JP4925956B2 - Method for producing catalyst for producing alkenyl acetate - Google Patents
Method for producing catalyst for producing alkenyl acetate Download PDFInfo
- Publication number
- JP4925956B2 JP4925956B2 JP2007193730A JP2007193730A JP4925956B2 JP 4925956 B2 JP4925956 B2 JP 4925956B2 JP 2007193730 A JP2007193730 A JP 2007193730A JP 2007193730 A JP2007193730 A JP 2007193730A JP 4925956 B2 JP4925956 B2 JP 4925956B2
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- solution
- catalyst
- palladium
- acetate
- 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 103
- -1 alkenyl acetate Chemical compound 0.000 title claims description 40
- 238000004519 manufacturing process Methods 0.000 title claims description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 163
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 111
- 239000000243 solution Substances 0.000 claims description 104
- 229910052763 palladium Inorganic materials 0.000 claims description 79
- 238000010521 absorption reaction Methods 0.000 claims description 67
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 64
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 58
- 239000010931 gold Substances 0.000 claims description 57
- 229910052737 gold Inorganic materials 0.000 claims description 56
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 53
- 239000012670 alkaline solution Substances 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 44
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 33
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 29
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 17
- 229910052788 barium Inorganic materials 0.000 claims description 15
- 230000009467 reduction Effects 0.000 claims description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 14
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 58
- 239000007864 aqueous solution Substances 0.000 description 54
- 239000000203 mixture Substances 0.000 description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 27
- 239000007789 gas Substances 0.000 description 25
- 238000002360 preparation method Methods 0.000 description 23
- 239000011734 sodium Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 235000011056 potassium acetate Nutrition 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 101150003085 Pdcl gene Proteins 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910004806 Na2 SiO3.9H2 O Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 229960003975 potassium Drugs 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000010306 acid treatment Methods 0.000 description 5
- 150000001553 barium compounds Chemical class 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910004373 HOAc Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion 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
- 238000010813 internal standard method Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 239000001508 potassium citrate Substances 0.000 description 2
- 229960002635 potassium citrate Drugs 0.000 description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 2
- 235000011082 potassium citrates Nutrition 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
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- 238000005245 sintering Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical group C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
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- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
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- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- PQTLYDQECILMMB-UHFFFAOYSA-L platinum(2+);sulfate Chemical compound [Pt+2].[O-]S([O-])(=O)=O PQTLYDQECILMMB-UHFFFAOYSA-L 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、酢酸、低級オレフィンおよび酸素を原料として酢酸アルケニルを合成する際に使用する酢酸アルケニル製造用触媒の製造方法およびその触媒を用いた酢酸アルケニルの製造方法に関する。 The present invention relates to a method for producing a catalyst for producing alkenyl acetate which is used when synthesizing alkenyl acetate using acetic acid, a lower olefin and oxygen as raw materials, and a method for producing alkenyl acetate using the catalyst.
酢酸ビニルは、酢酸ビニル樹脂の原料、ポリビニルアルコールの原料、さらにエチレン、スチレン、アクリレート、メタクリレート等との共重合用モノマーとして、塗料、接着剤、繊維処理剤等の広い分野に用いられている重要な工業材料である。 Vinyl acetate is used as a raw material for vinyl acetate resin, a raw material for polyvinyl alcohol, and a monomer for copolymerization with ethylene, styrene, acrylate, methacrylate, etc. Industrial material.
酢酸、低級オレフィンおよび酸素を原料とする酢酸アルケニル、特に酢酸ビニルの製造触媒として、Ｐｄ／Ａｕ／ＫＯＡｃ／ＳｉＯ２が広く用いられている。この反応における活性点はパラジウムと考えられ、助触媒の金はパラジウムのシンタリングを抑制したり、炭酸ガス生成反応を低減させ、酢酸アルケニル（例えば、酢酸ビニル）の選択率を向上させる役割があるとされる。また、かかる金の効果が発揮されるためには、パラジウムとの原子レベルでの混合が必要であるとの報告もある。 Pd / Au / KOAc / SiO 2 is widely used as a catalyst for producing alkenyl acetate, particularly vinyl acetate, using acetic acid, lower olefins and oxygen as raw materials. The active site in this reaction is considered to be palladium, and the promoter gold plays a role in suppressing palladium sintering, reducing the carbon dioxide generation reaction, and improving the selectivity of alkenyl acetate (for example, vinyl acetate). It is said. In addition, there is a report that mixing at the atomic level with palladium is necessary in order to exert such gold effects.
酢酸ビニルの製造において、酢酸ビニルの選択率を上げることは非常に重要な技術課題であり、また環境負荷の観点からも炭酸ガスの発生抑制が望まれている。さらに、酢酸ビニルを工業的に製造する場合には、触媒の長寿命化は経済的な観点からも大きな課題であり、パラジウムのシンタリングを抑制する金の働きを高めることは重要と考えられる。 In the production of vinyl acetate, increasing the selectivity of vinyl acetate is a very important technical issue, and suppression of carbon dioxide generation is also desired from the viewpoint of environmental impact. Further, when vinyl acetate is produced industrially, extending the life of the catalyst is a major issue from an economical viewpoint, and it is considered important to enhance the function of gold that suppresses palladium sintering.
また、酢酸ビニル製造用の触媒はパラジウムや金を担体の表面にのみ担持したいわゆるシェル型が反応性に優れると考えられている。シェル型触媒の調製法は特表２００４-５２６５５３号公報などに開示されている。ここでは、担体に原料金属塩溶液を含浸させた後、固定剤としてアルカリ溶液と接触させることでシェル型触媒を形成している。しかし、この方法ではシェル内でのパラジウムと金の担持位置がずれた触媒が形成され、また特に金の担持率が低いことが難点である。 Further, it is considered that a so-called shell type catalyst in which palladium or gold is supported only on the surface of a carrier is excellent in reactivity for producing vinyl acetate. A method for preparing a shell-type catalyst is disclosed in JP-T-2004-526553. Here, a shell-type catalyst is formed by impregnating a carrier with a raw metal salt solution and then contacting with an alkaline solution as a fixing agent. However, in this method, a catalyst in which the palladium and gold loading positions in the shell are shifted is formed, and in particular, the gold loading ratio is low.
また、イギリス特許第１２８３７３７号明細書や特開平８−３１８１５９号公報では、担体にアルカリ溶液を含浸した後に原料金属塩溶液を接触させることで、シェル型触媒を形成している。例えば、イギリス特許第１２８３７３７号明細書の実施例では、担体にアルカリ溶液を含浸した後に、担体から溶液を加熱除去する工程が用いられている。一方、特開平８−３１８１５９号公報では、アルカリ溶液と原料金属塩溶液の総量が、用いる担体の吸水量相当であることが必要とされている。これらの方法では、工程が煩雑であり、調製操作が難しく、パラジウムや金の担持斑ができやすいという欠点があった。 In British Patent No. 1283737 and JP-A-8-318159, a shell-type catalyst is formed by contacting a carrier with a raw metal salt solution after impregnating the carrier with an alkaline solution. For example, in the example of British Patent No. 1283737, a step of heating and removing the solution from the carrier after impregnating the carrier with an alkaline solution is used. On the other hand, Japanese Patent Application Laid-Open No. 8-318159 requires that the total amount of the alkali solution and the starting metal salt solution is equivalent to the water absorption amount of the carrier used. These methods have the disadvantages that the steps are complicated, the preparation operation is difficult, and palladium or gold carrying spots are easily formed.
さらに、特開平１０−１７５９１７号公報には、原料金属塩溶液を担体に含浸した後に遠心分離器で処理することで、シェル型に金属を担持する方法が開示されているが、この方法は操作が煩雑なため、改良が必要であった。 Furthermore, Japanese Patent Application Laid-Open No. 10-175717 discloses a method of supporting a metal in a shell mold by impregnating a carrier with a raw metal salt solution and then treating with a centrifuge. However, improvement was necessary.
本発明は、活性および選択性が向上した酢酸アルケニル製造用触媒を提供することを目的とする。 An object of the present invention is to provide a catalyst for producing alkenyl acetate having improved activity and selectivity.
本発明者らは上記課題を解決するために鋭意研究を重ねた。その結果、簡便にパラジウムと金を近接担持しうる触媒の調製法を見出した。すなわち、本発明は以下の［１］〜［８］に関する。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, a method for preparing a catalyst capable of easily supporting palladium and gold in proximity was found. That is, the present invention relates to the following [1] to [8].
［１］ 少なくとも以下の工程
１．担体にアルカリ溶液を含浸させる工程、
２．担体に少なくとも、パラジウムまたは白金を含む化合物および第１１族元素を含む化合物の溶液Ａを接触含浸させる工程、
３．還元処理を行う工程および
４．担体に酢酸塩を担持する工程
を含む酢酸アルケニル製造用触媒の製造方法であって、第１の工程において担体に担体の吸水量の０．９質量倍を超え、１．０質量倍以下のアルカリ溶液を含浸させた後、続けて第２の工程で溶液Ａと接触させて触媒前駆体とし、かつ、アルカリ溶液および溶液Ａの総量を担体の吸水量の１．１質量倍以上１０．０質量倍以下とすることを特徴とする、少なくとも（ａ）担体、（ｂ）パラジウムまたは白金、（ｃ）第１１族元素および（ｄ）酢酸塩からなる酢酸アルケニル製造用触媒の製造方法。
[1] At least the following steps 1. Impregnating a carrier with an alkaline solution,
2. A step of impregnating a support with a solution A of a compound containing at least palladium or platinum and a compound containing a Group 11 element;
3. 3. performing a reduction treatment; A method for producing a catalyst for producing alkenyl acetate comprising a step of supporting an acetate on a carrier, wherein the alkali in the first step exceeds 0.9 mass times the amount of water absorption of the carrier and is 1.0 mass times or less. After the impregnation with the solution, the catalyst precursor is subsequently brought into contact with the solution A in the second step, and the total amount of the alkaline solution and the solution A is 1.1 mass times or more and 10.0 masses of the water absorption amount of the carrier. A method for producing a catalyst for alkenyl acetate production comprising at least (a) a support, (b) palladium or platinum, (c) a Group 11 element, and (d) an acetate salt.
［２］ 溶液Ａがさらに（ｅ）アルカリ土類金属元素を含む化合物を溶解していることを特徴とする、少なくとも（ａ）担体、（ｂ）パラジウムまたは白金、（ｃ）第１１族元素、（ｄ）酢酸塩および（ｅ）アルカリ土類金属元素からなる上記［１］に記載の酢酸アルケニル製造用触媒の製造方法。 [2] The solution A further includes (e) a compound containing an alkaline earth metal element, at least (a) a support, (b) palladium or platinum, (c) a Group 11 element, The method for producing a catalyst for alkenyl acetate production according to the above [1], comprising (d) acetate and (e) an alkaline earth metal element.
［３］ （ｂ）パラジウムまたは白金がパラジウムである、上記［１］または［２］に記載の酢酸アルケニル製造用触媒の製造方法。 [3] (b) The method for producing a catalyst for producing alkenyl acetate according to the above [1] or [2], wherein the palladium or platinum is palladium.
［４］ （ｃ）第１１族元素が金または銅である、上記［１］〜［３］のいずれかに記載の酢酸アルケニル製造用触媒の製造方法。 [4] (c) The method for producing a catalyst for alkenyl acetate production according to any one of the above [1] to [3], wherein the Group 11 element is gold or copper.
［５］ （ｅ）アルカリ土類金属元素がバリウム、ストロンチウム、マグネシウム、カルシウムのすくなくとも１種である、上記［１］〜［４］のいずれかに記載の酢酸アルケニル製造用触媒の製造方法。 [5] (e) The method for producing a catalyst for alkenyl acetate production according to any one of the above [1] to [4], wherein the alkaline earth metal element is at least one of barium, strontium, magnesium and calcium.
［６］ 上記［１］〜［５］のいずれかに記載の方法で製造された触媒を用いることを特徴とする、低級オレフィン、酸素および酢酸を原料とする酢酸アルケニルの製造方法。 [6] A method for producing alkenyl acetate using a lower olefin, oxygen and acetic acid as raw materials, wherein the catalyst produced by the method according to any one of [1] to [5] is used.
［７］ 上記［１］〜［５］のいずれかに記載の方法で製造された触媒を用いることを特徴とする、エチレン、酸素および酢酸を原料とする酢酸ビニルの製造方法。 [7] A method for producing vinyl acetate using ethylene, oxygen and acetic acid as raw materials, wherein the catalyst produced by the method according to any one of [1] to [5] is used.
［８］ 上記［１］〜［５］のいずれかに記載の方法で製造された触媒を用いることを特徴とする、プロピレン、酸素および酢酸を原料とする酢酸アリルの製造方法。 [8] A method for producing allyl acetate using propylene, oxygen and acetic acid as raw materials, wherein the catalyst produced by the method according to any one of [1] to [5] is used.
本発明の方法によれば、簡便にパラジウムと金をシェル型担持した触媒を製造することができ、かつ、従来の方法と比較して、得られる触媒の初期活性、選択性を向上させることができる。 According to the method of the present invention, a catalyst in which palladium and gold are supported on a shell type can be easily produced, and the initial activity and selectivity of the resulting catalyst can be improved as compared with the conventional method. it can.
以下に本発明の好ましい実施の形態について説明するが、本発明はこれらの形態のみに限定されるものではなく、本発明の精神とその実施の範囲内において様々な変形が可能であることを理解されたい。 Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to these embodiments, and it is understood that various modifications can be made within the spirit and scope of the present invention. I want to be.
［触媒の製造工程］
本発明の酢酸アルケニル製造用触媒は以下に示す工程を含む方法によって製造できる。
１．担体に担体の吸水量の０．９質量倍を超え、１．０質量倍以下のアルカリ溶液を含浸させる工程
２．担体にパラジウムまたは白金を含む化合物、第１１族元素を含む化合物および、必要に応じて、アルカリ土類金属元素を含む化合物の溶液Ａを接触含浸させる工程
３．還元処理を行う工程および
４．担体に酢酸塩を担持する工程
[Catalyst production process]
The catalyst for producing alkenyl acetate of the present invention can be produced by a method including the following steps.
1. 1. impregnating a carrier with an alkali solution that exceeds 0.9 mass times and less than 1.0 mass times the water absorption amount of the carrier 2. Step of impregnating a solution A of a compound containing palladium or platinum, a compound containing a Group 11 element, and, if necessary, a compound containing an alkaline earth metal element on a support; 3. performing a reduction treatment; A process of supporting acetate on a carrier
本発明では１の工程の後、乾燥などの処理をすることなく、続けて２の工程を行うことが重要である。そして、パラジウムまたは白金を含む化合物、第１１族元素を含む化合物および、所望により、アルカリ土類金属元素を含む化合物を溶かした溶液Ａを担体に接触含浸させて、各化合物が担体に担持されている触媒前駆体とし、かつ、アルカリ溶液と溶液Ａの総量を担体の吸水量の１．１質量倍以上１０．０質量倍以下とする。 In the present invention, it is important to perform the second step after the first step without performing a treatment such as drying. Then, the support is impregnated with a solution A in which a compound containing palladium or platinum, a compound containing a Group 11 element, and, if desired, a compound containing an alkaline earth metal element is dissolved, and each compound is supported on the support. The total amount of the alkaline solution and the solution A is 1.1 mass times or more and 10.0 mass times or less of the water absorption amount of the carrier.
各工程は上記の順序で行うことが好ましいが、４の酢酸塩を担持する工程は最後でなくともよい。２の工程で担体にアルカリ土類金属元素を担持しない場合は、溶液Ａにはアルカリ土類金属元素を含む化合物は含まれない。溶液Ａには他の成分が含まれていてもよい。また、本発明の触媒の性能を向上させる目的で他の工程が含まれていてもよい。３の工程の還元処理はパラジウムまたは白金を含む化合物を金属パラジウム、金属白金とするためであるので、２の工程よりも後でなくてはならない。以下、各工程を詳細に説明する。 The steps are preferably performed in the above order, but the step of supporting 4 acetates may not be the last. When no alkaline earth metal element is supported on the support in step 2, the solution A does not contain a compound containing an alkaline earth metal element. The solution A may contain other components. In addition, other steps may be included for the purpose of improving the performance of the catalyst of the present invention. The reduction treatment in the third step is to convert the compound containing palladium or platinum into metallic palladium or metallic platinum, and therefore must be performed after the second step. Hereinafter, each process will be described in detail.
１．担体にアルカリ溶液を含浸させる工程
この工程では担体の吸水量の０．９質量倍を超え、１．０質量倍以下の量のアルカリ溶液を担体に含浸させる。操作は常温で行うことができる。アルカリ溶液が担体に均一に含浸されるようにする。含浸操作が完了したら、乾燥などの操作をせず、次の工程に進む。
1. Step of impregnating carrier with alkaline solution In this step, the carrier is impregnated with an alkaline solution in an amount exceeding 0.9 mass times the amount of water absorption of the carrier and 1.0 mass times or less. The operation can be performed at room temperature. The alkaline solution is uniformly impregnated on the support. When the impregnation operation is completed, the operation proceeds to the next step without performing an operation such as drying.
＜（ａ）担体＞
本発明で用いる担体に特に制限はない。一般に触媒用の担体として用いられている多孔質物質であればよい。好ましくはシリカ、アルミナ、シリカ−アルミナ、珪藻土、モンモリロナイトまたはチタニア等が挙げられ、より好ましくはシリカである。担体としてシリカを主成分とするものを用いる場合には、担体のシリカ含量は、担体の重量に対して通常少なくとも５０質量％、好適には少なくとも９０質量％である。
<(A) Carrier>
There is no restriction | limiting in particular in the support | carrier used by this invention. Any porous material generally used as a carrier for a catalyst may be used. Silica, alumina, silica-alumina, diatomaceous earth, montmorillonite, titania and the like are preferable, and silica is more preferable. When a carrier containing silica as a main component is used as a carrier, the silica content of the carrier is usually at least 50% by weight, preferably at least 90% by weight, based on the weight of the carrier.
担体はＢ．Ｅ．Ｔ．法で測定した比表面積が少なくとも０．０１ｍ２／ｇ、特に１０〜１０００ｍ２／ｇの範囲、とりわけ１００〜５００ｍ２／ｇの範囲であることが好ましい。また、吸水率は０．０５〜３ｇ／ｇ、特に０．１〜２ｇ／ｇであることが好ましい。 The carrier is B.I. E. T.A. Law in the measured specific surface area of at least 0.01 m 2 / g, especially 10 to 1000 m 2 / g range, especially is preferably in the range of 100 to 500 m 2 / g. Moreover, it is preferable that a water absorption is 0.05-3 g / g, especially 0.1-2 g / g.
ここで、担体の吸水率は、以下の測定方法で測定した数値をいう。
１．担体約５ｇを天秤で計量（Ｗ１ｇ）し、１００ｃｃのビーカーに入れる。
２．担体を完全に覆うように純水（イオン交換水）約１５ｍｌをビーカーに加える。
３．３０分間放置する。
４．金網上に担体と純水を空けて、純水をきる。
５．担体の表面に付着した水を、表面の光沢がなくなるまで紙タオルで軽く押して、除去する。
６．担体＋純水の重さを測定する（Ｗ２ｇ）。
７．以下の式から担体の吸水率を算出する。
Here, the water absorption rate of the carrier is a numerical value measured by the following measuring method.
1. About 5 g of the carrier is weighed with a balance (W1 g) and placed in a 100 cc beaker.
2. About 15 ml of pure water (ion exchange water) is added to the beaker so as to completely cover the carrier.
3. Leave for 30 minutes.
4). Empty the carrier and pure water on the wire mesh and drain the pure water.
5. The water adhering to the surface of the carrier is removed by gently pressing with a paper towel until the surface is no longer glossy.
6). The weight of carrier + pure water is measured (W2 g).
7). The water absorption rate of the carrier is calculated from the following formula.
吸水率（ｇ／ｇ−担体）＝（Ｗ２−Ｗ１）／Ｗ１
したがって、担体の吸水量（ｇ）は担体の吸水率（ｇ／ｇ）×使用した担体の重量（ｇ）により計算される。
Water absorption rate (g / g-carrier) = (W2-W1) / W1
Therefore, the water absorption amount (g) of the carrier is calculated by the water absorption rate of the carrier (g / g) × the weight (g) of the carrier used.
担体の形状には特に制限はない。具体的には、粉末状、球状、ペレット状等が挙げられるが、これらに限定されるものではない。 There is no restriction | limiting in particular in the shape of a support | carrier. Specific examples include powders, spheres, and pellets, but are not limited thereto.
用いられる担体の粒子直径に特に制限はない。好ましくは、１〜１０ｍｍの範囲であるのが好ましく、より好ましくは３〜８ｍｍである。管状反応器に触媒を充填して反応を行う場合、粒子直径が１ｍｍより小さいと、ガスを流通させるときに大きな圧力損失が生じ、有効にガス循環ができなくなる恐れがある。また、粒子直径が１０ｍｍより大きいと、管状反応器内へ充填される担持触媒の数が減少し、結果としてトータルの触媒表面積が小さくなり、担体の表面に偏在している触媒成分（Ｐｄ、Ａｕなど）が少なくなるため好ましくない。担体の細孔構造は、その細孔直径が１〜１０００ｎｍにあることが好ましく、２〜８００ｎｍの間がより好ましい。 There is no restriction | limiting in particular in the particle diameter of the support | carrier used. Preferably, it is in the range of 1 to 10 mm, more preferably 3 to 8 mm. When the reaction is carried out by filling the tubular reactor with a catalyst, if the particle diameter is smaller than 1 mm, a large pressure loss occurs when the gas is circulated, and there is a possibility that the gas cannot be effectively circulated. On the other hand, if the particle diameter is larger than 10 mm, the number of supported catalysts charged into the tubular reactor is reduced, resulting in a reduction in the total catalyst surface area, and catalyst components (Pd, Au) unevenly distributed on the surface of the support. Etc.) is not preferable. The pore structure of the carrier preferably has a pore diameter of 1 to 1000 nm, more preferably 2 to 800 nm.
＜アルカリ溶液＞
本発明に用いるアルカリ溶液は、いかなるアルカリ性の溶液であってもよい。例えば、アルカリ金属やアルカリ土類金属の水酸化物、アルカリ金属やアルカリ土類金属の重炭酸塩、アルカリ金属やアルカリ土類金属の炭酸塩、アルカリ金属やアルカリ土類金属のケイ酸塩といったアルカリ性化合物の溶液が挙げられる。アルカリ金属としては、リチウム、ナトリウムおよびカリウムが用いられる。アルカリ土類金属としては、バリウムやストロンチウムが用いられる。好適には、メタケイ酸ナトリウム、メタケイ酸カリウム、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、水酸化ストロンチウムが用いられる。
<Alkaline solution>
The alkaline solution used in the present invention may be any alkaline solution. For example, alkali metals such as alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal bicarbonates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal silicates A solution of the compound may be mentioned. As the alkali metal, lithium, sodium and potassium are used. Barium or strontium is used as the alkaline earth metal. Preferably, sodium metasilicate, potassium metasilicate, sodium hydroxide, potassium hydroxide, barium hydroxide, or strontium hydroxide is used.
アルカリ性化合物は、後述の（ｂ）パラジウムまたは白金や（ｃ）第１１族元素の合計に対して過剰に使用する。例えば、アルカリ性化合物は、（ｂ）パラジウムまたは白金１モル当たり好ましくは１〜３モル、より好ましくは１．２〜２．５モルの量で用いる。また、第１１族元素を含む化合物（以下においては、第１１族元素前駆物質ということがある）１モル当たり、好ましくは２〜１０モル、より好ましくは３〜８モルを使用する。
アルカリ溶液の溶媒は、水、メタノール、エタノールなどが挙げられる。好ましくは水である。
The alkaline compound is used in excess relative to the total of (b) palladium or platinum and (c) Group 11 elements described below. For example, the alkaline compound is used in an amount of (b) 1 to 3 mol, more preferably 1.2 to 2.5 mol, per mol of palladium or platinum. In addition, 2 to 10 moles, more preferably 3 to 8 moles are used per mole of a compound containing a Group 11 element (hereinafter sometimes referred to as a Group 11 element precursor).
Examples of the solvent for the alkaline solution include water, methanol, and ethanol. Preferably it is water.
アルカリ溶液を（ａ）担体に含浸させる方法は特に制限はないが、例えば、Ｉ）大量のアルカリ溶液に担体をしばらく浸漬した後、吸水量分のアルカリ溶液を含浸させた担体を取り出す方法や、ＩＩ）アルカリ性化合物を溶媒に溶解し、（ａ）担体の吸水量相当になるようにメスアップしたものを担体に含浸する方法などが挙げられる。廃液処理の観点からはＩＩ）の方法が望ましい。 The method for impregnating the alkaline solution into the carrier (a) is not particularly limited. For example, I) After the carrier is immersed in a large amount of alkaline solution for a while, the method of removing the carrier impregnated with the alkaline solution for the amount of water absorption, II) A method in which an alkaline compound is dissolved in a solvent, and (a) the carrier is impregnated with a solution that has been made up so as to correspond to the water absorption amount of the carrier. From the viewpoint of waste liquid treatment, the method II) is desirable.
アルカリ溶液は、（ａ）担体の吸水量の０．９質量倍を超え、１．０質量倍以下に相当する量で（ａ）担体に含浸されている必要がある。さらには、（ａ）担体の吸水量の０．９５質量倍以上、１．０質量倍以下であるのが好ましい。アルカリ溶液の量が担体の吸水量の０．９質量倍以下であると担持斑ができる恐れがあるので好ましくない。１．０質量倍を超えると、担体がアルカリ溶液をすべて吸収することができなくなる。なお、担体の吸水量は純水で測定した値であり、厳密にはアルカリ溶液（アルカリ水溶液）に対する値とは異なるが、便宜上そのまま使用する。 The alkaline solution needs to be impregnated in the carrier (a) in an amount corresponding to more than 0.9 times and less than 1.0 times the amount of water absorption of the carrier (a). Furthermore, (a) 0.95 mass times or more and 1.0 mass times or less of the water absorption amount of a support | carrier is preferable. If the amount of the alkaline solution is 0.9 mass times or less of the water absorption amount of the carrier, it is not preferable because there is a possibility that spotted spots are formed. When it exceeds 1.0 mass times, the carrier cannot absorb all the alkaline solution. The water absorption amount of the carrier is a value measured with pure water, and although strictly different from the value for an alkaline solution (alkaline aqueous solution), it is used as it is for convenience.
２．担体に溶液Ａを接触含浸させる工程
この工程では、アルカリ溶液を含浸させた担体に少なくともパラジウムまたは白金を含む化合物および第１１族元素を含む化合物を溶解した溶液Ａを接触含浸させる。アルカリ土類金属元素を担持する場合には、溶液Ａにアルカリ土類金属元素を含む化合物をも溶解させる。
2. Step of Contact Impregnating Support with Solution A In this step, the support impregnated with an alkaline solution is contact-impregnated with a solution A in which a compound containing at least palladium or platinum and a compound containing a Group 11 element are dissolved. In the case where an alkaline earth metal element is supported, a compound containing the alkaline earth metal element is also dissolved in the solution A.
＜（ｂ）パラジウムまたは白金＞
（ｂ）パラジウムまたは白金は主触媒成分であり、特に酢酸ビニル選択性が高いという点からパラジウムが好ましい。以下、パラジウムを例に説明するが、白金についても同様である。
<(B) Palladium or platinum>
(B) Palladium or platinum is the main catalyst component, and palladium is particularly preferred from the viewpoint of high vinyl acetate selectivity. Hereinafter, palladium will be described as an example, but the same applies to platinum.
本発明において、パラジウムはいずれの価数を持つものでも構わないが、好ましくは金属パラジウムである。「金属パラジウム」とは０価の価数を持つものである。金属パラジウムは、通常、２価および／または４価のパラジウムイオンを、還元剤であるヒドラジン、水素等を用いて還元することで得ることができる。この際、全てのパラジウムが、金属状態でなくても構わない。 In the present invention, palladium may have any valence, but is preferably metallic palladium. “Metallic palladium” has a valence of zero. Metallic palladium can be usually obtained by reducing divalent and / or tetravalent palladium ions using hydrazine, hydrogen or the like as a reducing agent. At this time, not all palladium may be in a metal state.
パラジウムの原料すなわちパラジウム元素を含む化合物には特に制限はない。金属パラジウムを用いることはもちろん、還元反応により金属パラジウムに転化可能なパラジウム塩を用いることも可能である。金属パラジウムに転化可能なパラジウム塩の例としては、塩化パラジウム、硝酸パラジウム、硫酸パラジウム、塩化パラジウム酸ナトリウム、塩化パラジウム酸カリウム、塩化パラジウム酸バリウム、酢酸パラジウムなどがあるがこれに限定されるものではない。特に好適には塩化パラジウム酸ナトリウムが用いられる。 There are no particular restrictions on the palladium raw material, that is, the compound containing palladium element. In addition to using metal palladium, it is also possible to use a palladium salt that can be converted to metal palladium by a reduction reaction. Examples of palladium salts that can be converted to metallic palladium include, but are not limited to, palladium chloride, palladium nitrate, palladium sulfate, sodium chloropalladate, potassium chloropalladate, barium chloropalladate, and palladium acetate. Absent. Particularly preferably, sodium chloropalladate is used.
白金の原料すなわち白金元素を含む化合物には特に制限はない。金属白金を用いることはもちろん、還元反応により金属白金に転化可能な白金塩を用いることも可能である。金属白金に転化可能な白金塩の例としては、塩化白金、硝酸白金、硫酸白金、塩化白金酸ナトリウム、塩化白金酸カリウム、塩化白金酸バリウム、酢酸白金などがあるがこれに限定されるものではない。 There is no particular limitation on the raw material of platinum, that is, the compound containing platinum element. In addition to using metal platinum, it is also possible to use a platinum salt that can be converted to metal platinum by a reduction reaction. Examples of platinum salts that can be converted to metallic platinum include, but are not limited to, platinum chloride, platinum nitrate, platinum sulfate, sodium chloroplatinate, potassium chloroplatinate, barium chloroplatinate, and platinum acetate. Absent.
（ｂ）パラジウムまたは白金と（ａ）担体との質量比は、好ましくは（ｂ）：（ａ）＝１：１０〜１０００であり、より好ましくは１：３０〜５００である。なお、例えば、パラジウム塩を担持する場合、この塩中のパラジウム元素の質量と担体の質量との比で計算する。 The mass ratio of (b) palladium or platinum to (a) support is preferably (b) :( a) = 1: 10 to 1000, more preferably 1:30 to 500. For example, when a palladium salt is supported, the calculation is performed based on the ratio of the mass of the palladium element in the salt to the mass of the carrier.
＜（ｃ）第１１族元素＞
本発明において、（ｃ）第１１族元素とは、ＩＵＰＡＣ無機化学命名法改訂版（１９８９）による周期律表の第１１族元素をさす。具体的には金、銀、銅を指し、好ましくは金あるいは銅である。
<(C) Group 11 element>
In the present invention, the (c) Group 11 element refers to a Group 11 element in the periodic table according to the revised IUPAC Inorganic Chemical Nomenclature (1989). Specifically, it refers to gold, silver and copper, preferably gold or copper.
（ｃ）第１１族元素は当該元素を含む化合物（第１１族元素前駆物質）の形で担体に担持されるが、最終的には「金属金」であることが好ましい。ここで言う「金属金」とは０価の価数を持つものである。金属金は、通常、第１１族元素前駆物質由来の１価および／または３価の金イオンを、還元剤であるヒドラジン、水素等を用いて還元することで得ることができる。この際、全ての金が金属状態になくても構わない。 (C) The Group 11 element is supported on the carrier in the form of a compound containing the element (Group 11 element precursor), but it is preferably “metal gold” in the end. The “metal gold” referred to here has a valence of zero. Metallic gold can usually be obtained by reducing monovalent and / or trivalent gold ions derived from a Group 11 element precursor using hydrazine, hydrogen or the like as a reducing agent. At this time, all the gold may not be in a metal state.
金や銀の原料すなわち第１１族元素を含む化合物には特に制限はない。金属金を用いることはもちろん、金属金に転化可能な金前駆体を用いることも可能である。金前駆体としては、塩化金酸や塩化金酸ナトリウム、塩化金酸カリウムなどが挙げられるが、好適には塩化金酸が用いられる。 There are no particular limitations on the gold or silver raw material, that is, the compound containing a Group 11 element. It is possible to use a gold precursor that can be converted into metal gold as well as metal gold. Examples of the gold precursor include chloroauric acid, sodium chloroaurate, and potassium chloroaurate. Preferably, chloroauric acid is used.
＜（ｅ）アルカリ土類金属元素＞
本発明に用いる（ｅ）アルカリ土類金属元素としては、Ｍｇ，Ｃａ，Ｂａ，Ｓｒなどが挙げられる。特に好適にはＢａ、Ｃａである。
<(E) Alkaline earth metal element>
Examples of the (e) alkaline earth metal element used in the present invention include Mg, Ca, Ba, Sr and the like. Particularly preferred are Ba and Ca.
アルカリ土類金属元素は当該元素を含む化合物を供給源とするが、これらの化合物には特に制限はない。アルカリ土類金属元素の、塩化物、酢酸塩、硝酸塩、硫酸塩、水酸化物などをそれぞれ調製条件によって選択することができる。特に好適にはＢａＣｌ２、（ＣＨ３ＣＯＯ）２Ｂａ、Ｂａ（ＮＯ３）２、Ｂａ（ＯＨ）２、ＣａＣｌ２、（ＣＨ３ＣＯＯ）２Ｃａが挙げられる。 The alkaline earth metal element is supplied from a compound containing the element, but these compounds are not particularly limited. The alkaline earth metal element chloride, acetate, nitrate, sulfate, hydroxide and the like can be selected depending on the preparation conditions. Particularly preferred are BaCl 2 , (CH 3 COO) 2 Ba, Ba (NO 3 ) 2 , Ba (OH) 2 , CaCl 2 , and (CH 3 COO) 2 Ca.
＜溶液（Ａ）＞
本発明に用いる溶液（Ａ）は、パラジウムまたは白金を含む化合物および第１１族元素を含む化合物の溶液である。アルカリ土類金属元素をも担持する場合には、アルカリ土類金属元素を含む化合物をも溶解したものである。必要に応じて他の成分が溶解されていてもよい。
<Solution (A)>
The solution (A) used in the present invention is a solution of a compound containing palladium or platinum and a compound containing a Group 11 element. When an alkaline earth metal element is also supported, the compound containing the alkaline earth metal element is also dissolved. Other components may be dissolved as necessary.
溶液Ａは、塩化パラジウム酸、塩化パラジウム酸ナトリウム、塩化パラジウム酸カリウムから選ばれた少なくとも１種および塩化金酸、塩化金酸ナトリウム、塩化金酸カリウムから選ばれた少なくとも１種を含むことが好ましい。アルカリ土類金属元素をも担持する場合には、さらに塩化バリウム、酢酸バリウム、硝酸バリウム、硫酸バリウム、塩化ストロンチウム、酢酸ストロンチウム、硝酸ストロンチウム、硫酸ストロンチウム、塩化マグネシウム、酢酸マグネシウム、硝酸マグネシウム、硫酸マグネシウム、塩化カルシウム、酢酸カルシウム、硝酸カルシウム、硫酸カルシウムから選ばれた少なくとも１種を含むことが好ましい。 Solution A preferably contains at least one selected from chloropalladic acid, sodium chloropalladate, and potassium chloropalladate and at least one selected from chloroauric acid, sodium chloroaurate, and potassium chloroaurate. . When also carrying alkaline earth metal elements, barium chloride, barium acetate, barium nitrate, barium sulfate, strontium chloride, strontium acetate, strontium nitrate, strontium sulfate, magnesium chloride, magnesium acetate, magnesium nitrate, magnesium sulfate, It is preferable to include at least one selected from calcium chloride, calcium acetate, calcium nitrate, and calcium sulfate.
溶液Ａの溶媒としては、水、アルコール、有機酸などが挙げられる。担体へのダメージや、含まれる化合物に対して反応性を有さない点から水が好ましい。 Examples of the solvent of the solution A include water, alcohol, and organic acid. Water is preferable from the viewpoint of damage to the carrier and lack of reactivity with the contained compound.
アルカリ溶液と溶液Ａの総量は、（ａ）担体の吸水量の１．１質量倍以上１０．０質量倍以下である。より好ましくは１．５〜８．０質量倍、最も好ましくは２．０〜６．０質量倍である。この総量が１．１質量倍未満では、触媒成分が担体に不均一に担持されることがあるため好ましくない。１０．０質量倍を超えると、触媒性能には影響しないが、排水量が増加するなど触媒製造上の問題が発生することがあるため好ましくない。 The total amount of the alkali solution and the solution A is 1.1 mass times or more and 10.0 mass times or less of the water absorption amount of the carrier (a). More preferably, it is 1.5-8.0 mass times, Most preferably, it is 2.0-6.0 mass times. If the total amount is less than 1.1 times by mass, the catalyst component may be unevenly supported on the carrier, which is not preferable. If it exceeds 10.0 mass times, the catalyst performance will not be affected, but it is not preferred because problems in catalyst production such as an increase in the amount of wastewater may occur.
第１の工程では、パラジウムまたは白金を含む化合物の溶液Ａ１、第１１族元素を含む化合物の溶液Ａ２、アルカリ土類金属元素を含む化合物の溶液Ａ３を作製しておき、各溶液を個別に担体に含浸させ、各化合物を担体に担持してもよい。この場合、アルカリ溶液と溶液Ａの総量は、アルカリ溶液、溶液Ａ１、溶液Ａ２および溶液Ａ３の総量になる。また、溶液Ａ１と溶液Ａ２を１つの溶液（溶液Ａ１＋２とする）として含浸操作を行ってもよい。この場合は、溶液Ａ１＋２、溶液Ａ３、アルカリ溶液の和がアルカリ溶液および溶液Ａの総量に相当する。その他の溶液の組み合わせについても同様にしてアルカリ溶液および溶液Ａとしての総量を計算する。 In the first step, a solution A 1 of a compound containing palladium or platinum, a solution A 2 of a compound containing a Group 11 element, and a solution A 3 of a compound containing an alkaline earth metal element are prepared. It is possible to impregnate the carrier individually and to support each compound on the carrier. In this case, the total amount of the alkaline solution and the solution A is the total amount of the alkaline solution, the solution A 1 , the solution A 2 and the solution A 3 . Further, the impregnation operation may be performed by using the solution A 1 and the solution A 2 as one solution (referred to as a solution A 1 + 2 ). In this case, the sum of the solution A 1 + 2 , the solution A 3 , and the alkali solution corresponds to the total amount of the alkali solution and the solution A. Similarly, the total amount of the alkaline solution and the solution A is calculated for other combinations of solutions.
溶液Ａの量は（ａ）担体の吸水量の１．０〜１０．０質量倍が好ましく、さらに好ましくは２．０〜８．０質量倍、もっとも好ましくは、２．０〜５．０質量倍である。 The amount of the solution A is preferably 1.0 to 10.0 times by mass of the amount of water absorption of the carrier (a), more preferably 2.0 to 8.0 times by mass, and most preferably 2.0 to 5.0 mass. Is double.
なお、溶液Ａ１を担体に含浸させ、アルカリ溶液（Ｂ１とする）と接触させた後、さらに溶液Ａ２を担体に含浸させ、別のアルカリ溶液（Ｂ２とする）と再度接触させる場合は、アルカリ溶液Ｂ１と溶液Ａ１の和およびアルカリ溶液Ｂ２と溶液Ａ２の和のいずれもが担体吸水量の１．１〜５倍であることが好ましい。溶液Ａ１と溶液Ａ２を１つの溶液（溶液Ａ１＋２とする）として含浸操作を行う場合は、アルカリ溶液と溶液Ａ１＋２の和が担体吸水量の１．１〜１０倍であることが好ましい。その他の溶液の組み合わせについても同様である。そして、アルカリ溶液と溶液Ａの総量も、（ａ）担体の吸水量の１．１質量倍以上１０．０質量倍以下の範囲内であるように溶液量を調製する。 In the case where the support is impregnated with the solution A 1 and brought into contact with the alkaline solution (referred to as B 1 ), then the support is further impregnated with the solution A 2 and brought into contact again with another alkaline solution (referred to as B 2 ). preferably, both of the sum of the alkali solution B 1 and the sum of solution a 1 and alkaline solutions B 2 and solution a 2 is 1.1 to 5 times the carrier water absorption. When the impregnation operation is performed using the solution A 1 and the solution A 2 as one solution (referred to as a solution A 1 + 2 ), the sum of the alkaline solution and the solution A 1 + 2 is preferably 1.1 to 10 times the carrier water absorption amount. . The same applies to other combinations of solutions. Then, the amount of the solution is prepared so that the total amount of the alkaline solution and the solution A is also in the range of 1.1 to 10.0 times the water absorption amount of the carrier (a).
本発明では、アルカリ溶液が含浸された担体と溶液Ａを接触させることで、原料金属塩を水不溶性物質に変換し、ＰｄやＡｕなどの金属成分が担体にシェル型に担持された触媒前駆体を形成することができる。その条件には制限はないが、接触時間は０．５〜１００時間、好適には３〜５０時間が望ましい。０．５時間未満では、触媒成分が所望の量担持されにくく、触媒性能が十分ではないことがある。また、１００時間より長時間接触させることで、（ａ）担体がダメージを受ける可能性があり、好ましくない。 In the present invention, a catalyst precursor in which a raw metal salt is converted into a water-insoluble substance by bringing the support impregnated with an alkaline solution into contact with the solution A, and a metal component such as Pd or Au is supported on the support in a shell shape. Can be formed. The conditions are not limited, but the contact time is preferably 0.5 to 100 hours, preferably 3 to 50 hours. If it is less than 0.5 hour, a desired amount of the catalyst component is hardly supported, and the catalyst performance may not be sufficient. In addition, it is not preferable to contact the substrate for a longer time than 100 hours because (a) the carrier may be damaged.
接触温度は、特に制限はないが、１０〜８０℃、好適には２０〜６０℃が望ましい。１０℃より低いと変換反応が不十分になる可能性がある。８０℃を超えるとパラジウムや金の凝集が進む恐れがある。 The contact temperature is not particularly limited, but is desirably 10 to 80 ° C, preferably 20 to 60 ° C. If it is lower than 10 ° C, the conversion reaction may be insufficient. If it exceeds 80 ° C., the aggregation of palladium and gold may proceed.
３．還元処理を行う工程
パラジウムまたは白金を含む化合物（パラジウム塩等）および第１１族元素前駆物質（塩化金酸等）が担持された担体に還元処理を行い、前記化合物を金属パラジウム、金属金とするのが望ましい。還元処理は、液相還元、気相還元のいずれによることもできる。
3. Step of performing reduction treatment A carrier carrying a compound containing palladium or platinum (such as a palladium salt) and a Group 11 element precursor (such as chloroauric acid) is subjected to a reduction treatment, and the compound is converted into metallic palladium or metallic gold. Is desirable. The reduction treatment can be performed by either liquid phase reduction or gas phase reduction.
液相還元は、アルコールや炭化水素類を用いた非水系、水系のいずれで行なわれてもよい。還元剤としてはカルボン酸およびその塩、アルデヒド、過酸化水素、糖類、多価フェノール、ジボラン、アミン、ヒドラジンなどが用いられる。カルボン酸およびその塩としてはシュウ酸、シュウ酸カリウム、ギ酸、ギ酸カリウム、クエン酸アンモニウムが例示され、糖類としてはグルコースが挙げられる。好ましい還元剤としてはヒドラジン、ホルムアルデヒド、アセトアルデヒド、ハイドロキノン、水素化ホウ素ナトリウム、クエン酸カリウムなどが挙げられ、最も好ましい還元剤はヒドラジンである。 The liquid phase reduction may be performed either in a non-aqueous system or an aqueous system using alcohol or hydrocarbons. As the reducing agent, carboxylic acid and its salt, aldehyde, hydrogen peroxide, saccharide, polyhydric phenol, diborane, amine, hydrazine and the like are used. Examples of the carboxylic acid and its salt include oxalic acid, potassium oxalate, formic acid, potassium formate, and ammonium citrate, and examples of the saccharide include glucose. Preferred reducing agents include hydrazine, formaldehyde, acetaldehyde, hydroquinone, sodium borohydride, potassium citrate and the like, and the most preferred reducing agent is hydrazine.
気相還元に用いる還元剤は、水素、一酸化炭素、アルコール、アルデヒド、エチレン、プロペン、イソブテンなどのオレフィンから選択される。好ましくは水素である。気相還元では希釈剤として、不活性ガスを加えてもよい。不活性ガスとしては、例えば、ヘリウム、アルゴン、窒素がある。 The reducing agent used for the gas phase reduction is selected from olefins such as hydrogen, carbon monoxide, alcohol, aldehyde, ethylene, propene and isobutene. Preferably it is hydrogen. In gas phase reduction, an inert gas may be added as a diluent. Examples of the inert gas include helium, argon, and nitrogen.
還元処理された担体には必要に応じて純水等で洗浄を行う。洗浄は連続であるいはバッチで行なわれてもよい。洗浄温度は、好ましくは５〜２００℃の範囲、より好ましくは１５〜８０℃の範囲である。洗浄時間には特に制限はない。残存する好ましくない不純物の除去という目的に対して十分な条件を選択すればよい。好ましくない不純物とはナトリウムや塩素が挙げられる。 The reduced carrier is washed with pure water or the like as necessary. Washing may be performed continuously or batchwise. The washing temperature is preferably in the range of 5 to 200 ° C, more preferably in the range of 15 to 80 ° C. There is no particular limitation on the cleaning time. A sufficient condition may be selected for the purpose of removing the remaining undesirable impurities. Undesirable impurities include sodium and chlorine.
還元処理された担体には必要に応じて酸を接触（「酸処理」という）させてもよい。酸と接触させることで、好ましくない不純物を除去し、特に（ｅ）アルカリ土類金属元素を添加した触媒では過剰の（ｅ）アルカリ土類金属元素をある程度除去することで触媒性能が向上する。酸処理は、これらの物質を除去する目的を達成できればどのような条件で行ってもよい。特に、（ｅ）アルカリ土類金属元素は金属の分散状態を向上させる働きがあるが、触媒中に大量に存在する状態では、好ましくない副反応を引き起こす可能性があるため、余剰分を除去することが必要な場合がある。 The reduced support may be contacted with an acid (referred to as “acid treatment”) as necessary. By contacting with an acid, undesirable impurities are removed. In particular, in the case of a catalyst to which (e) an alkaline earth metal element is added, the catalyst performance is improved by removing the excess (e) alkaline earth metal element to some extent. The acid treatment may be performed under any conditions as long as the purpose of removing these substances can be achieved. In particular, (e) the alkaline earth metal element works to improve the dispersion state of the metal, but in a state where the alkaline earth metal element is present in a large amount in the catalyst, it may cause an undesirable side reaction. Sometimes it is necessary.
酸処理の方法としては、担体を酸溶液に浸漬した後、水洗等によって酸溶液を洗い流す方法が挙げられる。酸処理に使用される酸としては、塩酸、硫酸、硝酸、リン酸、ヘテロポリ酸などの無機酸や、酢酸、シュウ酸、クエン酸などの有機酸が挙げられる。これらの酸は前述の目的を勘案して選択することができ、これらの酸の塩であってもかまわない。 Examples of the acid treatment method include a method of immersing the carrier in an acid solution and then washing off the acid solution by washing with water or the like. Examples of the acid used for the acid treatment include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacid, and organic acids such as acetic acid, oxalic acid, and citric acid. These acids can be selected in view of the above-mentioned purpose, and salts of these acids may be used.
４．担体に酢酸塩を担持する工程
（ｄ）酢酸塩は、担体に（ｄ）酢酸塩の必要量を含む担体吸水量の０．９〜１質量倍の溶液を含浸させ、乾燥することで担持する。担持するのは還元処理前でも後でもかまわない。好適には還元処理後である。
4). The step of supporting the acetate on the carrier (d) The acetate is supported by impregnating the carrier with a solution of 0.9 to 1 mass times the amount of water absorption of the carrier including the necessary amount of (d) acetate and drying. . It may be supported before or after the reduction treatment. Preferably after the reduction treatment.
＜（ｄ）酢酸塩＞
本発明に用いる（ｄ）酢酸塩は、好ましくは、アルカリ金属酢酸塩およびアルカリ土類金属酢酸塩から選ばれる少なくとも１種の化合物である。より好ましくはアルカリ金属酢酸塩である。具体的にはリチウム、ナトリウム、カリウムの酢酸塩などが挙げられる。なかでも酢酸ナトリウム、酢酸カリウムが好ましく、酢酸カリウムが特に好ましい。
<(D) Acetate>
The (d) acetate used in the present invention is preferably at least one compound selected from alkali metal acetates and alkaline earth metal acetates. More preferred is alkali metal acetate. Specific examples include lithium, sodium, and potassium acetate. Of these, sodium acetate and potassium acetate are preferable, and potassium acetate is particularly preferable.
＜触媒成分組成＞
本発明の酢酸アルケニル製造用触媒における（ｂ）パラジウムまたは白金、（ｃ）第１１族元素、（ｄ）酢酸塩、（ｅ）アルカリ土類金属元素の質量比は、好ましくは（ｂ）：（ｃ）：（ｄ）：（ｅ）＝１：０．００１〜１０：０．１〜１００：０〜１００であり、より好ましくは（ｂ）：（ｃ）：（ｄ）：（ｅ）＝１：０．１〜２：０．５〜２０：０〜３０である。なお、（ｂ）、（ｃ）、（ｅ）成分については当該元素を含む化合物中の当該元素自体の質量（金属自体の場合はその金属の質量）、（ｄ）は酢酸塩の質量での組成比である。また、触媒が（ｅ）成分を含まない場合、（ｅ）成分の比は０である。
<Catalyst component composition>
The mass ratio of (b) palladium or platinum, (c) group 11 element, (d) acetate, (e) alkaline earth metal element in the catalyst for producing alkenyl acetate of the present invention is preferably (b) :( c) :( d) :( e) = 1: 0.001 to 10: 0.1 to 100: 0 to 100, more preferably (b) :( c) :( d) :( e) = It is 1: 0.1-2: 0.5-20: 0-30. For the components (b), (c), and (e), the mass of the element itself in the compound containing the element (in the case of the metal itself, the mass of the metal), and (d) is the mass of the acetate salt. It is a composition ratio. When the catalyst does not contain the component (e), the ratio of the component (e) is 0.
溶液Ａに含まれる各触媒成分の原料化合物は所望の触媒組成になるように調整する。各溶液中の触媒成分の原料化合物の濃度は担体へ担持すべき原料化合物の量と溶液量とから計算することができる。実操作上は、まず、担体へ担持すべき原料化合物の所定量（ｇ数）をはかり取り、それを本発明で規定する溶媒量となるように溶媒に溶かせばよい。 The raw material compound of each catalyst component contained in the solution A is adjusted to have a desired catalyst composition. The concentration of the raw material compound of the catalyst component in each solution can be calculated from the amount of the raw material compound to be supported on the carrier and the amount of the solution. In actual operation, first, a predetermined amount (g number) of the raw material compound to be supported on the carrier is weighed and dissolved in a solvent so as to be a solvent amount specified in the present invention.
また、（ｂ）パラジウムまたは白金、（ｃ）第１１族元素、（ｅ）アルカリ土類金属元素は、溶液Ａに含まれる分とは別に別の溶液として逐次的に同様の工程で触媒前駆体に導入することができる。 In addition, (b) palladium or platinum, (c) Group 11 element, and (e) alkaline earth metal element are sequentially separated in the same process as separate solutions separately from the components contained in Solution A. Can be introduced.
（ｂ）パラジウムまたは白金、（ｃ）第１１族元素、（ｄ）酢酸塩、（ｅ）アルカリ土類金属元素の（ａ）担体への担持量は（ａ）担体１ｇあたり、（ｂ）０．００１〜０．０５ｇ、（ｃ）０．００１〜０．０５ｇ、（ｄ）０．０１〜１ｇ、（ｅ）０〜０．１ｇであるのが好ましい。 (B) Palladium or platinum, (c) Group 11 element, (d) Acetate, (e) Alkaline earth metal element supported on (a) support is (b) 0 per gram of support (a) 0.001 to 0.05 g, (c) 0.001 to 0.05 g, (d) 0.01 to 1 g, and (e) 0 to 0.1 g are preferable.
本発明の方法により得られる触媒は、担体の表面部分に（ｂ）パラジウム、（ｃ）第１１族元素の大部分が担持されたシェル構造（エッグシェル構造ともいう）をなしている。シェル部分の厚みは用いる担体やアルカリ溶液、原料金属塩水溶液の種類によって変化する。直径５ｍｍの球体シリカを担体として使用した場合には、シェル部分は０．０５〜２ｍｍの厚みを有することが望ましい。さらに好適には、０．１〜１ｍｍの厚みを有する。この厚みが０．０５ｍｍ未満では反応の間に担体表面部分のはがれなどによって活性低下が起こることがあるため望ましくない。２ｍｍより厚い場合には、シェル型担持のメリットが得られにくいことがある。 The catalyst obtained by the method of the present invention has a shell structure (also referred to as an egg shell structure) in which most of (b) palladium and (c) Group 11 elements are supported on the surface portion of the support. The thickness of the shell portion varies depending on the type of the carrier used, the alkali solution, and the raw material metal salt aqueous solution. When spherical silica having a diameter of 5 mm is used as the carrier, the shell portion preferably has a thickness of 0.05 to 2 mm. More preferably, it has a thickness of 0.1 to 1 mm. If the thickness is less than 0.05 mm, the activity may decrease due to peeling of the surface portion of the carrier during the reaction, which is not desirable. If it is thicker than 2 mm, it may be difficult to obtain the advantage of carrying the shell type.
本発明の方法で調製した触媒においては、（ｄ）酢酸塩、（ｅ）アルカリ土類金属はシェル型に担持されていてもよく、触媒全体に均一に存在していてもよい。 In the catalyst prepared by the method of the present invention, (d) acetate and (e) alkaline earth metal may be supported in a shell shape or may be present uniformly throughout the catalyst.
＜触媒調製法の具体例＞
本発明の触媒調製法の例を以下に示す。
工程１ 吸水量相当分のアルカリ溶液を（ａ）担体に含浸する。
工程２ （ｂ）パラジウム、（ｃ）第１１族元素、（ｅ）アルカリ土類金属元素の原料金属塩を（ａ）担体吸水量の２倍まで純水でメスアップした溶液に、（ａ）担体を浸漬し、触媒前駆体を形成する。
工程３ 工程２の溶液に還元剤を投入する。
工程４ 還元後の触媒前駆体を純水で洗浄する。
工程５ 洗浄後の触媒前駆体を乾燥する。
工程６ （ｄ）酢酸塩を所定量担持する。
工程７ 乾燥する。
<Specific example of catalyst preparation method>
An example of the catalyst preparation method of the present invention is shown below.
Step 1 (a) The support is impregnated with an alkali solution equivalent to the amount of water absorption.
Step 2 (b) Palladium, (c) Group 11 element, (e) Raw material metal salt of alkaline earth metal element was made up to (a) pure water up to twice the amount of carrier water absorption, (a) The support is immersed to form a catalyst precursor.
Step 3 A reducing agent is added to the solution of Step 2.
Step 4 The reduced catalyst precursor is washed with pure water.
Step 5 The catalyst precursor after washing is dried.
Step 6 (d) A predetermined amount of acetate is supported.
Step 7 Dry.
［酢酸アルケニルの製造］
以下、本発明で製造された酢酸アルケニル製造用触媒を用いた、酢酸アルケニルの製造法について説明する。本発明における酢酸アルケニルの製造のための反応は、酢酸、低級オレフィン、酸素を反応原料とし、気相で行うことが好ましい。
気相反応は、従来公知のいかなる形態で行ってもよいが、好ましくは固定床流通反応であることが望ましい。
[Production of alkenyl acetate]
Hereinafter, a method for producing alkenyl acetate using the alkenyl acetate production catalyst produced in the present invention will be described. The reaction for producing alkenyl acetate in the present invention is preferably carried out in the gas phase using acetic acid, lower olefin and oxygen as reaction raw materials.
The gas phase reaction may be performed in any conventionally known form, but is preferably a fixed bed flow reaction.
例えば、低級オレフィンがエチレンの場合には、反応式は次式のとおりである。
Ｃ２Ｈ４＋ＣＨ３ＣＯＯＨ＋１／２Ｏ２→ＣＨ２＝ＣＨＯＣＯＣＨ３＋Ｈ２Ｏ
原料の酢酸、低級オレフィン、酸素の比率は、モル比として酢酸：低級オレフィン：酸素＝１：０．０８〜１６：０．０１〜４であるのが好ましく、低級オレフィンがエチレンの場合は酢酸：エチレン：酸素＝１：０．２〜９：０．０７〜２であるのが好適である。また、低級オレフィンがプロピレンの場合は、酢酸：プロピレン: 酸素＝１：１〜１２：０．５〜２であるのが好ましい。
For example, when the lower olefin is ethylene, the reaction formula is as follows.
C 2 H 4 + CH 3 COOH + 1 / 2O 2 → CH 2 = CHOCOCH 3 + H 2 O
The ratio of acetic acid, lower olefin and oxygen as raw materials is preferably acetic acid: lower olefin: oxygen = 1: 0.08-16: 0.01-4 as a molar ratio. When the lower olefin is ethylene, acetic acid: It is preferred that ethylene: oxygen = 1: 0.2-9: 0.07-2. When the lower olefin is propylene, it is preferable that acetic acid: propylene: oxygen = 1: 1 to 12: 0.5 to 2.
反応原料ガスは、低級オレフィンと酢酸と酸素とを含み、さらに必要に応じて窒素、二酸化炭素または希ガスなどを希釈剤として含んでいてもよい。低級オレフィンと酢酸と酸素とを反応原料とすると、反応原料と希釈剤との比率は、モル比として反応原料：希釈剤＝１：０．０５〜９であるのが好ましく、より好ましくは反応原料：希釈剤＝１：０．１〜３である。 The reaction raw material gas contains a lower olefin, acetic acid, and oxygen, and may further contain nitrogen, carbon dioxide, or a rare gas as a diluent as necessary. When a lower olefin, acetic acid, and oxygen are used as reaction raw materials, the ratio of the reaction raw material to the diluent is preferably a reaction raw material: diluent = 1: 0.05 to 9, more preferably a reaction raw material. : Diluent = 1: 0.1-3.
固定床流通反応で反応を行う場合、反応原料ガスは、標準状態において、空間速度１０〜１５０００ｈｒ−１、特に３００〜８０００ｈｒ−１で反応器に通すのが好ましい。空間速度が１０ｈｒ−１より小さい場合、反応熱の除去が困難となる可能性がある。また、空間速度が１５０００ｈｒ−１より大きい場合、コンプレッサー等の設備が大きくなりすぎて、実用的でなくなることがある。 When the reaction is carried out in a fixed bed flow reaction, the reaction raw material gas, under standard conditions, space velocity 10～15000Hr -1, preferably particularly through the reactor at 300~8000hr -1. When the space velocity is smaller than 10 hr −1 , it may be difficult to remove reaction heat. Moreover, when space velocity is larger than 15000 hr < -1 >, equipment, such as a compressor, will become large and may become impractical.
反応原料ガス中には水を０．５〜２０ｍｏｌ％添加することが好ましい。さらに好適には、水を１〜１８ｍｏｌ％添加する。系内に水が存在することによって、理由は明かではないが、触媒からの（ｄ）酢酸塩の流出が減少する。一方、水を２０ｍｏｌ％より多く添加しても、上記効果は向上しないばかりか、酢酸アルケニルの加水分解が進む恐れがあるため、大量の水が存在するのは好ましくない。 It is preferable to add 0.5 to 20 mol% of water in the reaction raw material gas. More preferably, 1 to 18 mol% of water is added. The presence of water in the system reduces (d) acetate efflux from the catalyst for reasons that are not obvious. On the other hand, adding more than 20 mol% of water not only improves the above effect, but also promotes hydrolysis of alkenyl acetate. Therefore, it is not preferable that a large amount of water is present.
反応器の材質については特に制限はないが、好ましくは耐食性を有する材料で構成された反応器である。 The material of the reactor is not particularly limited, but is preferably a reactor composed of a material having corrosion resistance.
反応温度は、１００〜３００℃であるのが好ましく、より好ましくは１２０〜２５０℃である。反応温度が１００℃より低い場合、反応速度が遅くなりすぎる可能性があり、好ましくない。反応温度が３００℃よりも高い場合、反応熱の除熱が困難となる可能性があり、好ましくない。 The reaction temperature is preferably 100 to 300 ° C, more preferably 120 to 250 ° C. When the reaction temperature is lower than 100 ° C., the reaction rate may become too slow, which is not preferable. When the reaction temperature is higher than 300 ° C., it may be difficult to remove the heat of reaction, which is not preferable.
反応圧力は、好ましくは０〜３ＭＰａＧ（ゲージ圧）であり、より好ましくは０．１〜１．５ＭＰａＧである。反応圧力が０ＭＰａＧより小さい場合、反応速度が低下する恐れがあり、好ましくない。反応圧力が３ＭＰａＧより大きい場合、反応管等の設備が高価になり、実用的ではない。 The reaction pressure is preferably 0 to 3 MPaG (gauge pressure), more preferably 0.1 to 1.5 MPaG. If the reaction pressure is less than 0 MPaG, the reaction rate may decrease, which is not preferable. When the reaction pressure is larger than 3 MPaG, equipment such as a reaction tube becomes expensive, which is not practical.
反応原料のエチレン、プロピレン等の低級オレフィンには特に制限はない。一般的には高純度のものを用いることが好ましいが、メタン、エタン、プロパン等の低級飽和炭化水素が混入しても差し支えない。 There are no particular limitations on the lower olefins such as ethylene and propylene as reaction raw materials. In general, it is preferable to use a high-purity one, but it may be mixed with a lower saturated hydrocarbon such as methane, ethane or propane.
また、酸素にも特に制限はない。窒素、炭酸ガス等の不活性ガスで希釈されたもの、例えば、空気の形でも供給できるが、反応ガスを循環させる場合には、一般には高濃度の酸素、好適には９９％以上の純度の酸素を用いる方が有利である。 Also, oxygen is not particularly limited. Although diluted with an inert gas such as nitrogen or carbon dioxide, for example, in the form of air, it can be supplied, but when the reaction gas is circulated, it generally has a high concentration of oxygen, preferably a purity of 99% or more. It is advantageous to use oxygen.
酢酸アルケニルとして酢酸ビニルを製造する場合、エチレンと酸素と酢酸とを反応させて、酢酸ビニルを製造する際の反応温度に特に制限はない。好ましくは、１００〜３００℃であり、さらに好ましくは、１２０〜２５０℃である。また、反応圧力は設備の点から０．０〜３．０ＭＰａＧであることが実用上有利であるが、特に制限はない。より好ましくは０．１〜１．５ＭＰａＧの範囲である。 When vinyl acetate is produced as alkenyl acetate, there is no particular limitation on the reaction temperature for producing vinyl acetate by reacting ethylene, oxygen and acetic acid. Preferably, it is 100-300 degreeC, More preferably, it is 120-250 degreeC. Moreover, although it is practically advantageous that the reaction pressure is 0.0-3.0 MPaG from the point of an installation, there is no restriction | limiting in particular. More preferably, it is the range of 0.1-1.5 MPaG.
反応混合ガスは、標準状態において、空間速度１０〜１５０００ｈｒ-1、特に３００〜８０００ｈｒ-1で反応器に通すのが好ましい。 The reaction gas mixture, at standard conditions, space velocity 10～15000Hr -1, preferably particularly through the reactor at 300~8000hr -1.
反応形式としては、特に制限はなく、公知の方法、例えば固定床、流動床などの形式を採り得る。好ましくは、耐蝕性を有する反応管に前述の触媒を充填した固定床を採用することが、実用上有利である。 There is no restriction | limiting in particular as a reaction format, For example, formats, such as a fixed bed and a fluidized bed, can be taken. Preferably, it is practically advantageous to employ a fixed bed in which the above-described catalyst is packed in a reaction tube having corrosion resistance.
以下、実施例により本発明をさらに説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited only to these Examples.
実施例１ 触媒Ａの調製（アルカリ溶液＋溶液Ａが３．０倍）
シリカ球体担体（球体直径５ｍｍ、比表面積１５５ｍ２／ｇ、吸水率０．８５ｇ／ｇ、上海海源化工科技有限公司のＨＳＶ−Ｉ）を用いて、触媒を以下の手順で調製した。
Example 1 Preparation of catalyst A (alkaline solution + solution A is 3.0 times)
A catalyst was prepared by the following procedure using a silica sphere carrier (sphere diameter 5 mm, specific surface area 155 m 2 / g, water absorption 0.85 g / g, HSV-I from Shanghai Kaiyuan Chemical Technology Co., Ltd.).
工程１．担体２３ｇ（吸水量１９．７ｇ）に、Ｎａ２ＳｉＯ３・９Ｈ２Ｏ２．５ｇを含む担体吸水量相当（１倍）の量の水溶液を含浸させた。担体と水溶液が入った容器を静かに振り動かし、溶液を完全に含浸させた。なお、吸水量は担体量２３ｇ、吸水率０．８５ｇ／ｇより計算した（以下の実施例、比較例でも同じ）。 Step 1. 23 g of carrier (water absorption 19.7 g) was impregnated with an aqueous solution equivalent to (1 times) the amount of water absorption of carrier containing 2.5 g of Na 2 SiO 3 .9H 2 O. The container containing the carrier and the aqueous solution was gently shaken to completely impregnate the solution. The water absorption was calculated from the carrier amount 23 g and the water absorption 0.85 g / g (the same applies to the following examples and comparative examples).
工程２．工程１で得られた担体を５６質量％Ｎａ２ＰｄＣｌ４水溶液１．５ｇおよび１７質量％ＨＡｕＣｌ４１．５ｇを含む担体吸水量の２倍の水溶液に浸漬し、２０時間静置した。
工程３．工程２の水溶液に５２質量％ヒドラジン水和物水溶液３．３ｍｌを加え、静かに混合し、室温で４時間静置した。
Step 2. The carrier obtained in step 1 was immersed in an aqueous solution twice as much as the carrier water absorption containing 1.5 g of 56 mass% Na 2 PdCl 4 aqueous solution and 1.5 g of 17 mass% HAuCl 4, and allowed to stand for 20 hours.
Step 3. To the aqueous solution of step 2, 3.3 ml of a 52 mass% hydrazine hydrate aqueous solution was added, gently mixed, and allowed to stand at room temperature for 4 hours.
工程４．前工程で得られたパラジウム／金／担体組成物を水洗し、洗浄後の水中に塩化物イオンが無くなるまで継続した。洗浄したパラジウム／金／担体組成物を、約１１０℃で４時間乾燥した。
工程５．パラジウム／金／担体組成物に、２ｇの酢酸カリウムの担体吸水量相当の量の水溶液を含浸させ、１１０℃で４時間乾燥した。
Step 4. The palladium / gold / carrier composition obtained in the previous step was washed with water and continued until no chloride ions were present in the washed water. The washed palladium / gold / support composition was dried at about 110 ° C. for 4 hours.
Step 5. The palladium / gold / carrier composition was impregnated with an aqueous solution of 2 g of potassium acetate corresponding to the amount of water absorbed by the carrier, and dried at 110 ° C. for 4 hours.
実施例２ 触媒Ｂの調製（アルカリ溶液＋溶液Ａが３．０倍）
工程２．において、Ｎａ２ＰｄＣｌ４およびＨＡｕＣｌ４に加えてさらにＢａＣｌ２・２Ｈ２Ｏ１．９ｇを加えた担体吸水量の２倍の量の水溶液を用いた以外は実施例１の操作を繰り返した。
Example 2 Preparation of catalyst B (alkaline solution + solution A is 3.0 times)
Step 2. In Example 1, the procedure of Example 1 was repeated except that an aqueous solution having twice the amount of water absorption of the carrier obtained by adding 1.9 g of BaCl 2 .2H 2 O in addition to Na 2 PdCl 4 and HAuCl 4 was used.
比較例１ 触媒Ｃの調製（従来技術の例、アルカリ溶液＋溶液Ａが３．０倍）
シリカ球体担体（球体直径５ｍｍ、比表面積１５５ｍ２／ｇ、吸水率０．８５ｇ／ｇ、上海海源化工科技有限公司のＨＳＶ−Ｉ）を用いて、触媒を以下の手順で調製した。
工程１．担体２３ｇ（吸水量１９．７ｇ）に、５６質量％Ｎａ２ＰｄＣｌ４１．５ｇおよび１７質量％ＨＡｕＣｌ４１．５ｇを含む担体吸水量相当（１倍）の量の水溶液を含浸させた。担体と水溶液が入った容器を静かに振り動かし、溶液を完全に含浸させた。
工程２．工程１で得られた担体をＮａ２ＳｉＯ３・９Ｈ２Ｏ２．５ｇを含む担体吸水量の２倍の量の水溶液に浸漬し、２０時間静置した。
工程３．工程２の水溶液に５２質量％ヒドラジン水和物水溶液３．３ｍｌを加え、静かに混合し、室温で４時間静置した。
工程４．前工程で得られたパラジウム／金化合物担体組成物を水洗し、洗浄後の水中に塩化物イオンが無くなるまで継続した。洗浄したパラジウム／金／担体組成物を、約１１０℃で４時間乾燥した。
工程５．パラジウム／金／担体組成物に、２ｇの酢酸カリウムの担体吸水量相当の量の水溶液を含浸させ、１１０℃で４時間乾燥した。
Comparative Example 1 Preparation of catalyst C (prior art example, alkali solution + solution A is 3.0 times)
A catalyst was prepared by the following procedure using a silica sphere carrier (sphere diameter 5 mm, specific surface area 155 m 2 / g, water absorption 0.85 g / g, HSV-I from Shanghai Kaiyuan Chemical Technology Co., Ltd.).
Step 1. 23 g of carrier (water absorption 19.7 g) was impregnated with an aqueous solution equivalent to (1 ×) the amount of water absorption of carrier containing 1.5 g of 56 mass% Na 2 PdCl 4 and 1.5 g of 17 mass% HAuCl 4 . The container containing the carrier and the aqueous solution was gently shaken to completely impregnate the solution.
Step 2. The carrier obtained in Step 1 was immersed in an aqueous solution twice as much as the carrier water absorption containing 2.5 g of Na 2 SiO 3 .9H 2 O, and allowed to stand for 20 hours.
Step 3. To the aqueous solution of step 2, 3.3 ml of a 52 mass% hydrazine hydrate aqueous solution was added, gently mixed, and allowed to stand at room temperature for 4 hours.
Step 4. The palladium / gold compound carrier composition obtained in the previous step was washed with water until the chloride ion disappeared in the washed water. The washed palladium / gold / support composition was dried at about 110 ° C. for 4 hours.
Step 5. The palladium / gold / carrier composition was impregnated with an aqueous solution of 2 g of potassium acetate corresponding to the amount of water absorbed by the carrier, and dried at 110 ° C. for 4 hours.
比較例２ 触媒Ｄの調製（従来技術の例、アルカリ溶液＋溶液Ａが３．０倍）
工程２．において、Ｎａ２ＳｉＯ３・９Ｈ２Ｏに加えてさらにＢａＣｌ２・２Ｈ２Ｏ１．９ｇを加えた担体吸水量の２倍の量の水溶液を用いた以外は比較例１の操作を繰り返した。
Comparative Example 2 Preparation of Catalyst D (Example of Prior Art, Alkaline Solution + Solution A is 3.0 times)
Step 2. In, except for using 2 times the amount of the aqueous solution of Na 2 SiO 3 · 9H 2 O in addition to further BaCl 2 · 2H 2 O1.9g added carrier water absorption was repeated in Comparative Example 1.
実施例３ 触媒Ｅの調製（アルカリ溶液＋溶液Ａが３．０倍、酸処理あり）
工程４と工程５の間に以下の工程を加えた以外は実施例２の操作を繰り返した。
工程Ｅ−１．工程４で得られたパラジウム／金／バリウム／担体組成物を吸水量の３倍に相当する量の０．４５質量％酢酸水溶液に１時間浸漬させた。
工程Ｅ−２．工程Ｅ−１で得られたパラジウム／金／バリウム／担体組成物の水洗浄を１夜間継続した。
工程Ｅ−３．工程Ｅ−２で得られたパラジウム／金／バリウム／担体組成物を約１１０℃で４時間乾燥した。
Example 3 Preparation of catalyst E (alkaline solution + solution A is 3.0 times, with acid treatment)
The operation of Example 2 was repeated except that the following steps were added between Step 4 and Step 5.
Step E-1. The palladium / gold / barium / carrier composition obtained in step 4 was immersed in an aqueous 0.45 mass% acetic acid solution in an amount corresponding to three times the water absorption amount for 1 hour.
Step E-2. Water washing of the palladium / gold / barium / carrier composition obtained in step E-1 was continued for 1 night.
Step E-3. The palladium / gold / barium / support composition obtained in step E-2 was dried at about 110 ° C. for 4 hours.
実施例４ 触媒Ｆの調製（アルカリ溶液＋溶液Ａが３．０倍）
シリカ球体担体（球体直径５ｍｍ、比表面積１５５ｍ２／ｇ、吸水率０．８５ｇ／ｇ、上海海源化工科技有限公司のＨＳＶ−Ｉ）を用いて、触媒を以下の手順で調製した。
工程１．担体２３ｇ（吸水量１９．７ｇ）に、Ｎａ２ＳｉＯ３・９Ｈ２Ｏ２．５ｇを含む担体吸水量の０．９５倍量の水溶液を含浸させた。担体と水溶液が入った容器を静かに振り動かし、溶液を完全に含浸させた。
工程２．工程１で得られた担体を５６質量％Ｎａ２ＰｄＣｌ４水溶液１．５ｇおよび１７質量％ＨＡｕＣｌ４１．５ｇ、ＢａＣｌ２・２Ｈ２Ｏ１．９ｇを含む担体吸水量相当の２倍の量の水溶液に浸漬し、２０時間静置した。
工程３．工程２の水溶液にクエン酸カリウム０．５ｇを加え、静かに混合し、室温で４時間静置した。
工程４．前工程で得られたパラジウム／金／バリウム化合物／担体組成物を水洗し、洗浄後の水中に塩化物イオンが無くなるまで継続した。洗浄したパラジウム／金／担体組成物を、約１１０℃で４時間乾燥した。
工程５．パラジウム／金／バリウム化合物／担体組成物に、２ｇの酢酸カリウムの担体吸水量相当の量の水溶液を含浸させ、１１０℃で４時間乾燥した。
Example 4 Preparation of catalyst F (alkaline solution + solution A is 3.0 times)
A catalyst was prepared by the following procedure using a silica sphere carrier (sphere diameter 5 mm, specific surface area 155 m 2 / g, water absorption 0.85 g / g, HSV-I from Shanghai Kaiyuan Chemical Technology Co., Ltd.).
Step 1. The carrier 23 g (water absorption amount 19.7 g), was impregnated with 0.95 times the amount of the aqueous solution of the carrier water absorption containing Na 2 SiO 3 · 9H 2 O2.5g . The container containing the carrier and the aqueous solution was gently shaken to completely impregnate the solution.
Step 2. The carrier obtained in step 1 is 1.5 g of 56 wt% Na 2 PdCl 4 aqueous solution, 1.5 g of 17 wt% HAuCl 4 , and 1.9 g of BaCl 2 .2H 2 O. And soaked for 20 hours.
Step 3. To the aqueous solution in Step 2, 0.5 g of potassium citrate was added, mixed gently, and allowed to stand at room temperature for 4 hours.
Step 4. The palladium / gold / barium compound / carrier composition obtained in the previous step was washed with water and continued until no chloride ions were present in the washed water. The washed palladium / gold / support composition was dried at about 110 ° C. for 4 hours.
Step 5. The palladium / gold / barium compound / carrier composition was impregnated with an aqueous solution of 2 g of potassium acetate corresponding to the amount of water absorbed by the carrier, and dried at 110 ° C. for 4 hours.
実施例５ 触媒Ｇの調製（アルカリ溶液＋溶液Ａが３．０倍）
工程２．において、１７質量％ＨＡｕＣｌ４１．５ｇを１７質量％ＮａＡｕＣｌ４１．６ｇに変更した以外は実施例１の操作を繰り返した。
Example 5 Preparation of catalyst G (alkaline solution + solution A is 3.0 times)
Step 2. In Example 1, the procedure of Example 1 was repeated except that 1.5 g of 17 mass% HAuCl 4 was changed to 1.6 g of 17 mass% NaAuCl 4 .
実施例６ 触媒Ｈの調製（アルカリ溶液＋溶液Ａが３．０倍）
シリカ球体担体（球体直径５ｍｍ、比表面積１５５ｍ２／ｇ、吸水率０．８５ｇ／ｇ、上海海源化工科技有限公司のＨＳＶ−Ｉ）を用いて、触媒を以下の手順で調製した。
工程１．担体２３ｇ（吸水量１９．７ｇ）に、水酸化カリウム０．５２ｇを含む担体吸水量相当（１倍）の量の水溶液を含浸させた。担体と水溶液が入った容器を静かに振り動かし、溶液を完全に含浸させた。
工程２．工程１で得られた担体を５６質量％Ｎａ２ＰｄＣｌ４水溶液１．５ｇおよび１７質量％ＨＡｕＣｌ４１．５ｇ、ＢａＣｌ２・２Ｈ２Ｏ１．９ｇを含む担体吸水量の２倍相当の量の水溶液に浸漬し、２０時間静置した。
工程３．工程２の水溶液に５２質量％ヒドラジン水和物水溶液３．３ｍｌを加え、静かに混合し、室温で４時間静置した。
工程４．前工程で得られたパラジウム／金／バリウム化合物／担体組成物を水洗し、洗浄後の水中に塩化物イオンが無くなるまで継続した。洗浄したパラジウム／金／担体組成物を、約１１０℃で４時間乾燥した。
工程５．パラジウム／金／バリウム化合物／担体組成物に、２ｇの酢酸カリウムの担体吸水量相当の量の水溶液を含浸させ、１１０℃で４時間乾燥した。
Example 6 Preparation of catalyst H (alkaline solution + solution A is 3.0 times)
A catalyst was prepared by the following procedure using a silica sphere carrier (sphere diameter 5 mm, specific surface area 155 m 2 / g, water absorption 0.85 g / g, HSV-I from Shanghai Kaiyuan Chemical Technology Co., Ltd.).
Step 1. 23 g of carrier (water absorption 19.7 g) was impregnated with an aqueous solution equivalent to (1 times) the amount of water absorption containing 0.52 g of potassium hydroxide. The container containing the carrier and the aqueous solution was gently shaken to completely impregnate the solution.
Step 2. The carrier obtained in step 1 is 1.5 g of 56 wt% Na 2 PdCl 4 aqueous solution, 1.5 g of 17 wt% HAuCl 4 , and 1.9 g of BaCl 2 .2H 2 O. And soaked for 20 hours.
Step 3. To the aqueous solution of step 2, 3.3 ml of a 52 mass% hydrazine hydrate aqueous solution was added, gently mixed, and allowed to stand at room temperature for 4 hours.
Step 4. The palladium / gold / barium compound / carrier composition obtained in the previous step was washed with water and continued until no chloride ions were present in the washed water. The washed palladium / gold / support composition was dried at about 110 ° C. for 4 hours.
Step 5. The palladium / gold / barium compound / carrier composition was impregnated with an aqueous solution of 2 g of potassium acetate corresponding to the amount of water absorbed by the carrier, and dried at 110 ° C. for 4 hours.
比較例３ 触媒Ｉの調製（アルカリ溶液＋溶液Ａが１．０倍）
シリカ球体担体（球体直径５ｍｍ、比表面積１５５ｍ２／ｇ、吸水率０．８５ｇ／ｇ、上海海源化工科技有限公司のＨＳＶ−Ｉ）を用いて、触媒を以下の手順で調製した。
工程１．担体２３ｇ（吸水量１９．７ｇ）に、Ｎａ２ＳｉＯ３・９Ｈ２Ｏ２．５ｇを含む担体吸水量の０．５倍相当の量の水溶液を含浸させた。担体と水溶液が入った容器を静かに振り動かし、溶液を完全に含浸させた。
工程２．工程１で得られた担体を５６質量％Ｎａ２ＰｄＣｌ４水溶液１．５ｇおよび１７質量％ＨＡｕＣｌ４１．５ｇを含む担体吸水量の０．５倍相当の量の水溶液に浸漬し、２０時間静置した。
工程３．工程２の水溶液に５２質量％ヒドラジン水和物水溶液３．３ｍｌを加え、静かに混合し、室温で４時間静置した。
工程４．前工程で得られたパラジウム／金／担体組成物を水洗し、洗浄後の水中に塩化物イオンが無くなるまで継続した。洗浄したパラジウム／金／担体組成物を、約１１０℃で４時間乾燥した。
工程５．パラジウム／金／担体組成物に、２ｇの酢酸カリウムの担体吸水量相当の量の水溶液を含浸させ、１１０℃で４時間乾燥した。
Comparative Example 3 Preparation of Catalyst I (Alkaline solution + Solution A is 1.0 times)
A catalyst was prepared by the following procedure using a silica sphere carrier (sphere diameter 5 mm, specific surface area 155 m 2 / g, water absorption 0.85 g / g, HSV-I from Shanghai Kaiyuan Chemical Technology Co., Ltd.).
Step 1. 23 g of carrier (water absorption 19.7 g) was impregnated with an aqueous solution equivalent to 0.5 times the water absorption of carrier containing 2.5 g of Na 2 SiO 3 .9H 2 O. The container containing the carrier and the aqueous solution was gently shaken to completely impregnate the solution.
Step 2. The support obtained in step 1 is immersed in an aqueous solution equivalent to 0.5 times the water absorption amount of the carrier containing 1.5 g of 56 mass% Na 2 PdCl 4 aqueous solution and 1.5 g of 17 mass% HAuCl 4 , I put it.
Step 3. To the aqueous solution of step 2, 3.3 ml of a 52 mass% hydrazine hydrate aqueous solution was added, gently mixed, and allowed to stand at room temperature for 4 hours.
Step 4. The palladium / gold / carrier composition obtained in the previous step was washed with water and continued until no chloride ions were present in the washed water. The washed palladium / gold / support composition was dried at about 110 ° C. for 4 hours.
Step 5. The palladium / gold / carrier composition was impregnated with an aqueous solution of 2 g of potassium acetate corresponding to the amount of water absorbed by the carrier, and dried at 110 ° C. for 4 hours.
比較例４ 触媒Ｊの調製（アルカリ溶液＋溶液Ａが３．０倍、一旦乾燥）
シリカ球体担体（球体直径５ｍｍ、比表面積１５５ｍ２／ｇ、吸水率０．８５ｇ／ｇ、上海海源化工科技有限公司のＨＳＶ−Ｉ）を用いて、触媒を以下の手順で調製した。
工程１．担体２３ｇ（吸水量１９．７ｇ）に、Ｎａ２ＳｉＯ３・９Ｈ２Ｏ２．５ｇを含む担体吸水量相当（１倍）の量の水溶液を含浸させた。担体と水溶液が入った容器を静かに振り動かし、溶液を完全に含浸させた。
工程２．工程１で得られた担体を１１０℃、４時間空気中で乾燥した。
工程３．工程２で得られた担体を５６質量％Ｎａ２ＰｄＣｌ４水溶液１．５ｇおよび１７質量％ＨＡｕＣｌ４１．５ｇを含む担体吸水量の２倍相当の量の水溶液に浸漬し、２０時間静置した。
工程４．工程３の水溶液に５２質量％ヒドラジン水和物水溶液３．３ｍｌを加え、静かに混合し、室温で４時間静置した。
工程５．前工程で得られたパラジウム／金／担体組成物を水洗し、洗浄後の水中に塩化物イオンが無くなるまで継続した。洗浄したパラジウム／金／担体組成物を、約１１０℃で４時間乾燥した。
工程６．パラジウム／金／担体組成物に、２ｇの酢酸カリウムの担体吸水量相当の量の水溶液を含浸させ、１１０℃で４時間乾燥した。
Comparative Example 4 Preparation of catalyst J (alkaline solution + solution A is 3.0 times, once dried)
A catalyst was prepared by the following procedure using a silica sphere carrier (sphere diameter 5 mm, specific surface area 155 m 2 / g, water absorption 0.85 g / g, HSV-I from Shanghai Kaiyuan Chemical Technology Co., Ltd.).
Step 1. 23 g of carrier (water absorption 19.7 g) was impregnated with an aqueous solution equivalent to (1 times) the amount of water absorption of carrier containing 2.5 g of Na 2 SiO 3 .9H 2 O. The container containing the carrier and the aqueous solution was gently shaken to completely impregnate the solution.
Step 2. The support obtained in step 1 was dried in air at 110 ° C. for 4 hours.
Step 3. The carrier obtained in step 2 was immersed in an aqueous solution equivalent to twice the water absorption amount of the carrier containing 1.5 g of 56 mass% Na 2 PdCl 4 aqueous solution and 1.5 g of 17 mass% HAuCl 4 and allowed to stand for 20 hours. .
Step 4. To the aqueous solution in Step 3, 3.3 ml of a 52 mass% hydrazine hydrate aqueous solution was added, gently mixed, and allowed to stand at room temperature for 4 hours.
Step 5. The palladium / gold / carrier composition obtained in the previous step was washed with water and continued until no chloride ions were present in the washed water. The washed palladium / gold / support composition was dried at about 110 ° C. for 4 hours.
Step 6. The palladium / gold / carrier composition was impregnated with an aqueous solution of 2 g of potassium acetate corresponding to the amount of water absorbed by the carrier, and dried at 110 ° C. for 4 hours.
比較例５ 触媒Ｋの調製
工程２．において、さらにＣａＣｌ２０．５０ｇを加えた担体吸水量の２倍相当の量の水溶液を用いた以外は比較例１の操作を繰り返した。
Comparative Example 5 Preparation of Catalyst K Step 2. In Example 1, the procedure of Comparative Example 1 was repeated, except that an aqueous solution having an amount equivalent to twice the water absorption amount of the carrier added with 0.50 g of CaCl 2 was used.
比較例６ 触媒Ｌの調製
工程２．において、さらにＭｇＣｌ２・６Ｈ２Ｏ０．９１ｇを加えた担体吸水量の２倍相当の量の水溶液を用いた以外は比較例１の操作を繰り返した。
Comparative Example 6 Preparation of Catalyst L Step 2. In Example 1, the operation of Comparative Example 1 was repeated except that an aqueous solution having an amount equivalent to twice the water absorption amount of the carrier added with 0.91 g of MgCl 2 .6H 2 O was used.
実施例７ 触媒Ｍの調製
工程２．において、さらにＣａＣｌ２０．５０ｇを加えた担体吸水量の２倍相当の量の水溶液を用いた以外は実施例１の操作を繰り返した。
Example 7 Preparation of Catalyst M Step 2. In Example 1, the procedure of Example 1 was repeated except that an aqueous solution having an amount equivalent to twice the water absorption amount of the carrier with 0.50 g of CaCl 2 added was used.
実施例８ 触媒Ｎの調製
工程２．において、さらにＭｇＣｌ２・６Ｈ２Ｏ０．９１ｇを加えた担体吸水量の２倍相当の量の水溶液を用いた以外は実施例１の操作を繰り返した。
Example 8 Preparation of Catalyst N Step 2. In Example 1, the procedure of Example 1 was repeated except that an aqueous solution having an amount equivalent to twice the water absorption amount of the carrier added with 0.91 g of MgCl 2 .6H 2 O was used.
実施例９ 触媒Ｏの調製
工程４と工程５の間に以下の工程を加えた以外は実施例２の操作を繰り返した。
工程Ｏ−１．ケイタングステン酸９ｇを含む吸水量相当の量の水を、工程４で得られたパラジウム／金／バリウム化合物／担体組成物に含浸担持した。
工程Ｏ−２．工程Ｏ−１で得られたパラジウム／金／バリウム／ケイタングステン酸／担体組成物の水洗浄を１夜間継続した。
工程Ｅ−３．工程Ｏ−２で得られたパラジウム／金／バリウム／ケイタングステン酸／担体組成物を約１１０℃で４時間乾燥した。
Example 9 Preparation of Catalyst O The procedure of Example 2 was repeated except that the following steps were added between Step 4 and Step 5.
Step O-1. Water equivalent to the amount of water absorption including 9 g of silicotungstic acid was impregnated and supported on the palladium / gold / barium compound / support composition obtained in Step 4.
Step O-2. Water washing of the palladium / gold / barium / silicotungstic acid / support composition obtained in step O-1 was continued overnight.
Step E-3. The palladium / gold / barium / silicotungstic acid / support composition obtained in Step O-2 was dried at about 110 ° C. for 4 hours.
比較例７ 触媒Ｐの調製
工程４と工程５の間に以下の工程を加えた以外は比較例２の操作を繰り返した。
工程Ｐ−１．工程４で得られたパラジウム／金／バリウム／担体組成物を吸水量の３倍相当の量の０．４５質量％酢酸水溶液に１時間浸漬した。
工程Ｐ−２．工程Ｐ−１で得られたパラジウム／金／バリウム／担体組成物の水洗浄を１夜間継続した。
工程Ｐ−３．工程Ｐ−２で得られたパラジウム／金／バリウム／担体組成物を約１１０℃で４時間乾燥した。
Comparative Example 7 Preparation of Catalyst P The operation of Comparative Example 2 was repeated except that the following steps were added between Step 4 and Step 5.
Step P-1. The palladium / gold / barium / carrier composition obtained in Step 4 was immersed in an aqueous 0.45 mass% acetic acid solution in an amount equivalent to three times the water absorption amount for 1 hour.
Step P-2. Water washing of the palladium / gold / barium / carrier composition obtained in Step P-1 was continued for 1 night.
Step P-3. The palladium / gold / barium / support composition obtained in Step P-2 was dried at about 110 ° C. for 4 hours.
［触媒の評価］
金属担持量の測定
担持触媒サンプル３ｇを粉砕し、内径３ｃｍのディスク状にプレスする。このディスクの金属量をフィリップス社製蛍光Ｘ線分析装置ＰＷ２４０４を用いて測定した。
金属表面積の測定
大倉理研株式会社製Ｒ６０１５を用いて、ＣＯパルス吸着法で測定した。
[Evaluation of catalyst]
Measurement of metal loading 3 g of the supported catalyst sample is pulverized and pressed into a disk shape having an inner diameter of 3 cm. The metal amount of the disk was measured using a fluorescent X-ray analyzer PW2404 manufactured by Philips.
Measurement of metal surface area Using a R6015 manufactured by Okura Riken Co., Ltd., measurement was performed by the CO pulse adsorption method.
初期触媒活性評価試験Ａ
触媒３ｃｃをガラスビーズ７５ｃｃで希釈して反応管（ＳＵＳ３１６Ｌ製、内径２２ｍｍ、長さ４８０ｍｍ）に充填する。反応温度１５０℃、反応圧力０．６ＭＰａＧ、ガス組成Ｃ２Ｈ４／Ｏ２／Ｈ２Ｏ／ＨＯＡｃ／Ｎ２＝４７．３／６．１／５．６／２６．３／１４．７（ｍｏｌ％）のガスを流量２０ｎＬ／ｈで流通させ、反応を行った。
Initial catalytic activity evaluation test A
3 cc of catalyst is diluted with 75 cc of glass beads and filled into a reaction tube (manufactured by SUS316L, inner diameter 22 mm, length 480 mm). Reaction temperature 150 ° C., reaction pressure 0.6 MPaG, gas composition C 2 H 4 / O 2 / H 2 O / HOAc / N 2 = 47.3 / 6.1 / 5.6 / 26.3 / 14.7 ( mol%) gas was allowed to flow at a flow rate of 20 nL / h to carry out the reaction.
反応器出口ガスの分析を、以下の方法を用いて行った。
１．酸素
絶対検量線法を用い、流出ガスを５０ｍｌ採取し、ガスクロマトグラフィーに付属する１ｍｌのガスサンプラーに全量流し、以下の条件で分析を行った。
ガスクロマトグラフィー：島津ガスクロマトグラフ用ガスサンプラ−（ＭＧＳ−４：計量管１ｍｌ）付ガスクロマトグラフィー（島津製作所製ＧＣ−１４（Ｂ）
カラム：ＭＳ−５Ａ ＩＳ ６０／８０ｍｅｓｈ（３ｍｍΦ×３ｍ）
キャリアーガス：ヘリウム（流量２０ｍｌ／ｍｉｎ．）
温度条件：検出器温度、気化室温度が１１０℃、カラム温度は７０℃一定
検出器：ＴＣＤ（Ｈｅ圧７０ｋＰａＧ、Ｃｕｒｒｅｎｔ１００ｍ（Ａ）
The reactor outlet gas was analyzed using the following method.
1. Using an oxygen absolute calibration curve method, 50 ml of the effluent gas was sampled, and the entire amount was flowed to a 1 ml gas sampler attached to gas chromatography, and analysis was performed under the following conditions.
Gas chromatography: Shimadzu gas chromatograph gas sampler (MGS-4: measuring tube 1 ml) with gas chromatography (Shimadzu GC-14 (B)
Column: MS-5A IS 60/80 mesh (3 mmΦ × 3 m)
Carrier gas: helium (flow rate 20 ml / min.)
Temperature conditions: Detector temperature, vaporization chamber temperature is 110 ° C., column temperature is constant 70 ° C. Detector: TCD (He pressure 70 kPaG, Current 100 m (A)
２．酢酸
内部標準法を用い、反応液１０ｍｌに対し、内部標準として１，４−ジオキサンを１ｍｌ添加したものを分析液として、そのうちの０．２μｌを注入して以下の条件で分析を行った。
ガスクロマトグラフィー：島津製作所製ＧＣ−１４Ｂ
カラム：パックドカラムＴｈｅｒｍｏｎ ３０００（長さ３ｍ、内径０．３ｍｍ）
キャリアーガス：窒素（流量２０ｍｌ／ｍｉｎ．）
温度条件：検出器温度、気化室温度が１８０℃、カラム温度は分析開始から６分間は５０℃保持、その後１０℃／ｍｉｎの昇温速度で１５０℃まで昇温し、１５０℃で１０分間保持
検出器：ＦＩＤ（Ｈ2 圧４０ｋＰａＧ、空気圧１００ｋＰａＧ）
2. The acetic acid internal standard method was used, and 10 ml of the reaction solution was added with 1 ml of 1,4-dioxane as an internal standard, and 0.2 μl was injected as an analysis solution, and analysis was performed under the following conditions.
Gas chromatography: Shimadzu GC-14B
Column: Packed column Thermon 3000 (length 3 m, inner diameter 0.3 mm)
Carrier gas: Nitrogen (flow rate 20 ml / min.)
Temperature conditions: Detector temperature, vaporization chamber temperature is 180 ° C, column temperature is kept at 50 ° C for 6 minutes from the start of analysis, then raised to 150 ° C at a rate of 10 ° C / min, and kept at 150 ° C for 10 minutes. Detector: FID (H 2 pressure 40 kPaG, air pressure 100 kPaG)
３．酢酸ビニル
分析は内部標準法を用い、反応液６ｇに対し、内部標準として酢酸ｎ−プロピルを１ｇ添加したものを分析液として、そのうちの０．３μｌを注入して以下の条件で分析した。
ガスクロマトグラフィー：島津製作所製ＧＣ−９Ａ
カラム：キャピラリーカラムＴＣ−ＷＡＸ（長さ３０ｍ、内径０．２５ｍｍ、膜厚０．５μｍ）
キャリアーガス：窒素（流量３０ｍｌ／ｍｉｎ．）
温度条件：検出器温度、気化室温度が２００℃、カラム温度は分析開始から２分間は４５℃保持、その後４℃／ｍｉｎの昇温速度で１３０℃まで昇温し、１３０℃で１５分間保持し、その後２５℃／ｍｉｎの昇温速度で２００℃まで昇温し、２００℃で１０分間保持
検出器：ＦＩＤ（Ｈ2 圧６０ｋＰａＧ、空気圧１００ｋＰａＧ）
反応開始４時間後にサンプリングを行い、触媒の初期活性を測定した。評価結果を表１に示す。
3. Vinyl acetate was analyzed using an internal standard method. To 6 g of the reaction solution, 1 g of n-propyl acetate as an internal standard was added as an analysis solution, 0.3 μl of the solution was injected, and analysis was performed under the following conditions.
Gas chromatography: Shimadzu GC-9A
Column: Capillary column TC-WAX (length 30 m, inner diameter 0.25 mm, film thickness 0.5 μm)
Carrier gas: Nitrogen (flow rate 30 ml / min.)
Temperature conditions: Detector temperature, vaporization chamber temperature is 200 ° C, column temperature is maintained at 45 ° C for 2 minutes from the start of analysis, then heated to 130 ° C at a temperature increase rate of 4 ° C / min, and maintained at 130 ° C for 15 minutes. Then, the temperature is increased to 200 ° C. at a temperature increase rate of 25 ° C./min and held at 200 ° C. for 10 minutes. Detector: FID (H 2 pressure 60 kPaG, air pressure 100 kPaG)
Sampling was performed 4 hours after the start of the reaction, and the initial activity of the catalyst was measured. The evaluation results are shown in Table 1.
初期触媒活性評価試験Ｂ
触媒５ｃｃを酢酸カリウム４０ｇ／Ｌが担持されたシリカ担体２０ｃｃで希釈して反応管に充填する。反応温度１５０℃、反応圧力０．６ＭＰａＧ、ガス組成Ｃ２Ｈ４／Ｏ２／Ｈ２Ｏ／ＨＯＡｃ／Ｎ２＝６０／４／１．３／１７／１７．７（ｍｏｌ％）のガスを流量４５ｎＬ／ｈで流通させ、反応を行った。
反応器出口ガスの分析は、初期反応活性評価Ａと同様の方法を用いて行った。触媒の初期活性評価結果を表２に示す。
Initial catalytic activity evaluation test B
5 cc of the catalyst is diluted with 20 cc of silica support on which 40 g / L of potassium acetate is supported, and charged into the reaction tube. A gas having a reaction temperature of 150 ° C., a reaction pressure of 0.6 MPaG, and a gas composition of C 2 H 4 / O 2 / H 2 O / HOAc / N 2 = 60/4 / 1.3 / 17 / 17.7 (mol%) The reaction was carried out at a flow rate of 45 nL / h.
The analysis of the reactor outlet gas was performed using the same method as in the initial reaction activity evaluation A. The initial activity evaluation results of the catalyst are shown in Table 2.
初期触媒活性試験Ｃ
触媒１５ｃｃを酢酸カリウム４０ｇ／Ｌが担持されたシリカ担体６０ｃｃで希釈して評価試験Ａで用いたのと同様の反応管に充填する。反応温度１５０℃、反応圧力０．４ＭＰａＧ、ガス組成Ｃ２Ｈ４／Ｏ２／Ｈ２Ｏ／ＨＯＡｃ／Ｎ２＝４７．３／６．１／５．６／２６．３／１４．７（ｍｏｌ％）のガスを流量７５ｎＬ／ｈで流通させ、反応を行った。
反応器出口ガスの分析は、初期反応活性評価Ａと同様の方法を用いて行った。触媒の初期活性（反応開始４時間後の値）の評価結果を表３に示す。
Initial catalytic activity test C
15 cc of the catalyst is diluted with 60 cc of a silica carrier on which 40 g / L of potassium acetate is supported, and charged in the same reaction tube as used in the evaluation test A. Reaction temperature 150 ° C., reaction pressure 0.4 MPaG, gas composition C 2 H 4 / O 2 / H 2 O / HOAc / N 2 = 47.3 / 6.1 / 5.6 / 26.3 / 14.7 ( mol%) gas was circulated at a flow rate of 75 nL / h to carry out the reaction.
The analysis of the reactor outlet gas was performed using the same method as in the initial reaction activity evaluation A. Table 3 shows the evaluation results of the initial activity of the catalyst (value 4 hours after the start of the reaction).
長時間反応後の触媒活性低下試験
触媒１５ｃｃを酢酸カリウム４０ｇ／Ｌが担持されたシリカ担体６０ｃｃで希釈して評価試験Ａで用いたのと同様の反応管に充填する。反応温度１５０℃、反応圧力０．４ＭＰａＧ、ガス組成Ｃ２Ｈ４／Ｏ２／Ｈ２Ｏ／ＨＯＡｃ／Ｎ２＝４７．３／６．１／５．６／２６．３／１４．７（ｍｏｌ％）のガスを流量７５ｎＬ／ｈで流通させ、反応を行った。反応開始後約７００時間後の触媒性能を表４に示す。
Test for reducing catalyst activity after long-time reaction 15 cc of the catalyst is diluted with 60 cc of a silica support on which 40 g / L of potassium acetate is supported, and charged in the same reaction tube as used in the evaluation test A. Reaction temperature 150 ° C., reaction pressure 0.4 MPaG, gas composition C 2 H 4 / O 2 / H 2 O / HOAc / N 2 = 47.3 / 6.1 / 5.6 / 26.3 / 14.7 ( mol%) gas was circulated at a flow rate of 75 nL / h to carry out the reaction. Table 4 shows the catalyst performance after about 700 hours from the start of the reaction.
実施例１０ 触媒Ｑの調製（アルカリ溶液＋溶液Ａが３．０倍）
シリカ球体担体（球体直径５ｍｍ、比表面積１５５ｍ２／ｇ、吸水率０．８５ｇ／ｇ、上海海源化工科技有限公司のＨＳＶ−Ｉ）を用いて、触媒を以下の手順で調製した。
工程１．担体２３ｇ（吸水量１９．６ｇ）に、Ｎａ２ＳｉＯ３・９Ｈ２Ｏ１．９７ｇを含む担体吸水量相当（１倍）の量の水溶液を含浸させた。担体と水溶液が入った容器を静かに振り動かし、溶液を完全に含浸させた。
工程２．工程１で得られた担体を５６質量％Ｎａ２ＰｄＣｌ４水溶液１．５ｇ、ＢａＣｌ２・２Ｈ２Ｏ１．９ｇおよび１７質量％ＨＡｕＣｌ４１．５ｇを含む担体吸水量の２倍の水溶液に浸漬し、２０時間静置した。
工程３．工程２の水溶液に５２質量％ヒドラジン水和物水溶液３．３ｍｌを加え、静かに混合し、室温で４時間静置した。
工程４．パラジウム／金／担体組成物の洗浄を水洗水に塩化物イオンが無くなるまで継続した。洗浄したパラジウム／金／担体組成物を、約１１０℃で４時間乾燥した。
工程５．パラジウム／金／担体組成物に、２ｇの酢酸カリウムの担体吸水量相当の量の水溶液を含浸させ、１１０℃で４時間乾燥した。
Example 10 Preparation of catalyst Q (alkaline solution + solution A is 3.0 times)
A catalyst was prepared by the following procedure using a silica sphere carrier (sphere diameter 5 mm, specific surface area 155 m 2 / g, water absorption 0.85 g / g, HSV-I from Shanghai Kaiyuan Chemical Technology Co., Ltd.).
Step 1. 23 g of carrier (water absorption of 19.6 g) was impregnated with an aqueous solution equivalent to (1 ×) the amount of water absorption of carrier including 1.97 g of Na 2 SiO 3 .9H 2 O. The container containing the carrier and the aqueous solution was gently shaken to completely impregnate the solution.
Step 2. The carrier obtained in step 1 was immersed in an aqueous solution twice as much as the carrier water absorption containing 1.5 g of 56 mass% Na 2 PdCl 4 aqueous solution, 1.9 g of BaCl 2 .2H 2 O and 1.5 g of 17 mass% HAuCl 4. And left for 20 hours.
Step 3. To the aqueous solution of step 2, 3.3 ml of a 52 mass% hydrazine hydrate aqueous solution was added, gently mixed, and allowed to stand at room temperature for 4 hours.
Step 4. Washing of the palladium / gold / carrier composition was continued until the rinse water was free of chloride ions. The washed palladium / gold / support composition was dried at about 110 ° C. for 4 hours.
Step 5. The palladium / gold / carrier composition was impregnated with an aqueous solution of 2 g of potassium acetate corresponding to the amount of water absorbed by the carrier, and dried at 110 ° C. for 4 hours.
比較例８ 触媒Ｒの調製（アルカリ溶液＋溶液Ａが２．９倍）
工程１．において、Ｎａ２ＳｉＯ３・９Ｈ２Ｏ１．９７ｇを含む担体吸水量の０．９倍相当の量の水溶液を含浸させた以外は実施例１０の操作を繰り返した。
Comparative Example 8 Preparation of catalyst R (alkaline solution + solution A is 2.9 times)
Step 1. In Example 1, the operation of Example 10 was repeated except that an aqueous solution having an amount equivalent to 0.9 times the water absorption amount of the carrier containing 1.97 g of Na 2 SiO 3 .9H 2 O was impregnated.
比較例９ 触媒Ｓの調製（アルカリ溶液＋溶液Ａが３．０倍、工程１と工程２の間に乾燥工程）
工程１．と工程２．の間に、室温で４．５時間放置し、吸水量を０．９倍になるまで担体を乾燥させた以外は実施例２の操作を繰り返した。
Comparative Example 9 Preparation of catalyst S (alkaline solution + solution A is 3.0 times, drying step between step 1 and step 2)
Step 1. And step 2. In the meantime, the procedure of Example 2 was repeated except that the carrier was left to stand at room temperature for 4.5 hours, and the carrier was dried until the water absorption amount became 0.9 times.
初期触媒活性評価試験Ｄ
初期触媒活性評価Ａと同様の方法で反応開始４時間後の触媒の初期活性評価を行った。結果を表５に示す。
実施例１０と比較例８とではアルカリ溶液量を変えており、アルカリ溶液量が少ない場合には、活性が低下することがわかる。また、実施例２と比較例９を比較すると、アルカリ溶液担持後に乾燥工程を経て、溶液量を低下させることで活性が低下することが示される。
Initial catalytic activity evaluation test D
The initial activity of the catalyst was evaluated 4 hours after the start of the reaction in the same manner as in the initial catalyst activity evaluation A. The results are shown in Table 5.
In Example 10 and Comparative Example 8, the amount of the alkaline solution is changed, and it can be seen that the activity decreases when the amount of the alkaline solution is small. Moreover, when Example 2 and Comparative Example 9 are compared, it is shown that the activity decreases by decreasing the amount of the solution through a drying step after supporting the alkali solution.
本発明は、初期活性および選択性に優れる酢酸アルケニル製造用触媒を提供することができ、産業上有用である。 INDUSTRIAL APPLICABILITY The present invention can provide a catalyst for producing alkenyl acetate having excellent initial activity and selectivity, and is industrially useful.
Claims (8)
１．担体にアルカリ溶液を含浸させる工程、
２．担体に少なくとも、パラジウムまたは白金を含む化合物および第１１族元素を含む化合物の溶液Ａを接触含浸させる工程、
３．還元処理を行う工程および
４．担体に酢酸塩を担持する工程
を含む酢酸アルケニル製造用触媒の製造方法であって、第１の工程において担体に担体の吸水量の０．９質量倍を超え、１．０質量倍以下のアルカリ溶液を含浸させた後、乾燥処理をすることなく続けて第２の工程で溶液Ａと接触させて触媒前駆体とし、かつ、アルカリ溶液および溶液Ａの総量を担体の吸水量の１．５質量倍以上８．０質量倍以下とすることを特徴とする、少なくとも（ａ）担体、（ｂ）パラジウムまたは白金、（ｃ）第１１族元素および（ｄ）酢酸塩からなる酢酸アルケニル製造用触媒の製造方法。 At least the following steps 1. Impregnating a carrier with an alkaline solution,
2. A step of impregnating a support with a solution A of a compound containing at least palladium or platinum and a compound containing a Group 11 element;
3. 3. performing a reduction treatment; A method for producing a catalyst for producing alkenyl acetate comprising a step of supporting an acetate on a carrier, wherein the alkali in the first step exceeds 0.9 mass times the amount of water absorption of the carrier and is 1.0 mass times or less. After impregnating the solution, the catalyst A is brought into contact with the solution A in the second step without drying , and the total amount of the alkaline solution and the solution A is 1.5 mass of the water absorption amount of the carrier. characterized by more than doubled 8.0 times by mass or less, at least (a) a carrier, (b) palladium or platinum, (c), group 11 element and (d) a catalyst for alkenyl acetate production consisting acetate Production method.
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