JP7102286B2 - A method for producing an ammoxidation catalyst and a method for producing acrylonitrile. - Google Patents
A method for producing an ammoxidation catalyst and a method for producing acrylonitrile. Download PDFInfo
- Publication number
- JP7102286B2 JP7102286B2 JP2018158189A JP2018158189A JP7102286B2 JP 7102286 B2 JP7102286 B2 JP 7102286B2 JP 2018158189 A JP2018158189 A JP 2018158189A JP 2018158189 A JP2018158189 A JP 2018158189A JP 7102286 B2 JP7102286 B2 JP 7102286B2
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- JP
- Japan
- Prior art keywords
- catalyst
- ammoxidation
- molybdenum
- propylene
- ammonia
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims description 149
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 94
- 239000002002 slurry Substances 0.000 claims description 86
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 77
- 238000006243 chemical reaction Methods 0.000 claims description 71
- 229910052750 molybdenum Inorganic materials 0.000 claims description 66
- 239000011733 molybdenum Substances 0.000 claims description 66
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 66
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 66
- 239000007864 aqueous solution Substances 0.000 claims description 61
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 60
- 239000002243 precursor Substances 0.000 claims description 57
- 229910021529 ammonia Inorganic materials 0.000 claims description 42
- 229910052742 iron Inorganic materials 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000002441 X-ray diffraction Methods 0.000 claims description 26
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 25
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003638 chemical reducing agent Substances 0.000 claims description 22
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 20
- 229910001882 dioxygen Inorganic materials 0.000 claims description 20
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 17
- 229910052797 bismuth Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Chemical group 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 68
- 238000003756 stirring Methods 0.000 description 36
- 239000000377 silicon dioxide Substances 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 32
- 239000002184 metal Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 21
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 18
- 229910044991 metal oxide Inorganic materials 0.000 description 18
- 150000004706 metal oxides Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 12
- 235000014655 lactic acid Nutrition 0.000 description 12
- 239000004310 lactic acid Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 10
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 9
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 9
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 9
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 9
- -1 carboxylic acid compound Chemical class 0.000 description 8
- 239000002131 composite 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009489 vacuum treatment Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical group [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-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
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- JGJRCVAAUBSBFU-UHFFFAOYSA-N [Fe].C(C=C)#N Chemical compound [Fe].C(C=C)#N JGJRCVAAUBSBFU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- GDSDMHVBJOAAJI-UHFFFAOYSA-N bismuth;2-hydroxypropanoic acid Chemical compound [Bi].CC(O)C(O)=O GDSDMHVBJOAAJI-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940013688 formic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
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
本発明はアンモ酸化用触媒及びその製造方法、並びに当該触媒を用いたアクリロニトリルの製造方法に関する。 The present invention relates to an ammoxidation catalyst and a method for producing the same, and a method for producing acrylonitrile using the catalyst.
分子状酸素存在下でプロピレンとアンモニアとを反応させて、アクリロニトリルを製造する方法は「アンモ酸化反応」として知られており、この反応はアクリロニトリルの工業的製法として用いられている。この反応において、良好なアクリロニトリル収率を達成するために触媒が利用されており、Ｍｏ－Ｂｉ－Ｆｅ又はＭｏ－Ｓｂを必須元素とした触媒が多く工業的に用いられている。より良好なアクリロニトリル収率を達成するために、これらの必須元素に加えて、その他の元素を添加した触媒も多数開発されている（例えば、特許文献１及び２参照）。 A method for producing acrylonitrile by reacting propylene with ammonia in the presence of molecular oxygen is known as an "ammoxidation reaction", and this reaction is used as an industrial method for producing acrylonitrile. In this reaction, a catalyst is used to achieve a good acrylonitrile yield, and many catalysts containing Mo-Bi-Fe or Mo-Sb as an essential element are industrially used. In order to achieve better acrylonitrile yields, many catalysts have been developed in which other elements are added in addition to these essential elements (see, for example, Patent Documents 1 and 2).
一方、触媒の金属組成は共通であっても、触媒調製方法に改良を加えることでアクリロニトリル収率を向上させる試みも実施されている。例えば、特許文献３に記載の、Ｘ線回折分析において特定のピーク状態を形成する触媒は高いアクリロニトリル選択性を示すとされている。その理由としてはＸ線回折分析の結果を踏まえて、触媒前駆体スラリー調製時にビスマスに対して過剰量のカルボン酸化合物を添加することにより、ビスマスやモリブデンを含有する複合酸化物が高分散化していることを挙げている。また、例えば、特許文献４では触媒調製中に少なくとも１種類の熱分解性窒素含有化合物を添加することを含む触媒の製造方法が記載されている。当文献内で、熱分解性窒素含有化合物の添加により調製された触媒はアンモニア燃焼が少なく、効率的にアンモニアを反応に利用できると提唱している。 On the other hand, even if the metal composition of the catalyst is common, attempts have been made to improve the yield of acrylonitrile by improving the catalyst preparation method. For example, the catalyst described in Patent Document 3 that forms a specific peak state in X-ray diffraction analysis is said to exhibit high acrylonitrile selectivity. The reason is that, based on the results of X-ray diffraction analysis, by adding an excessive amount of carboxylic acid compound to bismuth at the time of preparing the catalyst precursor slurry, the composite oxide containing bismuth and molybdenum is highly dispersed. It mentions that there is. Further, for example, Patent Document 4 describes a method for producing a catalyst, which comprises adding at least one pyrolytic nitrogen-containing compound during catalyst preparation. In this document, it is proposed that the catalyst prepared by the addition of the pyrolytic nitrogen-containing compound has less ammonia combustion and can efficiently utilize ammonia for the reaction.
アンモ酸化用触媒の開発においては、現在に至るまで金属組成の変更が繰り返し実施されており、近年では組成の改良のみでは大きなアクリロニトリル収率向上を達成することは困難になってきている。一方で、触媒調製方法においては未だに改良の余地が多く残されている。特許文献３や４に記載の方法は、アクリロニトリル収率向上の観点からある程度の成果を挙げているものの、同じ金属組成であってもアクリロニトリル収率のより大幅な向上が可能となる新たな触媒調製法の改良が望まれている。 In the development of catalysts for ammoxidation, changes in metal composition have been repeatedly carried out until now, and in recent years it has become difficult to achieve a large improvement in acrylonitrile yield only by improving the composition. On the other hand, there is still much room for improvement in the catalyst preparation method. Although the methods described in Patent Documents 3 and 4 have achieved some results from the viewpoint of improving the acrylonitrile yield, a new catalyst preparation capable of further improving the acrylonitrile yield even with the same metal composition. Improvements in the law are desired.
本発明は上記の事情を鑑みてなされたものであり、アクリロニトリル収率の向上を可能にするアンモ酸化用触媒及びその製造方法、並びにその触媒を用いたアクリロニトリルの製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an ammoxidation catalyst and a method for producing the same, which can improve the yield of acrylonitrile, and a method for producing acrylonitrile using the catalyst. do.
本発明者らは、上記課題を解決するために検討した結果、Ｘ線回折における特定のピークに着目し、触媒調製法を工夫することにより、本発明を完成させた。 As a result of studies to solve the above problems, the present inventors have completed the present invention by focusing on a specific peak in X-ray diffraction and devising a catalyst preparation method.
すなわち、本発明は以下の通りである。
［１］
モリブデンと、ビスマスと、鉄と、を含有するアンモ酸化用触媒であり、
Ｘ線回折分析において、２θ＝２２．９±０．２°のピーク強度をＰ、２θ＝２６．４±０．３°のピーク強度をＱとした場合、Ｐ／Ｑが０．０３以下である、アンモ酸化用触媒。
［２］
触媒の前駆体となるモリブデン、ビスマス及び鉄を含む前駆体スラリーを調製する調製工程と、
前記前駆体スラリーを乾燥して乾燥粒子を得る乾燥工程と、
前記乾燥粒子を焼成してアンモ酸化用触媒を得る焼成工程と、
を有し、
前記前駆体スラリーの酸化還元電位が３００ｍＶ／ＡｇＣｌ以下、－３００ｍＶ／ＡｇＣｌ以上である、
［１］に記載のアンモ酸化用触媒の製造方法。
［３］
前記前駆体スラリーを調製する調製工程において、水溶液中の標準電極電位が０．７７Ｖ／ＳＨＥ以下である還元剤を添加する、
［２］に記載のアンモ酸化用触媒の製造方法。
［４］
前記還元剤がヒドラジン誘導体である、［３］に記載のアンモ酸化用触媒の製造方法。
［５］
［１］に記載のアンモ酸化用触媒、又は［２］～［４］のいずれかに記載の製造方法で得られるアンモ酸化用触媒の存在下、プロピレンと、分子状酸素と、アンモニアと、を反応させる工程を含む、アクリロニトリルの製造方法。
［６］
［１］に記載のアンモ酸化用触媒、又は［２］～［４］のいずれかに記載の製造方法で得られるアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応させる工程を含む、アクリロニトリルの製造方法。
［７］
前記分子状酸素源が空気であり、
プロピレンに対するアンモニア及び空気のモル比が、プロピレン／アンモニア／空気の比で１／（０．８～１．６）／（７～１２）の範囲である、［５］又は［６］に記載のアクリロニトリルの製造方法。
［８］
プロピレンと、分子状酸素と、アンモニアと、を反応させる温度が、３５０～５５０℃の温度範囲である、［５］～［７］のいずれかに記載のアクリロニトリルの製造方法。
That is, the present invention is as follows.
[1]
An ammoxidation catalyst containing molybdenum, bismuth, and iron.
In X-ray diffraction analysis, when the peak intensity of 2θ = 22.9 ± 0.2 ° is P and the peak intensity of 2θ = 26.4 ± 0.3 ° is Q, the P / Q is 0.03 or less. There is a catalyst for ammoxidation.
[2]
A preparation step for preparing a precursor slurry containing molybdenum, bismuth, and iron as catalyst precursors, and
A drying step of drying the precursor slurry to obtain dried particles, and
A firing step of calcining the dry particles to obtain a catalyst for ammoxidation, and
Have,
The redox potential of the precursor slurry is 300 mV / AgCl or less and −300 mV / AgCl or more.
The method for producing an ammoxidation catalyst according to [1].
[3]
In the preparation step for preparing the precursor slurry, a reducing agent having a standard electrode potential of 0.77 V / SHE or less in the aqueous solution is added.
The method for producing an ammoxidation catalyst according to [2].
[4]
The method for producing an ammoxidation catalyst according to [3], wherein the reducing agent is a hydrazine derivative.
[5]
In the presence of the ammoxidation catalyst according to [1] or the ammoxidation catalyst obtained by the production method according to any one of [2] to [4], propylene, molecular oxygen and ammonia are used. A method for producing acrylonitrile, which comprises a step of reacting.
[6]
The ammoxidation catalyst according to [1] or the ammoxidation catalyst obtained by the production method according to any one of [2] to [4] is supplied in advance to the flow reaction tank, and the catalyst is supplied into the flow reaction tank. A method for producing acrylonitrile, which comprises a step of reacting propylene, molecular oxygen, and ammonia while circulating in.
[7]
The molecular oxygen source is air,
[5] or [6], wherein the molar ratio of ammonia and air to propylene is in the range of 1 / (0.8 to 1.6) / (7 to 12) in the ratio of propylene / ammonia / air. Method for producing acrylonitrile.
[8]
The method for producing acrylonitrile according to any one of [5] to [7], wherein the temperature at which propylene, molecular oxygen, and ammonia are reacted is in the temperature range of 350 to 550 ° C.
本発明のアンモ酸化用触媒は、プロピレンのアンモ酸化反応において、良好なアクリロニトリル収率を示す。 The ammoxidation catalyst of the present invention shows a good acrylonitrile yield in the ammoxidation reaction of propylene.
以下に、本発明を実施するための形態（以下、単に「本実施形態」という）について詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、その要旨を逸脱しない範囲内で様々に変形が可能である。 Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to the following embodiments and does not deviate from the gist thereof. It can be transformed in various ways.
本実施形態のアンモ酸化用触媒は、モリブデンと、ビスマスと、鉄と、を含有するアンモ酸化用触媒であり、Ｘ線回折分析において、２θ＝２２．９±０．２°のピーク強度をＰ、２θ＝２６．４±０．３°のピーク強度をＱとした場合、Ｐ／Ｑが０．０３以下である。
なお、本実施形態において、アンモ酸化用触媒とは、プロピレンのアンモ酸化反応に用いられる触媒を意味する。
The ammoxidation catalyst of the present embodiment is an ammoxidation catalyst containing molybdenum, bismuth, and iron, and has a peak intensity of 2θ = 22.9 ± 0.2 ° in X-ray diffraction analysis. When the peak intensity of 2θ = 26.4 ± 0.3 ° is Q, P / Q is 0.03 or less.
In the present embodiment, the ammoxidation catalyst means a catalyst used for the ammoxidation reaction of propylene.
本実施形態のアンモ酸化用触媒はモリブデンと、ビスマスと、鉄とを含有する。モリブデンはプロピレンの吸着サイト及び、アンモニアの活性化サイトとしての役割を担っている。また、ビスマスはモリブデンと複合酸化物（モリブデート）を形成し、プロピレンを活性化させ、α位の水素を引き抜いて、πアリル種を生成させる役割を担っている。 The catalyst for ammoxidation of this embodiment contains molybdenum, bismuth, and iron. Molybdenum plays a role as an adsorption site for propylene and an activation site for ammonia. In addition, bismuth forms a composite oxide (molybdenum) with molybdenum, activates propylene, abstracts hydrogen at the α-position, and plays a role of producing π-allyl species.
鉄もビスマスと同様にモリブデートを形成し、３価の鉄を有する鉄モリブデートが２価の鉄を有する鉄モリブデートに還元されたり、逆に、２価の鉄を有する鉄モリブデートが３価の鉄を有する鉄モリブデートに酸化されたりする。このように鉄は３価／２価のレドックスによって気相に存在する酸素を触媒内に取り込むことで、反応で消費される格子酸素を補い、触媒活性点に供給する役割を担っている。理由は定かではないが、前駆体スラリー調製段階の工夫により、得られるアンモ酸化用触媒におけるモリブデート中の鉄を２価に還元しておくことで、鉄を３価の状態で調製した場合と比較して、アクリロニトリル収率が向上することが判明した。 Iron also forms molybdate like bismuth, and iron molybdate with trivalent iron is reduced to iron molybdate with divalent iron, and conversely, iron molybdate with divalent iron produces trivalent iron. It is oxidized by the iron molybdate that it has. In this way, iron takes in oxygen existing in the gas phase by trivalent / divalent redox into the catalyst, thereby supplementing the lattice oxygen consumed in the reaction and supplying it to the catalytic activity point. The reason is not clear, but by devising the precursor slurry preparation stage, iron in the acrylonitrile in the obtained ammoxidation catalyst is reduced to divalent iron, which is compared with the case where iron is prepared in a trivalent state. It was found that the yield of acrylonitrile was improved.
本実施形態のアンモ酸化用触媒は更にニッケル及び／又はコバルトを含有することが好ましい。ニッケル及びコバルトは適度の格子欠陥を有するモリブデートを形成し、酸素のバルク内移動を円滑にする役割を担っている。また、これらのモリブデートは２価の鉄イオンを固溶し、２価状態を安定化し、不可逆な３価への酸化を抑制する効果を有すると推定されている。 The ammoxidation catalyst of the present embodiment preferably further contains nickel and / or cobalt. Nickel and cobalt form molybdates with moderate lattice defects and play a role in facilitating the movement of oxygen within the bulk. In addition, these molybdates are presumed to have the effect of dissolving divalent iron ions in solid solution, stabilizing the divalent state, and suppressing irreversible oxidation to trivalent.
本実施形態のアンモ酸化用触媒の組成についてはモリブデンと、ビスマスと、鉄とを含有すること以外には特に限定されないが、好ましい一例として下記一般式（１）で表される組成が挙げられる。
Ｍｏ12ＢｉaＦｅbＸcＹdＺeＯf （１）
式（１）中、Ｘはニッケル、コバルト、マグネシウム、カルシウム、亜鉛、ストロンチウム、バリウムから選ばれる１種類以上の元素、Ｙはセリウム、クロム、ランタン、ネオジム、イットリウム、プラセオジウム、サマリウム、アルミニウム、ガリウム、及びインジウムから選ばれる１種以上の元素、Ｚはカリウム、ルビジウム及びセシウムから選ばれる１種以上の元素を示す。ａはモリブデン１２原子に対するビスマスの原子比を示し、好ましくは０．１≦ａ≦２．０であり、より好ましくは０．１５≦ａ≦１．０であり、更に好ましくは０．２≦ａ≦０．７である。ｂはモリブデン１２原子に対する鉄の原子比を示し、好ましくは０．１≦ｂ≦５．０であり、より好ましくは０．５≦ｂ≦４．５であり、更に好ましくは１．０≦ｂ≦４．０である。ｃはモリブデン１２原子に対するＸの原子比を示し、好ましくは０．１≦ｃ≦１０．０であり、より好ましくは３．０≦ｃ≦９．０であり、更に好ましくは５．０≦ｃ≦８．５である。ｄはモリブデン１２原子に対するＹの原子比を示し、好ましくは０．１≦ｄ≦３．０であり、より好ましくは０．２≦ｄ≦２．０であり、更に好ましくは０．３≦ｄ≦１．５である。ｅはモリブデン１２原子に対するＺの原子比を示し、好ましくは０．０１≦ｅ≦２．０であり、より好ましくは０．０５≦ｅ≦１．０である。ｆはモリブデン１２原子に対する酸素の原子比を示し、存在する他の元素の原子価要求を満足させるのに必要な酸素の原子数である。
The composition of the ammoxidation catalyst of the present embodiment is not particularly limited except that it contains molybdenum, bismuth, and iron, but a preferred example thereof is the composition represented by the following general formula (1).
Mo 12 Bia Fe b X c Y d Z e Of (1)
In formula (1), X is one or more elements selected from nickel, cobalt, magnesium, calcium, zinc, strontium, and barium, and Y is cerium, chromium, lantern, neodymium, yttrium, placeodium, samarium, aluminum, gallium, And one or more elements selected from indium, Z represents one or more elements selected from potassium, rubidium and cesium. a indicates the atomic ratio of bismuth to 12 atoms of molybdenum, preferably 0.1 ≦ a ≦ 2.0, more preferably 0.15 ≦ a ≦ 1.0, and further preferably 0.2 ≦ a. ≤0.7. b represents the atomic ratio of iron to 12 atoms of molybdenum, preferably 0.1 ≦ b ≦ 5.0, more preferably 0.5 ≦ b ≦ 4.5, and even more preferably 1.0 ≦ b. ≦ 4.0. c represents the atomic ratio of X to 12 atoms of molybdenum, preferably 0.1 ≦ c ≦ 10.0, more preferably 3.0 ≦ c ≦ 9.0, and even more preferably 5.0 ≦ c. ≦ 8.5. d represents the atomic ratio of Y to 12 atoms of molybdenum, preferably 0.1 ≦ d ≦ 3.0, more preferably 0.2 ≦ d ≦ 2.0, and even more preferably 0.3 ≦ d. ≦ 1.5. e represents the atomic ratio of Z to 12 atoms of molybdenum, preferably 0.01 ≦ e ≦ 2.0, and more preferably 0.05 ≦ e ≦ 1.0. f indicates the atomic ratio of oxygen to 12 atoms of molybdenum, and is the number of oxygen atoms required to satisfy the valence requirements of other existing elements.
本実施形態のアンモ酸化用触媒は、一般式（１）で表される組成を構成する成分の各金属原子比を以下の式に代入した場合に、αが－１≦α≦２の関係を満足することが好ましい。
α＝１２－１．５（ａ＋ｄ）－ｂ－ｃ
αは、酸化モリブデンとして、すなわち、モリブデンの複合酸化物を形成しない分のモリブデンの原子比率を表し、触媒性能をさらに高める上で重要となる指標である。モリブデン元素との複合酸化物を形成しない金属元素の量を増やし過ぎず、分解活性を低く保つ観点で、αは－１以上であるのが好ましい。また目的生成物の反応選択性を高くする観点でも、αは－１以上であるのが好ましい。一方、酸化モリブデンの量が多すぎず、触媒形状を良好にする観点で、αは２以下であるのが好ましい。モリブデンの量が多すぎると、反応時に触媒粒子から酸化モリブデンが析出して流動性が悪化したりする等、取扱性上、問題が発生しやすくなる傾向がある。即ち、反応性と取扱性との両面を向上させるために、上記式で計算されるαは、－１≦α≦２の関係を満足することが好ましい。
The ammoxidation catalyst of the present embodiment has a relationship of α of -1 ≦ α ≦ 2 when the metal atomic ratios of the components constituting the composition represented by the general formula (1) are substituted into the following formula. It is preferable to be satisfied.
α = 12-1.5 (a + d) -bc
α represents the atomic ratio of molybdenum as molybdenum oxide, that is, the amount of molybdenum that does not form a composite oxide of molybdenum, and is an important index for further enhancing the catalytic performance. Α is preferably -1 or more from the viewpoint of keeping the decomposition activity low without increasing the amount of the metal element that does not form a composite oxide with the molybdenum element. Further, from the viewpoint of increasing the reaction selectivity of the target product, α is preferably -1 or more. On the other hand, the amount of molybdenum oxide is not too large, and α is preferably 2 or less from the viewpoint of improving the catalyst shape. If the amount of molybdenum is too large, molybdenum oxide precipitates from the catalyst particles during the reaction and the fluidity deteriorates, which tends to cause problems in terms of handleability. That is, in order to improve both reactivity and handleability, it is preferable that α calculated by the above formula satisfies the relationship of -1≤α≤2.
本実施形態のアンモ酸化用触媒はＸ線回折分析において、特有のピークを示す。本実施形態におけるＸ線回折（以下「ＸＲＤ」とも記す）分析では、対陰極にＣｕＫαをＸ線源とし、例えば、図１に示すような縦軸を回折Ｘ線強度、横軸を２θ値とするスペクトルが得られる。この２θ値の回折パターンにおいて、２θ＝２２．９°±０．３°にピークトップを有するピーク（ピーク１）は、３価の鉄のモリブデートに由来し、そのピーク強度をＰとする。ここで、ピーク強度とはある範囲におけるピークトップである点から垂線をベースラインへ下ろした際の交点における回折Ｘ線強度との差である。また、２θ値の回折パターンにおいて、２θ＝２６．４°±０．３°にピークトップを有するピーク（ピーク２）は、２価の鉄モリブデートに由来し、アンモ酸化用触媒がニッケル及び／又はコバルトを含有する場合は２価の鉄とニッケル及び／コバルトとが固溶し、モリブデートを形成するため、高角シフトする。そのピーク強度をＱとする。この際のＰ／Ｑの値が０．０３以下、好ましくは０．０１以下である場合に、３価の鉄モリブデート形成が抑制された状態であり、このようなアンモ酸化用触媒を用いることにより、アクリロニトリル収率が増加する。Ｐ／Ｑの値の下限は、特に限定されないが、例えば、０以上である。本明細書におけるピークトップとは、所定の２θの範囲内において、極大値を示す位置を意味する。所定の２θの範囲内にピークトップが複数存在するとき、本明細書におけるピークトップは、最も極大値が大きいピークにおけるピークトップである。 The catalyst for ammoxidation of the present embodiment shows a peculiar peak in the X-ray diffraction analysis. In the X-ray diffraction (hereinafter, also referred to as “XRD”) analysis in the present embodiment, CuKα is used as the X-ray source for the countercathode, for example, the vertical axis as shown in FIG. 1 is the diffracted X-ray intensity, and the horizontal axis is the 2θ value. The spectrum to be obtained is obtained. In this diffraction pattern of 2θ value, the peak (peak 1) having a peak top at 2θ = 22.9 ° ± 0.3 ° is derived from trivalent iron molybdate, and its peak intensity is P. Here, the peak intensity is the difference from the diffracted X-ray intensity at the intersection when the perpendicular line is drawn from the point that is the peak top in a certain range to the baseline. Further, in the divalent pattern of 2θ value, the peak having the peak top at 2θ = 26.4 ° ± 0.3 ° (peak 2) is derived from divalent iron cobaltate, and the catalyst for ammoxidation is nickel and / or When cobalt is contained, divalent iron and nickel and / cobalt are solid-dissolved to form a molybdate, so that the angle shifts to a high angle. Let Q be the peak intensity. When the P / Q value at this time is 0.03 or less, preferably 0.01 or less, the formation of trivalent iron acrylonitrile is suppressed, and by using such an ammoxidation catalyst, , Acrylonitrile yield increases. The lower limit of the P / Q value is not particularly limited, but is, for example, 0 or more. The peak top in the present specification means a position showing a maximum value within a predetermined range of 2θ. When there are a plurality of peak tops within a predetermined range of 2θ, the peak top in the present specification is the peak top in the peak having the largest maximum value.
ベースラインとは、例えば２θ＝１０°～１５°付近のピークの無いポイントと、２θ＝３５°～４０°のピークの無いポイントを結んだ線である。なお、上記「ピークの無いポイント」とは、ＸＲＤ測定において、縦軸に回折Ｘ線強度を取り、横軸に２θを取ったチャートにおけるいわゆるベースライン上のポイントを意味し、ピークの存在しないポイントを示す。通常、ＸＲＤ測定においては、あるレベルのノイズ等を含むので、ピークの無い（回折点が無い）箇所でもあるレベルの回折Ｘ線強度を示す。そこで、測定機器の計算、すなわち、全体の分析結果からノイズ、バックグラウンドを計算することにより、回折Ｘ線強度がほぼゼロのラインを機械的に求め、これをベースラインとする。 The baseline is, for example, a line connecting a point without a peak near 2θ = 10 ° to 15 ° and a point without a peak around 2θ = 35 ° to 40 °. The above-mentioned "point without peak" means a point on the so-called baseline in a chart in which the vertical axis is the diffraction X-ray intensity and the horizontal axis is 2θ in the XRD measurement, and the point where the peak does not exist. Is shown. Normally, in the XRD measurement, since a certain level of noise or the like is included, the diffraction X-ray intensity at a level that is also a place without a peak (no diffraction point) is shown. Therefore, by calculating the measuring device, that is, calculating the noise and background from the entire analysis result, a line having almost zero diffracted X-ray intensity is mechanically obtained, and this is used as the baseline.
本実施形態のアンモ酸化用触媒は、上記複合酸化物と、その複合酸化物を担持する担体と、を有する担持型触媒であることが好ましい。担体としては、例えば、シリカ、アルミナ、シリカ－アルミナ、ジルコニア、チタニア等が挙げられるが、中でもシリカが好ましい。シリカは、アルミナ、シリカ－アルミナ、ジルコニア、チタニアに比べてそれ自体不活性であり、反応の目的生成物に対する活性触媒成分の選択性を減ずることなく、活性触媒成分である上記酸化物に対し良好なバインド作用を有する。担体におけるシリカの含有量は、担体の全質量に対して、好ましくは９０～１００質量％である。ただし、担体は、その全部がシリカであることが特に好ましいが、そのことに限定されるものではなく、触媒の形状や耐磨耗性、圧縮強度を向上させる上でジルコニア、チタニア等の通常一般的に触媒の担体に用いられる成分を、シリカに対して数質量％用いることも可能である。 The catalyst for ammoxidation of the present embodiment is preferably a supported catalyst having the above-mentioned composite oxide and a carrier that supports the composite oxide. Examples of the carrier include silica, alumina, silica-alumina, zirconia, titania and the like, and silica is preferable. Silica is itself less active than alumina, silica-alumina, zirconia, and titania, and is good for the above oxides, which are active catalyst components, without reducing the selectivity of the active catalyst component for the target product of the reaction. Has a binding action. The content of silica in the carrier is preferably 90 to 100% by mass with respect to the total mass of the carrier. However, it is particularly preferable that the carrier is entirely silica, but the carrier is not limited to this, and is usually used in general such as zirconia and titania in order to improve the shape of the catalyst, abrasion resistance, and compressive strength. It is also possible to use several mass% of the component used as the carrier of the catalyst with respect to silica.
アンモ酸化用触媒中の担体の含有量は、触媒の全質量に対して３０～７０質量％であることが好ましく、４０～６０質量％であることがより好ましい。担体の含有量がこの範囲であると、担体をより有効に用いることができる。担体の役割として触媒の強度を上げ、実用条件下において、耐破砕性を向上させることや耐磨耗性を上げることが挙げられる。耐破砕性や耐磨耗性といった強度の観点で、担体の含有量が３０質量％以上であるのが好ましい。十分な強度を有する触媒は、流動床触媒として実用に適している。一方、担体の含有量が７０質量％を超えると触媒の見掛比重が軽く、流動床触媒として実用的でなくなる傾向にある。特に、担体の全部がシリカである場合に、上述した効果は顕著となる。 The content of the carrier in the ammoxidation catalyst is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, based on the total mass of the catalyst. When the content of the carrier is in this range, the carrier can be used more effectively. The role of the carrier is to increase the strength of the catalyst, improve the crush resistance and the abrasion resistance under practical conditions. From the viewpoint of strength such as crush resistance and abrasion resistance, the content of the carrier is preferably 30% by mass or more. A catalyst having sufficient strength is suitable for practical use as a fluidized bed catalyst. On the other hand, when the content of the carrier exceeds 70% by mass, the apparent specific gravity of the catalyst is light, and it tends to be impractical as a fluidized bed catalyst. In particular, when the entire carrier is silica, the above-mentioned effect becomes remarkable.
本実施形態のアンモ酸化用触媒の製造方法は、触媒の前駆体となるモリブデン、ビスマス及び鉄を含む前駆体スラリーを調製する工程（工程１）、前記前駆体スラリーを乾燥して乾燥粒子を得る工程（工程２）、前記乾燥粒子を焼成してアンモ酸化用触媒を得る工程（工程３）を有し、前記前駆体スラリーの酸化還元電位が３００ｍＶ／ＡｇＣｌ以下、－３００ｍＶ／ＡｇＣｌ以上である。 The method for producing an ammoxidation catalyst of the present embodiment is a step of preparing a precursor slurry containing molybdenum, bismuth and iron as a catalyst precursor (step 1), and drying the precursor slurry to obtain dried particles. It has a step (step 2) and a step (step 3) of calcining the dried particles to obtain a catalyst for ammoxidation, and the oxidation-reduction potential of the precursor slurry is 300 mV / AgCl or less and −300 mV / AgCl or more.
工程１は、例えば、金属成分や担体などの触媒を構成する成分の原料を混合後、還元剤を添加し、触媒の前駆体スラリーを調製する工程であることが好ましい。また、工程３は、不活性ガス雰囲気下で行うことが好ましい。 Step 1 is preferably a step of preparing a precursor slurry of the catalyst by adding a reducing agent after mixing the raw materials of the components constituting the catalyst such as a metal component and a carrier, for example. Further, the step 3 is preferably performed in an inert gas atmosphere.
前駆体スラリーを調製する際の各成分の混合順は特に限定されないが、例えば、上記一般式（１）で表される組成の実施形態に関する好ましい一例としては下記の通りである。まず、温水に溶解させたモリブデンのアンモニウム塩（以下、モリブデン水溶液と称する）をシリカゾルに添加する（混合後の溶液を以下、シリカ・モリブデン水溶液と称する）。また、別の容器内にセリウム、鉄、クロム、ニッケル、マグネシウム、亜鉛、マンガン、コバルト、ルビジウム、セシウム、カリウム等の各元素の元素源の硝酸塩を水に溶解させた水溶液とビスマスの乳酸水溶液とを混合する（以下、金属塩水溶液と称する）。シリカ・モリブデン溶液に対し、金属塩水溶液を添加することでスラリーが形成される。また、前駆体スラリー中には必ずしも触媒を構成するすべての元素を含有している必要はなく、前駆体スラリー中に含有されていない元素の原料は焼成工程までに各工程で添加してもよく、乾燥後の触媒に含浸するなどの方法により添加してもよい。 The mixing order of each component when preparing the precursor slurry is not particularly limited, and for example, a preferable example of the embodiment of the composition represented by the general formula (1) is as follows. First, an ammonium salt of molybdenum dissolved in warm water (hereinafter referred to as a molybdenum aqueous solution) is added to the silica sol (the mixed solution is hereinafter referred to as a silica-molybdenum aqueous solution). Also, in another container, an aqueous solution in which nitrates of the element sources of each element such as cerium, iron, chromium, nickel, magnesium, zinc, manganese, cobalt, rubidium, cesium, and potassium are dissolved in water and an aqueous solution of bismuth lactic acid are used. (Hereinafter referred to as an aqueous metal salt solution). A slurry is formed by adding an aqueous metal salt solution to a silica-molybdenum solution. Further, the precursor slurry does not necessarily contain all the elements constituting the catalyst, and the raw materials of the elements not contained in the precursor slurry may be added in each step before the firing step. , It may be added by a method such as impregnating the catalyst after drying.
前述の原料スラリーの調製法に対して、アンモニア水や酸化力のない酸をシリカゾルやモリブデン溶液、金属硝酸塩水溶液に添加して、スラリーのｐＨを変化させることができる。 In contrast to the above-mentioned method for preparing a raw material slurry, aqueous ammonia or an acid having no oxidizing power can be added to a silica sol, a molybdenum solution, or an aqueous metal nitrate solution to change the pH of the slurry.
ここで、アンモ酸化用触媒中の３価の鉄モリブデートの形成を抑制し、Ｐ／Ｑを特定の範囲に制御する観点というから、前駆体スラリーの酸化還元電位は３００ｍＶ／ＡｇＣｌ以下、－３００ｍＶ／ＡｇＣｌ以上の範囲である。前駆体スラリーの酸化還元電位は２００ｍＶ／ＡｇＣｌ以下、－１５０ｍＶ／ＡｇＣｌ以上の範囲がより好ましく、１００ｍＶ／ＡｇＣｌ以下、０ｍＶ／ＡｇＣｌ以上の範囲がさらに好ましい。前駆体スラリーの酸化還元電位が３００ｍＶ／ＡｇＣｌ以下の場合は、アンモ酸化用触媒中の３価の鉄モリブデートの形成抑制が十分になり、－３００ｍＶ／ＡｇＣｌ以上の場合は、前記組成中のＸに該当する二価金属が還元され難くなり、単体として析出することが抑制されるため触媒性能が良好となる。本実施形態においては、前駆体スラリーの酸化還元電位測定には東亜ＤＫＫ社製のＨＭ－３１Ｐを使用することができる。酸化還元電位は複合電極（白金電極及び塩化銀電極）を用いた酸化還元電位（ＯＲＰ）計による測定が便利である。一般的にスラリーの酸化還元電位が低くなると、焼成後の触媒は還元的になり、高い場合には酸化的になる。 Here, from the viewpoint of suppressing the formation of trivalent iron molybdate in the ammoxidation catalyst and controlling P / Q within a specific range, the redox potential of the precursor slurry is 300 mV / AgCl or less, −300 mV /. The range is AgCl or higher. The redox potential of the precursor slurry is more preferably in the range of 200 mV / AgCl or less and −150 mV / AgCl or more, and further preferably in the range of 100 mV / AgCl or less and 0 mV / AgCl or more. When the redox potential of the precursor slurry is 300 mV / AgCl or less, the formation of trivalent iron molybdate in the ammoxidation catalyst is sufficiently suppressed, and when it is -300 mV / AgCl or more, X in the composition is set. The corresponding divalent metal is less likely to be reduced, and precipitation as a simple substance is suppressed, so that the catalytic performance is improved. In the present embodiment, HM-31P manufactured by Toa DKK Corporation can be used for measuring the redox potential of the precursor slurry. It is convenient to measure the redox potential with an oxidation-reduction potential (ORP) meter using a composite electrode (platinum electrode and silver chloride electrode). Generally, when the redox potential of the slurry is low, the catalyst after firing becomes reducing, and when it is high, it becomes oxidative.
前駆体スラリーの酸化還元電位を上記範囲にする手段としては、還元剤を添加して、前駆体スラリー中の３価の鉄を２価に還元し、スラリーを乾燥後に不活性ガス雰囲気下で焼成する方法と３価の鉄を含有したスラリーを乾燥後に還元ガス雰囲気下で還元焼成する方法とが挙げられるが、還元反応に伴う副反応の抑制のための反応条件制御が容易である前者が好ましい。 As a means for setting the redox potential of the precursor slurry in the above range, a reducing agent is added to reduce the trivalent iron in the precursor slurry to divalent, and the slurry is dried and then fired in an inert gas atmosphere. A method of reducing the amount of trivalent iron and a method of reducing and firing the slurry containing trivalent iron in a reducing gas atmosphere can be mentioned. The former method is preferable because it is easy to control the reaction conditions for suppressing side reactions associated with the reduction reaction. ..
還元剤とは酸化還元反応において他の化学種に電子を供給する物質のことである。還元剤の還元力の強度については標準電極電位を目安にすることができる。鉄の３価／２価の標準電極電位を踏まえると、還元剤の標準電極電位は０．７７Ｖ／ＳＨＥ（ＳＨＥ：標準水素電極）以下であることが好ましい。還元剤の標準電極電位の下限は、特に限定されないが、例えば、－３．０Ｖ／ＳＨＥ以上である。工程１で添加する還元剤はどの段階で添加してもよいが、金属成分及び担体などのアンモ酸化用触媒を構成する成分を全て混合した後に、還元剤を最後に添加することが好ましい。また添加する還元剤には特に制限はないが、後の工程２や工程３において、加熱下で分解し、最終的に得られる触媒粉に還元剤由来の成分が残存しないことが好ましい。その観点から好ましい還元剤の種類としては没食子酸、シュウ酸、蟻酸、アスコルビン酸、ヒドラジン水和物やヒドラジン塩などを含むヒドラジン誘導体などが挙げられるが、ヒドラジン誘導体がより好ましい。 A reducing agent is a substance that supplies electrons to other chemical species in a redox reaction. The standard electrode potential can be used as a guide for the strength of the reducing power of the reducing agent. Considering the trivalent / divalent standard electrode potential of iron, the standard electrode potential of the reducing agent is preferably 0.77 V / SHE (SHE: standard hydrogen electrode) or less. The lower limit of the standard electrode potential of the reducing agent is not particularly limited, but is, for example, −3.0 V / SHE or higher. The reducing agent added in step 1 may be added at any stage, but it is preferable to add the reducing agent last after mixing all the components constituting the ammoxidation catalyst such as the metal component and the carrier. The reducing agent to be added is not particularly limited, but it is preferable that the reducing agent-derived component does not remain in the catalyst powder that is finally obtained by decomposing under heating in the subsequent steps 2 and 3. From this point of view, preferred types of reducing agents include hydrazine derivatives containing gallic acid, oxalic acid, formic acid, ascorbic acid, hydrazine hydrate and hydrazine salts, but hydrazine derivatives are more preferable.
工程１で用いる溶媒としては、酸化力を持たない水を用いることが好ましい。硝酸は酸化剤として、工程１において添加する還元剤と反応するため溶媒として不適切である。各金属元素の元素源としては、一般的に水に可溶なアンモニウム塩、硝酸塩、有機酸塩等が挙げられる。これらは塩酸塩を使用した場合に生じる塩素の残留や硫酸塩を使用した場合に生じる硫黄の残留を生じない点で好ましい。 As the solvent used in step 1, it is preferable to use water having no oxidizing power. Nitric acid is not suitable as a solvent because it reacts with the reducing agent added in step 1 as an oxidizing agent. Examples of the element source of each metal element include water-soluble ammonium salts, nitrates, organic acid salts and the like. These are preferable in that they do not cause residual chlorine that occurs when hydrochloride is used or sulfur that occurs when sulfate is used.
上記元素源に関してビスマス塩は通常、酸性の水溶液にのみ溶解し、中性付近の水には溶解しない。そのため硝酸などの強酸を使用しない場合は均一なビスマス塩水溶液を得るためにはビスマスに対して乳酸やＥＤＴＡ（エチレンジアミン四酢酸）を含有する水溶液を使用するのが好ましい。これらはビスマスに配位し、可溶性の化合物を形成すると想定されている。乳酸を使用する場合はビスマスに対して３等量以上の乳酸を使用することが好ましい。 With respect to the above elemental sources, bismuth salts usually dissolve only in acidic aqueous solutions and not in near-neutral water. Therefore, when a strong acid such as nitric acid is not used, it is preferable to use an aqueous solution containing lactic acid or EDTA (ethylenediamine tetraacetic acid) with respect to bismuth in order to obtain a uniform bismuth salt aqueous solution. They are supposed to coordinate to bismuth and form soluble compounds. When lactic acid is used, it is preferable to use 3 or more equal amounts of lactic acid with respect to bismuth.
前駆体スラリー調製時に還元剤とは別にポリエチレングリコール、メチルセルロース、ポリビニルアルコール、ポリアクリル酸、ポリアクリルアミドなどの水溶性ポリマーやアミン類、カルボン酸、アミノカルボン酸類、その他の有機酸を適宜、シリカゾルやモリブデン溶液、金属硝酸塩水溶液に添加してもよい。 When preparing the precursor slurry, in addition to the reducing agent, water-soluble polymers such as polyethylene glycol, methyl cellulose, polyvinyl alcohol, polyacrylic acid, and polyacrylamide, amines, carboxylic acids, aminocarboxylic acids, and other organic acids are appropriately added to silica sol and molybdenum. It may be added to a solution or an aqueous solution of a metal nitrate.
工程２は、前駆体スラリーを乾燥して乾燥粒子を得る工程である。好ましくは、前駆体スラリーを噴霧乾燥し、乾燥粒子を得る工程である。前駆体スラリーを噴霧乾燥することによって流動層反応に適した球形微粒子を得ることができる。噴霧乾燥装置としては、回転円盤式、ノズル式等の一般的なものを用いることができる。噴霧乾燥条件を調節することにより、触媒の形状、表面状態及び粒径などの調整が可能になる。流動層触媒として用いる場合には、アンモ酸化用触媒の粒径は、好ましくは２５～１８０μｍである。好ましい噴霧乾燥条件の一例を記載すると、乾燥器上部の中央に設置された、皿型回転子を備えた遠心式噴霧化装置を用い、乾燥器の入口空気温度を１５０～３００℃、出口温度を１００～１８０℃に保持する条件が挙げられる。さらに乾燥粒子には２００℃以下で揮発する物質を含有しており、必要に応じて、真空下で加熱乾燥することで揮発性物質を除去することができる。 Step 2 is a step of drying the precursor slurry to obtain dried particles. Preferably, it is a step of spray-drying the precursor slurry to obtain dried particles. By spray-drying the precursor slurry, spherical fine particles suitable for the fluidized bed reaction can be obtained. As the spray drying device, a general device such as a rotary disk type or a nozzle type can be used. By adjusting the spray drying conditions, the shape, surface condition, particle size, etc. of the catalyst can be adjusted. When used as a fluidized bed catalyst, the particle size of the ammoxidation catalyst is preferably 25 to 180 μm. To describe an example of preferable spray drying conditions, a centrifugal atomizer equipped with a dish-shaped rotor, which is installed in the center of the upper part of the dryer, is used to set the inlet air temperature of the dryer to 150 to 300 ° C and the outlet temperature. The condition of holding the temperature at 100 to 180 ° C. can be mentioned. Further, the dried particles contain a substance that volatilizes at 200 ° C. or lower, and if necessary, the volatile substance can be removed by heating and drying under vacuum.
工程３は、乾燥によって得られた乾燥粒子を焼成してアンモ酸化用触媒を得る工程である。焼成温度は、好ましくは５７０～７００℃である。焼成温度が５７０℃以上であることにより、結晶成長が十分に進行し、得られる触媒のアクリロニトリル選択性がより向上する傾向にある。また、焼成温度が７００℃以下であることにより、得られるアンモ酸化用触媒の表面積が増大し、プロピレンの反応活性がより向上する傾向にある。焼成の際に用いるガス雰囲気は、窒素などの不活性ガス雰囲気であり、焼成中に触媒粉中の金属塩や還元剤及び添加剤の分解に伴い発生する気体を拡散させるために、焼成系中に不活性ガスが供給、排出され続ける状況が好ましい。また、理由は定かではないが、同じ金属組成で還元剤を使用せずに調製した触媒を空気雰囲気下で焼成する場合と比較して、還元剤を使用して調製した触媒を窒素雰囲気下で焼成する場合は昇温速度を緩やかにすると触媒性能が向上する。 Step 3 is a step of calcining the dried particles obtained by drying to obtain a catalyst for ammoxidation. The firing temperature is preferably 570 to 700 ° C. When the calcination temperature is 570 ° C. or higher, crystal growth tends to proceed sufficiently, and the acrylonitrile selectivity of the obtained catalyst tends to be further improved. Further, when the firing temperature is 700 ° C. or lower, the surface area of the obtained ammoxidation catalyst increases, and the reaction activity of propylene tends to be further improved. The gas atmosphere used at the time of firing is an inert gas atmosphere such as nitrogen, and in order to diffuse the gas generated by the decomposition of the metal salt, the reducing agent and the additive in the catalyst powder during the firing, the gas atmosphere is used in the firing system. It is preferable that the inert gas is continuously supplied and discharged. In addition, although the reason is not clear, the catalyst prepared using the reducing agent is subjected to the nitrogen atmosphere as compared with the case where the catalyst prepared with the same metal composition without using the reducing agent is calcined in the air atmosphere. When firing, the catalyst performance is improved by slowing the temperature rise rate.
本実施形態のアクリロニトリルの製造方法は、前述したアンモ酸化用触媒の存在下、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させてアクリロニトリルを製造する反応工程を有する。アンモ酸化反応によるアクリロニトリルの製造は固定床反応器又は流動床反応器（流動反応槽）により実施することができる。これらの中でも、反応の際に発生する熱を効率的に除去し、アクリロニトリルの収率を高める観点から、流動床反応器（流動反応槽）が好ましい。また、反応工程を流動反応槽で行う場合、アンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、アンモ酸化反応を行うことが好ましい。アンモ酸化反応の原料であるプロピレン及びアンモニアは必ずしも高純度である必要はなく、工業グレードのものを使用することができる。前記分子状酸素源が空気の場合、原料ガス中のプロピレンとアンモニアと空気のモル比（プロピレン／アンモニア／空気）は、好ましくは１／（０．８～１．６）／（７～１２）の範囲であり、より好ましくは１／（０．９～１．５）／（８～１１）の範囲である。反応温度は、好ましくは３５０～５５０℃であり、より好ましくは４００～５００℃の範囲である。また、反応圧力は、好ましくは常圧～０．３ＭＰａである。原料ガスとアンモ酸化用触媒との接触時間は、好ましくは３～６秒である。 The method for producing acrylonitrile of the present embodiment includes a reaction step of producing acrylonitrile by reacting (ammooxidation reaction) propylene, molecular oxygen, and ammonia in the presence of the above-mentioned ammoxidation catalyst. The production of acrylonitrile by an ammoxidation reaction can be carried out by a fixed bed reactor or a fluidized bed reactor (fluidized reactor). Among these, a fluidized bed reactor (fluidized bed reactor) is preferable from the viewpoint of efficiently removing heat generated during the reaction and increasing the yield of acrylonitrile. When the reaction step is carried out in a flow reaction tank, it is preferable to supply an ammoxidation catalyst to the flow reaction tank in advance and carry out the ammoxidation reaction while circulating the catalyst in the flow reaction tank. Propylene and ammonia, which are raw materials for the ammoxidation reaction, do not necessarily have to be of high purity, and industrial grade ones can be used. When the molecular oxygen source is air, the molar ratio of propylene, ammonia, and air (propylene / ammonia / air) in the raw material gas is preferably 1 / (0.8 to 1.6) / (7 to 12). It is in the range of 1 / (0.9 to 1.5) / (8 to 11), more preferably. The reaction temperature is preferably in the range of 350 to 550 ° C, more preferably 400 to 500 ° C. The reaction pressure is preferably normal pressure to 0.3 MPa. The contact time between the raw material gas and the ammoxidation catalyst is preferably 3 to 6 seconds.
プロピレンのアンモ酸化反応に使用する反応管には、特に限定されないが、例えば、１０メッシュの金網を１ｃｍ間隔で１６枚内蔵した内径２５ｍｍのパイレックス（登録商標）ガラス管を使用することができる。アンモ酸化反応の具体例としては、特に限定されないが、例えば、まず、アンモ酸化用触媒量５０ｃｃ、反応温度４３０℃、反応圧力０．１７ＭＰａに設定し、プロピレン容積９％の混合ガス（プロピレン、アンモニア、酸素、ヘリウム）を通過させる。そして、プロピレンに対するアンモニアの容積比は、下記式で定義される硫酸原単位が２０ｋｇ／Ｔ‐ＡＮとなるように設定する。この時のアンモニア／プロピレンのモル比をＮ／Ｃと定義する。プロピレンに対する酸素の容積比は、反応器出口ガスの酸素濃度が０．２±０．０２容積％になるように設定する。その際の酸素のモル量を空気は酸素を２１％含有しているとして空気のモル量に換算した。この時の空気／プロピレンのモル比をＡ／Ｃと定義する。また混合ガスの流速を変更することで、下記式で定義される接触時間を変更することができる。これによって下記式で定義されるプロピレン転化率が９９．３±０．２％となるように設定することができる。硫酸原単位、接触時間、プロピレン転化率、アクリロニトリル収率は下記式のように定義される。
以下に実施例を示して、本実施形態をより詳細に説明するが、本実施形態は以下に記載の実施例によって制限されるものではない。なお、実施例及び比較例に記載した触媒組成は各元素の仕込み組成と同じ値である。 The present embodiment will be described in more detail with reference to the following examples, but the present embodiment is not limited to the examples described below. The catalyst compositions described in Examples and Comparative Examples have the same values as the charged compositions of each element.
［ＸＲＤ分析］
実施例及び比較例で得られたアンモ酸化用触媒のＸＲＤ分析は下記条件で実施した。アンモ酸化用触媒は、粉砕せずにそのまま測定した。触媒を粉砕した場合は、粉砕時の衝撃によりβ型の２価金属のモリブデート結晶相がα型へ転移し、本来の回折パターンが得られない可能性がある。
測定条件
機器 ：Ｂｒｕｋｅｒ社 Ｄ８ ＡＤＶＡＮＣＥ
検出器 ：半導体検出器
管球 ：Ｃｕ
管電圧 ：４０ｋＶ
管電流 ：４０ｍＶ
発散スリット ：０．３°
ステップ幅 ：０．０２°／ｓｔｅｐ
計測時間 ：０．５°／ｓｔｅｐ
[XRD analysis]
The XRD analysis of the ammoxidation catalysts obtained in Examples and Comparative Examples was carried out under the following conditions. The catalyst for ammoxidation was measured as it was without pulverization. When the catalyst is pulverized, the molybdate crystal phase of the β-type divalent metal may be transferred to the α-type due to the impact during pulverization, and the original diffraction pattern may not be obtained.
Measurement conditions Equipment: Bruker D8 ADVANCE
Detector: Semiconductor detector Tube: Cu
Tube voltage: 40 kV
Tube current: 40 mV
Divergence slit: 0.3 °
Step width: 0.02 ° / step
Measurement time: 0.5 ° / step
［前駆体スラリーの酸化還元電位］
本実施例においては、前駆体スラリーの酸化還元電位測定には東亜ＤＫＫ社製のＨＭ－３１Ｐを使用した。酸化還元電位は複合電極（白金電極及び塩化銀電極）を用いた酸化還元電位（ＯＲＰ）計により測定した。
[Redox potential of precursor slurry]
In this example, HM-31P manufactured by Toa DKK Corporation was used for measuring the redox potential of the precursor slurry. The redox potential was measured by an oxidation-reduction potential (ORP) meter using a composite electrode (platinum electrode and silver chloride electrode).
［硫酸原単位、接触時間、プロピレン転化率、アクリロニトリル収率］
プロピレンのアンモ酸化反応に使用する反応管には、１０メッシュの金網を１ｃｍ間隔で１６枚内蔵した内径２５ｍｍのパイレックス（登録商標）ガラス管を使用した。アンモ酸化反応において、アンモ酸化用触媒量５０ｃｃ、反応温度４３０℃、反応圧力０．１７ＭＰａに設定し、プロピレン容積９％の混合ガス（プロピレン、アンモニア、酸素、ヘリウム）を通過させた。そして、プロピレンに対するアンモニアの容積比は、下記式で定義される硫酸原単位が２０ｋｇ／Ｔ‐ＡＮとなるように設定した。この時のアンモニア／プロピレンのモル比をＮ／Ｃと定義した。プロピレンに対する酸素の容積比は、反応器出口ガスの酸素濃度が０．２±０．０２容積％になるように設定した。その際の酸素のモル量を空気は酸素を２１％含有しているとして空気のモル量に換算した。この時の空気／プロピレンのモル比をＡ／Ｃと定義した。また混合ガスの流速を変更することで、下記式で定義される接触時間を変更した。これによって下記式で定義されるプロピレン転化率が９９．３±０．２％となるように設定した。硫酸原単位、接触時間、プロピレン転化率、アクリロニトリル収率は下記式のように定義した。
As the reaction tube used for the ammoxidation reaction of propylene, a Pyrex (registered trademark) glass tube having an inner diameter of 25 mm containing 16 10-mesh wire meshes at 1 cm intervals was used. In the ammoxidation reaction, the amount of catalyst for ammoxidation was set to 50 cc, the reaction temperature was set to 430 ° C., and the reaction pressure was set to 0.17 MPa, and a mixed gas (propylene, ammonia, oxygen, helium) having a propylene volume of 9% was passed through. The volume ratio of ammonia to propylene was set so that the sulfuric acid intensity defined by the following formula was 20 kg / T-AN. The molar ratio of ammonia / propylene at this time was defined as N / C. The volume ratio of oxygen to propylene was set so that the oxygen concentration of the reactor outlet gas was 0.2 ± 0.02 volume%. The molar amount of oxygen at that time was converted into the molar amount of air assuming that air contained 21% of oxygen. The molar ratio of air / propylene at this time was defined as A / C. In addition, the contact time defined by the following formula was changed by changing the flow velocity of the mixed gas. As a result, the propylene conversion rate defined by the following formula was set to be 99.3 ± 0.2%. The sulfuric acid intensity, contact time, propylene conversion rate, and acrylonitrile yield were defined by the following formulas.
［実施例１］
金属成分の組成がＭｏ12.00Ｂｉ0.33Ｃｅ0.73Ｆｅ3.97Ｎｉ2.40Ｃｏ2.99Ｒｂ0.08で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇを４０℃に保持した。別の容器に７２．３ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０９．１ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．４ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に１０．８ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、５４．８ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、２４．０ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、２９．７ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．３８ｇの硝酸ルビジウム［ＲｂＮＯ3］を水６０．５ｇに溶解後に、５．６ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］と乳酸３．１ｇとを３０ｇの水に溶解させた溶液と混合し、４０℃に保持し、金属塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記金属塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、ヒドラジン１水和物（ヒドラジンの標準電極電位：－０．３３Ｖ／ＳＨＥ）２５．８ｇを添加し、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は４２ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子は真空下、９０℃で１５時間保持した。さらに、真空処理後の乾燥粒子を窒素雰囲気下で３０℃から６４０℃まで９時間かけて昇温し、６４０℃で３時間３０分間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析（ＸＲＤ）の測定結果を図１に示す。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．０１と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Example 1]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.33 Ce 0.73 Fe 3.97 Ni 2.40 Co 2.99 Rb 0.08 is supported on silica is described below. Manufactured by the procedure.
First, 200.0 g of a silica sol containing 30% by mass of SiO 2 was maintained at 40 ° C. 72.3 g of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed in another container and dissolved in 109.1 g of warm water at 60 ° C. After cooling to 45 ° C., 5.4 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 10.8 g of cerium nitrate [Ce (NO 3 ) 3.6H 2 O], 54.8 g of iron nitrate [Fe (NO 3 ) 3.9 H 2 O], 24.0 g of nickel nitrate in another container. [Ni (NO 3 ) 2.6H 2 O], 29.7 g cobalt nitrate [Co (NO 3) 2.6 H 2 O], and 0.38 g rubidium nitrate [RbNO 3 ] are dissolved in 60.5 g of water. Later, 5.6 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O] and 3.1 g of lactic acid were mixed with a solution dissolved in 30 g of water and kept at 40 ° C. to prepare an aqueous metal salt solution. .. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the metal salt aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was held at 40 ° C. and stirred for 10 minutes, then 25.8 g of hydrazine monohydrate (standard electrode potential of hydrazine: −0.33 V / SHE) was added, and the slurry was heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 42 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. The dried particles were kept under vacuum at 90 ° C. for 15 hours. Further, the dried particles after the vacuum treatment were heated in a nitrogen atmosphere from 30 ° C. to 640 ° C. over 9 hours and calcined at 640 ° C. for 3 hours and 30 minutes to obtain an ammoxidation catalyst. The measurement result of the X-ray diffraction analysis (XRD) of the obtained ammoxidation catalyst is shown in FIG. The P / Q was calculated to be 0.01 by X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［比較例１］
金属成分の組成がＭｏ12.00Ｂｉ0.33Ｃｅ0.73Ｆｅ3.97Ｎｉ2.40Ｃｏ2.99Ｒｂ0.08で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇに乳酸３．１ｇを３０．０ｇの水に溶解させた水溶液を添加し、４０℃に保持した。別の容器に７２．３ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０９．１ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．４ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に５．６ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］、１０．８ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、５４．８ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、２４．０ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、２９．７ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．３８ｇの硝酸ルビジウム［ＲｂＮＯ3］を、１６．６質量％の硝酸６０．５ｇに溶解後、４０℃に保持し、硝酸塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記硝酸塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は９００ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子を空気雰囲気下で２００℃５分間保持し、２００℃から４５０℃まで２．５℃／分で昇温し、４５０℃で２０分保持することで前焼成を施した。その後、６００℃で２時間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．４２と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Comparative Example 1]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.33 Ce 0.73 Fe 3.97 Ni 2.40 Co 2.99 Rb 0.08 is supported on silica is described below. Manufactured by the procedure.
First, an aqueous solution prepared by dissolving 3.1 g of lactic acid in 30.0 g of water was added to 200.0 g of a silica sol containing 30% by mass of SiO 2 , and the temperature was maintained at 40 ° C. 72.3 g of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed in another container and dissolved in 109.1 g of warm water at 60 ° C. After cooling to 45 ° C., 5.4 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 5.6 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O], 10.8 g of cerium nitrate [Ce (NO 3) 3.6H 2 O ] , 54.8 g of iron nitrate in another container. [Fe (NO 3 ) 3.9H 2 O], 24.0 g of nickel nitrate [Ni (NO 3 ) 2.6H 2 O], 29.7 g of cobalt nitrate [Co ( NO 3 ) 2.6H 2 O] , And 0.38 g of rubidium nitrate [RbNO 3 ] was dissolved in 16.6 mass% of nitric acid (60.5 g) and then kept at 40 ° C. to prepare an aqueous nitrate solution. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the nitrate aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was held at 40 ° C., stirred for 10 minutes, and then heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 900 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. Pre-baking was performed by holding the dried particles in an air atmosphere at 200 ° C. for 5 minutes, raising the temperature from 200 ° C. to 450 ° C. at 2.5 ° C./min, and holding at 450 ° C. for 20 minutes. Then, it was calcined at 600 degreeC for 2 hours to obtain a catalyst for ammoxidation. The P / Q was calculated to be 0.42 by the X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［比較例２］
金属成分の組成がＭｏ12.00Ｂｉ0.33Ｃｅ0.73Ｆｅ3.97Ｎｉ2.40Ｃｏ2.99Ｒｂ0.08で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇに乳酸３．１ｇ、シュウ酸３．８ｇを３０．０ｇの水に溶解させた水溶液を添加し、４０℃に保持した。別の容器に７２．３ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０９．１ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．４ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に５．６ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］、１０．８ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、５４．８ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、２４．０ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、２９．７ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．３８ｇの硝酸ルビジウム［ＲｂＮＯ3］を、１６．６質量％の硝酸６０．５ｇに溶解後、４０℃に保持し、硝酸塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記硝酸塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は８８４ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子を空気雰囲気下で２００℃５分間保持し、２００℃から４５０℃まで２．５℃／分で昇温し、４５０℃で２０分保持することで前焼成を施した。その後、６００℃で２時間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．４１と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Comparative Example 2]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.33 Ce 0.73 Fe 3.97 Ni 2.40 Co 2.99 Rb 0.08 is supported on silica is described below. Manufactured by the procedure.
First, an aqueous solution prepared by dissolving 3.1 g of lactic acid and 3.8 g of oxalic acid in 30.0 g of water was added to 200.0 g of a silica sol containing 30% by mass of SiO 2 and maintained at 40 ° C. 72.3 g of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed in another container and dissolved in 109.1 g of warm water at 60 ° C. After cooling to 45 ° C., 5.4 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 5.6 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O], 10.8 g of cerium nitrate [Ce (NO 3) 3.6H 2 O ] , 54.8 g of iron nitrate in another container. [Fe (NO 3 ) 3.9H 2 O], 24.0 g of nickel nitrate [Ni (NO 3 ) 2.6H 2 O], 29.7 g of cobalt nitrate [Co ( NO 3 ) 2.6H 2 O] , And 0.38 g of rubidium nitrate [RbNO 3 ] was dissolved in 16.6 mass% of nitric acid (60.5 g) and then kept at 40 ° C. to prepare an aqueous nitrate solution. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the nitrate aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was held at 40 ° C., stirred for 10 minutes, and then heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 884 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. Pre-baking was performed by holding the dried particles in an air atmosphere at 200 ° C. for 5 minutes, raising the temperature from 200 ° C. to 450 ° C. at 2.5 ° C./min, and holding at 450 ° C. for 20 minutes. Then, it was calcined at 600 degreeC for 2 hours to obtain a catalyst for ammoxidation. The P / Q was calculated to be 0.41 by X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［実施例２］
金属成分の組成がＭｏ12.00Ｂｉ0.53Ｃｅ1.18Ｆｅ3.34Ｎｉ2.41Ｃｏ2.99Ｒｂ0.08で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇを４０℃に保持した。別の容器に７０．６ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０６．０ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．３ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に１６．９ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、４４．９ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、２３．４ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、２９．３ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、０．３７ｇの硝酸ルビジウム［ＲｂＮＯ3］を水５４．８ｇに溶解後に、８．６ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］と乳酸４．７ｇとを３０ｇの水に溶解させた溶液と混合し、４０℃に保持し、金属塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記金属塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、ヒドラジン１水和物２５．８ｇを添加し、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は６９ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子は真空下、９０℃で１５時間保持した。さらに、真空処理後の乾燥粒子を窒素雰囲気下で３０℃から６６５℃まで９時間かけて昇温し、６６５℃で３時間３０分間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．０１と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Example 2]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.53 Ce 1.18 Fe 3.34 Ni 2.41 Co 2.99 Rb 0.08 is supported on silica is described below. Manufactured by the procedure.
First, 200.0 g of a silica sol containing 30% by mass of SiO 2 was maintained at 40 ° C. In another container, 70.6 g of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed and dissolved in 106.0 g of warm water at 60 ° C. After cooling to 45 ° C., 5.3 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 16.9 g of cerium nitrate [Ce (NO 3 ) 3.6H 2 O], 44.9 g of iron nitrate [Fe (NO 3 ) 3.9H 2 O], 23.4 g of nickel nitrate in another container. After dissolving [Ni (NO 3 ) 2.6H 2 O], 29.3 g of cobalt nitrate [Co (NO 3) 2.6 H 2 O], and 0.37 g of rubidium nitrate [RbNO 3 ] in 54.8 g of water. , 8.6 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O] and 4.7 g of lactic acid were mixed with a solution of 30 g of water and kept at 40 ° C. to prepare an aqueous metal salt solution. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the metal salt aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was kept at 40 ° C., stirred for 10 minutes, 25.8 g of hydrazine monohydrate was added, and the slurry was heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 69 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. The dried particles were kept under vacuum at 90 ° C. for 15 hours. Further, the dried particles after the vacuum treatment were heated in a nitrogen atmosphere from 30 ° C. to 665 ° C. over 9 hours and calcined at 665 ° C. for 3 hours and 30 minutes to obtain an ammoxidation catalyst. The P / Q was calculated to be 0.01 by X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［比較例３］
金属成分の組成がＭｏ12.00Ｂｉ0.53Ｃｅ1.18Ｆｅ3.34Ｎｉ2.41Ｃｏ2.99Ｒｂ0.08で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇに乳酸４．７ｇを３０．０ｇの水に溶解させた水溶液を添加し、４０℃に保持した。別の容器に７０．６ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０６．０ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．３ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に８．６ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］、１６．９ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、４４．９ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、２３．４ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、２９．３ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．３７ｇの硝酸ルビジウム［ＲｂＮＯ3］を、１６．６質量％の硝酸５４．８ｇに溶解後、４０℃に保持し、硝酸塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記硝酸塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は８７７ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子を空気雰囲気下で２００℃５分間保持し、２００℃から４５０℃まで２．５℃／分で昇温し、４５０℃で２０分保持することで前焼成を施した。その後、６００℃で２時間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．３２と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Comparative Example 3]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.53 Ce 1.18 Fe 3.34 Ni 2.41 Co 2.99 Rb 0.08 is supported on silica is described below. Manufactured by the procedure.
First, an aqueous solution prepared by dissolving 4.7 g of lactic acid in 30.0 g of water was added to 200.0 g of a silica sol containing 30% by mass of SiO 2 , and the temperature was maintained at 40 ° C. In another container, 70.6 g of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed and dissolved in 106.0 g of warm water at 60 ° C. After cooling to 45 ° C., 5.3 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 8.6 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O], 16.9 g of cerium nitrate [Ce (NO 3 ) 3.6H 2 O], 44.9 g of iron nitrate in another container. [Fe (NO 3 ) 3.9H 2 O], 23.4 g of nickel nitrate [Ni (NO 3 ) 2.6 H 2 O], 29.3 g of cobalt nitrate [Co (NO 3 ) 2.6 H 2 O] , And 0.37 g of rubidium nitrate [RbNO 3 ] was dissolved in 16.6 mass% of nitric acid (54.8 g) and kept at 40 ° C. to prepare an aqueous nitrate solution. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the nitrate aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was held at 40 ° C., stirred for 10 minutes, and then heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 877 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. Pre-baking was performed by holding the dried particles in an air atmosphere at 200 ° C. for 5 minutes, raising the temperature from 200 ° C. to 450 ° C. at 2.5 ° C./min, and holding at 450 ° C. for 20 minutes. Then, it was calcined at 600 degreeC for 2 hours to obtain a catalyst for ammoxidation. The P / Q was calculated to be 0.32 by the X-ray diffraction analysis of the obtained ammoxidation catalyst. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［実施例３］
金属成分の組成がＭｏ12.00Ｂｉ0.40Ｃｅ0.87Ｆｅ1.63Ｎｉ3.52Ｃｏ4.39Ｒｂ0.15で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇを４０℃に保持した。別の容器に７１．２ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０７．０ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．３ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に１２．６ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、２２．２ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、３４．５ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、４３．０ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．７５ｇの硝酸ルビジウム［ＲｂＮＯ3］を水５４．５ｇに溶解後に、６．５ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］と乳酸３．６ｇとを３０ｇの水に溶解させた溶液と混合し、４０℃に保持し、金属塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記金属塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、ヒドラジン１水和物２０．０ｇを添加し、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は１１０ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子は真空下、９０℃で１５時間保持した。さらに、真空処理後の乾燥粒子を窒素雰囲気下で３０℃から６００℃まで９時間かけて昇温し、６００℃で３時間３０分間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．０２と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Example 3]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.40 Ce 0.87 Fe 1.63 Ni 3.52 Co 4.39 Rb 0.15 is supported on silica is described below. Manufactured by the procedure.
First, 200.0 g of a silica sol containing 30% by mass of SiO 2 was maintained at 40 ° C. 71.2 g of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed in another container and dissolved in 107.0 g of warm water at 60 ° C. After cooling to 45 ° C., 5.3 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 12.6 g of cerium nitrate [Ce (NO 3 ) 3.6H 2 O], 22.2 g of iron nitrate [Fe (NO 3 ) 3.9H 2 O], and 34.5 g of nickel nitrate in another container. [Ni (NO 3 ) 2.6H 2 O], 43.0 g of cobalt nitrate [Co (NO 3 ) 2.6H 2 O] , and 0.75 g of rubidium nitrate [RbNO 3 ] are dissolved in 54.5 g of water. Later, 6.5 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O] and 3.6 g of lactic acid were mixed with a solution dissolved in 30 g of water and kept at 40 ° C. to prepare a metal salt aqueous solution. .. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the metal salt aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was kept at 40 ° C., stirred for 10 minutes, 20.0 g of hydrazine monohydrate was added, and the slurry was heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 110 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. The dried particles were kept under vacuum at 90 ° C. for 15 hours. Further, the dried particles after the vacuum treatment were heated in a nitrogen atmosphere from 30 ° C. to 600 ° C. over 9 hours and calcined at 600 ° C. for 3 hours and 30 minutes to obtain a catalyst for ammoxidation. The P / Q was calculated to be 0.02 by X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［比較例４］
金属成分の組成がＭｏ12.00Ｂｉ0.40Ｃｅ0.87Ｆｅ1.63Ｎｉ3.52Ｃｏ4.39Ｒｂ0.15で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇに乳酸３．６ｇを３０．０ｇの水に溶解させた水溶液を添加し、４０℃に保持した。別の容器に７１．２ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０７．０ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．３ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に６．５ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］、１２．６ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、２２．２ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、３４．５ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、４３．０ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．７５ｇの硝酸ルビジウム［ＲｂＮＯ3］を、１６．６質量％の硝酸５４．５ｇに溶解後、４０℃に保持し、硝酸塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記硝酸塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は８０９ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子を空気雰囲気下で２００℃５分間保持し、２００℃から４５０℃まで２．５℃／分で昇温し、４５０℃で２０分保持することで前焼成を施した。その後、５９０℃で２時間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．１１と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Comparative Example 4]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.40 Ce 0.87 Fe 1.63 Ni 3.52 Co 4.39 Rb 0.15 is supported on silica is described below. Manufactured by the procedure.
First, an aqueous solution prepared by dissolving 3.6 g of lactic acid in 30.0 g of water was added to 200.0 g of a silica sol containing 30% by mass of SiO 2 , and the temperature was maintained at 40 ° C. 71.2 g of ammonium paramolybdate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed in another container and dissolved in 107.0 g of warm water at 60 ° C. After cooling to 45 ° C., 5.3 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 6.5 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O], 12.6 g of cerium nitrate [Ce (NO 3 ) 3.6H 2 O], 22.2 g of iron nitrate in another container. [Fe (NO 3 ) 3.9H 2 O], 34.5 g of nickel nitrate [Ni (NO 3 ) 2.6H 2 O], 43.0 g of cobalt nitrate [Co ( NO 3 ) 2.6H 2 O] , And 0.75 g of rubidium nitrate [RbNO 3 ] was dissolved in 16.6 mass% of nitric acid (54.5 g) and kept at 40 ° C. to prepare an aqueous nitrate solution. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the nitrate aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was held at 40 ° C., stirred for 10 minutes, and then heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 809 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. Pre-baking was performed by holding the dried particles in an air atmosphere at 200 ° C. for 5 minutes, raising the temperature from 200 ° C. to 450 ° C. at 2.5 ° C./min, and holding at 450 ° C. for 20 minutes. Then, it was calcined at 590 ° C. for 2 hours to obtain a catalyst for ammoxidation. The P / Q was calculated to be 0.11 by the X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［実施例４］
金属成分の組成がＭｏ12.00Ｂｉ0.16Ｃｅ0.89Ｆｅ3.66Ｎｉ2.56Ｃｏ3.19Ｒｂ0.16で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇを４０℃に保持した。別の容器に７２．５ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０９．５ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．４ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に１３．１ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、５０．６ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、２５．５ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、３１．８ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．８０ｇの硝酸ルビジウム［ＲｂＮＯ3］を水６０．１ｇに溶解後に、２．７ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］と乳酸１．５ｇとを３０ｇの水に溶解させた溶液と混合し、４０℃に保持し、金属塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記金属塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、ヒドラジン１水和物２６．０ｇを添加し、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は７７ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子は真空下、９０℃で１５時間保持した。さらに、真空処理後の乾燥粒子を窒素雰囲気下で３０℃から６３５℃まで９時間かけて昇温し、６３５℃で３時間３０分間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．０１と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Example 4]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.16 Ce 0.89 Fe 3.66 Ni 2.56 Co 3.19 Rb 0.16 is supported on silica is described below. Manufactured by the procedure.
First, 200.0 g of a silica sol containing 30% by mass of SiO 2 was maintained at 40 ° C. 72.5 g of ammonium paramolybate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed in another container and dissolved in 109.5 g of warm water at 60 ° C. After cooling to 45 ° C., 5.4 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 13.1 g of cerium nitrate [Ce (NO 3 ) 3.6H 2 O], 50.6 g of iron nitrate [Fe (NO 3) 3.9H 2 O ] , and 25.5 g of nickel nitrate in another container. [Ni (NO 3 ) 2.6H 2 O], 31.8 g cobalt nitrate [Co (NO 3) 2.6 H 2 O], and 0.80 g rubidium nitrate [RbNO 3 ] are dissolved in 60.1 g of water. Later, 2.7 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O] and 1.5 g of lactic acid were mixed with a solution of 30 g of water and kept at 40 ° C. to prepare an aqueous metal salt solution. .. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the metal salt aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was kept at 40 ° C., stirred for 10 minutes, 26.0 g of hydrazine monohydrate was added, and the slurry was heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 77 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. The dried particles were kept under vacuum at 90 ° C. for 15 hours. Further, the dried particles after the vacuum treatment were heated in a nitrogen atmosphere from 30 ° C. to 635 ° C. over 9 hours and calcined at 635 ° C. for 3 hours and 30 minutes to obtain an ammoxidation catalyst. The P / Q was calculated to be 0.01 by X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
［比較例５］
金属成分の組成がＭｏ12.00Ｂｉ0.16Ｃｅ0.89Ｆｅ3.66Ｎｉ2.56Ｃｏ3.19Ｒｂ0.16で表される金属酸化物をシリカに担持した触媒（金属酸化物：６０質量％、シリカ：４０質量％）を以下の手順で製造した。
まず、３０質量％のＳｉＯ2を含有するシリカゾル２００．０ｇに乳酸１．５ｇを３０．０ｇの水に溶解させた水溶液を添加し、４０℃に保持した。別の容器に７２．５ｇのパラモリブデン酸アンモニウム［（ＮＨ4）6Ｍｏ7Ｏ24・４Ｈ2Ｏ］を入れ、１０９．５ｇの６０℃の温水に溶解させた。４５℃に冷却した後に、５．４ｇの１５質量％のアンモニア水溶液を添加し、モリブデン水溶液とした。さらに、別の容器に２．７ｇの硝酸ビスマス［Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ］、１３．１ｇの硝酸セリウム［Ｃｅ（ＮＯ3）3・６Ｈ2Ｏ］、５０．６ｇの硝酸鉄［Ｆｅ（ＮＯ3）3・９Ｈ2Ｏ］、２５．５ｇの硝酸ニッケル［Ｎｉ（ＮＯ3）2・６Ｈ2Ｏ］、３１．８ｇの硝酸コバルト［Ｃｏ（ＮＯ3）2・６Ｈ2Ｏ］、及び０．８０ｇの硝酸ルビジウム［ＲｂＮＯ3］を、１６．６質量％の硝酸６０．１ｇに溶解後、４０℃に保持し、硝酸塩水溶液とした。上記シリカゾルに対し、４０℃に保持し、撹拌しながら、上記モリブデン水溶液を添加してシリカ・モリブデン水溶液を得た。５分間撹拌後、引き続き４０℃に保持し、撹拌しながら上記シリカ・モリブデン水溶液に上記硝酸塩水溶液を添加し、スラリーを調製した。スラリーを４０℃に保持し、１０分間攪拌後、スラリーを６０℃に加熱した。その後、６０℃で９０分間撹拌することにより、前駆体スラリーを調製した。得られた前駆体スラリーの酸化還元電位は８８６ｍＶ／ＡｇＣｌであった。得られた前駆体スラリーは回転円盤式の噴霧乾燥器を用いて乾燥させて乾燥粒子を得た。このとき、乾燥器入口の空気温度は２７０℃とし、出口の空気温度は１５５℃とした。また、円盤の回転数は９０００ｒｐｍに設定した。乾燥粒子を空気雰囲気下で２００℃５分間保持し、２００℃から４５０℃まで２．５℃／分で昇温し、４５０℃で２０分保持することで前焼成を施した。その後、５７０℃で２時間焼成して、アンモ酸化用触媒を得た。得られたアンモ酸化用触媒のＸ線回折分析によりＰ／Ｑは０．２６と算出された。また、得られたアンモ酸化用触媒を流動反応槽に予め供給し、前記触媒を流動反応槽内で循環させながら、プロピレンと、分子状酸素と、アンモニアと、を反応（アンモ酸化反応）させることにより、アクリロニトリルを製造し、アンモニア／プロピレンのモル比（Ｎ／Ｃ）、空気／プロピレンのモル比（Ａ／Ｃ）、アクリロニトリル収率を求めた。その結果を表１に示す。
[Comparative Example 5]
A catalyst (metal oxide: 60% by mass, silica: 40% by mass) in which a metal oxide having a metal component composition represented by Mo 12.00 Bi 0.16 Ce 0.89 Fe 3.66 Ni 2.56 Co 3.19 Rb 0.16 is supported on silica is described below. Manufactured by the procedure.
First, an aqueous solution prepared by dissolving 1.5 g of lactic acid in 30.0 g of water was added to 200.0 g of a silica sol containing 30% by mass of SiO 2 , and the temperature was maintained at 40 ° C. 72.5 g of ammonium paramolybate [(NH 4 ) 6 Mo 7 O 24.4H 2 O] was placed in another container and dissolved in 109.5 g of warm water at 60 ° C. After cooling to 45 ° C., 5.4 g of a 15% by mass aqueous ammonia solution was added to prepare a molybdenum aqueous solution. In addition, 2.7 g of bismuth nitrate [Bi (NO 3 ) 3.5H 2 O], 13.1 g of cerium nitrate [Ce (NO 3 ) 3.6H 2 O], and 50.6 g of iron nitrate in another container. [Fe (NO 3 ) 3.9H 2 O], 25.5 g of nickel nitrate [Ni (NO 3 ) 2.6H 2 O], 31.8 g of cobalt nitrate [Co ( NO 3 ) 2.6H 2 O] , And 0.80 g of rubidium nitrate [RbNO 3 ] was dissolved in 16.6 mass% of nitric acid (60.1 g) and kept at 40 ° C. to prepare an aqueous nitrate solution. The silica sol was kept at 40 ° C. and the molybdenum aqueous solution was added while stirring to obtain a silica-molybdenum aqueous solution. After stirring for 5 minutes, the temperature was continuously maintained at 40 ° C., and the nitrate aqueous solution was added to the silica / molybdenum aqueous solution while stirring to prepare a slurry. The slurry was held at 40 ° C., stirred for 10 minutes, and then heated to 60 ° C. Then, the precursor slurry was prepared by stirring at 60 ° C. for 90 minutes. The redox potential of the obtained precursor slurry was 886 mV / AgCl. The obtained precursor slurry was dried using a rotary disk type spray dryer to obtain dried particles. At this time, the air temperature at the inlet of the dryer was 270 ° C, and the air temperature at the outlet was 155 ° C. The rotation speed of the disk was set to 9000 rpm. Pre-baking was performed by holding the dried particles in an air atmosphere at 200 ° C. for 5 minutes, raising the temperature from 200 ° C. to 450 ° C. at 2.5 ° C./min, and holding at 450 ° C. for 20 minutes. Then, it was calcined at 570 ° C. for 2 hours to obtain a catalyst for ammoxidation. The P / Q was calculated to be 0.26 by X-ray diffraction analysis of the obtained catalyst for ammoxidation. Further, the obtained catalyst for ammoxidation is supplied to the flow reaction tank in advance, and propylene, molecular oxygen, and ammonia are reacted (ammooxidation reaction) while circulating the catalyst in the flow reaction tank. Acrylonitrile was produced, and the molar ratio of ammonia / propylene (N / C), the molar ratio of air / propylene (A / C), and the yield of acrylonitrile were determined. The results are shown in Table 1.
表１から明らかなように、実施例１と比較例１及び２、実施例２と比較例３、実施例３と比較例４、実施例４と比較例５で得られたアンモ酸化用触媒は同じ金属組成であるにもかかわらず、前駆体スラリー調製段階の還元剤の使用の有無及び還元剤の特性により前駆体スラリーの酸化還元電位が異なるため、いずれの場合も実施例１～４で得られたアンモ酸化用触媒の方が高収率でアクリロニトリルを合成することが出来た。 As is clear from Table 1, the ammoxidation catalysts obtained in Example 1 and Comparative Examples 1 and 2, Example 2 and Comparative Example 3, Example 3 and Comparative Example 4, and Example 4 and Comparative Example 5 are Although the metal composition is the same, the redox potential of the precursor slurry differs depending on the presence or absence of the reducing agent in the precursor slurry preparation stage and the characteristics of the reducing agent. The ammoxidation catalyst obtained was able to synthesize acrylonitrile in a higher yield.
Claims (8)
Ｘ線回折分析において、２θ＝２２．９±０．２°のピーク強度をＰ、２θ＝２６．４±０．３°のピーク強度をＱとした場合、Ｐ／Ｑが０．０３以下であり、
下記一般式（１）で表される組成を有する、アンモ酸化用触媒。
Ｍｏ 12 Ｂｉ a Ｆｅ b Ｘ c Ｙ d Ｚ e Ｏ f （１）
（式（１）中、Ｘはニッケル、コバルト、マグネシウム、カルシウム、亜鉛、ストロンチウム、バリウムから選ばれる１種類以上の元素、Ｙはセリウム、クロム、ランタン、ネオジム、イットリウム、プラセオジウム、サマリウム、アルミニウム、ガリウム、及びインジウムから選ばれる１種以上の元素、Ｚはカリウム、ルビジウム及びセシウムから選ばれる１種以上の元素を示す。ａはモリブデン１２原子に対するビスマスの原子比を示し、０．１≦ａ≦２．０であり、ｂはモリブデン１２原子に対する鉄の原子比を示し、１．０≦ｂ≦５．０であり、ｃはモリブデン１２原子に対するＸの原子比を示し、０．１≦ｃ≦１０．０であり、ｄはモリブデン１２原子に対するＹの原子比を示し、０．１≦ｄ≦３．０であり、ｅはモリブデン１２原子に対するＺの原子比を示し、０．０１≦ｅ≦２．０であり、ｆはモリブデン１２原子に対する酸素の原子比を示し、存在する他の元素の原子価要求を満足させるのに必要な酸素の原子数である。） An ammoxidation catalyst containing molybdenum, bismuth, and iron.
In X-ray diffraction analysis, when the peak intensity of 2θ = 22.9 ± 0.2 ° is P and the peak intensity of 2θ = 26.4 ± 0.3 ° is Q, the P / Q is 0.03 or less. Yes,
An ammoxidation catalyst having a composition represented by the following general formula (1) .
Mo 12 Bia Fe b X c Y d Z e Of ( 1 )
(In formula (1), X is one or more elements selected from nickel, cobalt, magnesium, calcium, zinc, strontium, and barium, and Y is cerium, chromium, lantern, neodymium, ittrium, placeodium, samarium, aluminum, and gallium. , And one or more elements selected from indium, Z indicates one or more elements selected from potassium, rubidium and cesium. A indicates the atomic ratio of bismuth to 12 atoms of molybdenum, 0.1 ≦ a ≦ 2. .0, b indicates the atomic ratio of iron to 12 molybdenum atoms, 1.0 ≦ b ≦ 5.0, c indicates the atomic ratio of X to 12 molybdenum atoms, 0.1 ≦ c ≦ 10. .0, d indicates the atomic ratio of Y to 12 molybdenum atoms, 0.1 ≦ d ≦ 3.0, e indicates the atomic ratio of Z to 12 molybdenum atoms, 0.01 ≦ e ≦ 2. It is .0, where f indicates the atomic ratio of oxygen to 12 atoms of molybdenum, which is the number of oxygen atoms required to satisfy the valence requirements of other existing elements.)
前記前駆体スラリーを乾燥して乾燥粒子を得る乾燥工程と、
前記乾燥粒子を焼成してアンモ酸化用触媒を得る焼成工程と、
を有し、
前記前駆体スラリーの酸化還元電位が３００ｍＶ／ＡｇＣｌ以下、－３００ｍＶ／ＡｇＣｌ以上である、
請求項１に記載のアンモ酸化用触媒の製造方法。 A preparation step for preparing a precursor slurry containing molybdenum, bismuth, and iron as catalyst precursors, and
A drying step of drying the precursor slurry to obtain dried particles, and
A firing step of calcining the dry particles to obtain a catalyst for ammoxidation, and
Have,
The redox potential of the precursor slurry is 300 mV / AgCl or less and −300 mV / AgCl or more.
The method for producing an ammoxidation catalyst according to claim 1.
請求項２に記載のアンモ酸化用触媒の製造方法。 In the preparation step for preparing the precursor slurry, a reducing agent having a standard electrode potential of 0.77 V / SHE or less in the aqueous solution is added.
The method for producing an ammoxidation catalyst according to claim 2.
プロピレンに対するアンモニア及び空気のモル比が、プロピレン／アンモニア／空気の比で１／（０．８～１．６）／（７～１２）の範囲である、請求項５又は６に記載のアクリロニトリルの製造方法。 The molecular oxygen source is air,
The acrylonitrile according to claim 5 or 6, wherein the molar ratio of ammonia and air to propylene is in the range of 1 / (0.8 to 1.6) / (7 to 12) in the ratio of propylene / ammonia / air. Production method.
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| JP2013522036A (en) | 2010-03-23 | 2013-06-13 | イネオス ユーエスエイ リミテッド ライアビリティ カンパニー | Wear resistant mixed metal oxide ammoxidation catalyst |
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