらのうちで、特に硝
酸塩、酢酸塩、シュウ酸塩などが好ましい。Rare earth metal oxide (La) as the third component
2 O 3 , Ce 2 O 3 ) prevent crystallization of titanium oxide,
It is effective in increasing the surface area and improving the reaction activity. Sources of rare earth metal oxides used in the production of catalysts include chlorides, carbonates, sulphates, nitrates, acetates, oxalates, among which, among others, nitrates, acetates, oxalates, among others. Acid salts and the like are preferable.
【００３４】本発明の触媒で、さらに上記ＳｉＯ2 、Ｂ
2 Ｏ3 またはＬａ2 Ｏ3 を含有する触媒は活性および選
択性が高く、高い耐摩耗性を有すると同時に、流動化に
適当な嵩比重を有するので好適である。The catalyst of the present invention further comprises the above-mentioned SiO 2 , B.
A catalyst containing 2 O 3 or La 2 O 3 is preferable because it has high activity and selectivity, has high abrasion resistance, and at the same time has a bulk density suitable for fluidization.
【００３５】本発明の触媒は芳香族炭化水素を気相酸化
して対応する無水カルボン酸を得るために使用できる。
適切な炭化水素の代表例としてはｏ−キシレン、クメ
ン、プソイドクメン、デュレン、ジフェニル、およびそ
れらの混合物を包含する。かくして本発明の触媒はデュ
レンを無水ピロメリット酸に、ジフェニルをフェニルマ
レイン酸に、ならびにｏ−キシレンおよびナフタレンを
無水フタル酸に転化するのに使用できる。The catalysts of this invention can be used to vapor-phase oxidize aromatic hydrocarbons to give the corresponding carboxylic anhydrides.
Representative examples of suitable hydrocarbons include o-xylene, cumene, pseudocumene, durene, diphenyl, and mixtures thereof. Thus, the catalyst of the present invention can be used to convert durene to pyromellitic dianhydride, diphenyl to phenylmaleic acid, and o-xylene and naphthalene to phthalic anhydride.
【００３６】本発明の触媒を用いて無水フタル酸を製造
するための好ましい炭化水素供給源はｏ−キシレン、よ
り好ましくは、少なくとも１０モル％以上のｏ−キシレ
ンを含む芳香族留分である。それ故下記の例示において
は、ｏ−キシレンが無水フタル酸製造例として、本発明
の触媒の使用を説明する主要例において使用される。但
しこれに限定されるものではなく、例えばナフタレンも
また無水フタル酸製造用炭化水素供給源として使用しう
る。また、デュレンは無水ピロメリット酸製造用炭化水
素供給源として使用される。The preferred hydrocarbon source for the production of phthalic anhydride using the catalysts of the present invention is o-xylene, more preferably an aromatic cut containing at least 10 mol% o-xylene. Therefore, in the examples below, o-xylene is used as the phthalic anhydride preparation example in the primary example illustrating the use of the catalyst of the present invention. However, the present invention is not limited to this, and for example, naphthalene can also be used as a hydrocarbon source for producing phthalic anhydride. Further, durene is used as a hydrocarbon source for producing pyromellitic dianhydride.
【００３７】ｏ−キシレンあるいはナフタレンの無水フ
タル酸への酸化およびデュレンの無水ピロメリット酸へ
の酸化において、酸素の供給源としては空気が全体的に
好ましいが、酸素と窒素・炭酸ガスなどの希釈ガスとの
合成混合ガスもまた使用できる。酸素に富んだ空気も勿
論使用できる。該酸素含有ガス供給源（例えば空気）
は、それが反応器に導入される前に、好ましくは予備加
熱（例えば１００〜３００℃）される。In the oxidation of o-xylene or naphthalene to phthalic anhydride and the oxidation of durene to pyromellitic dianhydride, air is generally preferred as a source of oxygen, but oxygen and nitrogen, carbon dioxide, etc. are diluted. Synthetic gas mixtures with gas can also be used. Of course, oxygen-rich air can also be used. The oxygen-containing gas source (eg, air)
Is preferably preheated (eg 100-300 ° C.) before it is introduced into the reactor.
【００３８】該反応は大気圧、大気圧以上、または大気
圧以下でも実施できる。一般には０．５〜３．０気圧が
好適である。The reaction can be carried out at atmospheric pressure, above atmospheric pressure, or below atmospheric pressure. Generally, 0.5 to 3.0 atm is suitable.
【００３９】[0039]
【実施例】以下に本発明を実施例に基づき、具体的に説
明する。下記実施例は特許請求の範囲に記載の発明の特
定の説明を与えるものであるが、本発明は実施例に記載
された特定の詳細事項に限定されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. The following examples provide a specific description of the invention as claimed, but the invention is not limited to the particular details described in the examples.
【００４０】（実施例１）ＴｉＯ2 として５重量％を含
む硫酸チタニル水溶液６００ｋｇを１５℃に冷却したの
ち、よく撹拌しながら、１５重量％アンモニア水１４０
ｋｇを５時間で注加して中和し、水酸化チタンのゲルを
得た。このゲルのｐＨは８．５、温度は２３℃であっ
た。このゲルのスラリー２０ｋｇを採り、平板式フィル
ターにより減圧脱水して得られたゲルに、さらに３００
Ｌの純水を徐々に注ぎ、中和により生成した硫酸アンモ
ニウムを除去した。洗浄を繰り返して得た水酸化チタン
ゲル中のＴｉＯ2 濃度は１２．５重量％であった。この
ゲルの一部を採り、３００℃で乾燥して得られた粉末の
Ｘ線回折図の２θ＝２５．３°における回折ピークより
求めたアナターゼ型酸化チタンの結晶子径は５１Åであ
った。Example 1 600 kg of a titanyl sulfate aqueous solution containing 5% by weight of TiO 2 was cooled to 15 ° C., and then stirred well and 140% of 15% by weight ammonia water was added.
Kg was added over 5 hours for neutralization to obtain a titanium hydroxide gel. The pH of this gel was 8.5 and the temperature was 23 ° C. 20 kg of this gel slurry was taken and dehydrated under reduced pressure with a flat plate filter to obtain 300 gel.
L of pure water was gradually poured to remove ammonium sulfate generated by neutralization. The TiO 2 concentration in the titanium hydroxide gel obtained by repeating the washing was 12.5% by weight. A crystallite diameter of anatase-type titanium oxide was 51Å, which was determined from a diffraction peak at 2θ = 25.3 ° of an X-ray diffraction pattern of a powder obtained by taking a part of this gel and drying at 300 ° C.
【００４１】このゲル１００ｋｇを採り、よく撹拌しな
がら純水５０ｋｇを加えて、ＴｉＯ 2 濃度８．３重量％
のスラリーとした。スチームジャケット付の３００Ｌス
テンレス槽に予め調製した８．３重量％のＴｉＯ2 ゲル
スラリーの全量を入れ、撹拌しながら、硫酸アンモニウ
ム結晶０．５８ｋｇ、８５％リン酸水溶液０．０４６ｋ
ｇ、硫酸バナジル水溶液（Ｖ2 Ｏ5 濃度；１９．５重量
％）４．２ｋｇ、硫酸セシウム水溶液（Ｃｓ2 ＳＯ4 濃
度；５０．０重量％）１．３０ｋｇを順次添加した。こ
の時のｐＨは２．１であった。得られたスラリーを十分
に撹拌しながら、加熱して水分を蒸発させ、（ＴｉＯ2
＋Ｖ2 Ｏ5 ＋Ｃｓ2 ＳＯ4 ＋ＳＯ3 ＋Ｐ 2 Ｏ5 ）として
１５重量％の濃度に濃縮した。このスラリーをホモジナ
イザーにより、よりよく分散したのち、ディスク式スプ
レードライヤーにて噴霧乾燥して得た粉末を、１５０℃
で一昼夜乾燥したのち５５０℃にて焼成して触媒Ｂを得
た。Take 100 kg of this gel and mix well.
Add 50 kg of pure water and add TiO 2. Two Concentration 8.3% by weight
Of the slurry. 300L steamer with steam jacket
Pre-prepared 8.3 wt% TiO in a stainless steel tankTwo gel
Add all of the slurry and, while stirring, use ammonium sulfate.
Mu crystals 0.58 kg, 85% phosphoric acid aqueous solution 0.046 k
g, vanadyl sulfate aqueous solution (VTwo OFive Concentration; 19.5 weight
%) 4.2 kg, cesium sulfate aqueous solution (CsTwo SOFour Dark
Degree; 50.0 wt%) 1.30 kg were added sequentially. This
The pH at that time was 2.1. Enough of the resulting slurry
While stirring, heat to evaporate the water,Two
+ VTwo OFive + CsTwo SOFour + SOThree + P Two OFive As)
Concentrated to a concentration of 15% by weight. Homogenize this slurry
Disperses better with an easer and then uses a disc-type sp
The powder obtained by spray drying with a ray dryer is 150 ° C.
After drying for 24 hours, it is calcined at 550 ° C to obtain catalyst B.
Was.
【００４２】（実施例２、３、比較例１、２） 触媒Ｂと同様の方法でリン酸水溶液の添加量を変えて表
１に示すように触媒組成中のＰ2 Ｏ5 （五酸化リン）の
含有量を変えた触媒Ａ、Ｃ、Ｄ、Ｅを調製した。触媒Ａ
はＰ2 Ｏ5 を含有しない。触媒ＥはＰ2 Ｏ5 の含有量の
多い参照触媒である。 (Examples 2 and 3, Comparative Examples 1 and 2) P 2 O 5 (phosphorus pentoxide) in the catalyst composition was changed as shown in Table 1 by changing the addition amount of the phosphoric acid aqueous solution in the same manner as the catalyst B. Catalysts A, C, D and E having different contents of) were prepared. Catalyst A
Contains no P 2 O 5 . Catalyst E is a reference catalyst with a high P 2 O 5 content.
【００４３】（実施例４） 顔料用酸化チタンを製造するための中間品であるメタチ
タン酸スラリーを希釈後、実施例１と同様の中和と洗浄
操作を行って、不純物として共存する硫酸分を除去した
水酸化チタンゲルを得た。ＴｉＯ2 濃度２９．０重量％
のゲル２０ｋｇを採り、よく撹拌しながら純水９ｋｇを
加えて、ＴｉＯ2 濃度２０．０重量％のスラリーとし
た。このゲルの一部を採り、３００℃で乾燥して得られ
た粉末の結晶子径は１６０Åであった。Example 4 After diluting the metatitanic acid slurry, which is an intermediate product for producing titanium oxide for pigments, the same neutralization and washing operations as in Example 1 were carried out to remove the sulfuric acid content coexisting as impurities. A removed titanium hydroxide gel was obtained. TiO 2 concentration 29.0% by weight
20 kg of the above gel was taken, and 9 kg of pure water was added while stirring well to obtain a slurry having a TiO 2 concentration of 20.0% by weight. A part of this gel was taken and dried at 300 ° C., and the powder obtained had a crystallite diameter of 160Å.
【００４４】平均粒径５ｎｍから成る市販シリカゾル
（カタロイドＳＩ−５５０、触媒化成工業（株）製）を
予め陽イオン交換樹脂層を通し、脱Ｎａシリカゾルを得
た。脱ＮａシリカゾルのＳｉＯ2 濃度は１０．３重量％
で、Ｎａ2 Ｏ／ＳｉＯ2 重量比は０．００２であった。
２００Ｌスチームジャケット付ステンレス製槽に予め調
製した２０．０重量％の水酸化チタンゲルスラリーを全
量加え、よく撹拌しながら前記脱Ｎａシリカゾル４８．
５ｋｇ、硫酸アンモニウム結晶０．５１ｋｇ、硝酸第２
鉄（Ｆｅ2 Ｏ3 濃度；１９．５重量％）１．５６ｋｇを
添加した。次いでホウ酸水溶液（Ｈ3 ＢＯ3 濃度；２．
８重量％）４１ｋｇ、硫酸バナジル水溶液（Ｖ2 Ｏ5 濃
度；１９．５重量％）３．８ｋｇ、硫酸セシウム水溶液
（Ｃｓ2 ＳＯ4 ；５０．０重量％）１．２５ｋｇを順次
添加した。この時のｐＨは２．４であった。以後実施例
１と同様の方法で酸化チタン、シリカ、活性成分（Ｖ2
Ｏ5＋Ｃｓ2 ＳＯ4 ＋ＳＯ3 ）、酸化鉄、酸化ホウ素を
含有する粉末を得たのち６００℃にて焼成して触媒Ｆを
得た。触媒Ｆの化学組成と物理性状を表１に示す。A commercially available silica sol having an average particle diameter of 5 nm (Cataloid SI-550, manufactured by Catalysts & Chemicals Industry Co., Ltd.) was passed through a cation exchange resin layer in advance to obtain a Na-free silica sol. SiO 2 concentration of Na-free silica sol is 10.3% by weight
The Na 2 O / SiO 2 weight ratio was 0.002.
The total amount of 20.0 wt% titanium hydroxide gel slurry prepared in advance was added to a 200 L steam-jacketed stainless steel tank, and the Na-free silica sol 48.
5kg, ammonium sulfate crystal 0.51kg, nitric acid second
1.56 kg of iron (Fe 2 O 3 concentration; 19.5% by weight) was added. Then, a boric acid aqueous solution (H 3 BO 3 concentration; 2.
8 wt%) 41 kg, vanadyl sulfate aqueous solution (V 2 O 5 concentration; 19.5 wt%) 3.8 kg, and cesium sulfate aqueous solution (Cs 2 SO 4 ; 50.0 wt%) 1.25 kg were sequentially added. The pH at this time was 2.4. Thereafter, in the same manner as in Example 1, titanium oxide, silica, active ingredient (V 2
O 5 + Cs 2 SO 4 + SO 3 ), iron oxide, and boron oxide-containing powder were obtained and then calcined at 600 ° C. to obtain a catalyst F. Table 1 shows the chemical composition and physical properties of Catalyst F.
【００４５】（実施例５） 実施例１にて得られた水酸化チタンゲル（ＴｉＯ2 濃
度；１２．５重量％）７０ｋｇを２００Ｌスチームジャ
ケット付ステンレス製槽に投入し、等量の純水を加え
た。さらに硫酸アンモニウム結晶０．４３ｋｇ、硝酸バ
リウム０．５８ｋｇ、硫酸バナジル水溶液（Ｖ2 Ｏ5 濃
度；１９．５重量％）６．３５ｋｇ、硫酸セシウム水溶
液（Ｃｓ2 ＳＯ4 濃度；５０．０重量％）１．０６ｋｇ
を添加した。得られるスラリーを（ＴｉＯ2 ＋ＳＯ3 ＋
ＢａＯ＋Ｖ2 Ｏ5 ＋Ｃｓ2 ＳＯ4 ）として１８重量％ま
で濃縮したのち、噴霧乾燥を行ない、５３０℃にて焼成
して触媒Ｇを得た。触媒Ｇの化学組成と物理性状を表１
に示す。Example 5 70 kg of the titanium hydroxide gel (TiO 2 concentration; 12.5% by weight) obtained in Example 1 was put into a 200 L steam jacketed stainless steel tank, and an equal amount of pure water was added. It was Further, ammonium sulfate crystals 0.43 kg, barium nitrate 0.58 kg, vanadyl sulfate aqueous solution (V 2 O 5 concentration; 19.5 wt%) 6.35 kg, cesium sulfate aqueous solution (Cs 2 SO 4 concentration; 50.0 wt%) 1 0.06 kg
Was added. The resulting slurry is (TiO 2 + SO 3 +
BaO + V 2 O 5 + Cs 2 SO 4 ) was concentrated to 18% by weight, spray-dried and calcined at 530 ° C. to obtain catalyst G. Table 1 shows the chemical composition and physical properties of catalyst G.
Shown in
【００４６】（実施例６） 実施例１で得られた水酸化チタンゲル（ＴｉＯ2 濃度：
１２．５重量％）を純水でゲル濃度６．０重量％まで希
釈し、さらに６３％硝酸を加えてｐＨ２に調整した。こ
のスラリーを還流器付熱成槽に入れ、撹拌しながら９５
℃で１７時間加温した。得られた水酸化チタンの３００
℃乾燥粉末の結晶子径は１０７Åであった。この水酸化
チタンを用い、実施例１と同様の方法で硫酸アンモニウ
ム結晶、硝酸第２鉄結晶、硫酸バナジル水溶液、硫酸セ
シウム水溶液を添加し、触媒Ｈを得た。触媒Ｈの化学組
成と物理性状を表１に示す。Example 6 The titanium hydroxide gel obtained in Example 1 (TiO 2 concentration:
12.5% by weight) was diluted with pure water to a gel concentration of 6.0% by weight, and 63% nitric acid was further added to adjust the pH to 2. This slurry is put in a heat-generating tank with a reflux device and stirred with stirring.
It was heated at ℃ for 17 hours. 300 of the obtained titanium hydroxide
The crystallite size of the dry powder at ℃ was 107Å. Using this titanium hydroxide, ammonium sulfate crystals, ferric nitrate crystals, vanadyl sulfate aqueous solution, and cesium sulfate aqueous solution were added in the same manner as in Example 1 to obtain catalyst H. Table 1 shows the chemical composition and physical properties of Catalyst H.
【００４７】（実施例７） 実施例４で得られた水酸化チタンゲル（ＴｉＯ2 濃度：
２９重量％）１００ｋｇに純水９３ｋｇを加え、ゲル濃
度を１５重量％に希釈し、これに硝酸を加えてｐＨ２．
０に調整した。このスラリーを外熱式オートクレーブに
入れ、撹拌しながら１５０℃で４５時間加熱した。得ら
れた水酸化チタンの３００℃乾燥粉末の結晶子径は３０
０Åであった。オートクレーブで処理されたＴｉＯ2 濃
度１５重量％の水酸化チタンゲルのスラリー１００ｋｇ
に純水５０ｋｇを添加し、ＴｉＯ2 濃度を１０重量％に
希釈した。次いでジャケット付ステンレス製槽に入れ、
硝酸およびパラタングステン酸アンモニウム水溶液（Ｗ
Ｏ3 濃度：１重量％）を加え、よく撹拌しながら９５℃
で８時間加熱した。この時のｐＨは０．９であった。こ
れに実施例１と同様の方法により平均粒子径１７ｎｍの
シリカゾル（カタロイドＳ−２０Ｌ：ＳｉＯ2 濃度、２
０．５重量％、触媒化成工業（株）製）、硫酸アンモニ
ウム結晶、ホウ酸結晶、硫酸バナジル溶液および硫酸セ
シウム水溶液を添加し、表１に示す化学組成と物理性状
を有する触媒Ｉを得た。Example 7 The titanium hydroxide gel obtained in Example 4 (TiO 2 concentration:
(29 wt%) 100 kg of pure water 93 kg is added to dilute the gel concentration to 15 wt%, and nitric acid is added thereto to adjust the pH to 2.
Adjusted to zero. The slurry was placed in an external heating autoclave and heated at 150 ° C. for 45 hours while stirring. The crystallite diameter of the obtained 300 ° C. dry powder of titanium hydroxide is 30.
It was 0 °. 100 kg of autoclaved titanium hydroxide gel slurry with TiO 2 concentration of 15% by weight
50 kg of pure water was added to the mixture to dilute the TiO 2 concentration to 10% by weight. Then put it in a jacketed stainless steel tank,
Nitric acid and ammonium paratungstate aqueous solution (W
O 3 concentration: 1% by weight) was added, and well stirred, at 95 ° C.
For 8 hours. The pH at this time was 0.9. In the same manner as in Example 1, silica sol having an average particle diameter of 17 nm (cataloid S-20L: SiO 2 concentration, 2
0.5 wt%, manufactured by Catalysts & Chemicals Industry Co., Ltd., ammonium sulfate crystal, boric acid crystal, vanadyl sulfate solution and cesium sulfate aqueous solution were added to obtain a catalyst I having the chemical composition and physical properties shown in Table 1.
【００４８】（実施例８） ＴｉＯ2 として５重量％含有する硫酸チタニル水溶液６
００ｋｇを１２℃に冷却したのち、これに８５％リン酸
水溶液１．３５ｋｇを添加し、硫酸チタニル−リン酸混
合溶液を調製した。この時のｐＨは０．９２であった。
上記溶液を十分に撹拌しながら１５重量％アンモニア水
１４０ｋｇを約１０分で注加して中和し、水酸化チタン
−リンの共沈ゲルを得た。このゲルのｐＨは８．６、温
度２７℃であった。Example 8 Titanyl Sulfate Aqueous Solution 6 Containing 5% by Weight of TiO 2
After cooling 00 kg to 12 ° C., 1.35 kg of 85% phosphoric acid aqueous solution was added thereto to prepare a titanyl sulfate-phosphoric acid mixed solution. At this time, the pH was 0.92.
While sufficiently stirring the solution, 140 kg of 15% by weight ammonia water was added over about 10 minutes for neutralization to obtain a titanium hydroxide-phosphorus coprecipitated gel. The pH of this gel was 8.6 and the temperature was 27 ° C.
【００４９】このゲルでスラリーを実施例１と同様に平
板式フィルターを用いて洗浄し、ゲル濃度が１１．８重
量％の水酸化チタン−リン共沈ゲルを得た。この共沈ゲ
ルの一部を採り、３００℃で乾燥して得られた粉末の結
晶子径は４１Åであった。３００Ｌ槽に上記ゲル１００
ｋｇを採り、よく撹拌しながら純水３５ｋｇを加え、Ｔ
ｉＯ2 −Ｐ2 Ｏ5 濃度８．７重量％のスラリーとした。
これに平均粒径５ｎｍの脱Ｎａシリカゾル（ＳｉＯ2 濃
度：１５重量％）６９ｋｇを加え、次いで硫酸アンモニ
ウム結晶、ホウ酸結晶、硫酸バナジル水溶液（Ｖ2 Ｏ5
濃度：１９．５重量％）、硫酸セシウム水溶液（Ｃｓ2
ＳＯ4 濃度：５０．０重量％）を順次添加した。以後実
施例１と同様の方法で噴霧乾燥したのち、５７０℃で焼
成して触媒Ｊを得た。触媒Ｊの化学組成と物理性状を表
１に示す。The slurry was washed with this gel using a flat plate filter in the same manner as in Example 1 to obtain a titanium hydroxide-phosphorus coprecipitated gel having a gel concentration of 11.8% by weight. A part of this coprecipitated gel was dried at 300 ° C., and the powder obtained had a crystallite size of 41 °. Gel 100 in 300L tank
Take 35 kg, add 35 kg of pure water while stirring well, and
A slurry having an iO 2 —P 2 O 5 concentration of 8.7 wt% was prepared.
69 kg of de-Na silica sol having an average particle size of 5 nm (SiO 2 concentration: 15% by weight) was added to this, and then ammonium sulfate crystals, boric acid crystals, vanadyl sulfate aqueous solution (V 2 O 5
Concentration: 19.5% by weight), cesium sulfate aqueous solution (Cs 2
SO 4 concentration: 50.0% by weight) were sequentially added. Thereafter, the catalyst was dried by spraying in the same manner as in Example 1 and then calcined at 570 ° C. to obtain a catalyst J. Table 1 shows the chemical composition and physical properties of Catalyst J.
【００５０】（比較例３） 実施例１で得られた水酸化チタンゲル（ＴｉＯ2 濃度：
１２．５重量％）５５ｋｇに純水２５ｋｇを加えて、Ｔ
ｉＯ2 濃度８．６重量％のスラリーとした。１００Ｌス
チームジャケット付ステンレス製槽に上記水酸化チタン
スラリーの全量を仕込み、６３％硝酸でｐＨ３に調整し
たのち、硫酸アンモニウム結晶０．３１ｋｇ、硝酸ラン
タン結晶（Ｌａ2 Ｏ3 濃度：３７．６重量％）０．５６
ｋｇ、硫酸バナジル水溶液（Ｖ2 Ｏ5 濃度：１９．５重
量％）２．５ｋｇ、硫酸セシウム水溶液（Ｃｓ2 ＳＯ4
濃度：５０．０重量％）０．７６ｋｇを加えた。(Comparative Example 3 ) The titanium hydroxide gel (TiO 2 concentration:
12.5% by weight) 55 kg, pure water 25 kg,
A slurry having an iO 2 concentration of 8.6% by weight was prepared. A 100 L steam jacketed stainless steel tank was charged with the entire amount of the titanium hydroxide slurry and adjusted to pH 3 with 63% nitric acid, and then ammonium sulfate crystals 0.31 kg and lanthanum nitrate crystals (La 2 O 3 concentration: 37.6% by weight). 0.56
kg, vanadyl sulfate aqueous solution (V 2 O 5 concentration: 19.5% by weight) 2.5 kg, cesium sulfate aqueous solution (Cs 2 SO 4
(Concentration: 50.0% by weight) 0.76 kg was added.
【００５１】このスラリーを撹拌しながら加熱し１２．
９重量％の濃縮スラリー（ＴｉＯ2＋Ｌａ2 Ｏ3 ＋Ｖ2
Ｏ5 ＋Ｃｓ2 ＳＯ4 ＋ＳＯ3 ）を得た。さらにホモジナ
イザーによりスラリーをよく分散後、ディスク式スプレ
ードライヤーにより噴霧乾燥し、粉末を得た。これを１
５０℃で乾燥したのち５７０℃にて焼成し、触媒Ｋを得
た。触媒Ｋの化学組成と物理性状を表１に示す。This slurry is heated with stirring 12.
9 wt% concentrated slurry (TiO 2 + La 2 O 3 + V 2
O 5 + Cs 2 SO 4 + SO 3) was obtained. Further, the slurry was well dispersed by a homogenizer and then spray-dried by a disc type spray dryer to obtain a powder. This one
After being dried at 50 ° C., it was calcined at 570 ° C. to obtain a catalyst K. Table 1 shows the chemical composition and physical properties of the catalyst K.
【００５２】（実施例９） 比較例３で得られた１２．９重量％の濃縮スラリー（Ｔ
ｉＯ2 ＋Ｌａ2 Ｏ3 ＋Ｖ2 Ｏ5 ＋Ｃｓ2 ＳＯ4 ＋Ｓ
Ｏ3 ）２０ｋｇに硝酸第２鉄水溶液（Ｆｅ2 Ｏ3 濃度：
２．０重量％）１２．５ｋｇを加えた。上記スラリーを
濃縮後、ホモジナイザーにより均一化したのちディスク
式スプレードライヤーにより噴霧乾燥し、粉末を得た。
これを１５０℃で乾燥後、５７０℃で焼成し、触媒Ｌを
得た。触媒Ｌの化学組成と物理性状を表１に示す。Example 9 12.9 wt% concentrated slurry (T) obtained in Comparative Example 3
iO 2 + La 2 O 3 + V 2 O 5 + Cs 2 SO 4 + S
O 3) ferric nitrate aqueous solution 20 kg (Fe 2 O 3 concentration:
2.0 wt%) 12.5 kg was added. The slurry was concentrated, homogenized with a homogenizer, and then spray-dried with a disc spray dryer to obtain a powder.
This was dried at 150 ° C and then calcined at 570 ° C to obtain a catalyst L. Table 1 shows the chemical composition and physical properties of the catalyst L.
【００５３】（実施例１０） 実施例１で得られた水酸化チタンゲル（ＴｉＯ2 濃度：
１２．５重量％）に６３％硝酸を加えてｐＨ２．０に調
整した。これをスチームジャケット付ステンレス製槽内
に投入して十分に撹拌しながら硫酸アンモニウム結晶、
パラタングステン酸アンモニウム結晶を加えたのち、実
施例１と同様の方法で硫酸バナジル水溶液と硫酸セシウ
ム水溶液を添加した。上記スラリーを１３．５重量％ま
で濃縮したのち噴霧乾燥して粉末を得た。得られた粉末
を１５０℃で乾燥後５７０℃で焼成し、触媒Ｍを得た。
触媒Ｍの化学組成と物理性状を表１に示す。(Example 10 ) The titanium hydroxide gel obtained in Example 1 (TiO 2 concentration:
12.5 wt%) was added with 63% nitric acid to adjust the pH to 2.0. This is put into a stainless steel tank with a steam jacket, and ammonium sulfate crystals are stirred with sufficient stirring.
After the ammonium paratungstate crystal was added, the vanadyl sulfate aqueous solution and the cesium sulfate aqueous solution were added in the same manner as in Example 1. The above slurry was concentrated to 13.5% by weight and then spray dried to obtain a powder. The powder obtained was dried at 150 ° C. and then calcined at 570 ° C. to obtain a catalyst M.
Table 1 shows the chemical composition and physical properties of the catalyst M.
【００５４】（実施例１１） 実施例１において得られた水酸化チタンゲル（ＴｉＯ2
濃度：１２．５重量％）１００ｋｇと純水５０ｋｇを２
００Ｌジャケット付ステンレス製槽に投入して、８．３
重量％のスラリーとした。６３％硝酸を加えてｐＨ２．
５に調整したのち、硫酸アンモニウム結晶０．５ｋｇ、
８５％リン酸水溶液０．５ｋｇ、硝酸第２鉄（Ｆｅ2 Ｏ
3 濃度：１９．５重量％）１．７ｋｇ、硫酸バナジル水
溶液（Ｖ2 Ｏ5 濃度：１９．５重量％）４．３ｋｇを添
加して最後に硫酸セシウム水溶液（Ｃｓ2 ＳＯ4 濃度：
５０．０重量％）１．４ｋｇを加えた。この時のｐＨは
１．９であった。以後実施例１と同様の方法にて乾燥粉
末を得た。この粉末を５７０℃で焼成して触媒Ｎを得
た。触媒Ｎの化学組成と物理性状を表１に示す。Example 11 The titanium hydroxide gel (TiO 2 obtained in Example 1 was used.
Concentration: 12.5 wt%) 100 kg and pure water 50 kg 2
Put it in a stainless steel tank with a 00L jacket to make it 8.3.
It was a slurry of weight%. PH of 2. by adding 63% nitric acid.
After adjusting to 5, ammonium sulfate crystals 0.5kg,
0.5 kg of 85% phosphoric acid aqueous solution, ferric nitrate (Fe 2 O
3 concentration: 19.5% by weight) 1.7 kg, vanadyl sulfate aqueous solution (V 2 O 5 concentration: 19.5% by weight) 4.3 kg, and finally cesium sulfate aqueous solution (Cs 2 SO 4 concentration:
1.4 kg (50.0% by weight) was added. The pH at this time was 1.9. Thereafter, a dry powder was obtained in the same manner as in Example 1. This powder was calcined at 570 ° C. to obtain catalyst N. Table 1 shows the chemical composition and physical properties of the catalyst N.
【００５５】（実施例１２） 実施例１〜１１、比較例１、２、３において得られた触
媒Ａ〜Ｎについて固定床マイクロ反応器（ステンレス製
１０ｍｍφ×２００ｍｍＬ）を用いてｏ−キシレンの気
相酸化による無水フタル酸製造のための短期活性試験を
行った。また触媒の寿命を推定する目的で別途固定床反
応器（パイレックス製４０ｍｍφ×４００ｍｍＬ）中で
予め水熱処理したのち前記固定床マイクロ反応器にて触
媒活性の変化を測定した。活性試験および水熱処理条件
を以下に、また結果を表２に示す。Example 12 The catalysts A to N obtained in Examples 1 to 11 and Comparative Examples 1 , 2 and 3 were mixed with o-xylene gas using a fixed bed microreactor (stainless steel 10 mmφ × 200 mmL). A short-term activity test for phthalic anhydride production by phase oxidation was carried out. Further, for the purpose of estimating the life of the catalyst, hydrothermal treatment was carried out in advance in a fixed bed reactor (Pyrex 40 mmφ × 400 mmL), and then the change in catalyst activity was measured in the fixed bed microreactor. The activity test and hydrothermal treatment conditions are shown below, and the results are shown in Table 2.
【００５６】 ＜活性試験条件（固定床マイクロ反応器）＞ ｏ−キシレン供給速度 ０．５ｇ／ｈｒ 硫黄濃度５００ｐｐｍ 窒素濃度５００ｐｐｍ 空気量 ７．５Ｎｌ／ｈｒ （６７ｇ−ｏ−キシレン／Ｎｍ3 −空気） 触媒量 １ｇ （Ｗ／Ｆ＝２．０ｈｒ） 反応温度−時間 ３６０℃−２１ｈｒ 未反応ｏ−キシレン、反応生成物としての無水フタル
酸、フタリド、トルアルデヒド、無水マレイン酸、ＣＯ
＋ＣＯ2 はすべてガスクロマトグラフにより分析した。
ｏ−キシレン転化率、無水フタル酸選択率、無水フタル
酸収率、反応速度定数、比活性および比収率は次式によ
り計算した。<Activity Test Conditions (Fixed Bed Micro Reactor)> o-Xylene Supply Rate 0.5 g / hr Sulfur Concentration 500 ppm Nitrogen Concentration 500 ppm Air Amount 7.5 Nl / hr (67 g-o-xylene / Nm 3 -Air) Amount of catalyst 1 g (W / F = 2.0 hr) Reaction temperature-hour 360 ° C.-21 hr Unreacted o-xylene, phthalic anhydride as reaction product, phthalide, tolualdehyde, maleic anhydride, CO
All + CO 2 was analyzed by gas chromatography.
The o-xylene conversion rate, phthalic anhydride selectivity, phthalic anhydride yield, reaction rate constant, specific activity and specific yield were calculated by the following formulas.
【数２】 (Equation 2)
【００５７】＜水熱処理条件＞ 空気量 ７８Ｎｌ／ｈｒ（１００．４ｇ／ｈｒ） 水 分 １１．２ｇ／ｈｒ 水分／水分＋空気 ０．１０ｗｔ／ｗｔ 触媒量 ２００ｇ 温度−時間 ４５０℃−５００ｈｒ<Hydrothermal treatment conditions> Air amount 78 Nl / hr (100.4 g / hr) Water content 11.2 g / hr Moisture / moisture + air 0.10 wt / wt Catalyst amount 200 g Temperature-hour 450 ° C.-500 hr
【００５８】（実施例１３） 実施例１２において活性試験を行った触媒のうち、Ａ、
Ｃ、Ｊ、Ｋについて流動層反応器（ステンレス製、８３
ｍｍφ×３４００ｍｍＬ）を用いてｏ−キシレンの気相
酸化により無水フタル酸の製造のための長期活性試験を
行った。活性試験条件を以下に、結果を図１に示す。(Example 13 ) Of the catalysts subjected to the activity test in Example 12 , A,
Fluidized bed reactor for C, J, K (stainless steel, 83
mmφ × 3400 mmL) was used to perform a long-term activity test for the production of phthalic anhydride by gas phase oxidation of o-xylene. The activity test conditions are shown below, and the results are shown in FIG.
【００５９】 ＜活性条件＞ ｏ−キシレン供給速度 ２３０ｇ／ｈｒ（硫黄濃度１０００ｐｐｍ） 空気量 ２２００Ｎｌ／ｈｒ 線速度（空塔基準） １６ｃｍ／ｓｅｃ 空気／ｏ−キシレン比 １２．４ｋｇ／ｋｇ 圧 力 １．０ｋｇ／ｃｍ2 Ｇ 触媒量 ４０００ｃｃ 反応温度 ３２０℃ 分析方法および反応成績の計算式は、実施例１０の場合
と同じである。<Activation Conditions> o-xylene supply rate 230 g / hr (sulfur concentration 1000 ppm) air amount 2200 Nl / hr linear velocity (empty column standard) 16 cm / sec air / o-xylene ratio 12.4 kg / kg pressure 1. 0 kg / cm 2 G catalyst amount 4000 cc reaction temperature 320 ° C. The analytical method and the calculation formula of the reaction results are the same as in the case of Example 10 .
【００６０】（実施例１４） 実施例１３と同様の触媒と流動層反応器を用いてナフタ
レンの気相酸化による無水フタル酸の製造のための長期
活性試験を行った。活性試験条件を以下に、結果を図２
に示す。Example 14 Using the same catalyst and fluidized bed reactor as in Example 13 , a long-term activity test for producing phthalic anhydride by gas phase oxidation of naphthalene was conducted. The activity test conditions are shown below, and the results are shown in FIG.
Shown in
【００６１】＜活性試験条件＞ ナフタレン供給速度 ２７５ｇ／ｈｒ 硫黄濃度１０００ｐｐｍ 窒素濃度 ５００ｐｐｍ 空気量 ２２００Ｎｌ／ｈｒ 線速度（空塔基準） １６ｃｍ／ｓｅｃ 空気／ナフタレン比 １０．３ｋｇ／ｋｇ 圧 力 １．０ｋｇ／ｃｍ2 Ｇ 触媒量 ４０００ｃｃ 反応温度 ３２０℃ 分析方法および反応成績の計算式は、実施例１０の場合
と同じである。<Activity test conditions> Naphthalene supply rate 275 g / hr Sulfur concentration 1000 ppm Nitrogen concentration 500 ppm Air amount 2200 Nl / hr Linear velocity (empty column standard) 16 cm / sec Air / naphthalene ratio 10.3 kg / kg Pressure 1.0 kg / cm 2 G Catalyst amount 4000 cc Reaction temperature 320 ° C. Analysis method and calculation formula of reaction results are the same as in the case of Example 10.
【００６２】（実施例１５） 実施例１２において活性試験を行った触媒のうちＡ、
Ｃ、Ｊ、Ｋについて実施例１１と同様な方法により流動
床反応器を用いてデュレンの気相酸化による無水ピロメ
リット酸の製造のため、長期活性試験を行った。活性試
験条件を以下に、結果を表３に示した。(Example 15 ) Of the catalysts tested for activity in Example 12 , A
For C, J and K, a long-term activity test was carried out in the same manner as in Example 11 for the production of pyromellitic dianhydride by gas phase oxidation of durene using a fluidized bed reactor. The activity test conditions are shown below, and the results are shown in Table 3.
【００６３】 ＜活性試験条件＞ デュレン供給速度 １６０ｇ／ｈｒ 空気量 ２２００Ｎｌ／ｈｒ 線速度（空塔基準） １６ｃｍ／ｓｅｃ 空気／デュレン比 １７．７ｋｇ／ｋｇ 圧力 １．０ｋｇ／ｃｍ2 Ｇ 触媒量 ５０００ｃｃ 反応温度 ３００℃ 反応ガスは水蒸気と触媒させることにより未反応デュレ
ン、無水ピロメリット酸、無水メチルトリメリット酸、
無水ジメチルフタル酸を吸収・回収した。吸収液を蒸発
乾固後、三フッ化ホウ素−メタノール錯体によりメチル
エステル化したのち、ガスクロマトグラフにて分析し
た。一方、ＣＯ、ＣＯ2 は別途捕集し、同様にガスクロ
マトグラフにて分析した。なお、デュレン転化率および
無水ピロメリット酸選択率は実施例１０の場合と同様に
計算した。<Activity test conditions> Duren supply rate 160 g / hr Air amount 2200 Nl / hr Linear velocity (empty column standard) 16 cm / sec Air / Durene ratio 17.7 kg / kg Pressure 1.0 kg / cm 2 G Catalyst amount 5000 cc Reaction Temperature 300 ℃ Reaction gas is catalyzed by water vapor and unreacted durene, pyromellitic dianhydride, methyl trimellitic dianhydride,
Dimethylphthalic anhydride was absorbed and recovered. The absorbent was evaporated to dryness, methylesterified with boron trifluoride-methanol complex, and then analyzed by gas chromatography. On the other hand, CO and CO 2 were separately collected and similarly analyzed by gas chromatography. The durene conversion and the pyromellitic dianhydride selectivity were calculated in the same manner as in Example 10 .
【００６４】[0064]
【表１】 [Table 1]
【表２】 [Table 2]
【００６５】[0065]
【表３】 [Table 3]
【表４】 [Table 4]
【００６６】 表 ３ デュレンの流動床気相触媒酸化における反応成績 ─────────────────────────────────── 触 媒 デュレン転化率 (モル%) 無水ピロメリット酸選択率 (モル%) No. ────────── ─────────────── 100hr後 1000hr後 100hr後 1000hr後 ─────────────────────────────────── Ａ 84.5 60.8 25.7 27.6 Ｃ 76.9 68.8 53.8 54.4 Ｊ 74.2 69.5 57.9 58.1 Ｋ 82.3 70.2 40.3 42.2 ───────────────────────────────────Table 3 Reaction results of fluidized bed gas-phase catalytic oxidation of durene ─────────────────────────────────── ─Catalyst Duren conversion (mol%) Pyromellitic anhydride selectivity (mol%) No. ────────── ─────────────── 1000hr after 100hr After 100hr After 1000hr ─────────────────────────────────── A 84.5 60.8 25.7 27.6 C 76.9 68.8 53.8 54.4 J 74.2 69.5 57.9 58.1 K 82.3 70.2 40.3 42.2 ────────────────────────────────────
【００６７】[0067]
【発明の効果】本発明の触媒は、流動層によるｏ−キシ
レン、ナフタレンおよびデュレンのような芳香族炭化水
素の気相酸化により無水フタル酸および無水ピロメリッ
ト酸のような酸無水物を製造するにあたり、特定比のバ
ナジウム化合物−アルカリ金属化合物−硫酸化合物−酸
化チタン組成物に対して一定量添加された酸化鉄、五酸
化リン、酸化タングステン、酸化バリウムの作用により
反応熱や水熱作用による担体酸化チタンの結晶成長（ア
ナターゼ型）を強く抑制するため長期間の連続使用に対
しても非常に安定で活性劣化の少ない特徴を有する。ま
た同時にこれらＦｅ、Ｐ、Ｗ、Ｂａなどの成分の添加は
いずれも過剰酸化反応を抑制するため、目的物芳香族カ
ルボン酸無水物への選択性の向上に対しても優れた効果
を発揮する。The catalyst of the present invention produces acid anhydrides such as phthalic anhydride and pyromellitic dianhydride by gas phase oxidation of aromatic hydrocarbons such as o-xylene, naphthalene and durene in a fluidized bed. At this time, a carrier by reaction heat or hydrothermal action by the action of iron oxide, phosphorus pentoxide, tungsten oxide, barium oxide added in a certain amount to a vanadium compound-alkali metal compound-sulfuric acid compound-titanium oxide composition of a specific ratio. Since it strongly suppresses the crystal growth (anatase type) of titanium oxide, it has characteristics that it is very stable even after continuous use for a long period of time and has little activity deterioration. At the same time, addition of these components such as Fe, P, W, and Ba suppresses the excessive oxidation reaction, so that it also exhibits an excellent effect in improving the selectivity to the target aromatic carboxylic acid anhydride. .
【図１】 触媒Ａ、Ｃ、Ｊ、Ｋによるｏ−キシレンの流
動床気相接触酸化における反応成績を示す図である。FIG. 1 is a diagram showing reaction results in fluidized bed gas phase catalytic oxidation of o-xylene with catalysts A, C, J, and K.
【図２】 触媒Ａ、Ｃ、Ｊ、Ｋによるナフタレンの流動
床気相接触酸化における反応成績を示す図である。FIG. 2 is a diagram showing reaction results in fluidized bed gas phase catalytic oxidation of naphthalene with catalysts A, C, J and K.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 青 野 利 直 千葉県千葉市川崎町１番地 川崎製鉄株 式会社千葉製鉄所内 (72)発明者 高 木 克 彦 千葉県千葉市川崎町１番地 川崎製鉄株 式会社技術研究本部内 (72)発明者 成 瀬 義 弘 千葉県千葉市川崎町１番地 川崎製鉄株 式会社技術研究本部内 (72)発明者 藤 井 進 福岡県北九州市若松区北湊町13−２ 触 媒化成工業株式会社若松工場内 (72)発明者 荒 川 誠 治 福岡県北九州市若松区北湊町13−２ 触 媒化成工業株式会社若松工場内 (56)参考文献 特開 昭63−190846（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshinao Aono 1 Kawasaki-cho, Chiba-shi, Chiba Kawasaki Steel Co., Ltd. Chiba Works (72) Inventor Katsuhiko Takagi 1 Kawasaki-cho, Chiba, Chiba Kawasaki (72) Inventor Yoshihiro Naruse 1st Kawasaki-cho, Chiba City, Chiba Prefecture In-house Technology Research Division, Kawasaki Steel Co., Ltd. (72) Inventor Susumu Fujii Kitaminato-cho, Wakamatsu-ku, Kitakyushu, Fukuoka 13-2 Catalytic Chemical Industry Co., Ltd. Wakamatsu Factory (72) Inventor Seiji Arakawa 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu City, Fukuoka Prefecture 13-2 Catalytic Chemical Industry Co., Ltd. Wakamatsu Factory (56) Reference JP-A-63 -190846 (JP, A)
Claims (2)
および／またはルビジウム化合物、硫酸化合物を必須成
分とし、鉄（Ｆｅ）、リン（Ｐ）、タングステン
（Ｗ）、およびバリウム（Ｂａ）から選ばれる少なくと
も一種の元素を酸化物として０．３〜１５重量％含有す
ることを特徴とする芳香族炭化水素の気相接触酸化によ
る芳香族カルボン酸無水物製造用流動触媒。1. Titanium oxide, vanadium compound, cesium
And / or a rubidium compound, a sulfuric acid compound as an essential component, and at least one element selected from iron (Fe), phosphorus (P), tungsten (W), and barium (Ba) as an oxide 0.3 to 15 weight % in the vapor phase catalytic oxidation of aromatic hydrocarbons, characterized by containing
A fluid catalyst for the production of aromatic carboxylic acid anhydrides .
金属の酸化物を含有する請求項１に記載の芳香族炭化水
素の気相接触酸化による芳香族カルボン酸無水物製造用
流動触媒。2. A fluidized catalyst for producing an aromatic carboxylic acid anhydride by vapor phase catalytic oxidation of an aromatic hydrocarbon according to claim 1, which further contains silica, boron oxide or an oxide of a rare earth metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4035213A JP2690652B2 (en) | 1991-03-28 | 1992-02-21 | Fluidized catalyst for vapor phase catalytic oxidation of aromatic hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6442191 | 1991-03-28 | ||
| JP3-64421 | 1991-03-28 | ||
| JP4035213A JP2690652B2 (en) | 1991-03-28 | 1992-02-21 | Fluidized catalyst for vapor phase catalytic oxidation of aromatic hydrocarbons |
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|---|---|
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| CN102811808A (en) * | 2010-03-19 | 2012-12-05 | 巴斯夫欧洲公司 | Catalyst for gas-phase oxidations on the basis of sulfur- and calcium-poor titanium dioxide |
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