JP2001300328A - Supported catalyst and manufacturing method - Google Patents
Supported catalyst and manufacturing methodInfo
- Publication number
- JP2001300328A JP2001300328A JP2000121478A JP2000121478A JP2001300328A JP 2001300328 A JP2001300328 A JP 2001300328A JP 2000121478 A JP2000121478 A JP 2000121478A JP 2000121478 A JP2000121478 A JP 2000121478A JP 2001300328 A JP2001300328 A JP 2001300328A
- Authority
- JP
- Japan
- Prior art keywords
- supported catalyst
- oxide carrier
- oxide
- silica
- pore volume
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000011148 porous material Substances 0.000 claims abstract description 135
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000009826 distribution Methods 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 30
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 230000008020 evaporation Effects 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 150000003058 platinum compounds Chemical group 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 61
- 239000012736 aqueous medium Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 150000002736 metal compounds Chemical class 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- -1 platinum group metal compound Chemical class 0.000 claims description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 239000006069 physical mixture Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 6
- 150000002941 palladium compounds Chemical class 0.000 claims 2
- 150000003284 rhodium compounds Chemical class 0.000 claims 2
- 150000003304 ruthenium compounds Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052763 palladium Inorganic materials 0.000 abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 20
- 239000012224 working solution Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 230000009467 reduction Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- INPHIYULSHLAHR-UHFFFAOYSA-N 1-pentylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCCC INPHIYULSHLAHR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 2
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RKMPHYRYSONWOL-UHFFFAOYSA-N 1-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CC)CCC2 RKMPHYRYSONWOL-UHFFFAOYSA-N 0.000 description 1
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- LZNGSHFBWBKBFH-UHFFFAOYSA-N 1-pentyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(CCCCC)CCC2 LZNGSHFBWBKBFH-UHFFFAOYSA-N 0.000 description 1
- OIDFWDRICABFFC-UHFFFAOYSA-N 1-tert-butyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(C(C)(C)C)CCC2 OIDFWDRICABFFC-UHFFFAOYSA-N 0.000 description 1
- BGJQNPIOBWKQAW-UHFFFAOYSA-N 1-tert-butylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)(C)C BGJQNPIOBWKQAW-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 235000013345 egg yolk Nutrition 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002609 medium Substances 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化物担体に金属
化合物を担持させた担持触媒及びその製造方法に関す
る。また、本発明の担持触媒存在下においてアントラキ
ノン類の水素化反応を行い、過酸化水素を製造する方法
に関する。The present invention relates to a supported catalyst in which a metal compound is supported on an oxide carrier, and a method for producing the same. Also, the present invention relates to a method for producing hydrogen peroxide by performing a hydrogenation reaction of anthraquinones in the presence of a supported catalyst.
【０００２】[0002]
【従来の技術】酸化物担体に金属が担持された担持触媒
は、例えば、白崎高保、藤堂尚之編、触媒調製、（１９
７４）講談社に記載されているように種々の化学反応に
利用される。活性成分として用いられる金属は、一般的
に周期律表において第４、第５、第６周期の第IIIＡ族
から第ＩＢ族に属する遷移金属である。なかでもパラジ
ウム触媒や白金触媒などの白金族金属は、水素化反応な
どにおいて良好な活性、選択性を示すことから、工業的
に利用されている触媒の一つである。これらの触媒の活
性成分である白金族金属は比較的高価なため、一般的に
担体に担持された担持触媒として用いられる。担持触媒
の金属成分による活性や選択性の序列化は、古くから行
われてきた。2. Description of the Related Art A supported catalyst in which a metal is supported on an oxide carrier is described in, for example, Takayasu Shirasaki and Naoyuki Todo, Catalyst Preparation, (19)
74) Used for various chemical reactions as described in Kodansha. The metal used as the active ingredient is generally a transition metal belonging to Groups IVA to IB of the fourth, fifth and sixth periods in the periodic table. Among them, platinum group metals such as palladium catalysts and platinum catalysts are one of the industrially used catalysts because they exhibit good activity and selectivity in hydrogenation reactions and the like. Since the platinum group metal which is an active component of these catalysts is relatively expensive, it is generally used as a supported catalyst supported on a carrier. The ordering of activity and selectivity by the metal component of the supported catalyst has been performed for a long time.
【０００３】一方、担持触媒の物性の中では、平均細孔
直径、ＢＥＴ比表面積と全細孔容積が重要であること
が、触媒学会編、“触媒講座第５巻（工学編１） 触媒
設計”、ｐ１２２−１３３（１９８５）講談社に記載さ
れている。五十嵐、“化学工学”、６０（４）、２３２
（１９９６）では、工業触媒の触媒機能を最大限に発揮
するためには担持触媒の構造的要因の最適化が重要であ
ると記載されている。小沼、“表面”、２３（８）、４
８２（１９８５）では、担体の細孔制御が触媒を設計す
る上で重要であり、触媒構造の最適化はほとんどの場合
触媒製造に用いる担体の細孔を制御することにより行わ
れるとしている。このように、従来担持触媒の細孔構造
は、担体の細孔構造が保持されることを前提としてお
り、担持触媒の構造を最適化するために、担体の平均細
孔直径、全細孔容積、ＢＥＴ比表面積等を制御すること
が行われてきた。On the other hand, the average pore diameter, BET specific surface area and total pore volume are important in the physical properties of a supported catalyst. ", P 122-133 (1985) Kodansha. Igarashi, "Chemical Engineering", 60 (4), 232
(1996) states that it is important to optimize the structural factors of a supported catalyst in order to maximize the catalytic function of an industrial catalyst. Onuma, “surface”, 23 (8), 4
82 (1985) states that control of the pores of the support is important in designing the catalyst, and optimization of the catalyst structure is almost always performed by controlling the pores of the support used in the production of the catalyst. As described above, the pore structure of the conventionally supported catalyst is based on the premise that the pore structure of the carrier is maintained. In order to optimize the structure of the supported catalyst, the average pore diameter of the carrier and the total pore volume are optimized. , BET specific surface area and the like have been controlled.
【０００４】酸化物担体を用いた担持触媒は、例えば化
学工学協会、“化学工学の進歩 第１５集 触媒設
計”、ｐ４０−５４（１９８１）槇書店に記載されてい
るＡｄｓｏｒｐｔｉｎ法、Ｐｏｒｅ−ｆｉｌｌｉｎｇ
法、Ｉｎｃｉｐｉｅｎｔ ｗｅｔｎｅｓｓ法、Ｅｖａｐ
ｏｒａｔｉｏｎ ｔｏ ｄｒｙｎｅｓｓ法、Ｓｐｒａｙ
法などの含浸法あるいはイオン交換法などにより金属化
合物を担持し、その後必要に応じて分離、洗浄、乾燥、
酸化、焼成、還元等の工程を経て製造されている。A supported catalyst using an oxide carrier is described in, for example, the Adsorbtin method, Pore-filling described in Maki Shoten, p.
Method, Incipient wetness method, Evap
Oration to dryness method, Spray
The metal compound is supported by an impregnation method such as a method or an ion exchange method, and then, if necessary, separated, washed, dried,
It is manufactured through processes such as oxidation, firing, and reduction.
【０００５】このようにして製造された担持触媒は、例
えばアントラキノン法による過酸化水素の製造におい
て、アントラキノン類の水素化反応に使用され得る。現
在、工業的に行われている過酸化水素の主な製造方法
は、アントラキノン類を反応媒体とする方法でアントラ
キノン法と呼ばれる。一般に、アントラキノン類は、適
当な有機溶媒に溶解して使用される。アントラキノン類
を有機溶媒に溶かして調製した溶液は、作動溶液と呼ば
れる。有機溶媒は、単独あるいは混合物として用いられ
るが、通常２種類の有機溶媒の混合物が使用される。ア
ントラキノン法では、還元工程において上記の作動溶液
中のアントラキノン類を触媒の存在下で水素により還元
し、対応するアントラヒドロキノン類を生成させる。次
いで、酸化工程においてそのアントラヒドロキノン類を
空気もしくは酸素を含有する気体によって酸化してアン
トラキノン類に再度転化し、同時に過酸化水素を生成さ
せる。作動溶液中に生成した過酸化水素は、抽出工程に
おいて通常水を用いて抽出され、作動溶液から分離され
る。過酸化水素が抽出された作動溶液は、再び還元工程
に戻され、循環プロセスを形成する。このプロセスは、
実質的に水素と空気から過酸化水素を製造するものであ
り、極めて効率的なプロセスである。既にこの循環プロ
セスを用いて、過酸化水素が工業的に製造されている。[0005] The supported catalyst thus produced can be used for the hydrogenation reaction of anthraquinones, for example, in the production of hydrogen peroxide by the anthraquinone method. At present, the main method for producing hydrogen peroxide industrially is a method using anthraquinones as a reaction medium and is called an anthraquinone method. Generally, anthraquinones are used after being dissolved in a suitable organic solvent. A solution prepared by dissolving anthraquinones in an organic solvent is called a working solution. The organic solvent is used alone or as a mixture, but usually a mixture of two organic solvents is used. In the anthraquinone method, in the reduction step, anthraquinones in the above working solution are reduced with hydrogen in the presence of a catalyst to produce corresponding anthrahydroquinones. Next, in the oxidation step, the anthrahydroquinone is oxidized by air or a gas containing oxygen to be converted again into anthraquinone, and at the same time, hydrogen peroxide is generated. Hydrogen peroxide generated in the working solution is usually extracted with water in the extraction step and separated from the working solution. The working solution from which the hydrogen peroxide has been extracted is returned again to the reduction step, forming a circulation process. This process is
It produces hydrogen peroxide substantially from hydrogen and air, a very efficient process. Hydrogen peroxide has already been produced industrially using this circulation process.
【０００６】上記の循環プロセスの還元工程でアントラ
キノン類の水素化反応に使用される触媒としては、ラネ
ーニッケル触媒、パラジウム黒触媒、担体に担持された
パラジウム担持触媒が知られている。ラネーニッケル触
媒は、高活性であるが、作動溶液中の微量過酸化水素に
より顕著に劣化すること、発火金属であるため取り扱い
上の危険を伴うこと及び選択性が低いことなど多くの欠
点を有する。パラジウム黒触媒は、活性や選択性に優れ
る。しかし、作動溶液からの分離が困難であり、パラジ
ウム存在下で分解しやすい過酸化水素を工業的に製造す
るには致命的な欠点を有する。担体に担持されたパラジ
ウム担持触媒は、活性や選択性がパラジウム黒触媒より
やや劣るものの、作動溶液からの分離が容易であり、過
酸化水素を工業的に製造するために適した触媒である。
パラジウム担持触媒としては、シリカ、アルミナ、ジル
コニア、シリカ・アルミナ、アルミノ珪酸塩、アルカリ
土類金属の炭酸塩や活性炭など種々の担体に担持された
担持触媒が提案されている。しかし、これら全ての担持
触媒が工業用触媒として必要な安価で、触媒強度が強
く、活性や選択性が高いという条件を満たしているわけ
ではなく、実際に工業的に利用できるのは上記の担持触
媒のごく一部である。[0006] Raney nickel catalysts, palladium black catalysts, and palladium-supported catalysts supported on carriers are known as catalysts used in the hydrogenation reaction of anthraquinones in the reduction step of the above-mentioned circulation process. Although Raney nickel catalyst is highly active, it has many drawbacks, such as being significantly degraded by a trace amount of hydrogen peroxide in the working solution, being dangerous because it is an ignition metal, and having low selectivity. Palladium black catalyst is excellent in activity and selectivity. However, it is difficult to separate it from the working solution and has a fatal drawback for industrially producing hydrogen peroxide which is easily decomposed in the presence of palladium. The palladium-supported catalyst supported on a carrier has a slightly lower activity and selectivity than a palladium black catalyst, but is easily separated from a working solution, and is a catalyst suitable for industrially producing hydrogen peroxide.
As a supported palladium catalyst, a supported catalyst supported on various supports such as silica, alumina, zirconia, silica-alumina, aluminosilicate, carbonate of alkaline earth metal and activated carbon has been proposed. However, not all of these supported catalysts satisfy the conditions of low cost, high catalyst strength, high activity and high selectivity required for industrial catalysts. Only a small part of the catalyst.
【０００７】アルミナに担持されたパラジウム担持触媒
は、工業的に利用できる数少ない担持触媒の一つであ
り、活性、強度が比較的高いという利点を有する。米国
特許５，７７２，９９７では、特定の結晶相、平均細孔
直径、粒子径及びＢＥＴ比表面積を有するアルミナ、シ
リカ、チタニア、ジルコニア、シリカ・アルミナ、シリ
カ・アルミナ・マグネシア等の焼成酸化物を担体として
製造された触媒を使用することによってアントラキノン
法の改良に成功している。A palladium-supported catalyst supported on alumina is one of the few supported catalysts that can be industrially used, and has the advantage of relatively high activity and strength. In U.S. Pat. No. 5,772,997, a calcined oxide such as alumina, silica, titania, zirconia, silica-alumina, silica-alumina-magnesia having a specific crystal phase, average pore diameter, particle diameter and BET specific surface area is prepared. The anthraquinone process has been successfully improved by using a prepared catalyst as a support.
【０００８】特公昭６３−２９５８８では、アルミナに
担持されたパラジウム担持触媒より優れた担持触媒とし
てシリカを担体としてパラジウムの他にジルコニウム、
トリウム、セリウム、チタン及びアルミニウムから選ば
れた少なくとも１種類の金属を添加した担持触媒とその
製造方法が提案されている。Japanese Patent Publication No. 63-29588 discloses a catalyst which is superior to a palladium-supported catalyst supported on alumina.
A supported catalyst to which at least one metal selected from thorium, cerium, titanium and aluminum has been added and a method for producing the same have been proposed.
【０００９】米国特許５，８５３，６９３では、シリカ
に担持されたパラジウムと少なくとも１種類のアルカリ
金属からなる担持触媒およびその製造方法が開示されて
いる。その中で、担持触媒の活性や強度を支配する重要
な因子として平均細孔直径、細孔容積、粒子径、粒子形
状が挙げられ、８〜４０ｎｍの平均細孔直径を有する担
持触媒は、活性が高く、活性劣化速度が小さいとしてい
る。更に、用いる担体の平均細孔直径範囲を制限して
も、得られる担持触媒の平均細孔直径は焼成や処理する
アルカリ水溶液のｐＨなどの触媒製造条件によって多少
変化することが指摘されている。しかし、担持触媒製造
時の焼成温度によって平均細孔直径を変化させるには、
かなりの高温を要し、なおかつ平均細孔直径と共に全細
孔容積やＢＥＴ比表面積も低下するため、担持触媒の活
性が著しく低下する。また、触媒製造時のｐＨによって
平均細孔直径を変化させるには、ｐＨを過度に高める必
要があり、担持触媒の強度や収率の低下を招く。US Pat. No. 5,853,693 discloses a supported catalyst comprising palladium supported on silica and at least one alkali metal and a method for producing the same. Among them, important factors governing the activity and strength of the supported catalyst include average pore diameter, pore volume, particle diameter, and particle shape. Supported catalysts having an average pore diameter of 8 to 40 nm have a high activity. And the activity degradation rate is low. Further, it has been pointed out that even if the average pore diameter range of the carrier used is limited, the average pore diameter of the obtained supported catalyst slightly varies depending on catalyst production conditions such as the pH of the alkaline aqueous solution to be calcined or treated. However, to change the average pore diameter depending on the calcination temperature during the production of a supported catalyst,
Since a considerably high temperature is required and the total pore volume and the BET specific surface area are reduced along with the average pore diameter, the activity of the supported catalyst is significantly reduced. Further, in order to change the average pore diameter depending on the pH at the time of the production of the catalyst, it is necessary to excessively increase the pH, which causes a decrease in the strength and yield of the supported catalyst.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、アン
トラキノン類の水素化反応などに好適な担持触媒を提供
すること、および、担持触媒製造時に活性や強度を低下
させることなく、平均細孔直径を選択的に変化させ、所
望の平均細孔直径を有する担持触媒を製造する方法を提
供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a supported catalyst suitable for the hydrogenation reaction of anthraquinones and the like, and to reduce the average pore size without lowering the activity or strength during the production of the supported catalyst. It is an object of the present invention to provide a method for producing a supported catalyst having a desired average pore diameter by selectively changing the diameter.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、担持触媒
の細孔構造の骨格を決めるという意味で担体の細孔構造
が重要であり、担持触媒の細孔構造を決定する上で担持
触媒の製造方法が重要であるとの認識のもと、上記課題
を解決するため鋭意検討した結果、担持触媒の製造にお
いて乾燥工程が、単に水分を除去するものではなく、酸
化物担体に金属化合物を担持するのと同時に、又は、担
持させた後に、酸化物担体を水媒体で接触処理して特定
ｐＨの水媒体を酸化物担体に含浸させ、これに引き続
き、特定の温度、特定の平均蒸発速度で酸化物担体中に
残存する水媒体を蒸発させる乾燥処理することにより、
活性や強度を低下させることなく担持触媒の平均細孔直
径を選択的に変化させられることを見出した。更に、そ
のような製造方法により製造された担持触媒は、細孔容
積−細孔直径分布曲線において細孔容積のピークが細孔
直径の大きい方に移動した細孔分布を有し、アントラキ
ノン類の水素化反応などに対し高活性を示すことを見出
した。本発明はこれらの知見に基づきなされた。Means for Solving the Problems The present inventors have determined that the pore structure of the carrier is important in determining the skeleton of the pore structure of the supported catalyst. Based on the recognition that the method for producing the catalyst is important, as a result of intensive studies to solve the above-mentioned problems, the drying step in the production of the supported catalyst does not simply remove moisture, but the metal compound is added to the oxide carrier. Simultaneously with or after loading, the oxide carrier is contact-treated with an aqueous medium to impregnate the oxide carrier with an aqueous medium having a specific pH, followed by a specific temperature and a specific average evaporation. By performing a drying treatment to evaporate the aqueous medium remaining in the oxide carrier at a speed,
It has been found that the average pore diameter of the supported catalyst can be selectively changed without lowering the activity or strength. Further, the supported catalyst produced by such a production method has a pore distribution in which the peak of the pore volume moves to the larger pore diameter in the pore volume-pore diameter distribution curve, and the anthraquinones It has been found that it shows high activity against hydrogenation reaction and the like. The present invention has been made based on these findings.
【００１２】すなわち、本発明は酸化物担体と酸化物担
体の重量に対して０．１〜１０重量％の金属から本質的
になる担持触媒であって、細孔容積−細孔直径分布曲線
において細孔直径が１０ｎｍ以上の領域に細孔容積のピ
ークが存在する細孔分布を有し、メジアン径変化率が４
％以下であることを特徴とする担持触媒に関する。That is, the present invention relates to a supported catalyst consisting essentially of an oxide carrier and 0.1 to 10% by weight of a metal based on the weight of the oxide carrier, and having a pore volume-pore diameter distribution curve. It has a pore distribution in which a pore volume peak exists in a region where the pore diameter is 10 nm or more, and the median diameter change rate is 4
% Or less.
【００１３】更に、本発明は、酸化物担体と酸化物担体
の重量に対して０．１〜１０重量％の金属から本質的に
なる担持触媒を製造する方法であり、金属化合物を酸化
物担体に担持するのと同時に、又は、担持した後に、酸
化物担体を水媒体で接触処理してｐＨ６．０〜１１．０
の水媒体を酸化物担体に含浸させる工程と、これに引き
続く５０℃以上の乾燥温度、酸化物担体の重量に対して
０．５５ｍｌ／（ｇ・ｈ）以下の平均蒸発速度で酸化物
担体中に残存する水媒体を蒸発させる乾燥処理工程を含
むことを特徴とする担持触媒の製造方法に関する。Further, the present invention relates to a method for producing a supported catalyst consisting essentially of 0.1 to 10% by weight of a metal based on the weight of an oxide carrier and the oxide carrier. Simultaneously with or after loading, the oxide carrier is contacted with an aqueous medium to obtain a pH of 6.0 to 11.0.
Impregnating the oxide carrier with an aqueous medium, followed by a drying temperature of 50 ° C. or higher and an average evaporation rate of 0.55 ml / (g · h) or less with respect to the weight of the oxide carrier. The present invention relates to a method for producing a supported catalyst, which comprises a drying treatment step of evaporating an aqueous medium remaining in the catalyst.
【００１４】[0014]
【発明の実施の形態】本発明に用いられる酸化物担体と
しては、通常用いられる触媒担体であるシリカ、アルミ
ナ、チタニア、ジルコニアなどの酸化物、シリカ・アル
ミナ、シリカ・チタニア、シリカ・アルミナ・チタニア
などの複合酸化物及びこれらの２以上の物理的混合物が
挙げられる。中でも、少なくとも無定形シリカ粒子を含
む酸化物担体が好ましく、無定形シリカ粒子を５０重量
％以上含む酸化物担体がより好ましく、無定形シリカを
８０重量％以上含むものが最も好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Examples of the oxide carrier used in the present invention include commonly used catalyst carriers such as oxides such as silica, alumina, titania and zirconia, silica-alumina, silica-titania, silica-alumina-titania. And a physical mixture of two or more thereof. Among them, an oxide carrier containing at least amorphous silica particles is preferable, an oxide carrier containing 50% by weight or more of amorphous silica particles is more preferable, and an oxide carrier containing 80% by weight or more of amorphous silica is most preferable.
【００１５】酸化物担体の粒子径、粒度分布および粒子
形状は、特に制限はない。通常の触媒担体として使用さ
れる酸化物担体の粒子径、粒度分布および粒子形状であ
ればよく、担持触媒を使用する反応プロセスに応じて選
ばれる。例えば、アントラキノン類の水素化反応用とし
ては、通常、酸化物担体のメジアン径が１μｍ〜２００
μｍであり、好ましくは２０〜１８０μｍであり、より
好ましくは３０〜１５０μｍである。酸化物担体の形状
としては、不定形、球状、円柱、三つ葉、四つ葉、リン
グおよびハニカム等が例示される。The particle size, particle size distribution and particle shape of the oxide carrier are not particularly limited. The particle diameter, particle size distribution and particle shape of the oxide carrier used as a usual catalyst carrier may be selected, depending on the reaction process using the supported catalyst. For example, for a hydrogenation reaction of anthraquinones, usually, the median diameter of the oxide carrier is 1 μm to 200 μm.
μm, preferably 20 to 180 μm, more preferably 30 to 150 μm. Examples of the shape of the oxide carrier include amorphous, spherical, cylindrical, three-leaf, four-leaf, ring, and honeycomb.
【００１６】本発明において、酸化物担体の全細孔容積
は、酸化物担体単位重量当たりの全細孔容積で定義さ
れ、通常０．２〜２．０ｍｌ／ｇであり、好ましくは
０．３〜１．５ｍｌ／ｇ、より好ましくは０．５〜１．
０ｍｌ／ｇである。本発明では、酸化物担体の全細孔容
積が前記範囲内である限り、他の特徴は実質的に制限さ
れず、目的とする担持触媒を製造することができる。従
って、本発明に用いられる酸化物担体の平均細孔直径は
特に制限されないが、任意の平均細孔直径を有する触媒
を製造するためには、通常０．１〜１００ｎｍであり、
好ましくは１〜５０ｎｍであり、より好ましくは１〜２
５ｎｍである。また、酸化物担体の細孔直径分布は、特
に制限はなく、単一のピークや複数のピークを有しても
良いし、これらのピークがブロードでもシャープでも良
い。In the present invention, the total pore volume of the oxide carrier is defined as the total pore volume per unit weight of the oxide carrier, and is usually 0.2 to 2.0 ml / g, preferably 0.3 to 2.0 ml / g. -1.5 ml / g, more preferably 0.5-1.
0 ml / g. In the present invention, as long as the total pore volume of the oxide carrier is within the above range, other characteristics are not substantially limited, and a desired supported catalyst can be produced. Therefore, the average pore diameter of the oxide carrier used in the present invention is not particularly limited, but in order to produce a catalyst having an arbitrary average pore diameter, it is usually 0.1 to 100 nm,
It is preferably 1 to 50 nm, more preferably 1 to 2 nm.
5 nm. The pore diameter distribution of the oxide carrier is not particularly limited, and may have a single peak or a plurality of peaks, and these peaks may be broad or sharp.
【００１７】本発明に用いられる酸化物担体のＢＥＴ比
表面積もまた特に制限はないが、通常５０ｍ2／ｇ以上
であり、好ましくは１００ｍ2／ｇ以上であり、より好
ましくは１５０ｍ2／ｇ以上である。ＢＥＴ比表面積が
小さいと、金属化合物ロスの増大を招いたり、担持され
る金属化合物の含有率を高めるために担持操作を繰り返
し行う必要が生じる。The BET specific surface area of the oxide carrier used in the present invention is also not particularly limited, but is usually at least 50 m 2 / g, preferably at least 100 m 2 / g, more preferably at least 150 m 2 / g. It is. If the BET specific surface area is small, the loss of the metal compound increases, and the loading operation needs to be repeated in order to increase the content of the loaded metal compound.
【００１８】本発明の担持触媒は、酸化物担体の重量に
対して金属として通常０．１〜１０重量％、好ましくは
０．５〜５重量％の金属活性種を含む。金属としては、
周期律表第ＩＡ族のＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓなどの
アルカリ金属、第IIＡ族のＢｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂ
ａなどのアルカリ土類金属、第４、第５、第６周期の第
IIIＡ族から第ＩＢ族に属するＳｃ、Ｙ、Ｔｉ、Ｚｒ、
Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、
Ｒｅ、Ｆｅ、Ｒｕ、Ｏｓ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐ
ｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕなどの遷移金属、第IIＢ族
のＺｎなどが例示され、それぞれ単独でも混合物でも用
いられる。有機化合物の接触水素化反応用としては、上
記金属の中ではルテニウム、ロジウム、パラジウム、白
金などの白金族金属が優れる。アントラキノン類の水素
化反応では、特にパラジウムや白金が好適であり、少な
くともこれらの金属を単独あるいは混合物として含有す
る担持触媒が望ましい。なお、金属活性種は金属、酸化
物などの状態で存在する。The supported catalyst of the present invention contains 0.1 to 10% by weight, preferably 0.5 to 5% by weight of a metal active species as a metal based on the weight of the oxide carrier. As metal,
Alkali metals such as Li, Na, K, Rb and Cs of Group IA of the periodic table, Be, Mg, Ca, Sr and B of Group IIA
alkaline earth metals such as a, the fourth, fifth and sixth
Sc, Y, Ti, Zr, belonging to group IIIA to group IB
Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc,
Re, Fe, Ru, Os, Co, Rh, Ir, Ni, P
Examples thereof include transition metals such as d, Pt, Cu, Ag, and Au, and Zn of Group IIB, and these may be used alone or in a mixture. For the catalytic hydrogenation reaction of organic compounds, among the above metals, platinum group metals such as ruthenium, rhodium, palladium and platinum are excellent. In the hydrogenation reaction of anthraquinones, palladium and platinum are particularly suitable, and a supported catalyst containing at least one of these metals alone or as a mixture is desirable. The metal active species exists in a state such as a metal and an oxide.
【００１９】金属の担持様式、すなわち酸化物担体中の
金属の分布は、特に制限はない。担持触媒を使用する反
応プロセスに応じて選ばれる。担持様式は、ｅｇｇ ｓ
ｈｅｌｌ、ｅｇｇ ｗｈｉｔｅ、ｅｇｇ ｙｏｌｋおよ
びｕｎｉｆｏｒｍが例示される。例えば、アントラキノ
ン類の水素化反応では、ｅｇｇ ｓｈｅｌｌあるいはｕ
ｎｉｆｏｒｍの担持様式が好適である。The manner of metal loading, that is, the distribution of the metal in the oxide carrier, is not particularly limited. The choice is made according to the reaction process using the supported catalyst. The loading mode is eggs
, egg white, egg yolk and uniform are exemplified. For example, in the hydrogenation reaction of anthraquinones, eggg shell or u
Niform loading modes are preferred.
【００２０】酸化物担体への金属化合物の担持は、従来
公知のＡｄｓｏｒｐｔｉｏｎ法、Ｐｏｒｅ−ｆｉｌｌｉ
ｎｇ法、Ｉｎｃｉｐｉｅｎｔ ｗｅｔｎｅｓｓ法、Ｅｖ
ａｐｏｒａｔｉｏｎ ｔｏ ｄｒｙｎｅｓｓ法、Ｓｐｒ
ａｙ法などの含浸法あるいはイオン交換法により行うこ
とができる。The loading of the metal compound on the oxide carrier can be carried out by a conventionally known Adsorption method, Pore-filli.
ng method, Incipient wetness method, Ev
aporation to dryness method, Spr
It can be performed by an impregnation method such as the ay method or an ion exchange method.
【００２１】含浸法では、基本的に金属化合物の溶液と
酸化物担体を接触させる。この方法による金属化合物
は、水や脂肪族炭化水素、芳香族炭化水素、有機ハロゲ
ン化物、アルコール、エーテル、アミドなどの有機溶媒
に溶解する任意の金属化合物を用いることができる。よ
り具体的には、塩化物、硝酸塩、硫酸塩、酢酸塩、水酸
化物、錯塩などが例示される。溶液の金属化合物濃度
は、酸化物担体に対して金属として０．１〜１０重量％
の金属活性種を担持する触媒が得られるように適宜選択
される。金属活性種が二種類の場合、同時に担持しても
よく別々に担持してもよい。金属化合物を担持した後、
必要に応じて分離、洗浄、乾燥、酸化、焼成、還元、成
形およびこれらの組み合わせによる処理が行われる。こ
こで、担持とは、酸化物担体に金属化合物または金属を
物理的または化学的に吸着させることをいう。In the impregnation method, basically, a solution of a metal compound is brought into contact with an oxide carrier. As the metal compound according to this method, any metal compound soluble in an organic solvent such as water, an aliphatic hydrocarbon, an aromatic hydrocarbon, an organic halide, an alcohol, an ether, or an amide can be used. More specifically, chloride, nitrate, sulfate, acetate, hydroxide, complex salt and the like are exemplified. The concentration of the metal compound in the solution is 0.1 to 10% by weight as a metal relative to the oxide carrier.
Are appropriately selected so as to obtain a catalyst supporting the metal active species of When two kinds of metal active species are used, they may be supported simultaneously or separately. After supporting the metal compound,
Separation, washing, drying, oxidation, calcination, reduction, molding, and a combination thereof are performed as necessary. Here, the term “support” means that a metal compound or a metal is physically or chemically adsorbed on an oxide carrier.
【００２２】イオン交換法は、無定形シリカを含有する
酸化物担体へ金属化合物を担持させるために好ましく用
いられる。酸化物担体をアンモニウムイオンを含有する
溶液に接触させプロトンをアンモニウムイオンにイオン
交換させた後、金属化合物の溶液と接触させアンモニウ
ムイオンを金属活性種を含むイオンとイオン交換させ
る。アンモニウムイオンとのイオン交換と金属活性種を
含むイオンとのイオン交換は別々の溶液で順次行っても
よいが、同一の溶液で同時に行うこともできる。必要に
応じて分離、洗浄、乾燥、酸化、焼成あるいは還元とこ
れらの組み合わせ処理が行われる。The ion exchange method is preferably used for supporting a metal compound on an oxide carrier containing amorphous silica. After the oxide carrier is brought into contact with a solution containing ammonium ions and protons are ion-exchanged to ammonium ions, the oxide carrier is brought into contact with a solution of a metal compound to ion-exchange ammonium ions with ions containing metal active species. The ion exchange with the ammonium ion and the ion exchange with the ion containing the metal active species may be sequentially performed in separate solutions, or may be simultaneously performed in the same solution. If necessary, separation, washing, drying, oxidation, calcination or reduction and a combination thereof are performed.
【００２３】例えば、金属化合物を担持した酸化物担体
は、適当な方法により分離され、酸化物担体１ｇに対し
て１０〜２０ｍｌのイオン交換水などの水で、バッチ式
（デカンテーション）、流通式などの方法により洗浄さ
れる。洗浄された酸化物担体は乾燥後、又は、独立の乾
燥工程を経ることなく直接焼成される。乾燥工程は、５
０〜２００℃、好ましくは１００〜１６０℃でバッチ
式、連続式などの方法で行われる。乾燥処理により細孔
直径が変わる可能性がある場合には、真空乾燥が用いら
れる。焼成は、金属化合物を担持した酸化物担体は空気
中、３００〜９００℃で０．１〜４８時間焼成される。
前記の焼成工程に換えて、或いは、焼成工程前または後
に、酸化処理または還元処理を行ってもよい。酸化処理
は酸化剤水溶液と金属化合物を担持した酸化物担体を室
温〜１００℃（水の沸点）の温度で接触させることによ
り行われる。酸化剤としては水溶性過酸化物、過塩素
酸、塩素酸などの過酸化物とその塩類、アルカリ金属の
過酸化物、過酸化水素などが用いられる。還元処理はホ
ルムアルデヒド、蟻酸、ヒドラジンなどの還元剤を含む
水溶液と金属化合物を担持した酸化物担体を室温〜１０
０℃（水の沸点）の温度で接触させることにより行われ
る。For example, an oxide carrier supporting a metal compound is separated by an appropriate method, and a batch type (decantation) and a flow type are carried out with 10 to 20 ml of water such as ion exchange water per 1 g of the oxide carrier. It is washed by such a method. The washed oxide carrier is calcined directly after drying or without a separate drying step. The drying process is 5
The reaction is performed at a temperature of 0 to 200 ° C, preferably 100 to 160 ° C, by a batch method, a continuous method, or the like. When there is a possibility that the pore diameter is changed by the drying treatment, vacuum drying is used. In the firing, the oxide carrier supporting the metal compound is fired in air at 300 to 900 ° C. for 0.1 to 48 hours.
Oxidation treatment or reduction treatment may be performed instead of the above-described firing step, or before or after the firing step. The oxidation treatment is performed by bringing an aqueous solution of an oxidizing agent into contact with an oxide carrier supporting a metal compound at a temperature of room temperature to 100 ° C. (boiling point of water). As the oxidizing agent, peroxides such as water-soluble peroxides, perchloric acid and chloric acid and salts thereof, peroxides of alkali metals, hydrogen peroxide and the like are used. In the reduction treatment, an aqueous solution containing a reducing agent such as formaldehyde, formic acid, or hydrazine and an oxide carrier supporting a metal compound are kept at room temperature to 10 ° C.
The contact is performed at a temperature of 0 ° C. (boiling point of water).
【００２４】本発明の担持触媒の製造方法では、含浸法
又はイオン交換法により金属化合物を担持するのと同時
に、又は、担持した後に、酸化物担体を水媒体で接触処
理してｐＨ６．０〜１１．０の水媒体を酸化物担体に含
浸させる工程と、これに引き続く５０℃以上の乾燥温度
で、酸化物担体の重量に対して０．５５ｍｌ／（ｇ・
ｈ）以下の平均蒸発速度で酸化物担体中に残存する水媒
体を蒸発させる乾燥処理工程が含まれる。本発明の製造
方法では、金属化合物担持と同時に上記処理工程を行う
か、金属化合物担持後に上記処理工程を行えばよい。ま
た、上記処理工程は金属化合物担持後の任意の段階で行
うこともできるが、焼成後に行うのが特に好ましい。ま
た、必要に応じて、分離、洗浄、酸化、焼成や還元など
の処理を組み合わせても良いし、上記処理工程を繰り返
し行っても良い。In the method for producing a supported catalyst according to the present invention, at the same time as or after supporting the metal compound by the impregnation method or the ion exchange method, the oxide carrier is contact-treated with an aqueous medium to obtain a pH of 6.0 to 6.0. In a step of impregnating the oxide carrier with an aqueous medium of 11.0, followed by a drying temperature of 50 ° C. or more, 0.55 ml / (g · g) based on the weight of the oxide carrier.
h) a drying step of evaporating the aqueous medium remaining in the oxide carrier at the following average evaporation rate. In the production method of the present invention, the above treatment step may be performed simultaneously with the loading of the metal compound, or the above treatment step may be performed after the loading of the metal compound. In addition, the above-described treatment step can be performed at any stage after the metal compound is supported, but is particularly preferably performed after firing. Further, if necessary, processes such as separation, washing, oxidation, calcination, and reduction may be combined, or the above process may be repeated.
【００２５】本発明の接触処理に用いる水媒体のｐＨ
は、水に酸、塩基あるいは酸および塩基を添加すること
により、酸化物担体に含浸させた水媒体が下記に示すｐ
Ｈを有するように調整される。酸としては、硫酸、硝
酸、塩酸、燐酸などの水溶性無機酸あるいは蟻酸、酢酸
などの水溶性有機酸が好適に用いられる。塩基として
は、アルカリ金属もしくはアルカリ土類金属の炭酸塩も
しくは水酸化物、アンモニアなどの水溶性無機塩基ある
いは第１級、第２級、第３級のアルキルアミン類などの
水溶性有機塩基が好適に用いられる。The pH of the aqueous medium used in the contact treatment of the present invention
Is that an aqueous medium impregnated in an oxide carrier by adding an acid, a base or an acid and a base to water has the following p
Adjusted to have H. As the acid, a water-soluble inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid or a water-soluble organic acid such as formic acid or acetic acid is suitably used. The base is preferably a water-soluble inorganic base such as an alkali metal or alkaline earth metal carbonate or hydroxide, ammonia or a water-soluble organic base such as a primary, secondary or tertiary alkylamine. Used for
【００２６】接触処理は好ましくは５０〜２２０℃で、
全細孔容積の０．５〜１．５倍量の水媒体を用いて行
う。処理時間は、下記式で表される乾燥減率： 乾燥減率＝１００×（乾燥前重量−１６０℃乾燥後重
量）／乾燥前重量 が５％以下になるように決めるのが好ましく、通常は
０．１〜４８時間である。The contact treatment is preferably carried out at 50 to 220 ° C.
This is performed using an aqueous medium of 0.5 to 1.5 times the total pore volume. The treatment time is preferably determined so that the drying loss rate represented by the following formula: drying loss rate = 100 × (weight before drying−weight after drying at 160 ° C.) / Weight before drying is 5% or less, and usually, 0.1-48 hours.
【００２７】接触処理後に酸化物担体に残存する水媒体
のｐＨは、接触処理後に得られた担持触媒を０．０５ｇ
／ｍｌの濃度で分散した水性分散液のｐＨとして定義す
る。残存水媒体のｐＨは、通常６．０〜１１．０であ
り、７．０〜１０．５が好ましく、８．０〜１０．０が
最も好ましい。このようなｐＨの制限は、無定形シリカ
を含有する酸化物担体を用いる場合に有効であり、無定
形シリカを５０重量％以上含有する酸化物担体を用いる
場合に特に有効である。低いｐＨでは確実な効果を得る
ことは難しく、高いｐＨでは触媒強度の低下や収率の低
下を招く。残存水媒体の量は、通常、酸化物担体の全細
孔容積に対して０．５〜１．５倍であり、好ましくは
０．５〜１．０倍である。The pH of the aqueous medium remaining on the oxide carrier after the contact treatment was determined by measuring 0.05 g of the supported catalyst obtained after the contact treatment.
/ Ml of aqueous dispersion dispersed at a concentration of / ml. The pH of the residual aqueous medium is usually 6.0 to 11.0, preferably 7.0 to 10.5, and most preferably 8.0 to 10.0. Such restriction of pH is effective when using an oxide carrier containing amorphous silica, and particularly effective when using an oxide carrier containing 50% by weight or more of amorphous silica. If the pH is low, it is difficult to obtain a certain effect, and if the pH is high, the catalyst strength is reduced and the yield is reduced. The amount of the residual aqueous medium is usually 0.5 to 1.5 times, preferably 0.5 to 1.0 times the total pore volume of the oxide carrier.
【００２８】接触処理した酸化物担体は、吸引濾過など
により分離し、必要に応じて水などで洗浄した後、乾燥
処理される。乾燥温度は、処理雰囲気の温度を意味し、
通常５０℃以上であり、５０〜２２０℃が好ましく、８
０〜１５０℃がより好ましい。低温では、確実な効果を
得ることは難しい。高温では、酸化物担体に残存する水
媒体の平均蒸発速度の制御が難しく、処理コストも高く
なる。The contact-treated oxide carrier is separated by suction filtration, washed with water or the like as necessary, and then dried. The drying temperature means the temperature of the processing atmosphere,
Usually 50 ° C. or higher, preferably 50 to 220 ° C., 8
0-150 degreeC is more preferable. At low temperatures, it is difficult to obtain a certain effect. At a high temperature, it is difficult to control the average evaporation rate of the aqueous medium remaining on the oxide carrier, and the processing cost increases.
【００２９】酸化物担体に残存する水媒体の平均蒸発速
度は、乾燥処理開始から０．２５時間後までに蒸発した
水容量（ｍｌ）／（処理に使用した酸化物担体重量
（ｇ）×０．２５時間（ｈ））なる式により定義する。
残存水媒体の平均蒸発速度は、通常０．５５ｍｌ／（ｇ
・ｈ）以下であり、０．４５ｍｌ／（ｇ・ｈ）以下がよ
り好ましい。残存水媒体のｐＨ、乾燥温度を制限すると
同時に平均蒸発速度を制限することによって、活性や強
度を低下させることなく所望の平均細孔直径を有する担
持触媒を得ることができる。The average evaporation rate of the aqueous medium remaining on the oxide carrier is: water volume (ml) evaporated by 0.25 hours after the start of drying treatment / (weight of oxide carrier used in treatment (g) × 0). .25 hours (h)).
The average evaporation rate of the residual aqueous medium is usually 0.55 ml / (g
H) or less, more preferably 0.45 ml / (g · h) or less. By limiting the average evaporation rate at the same time as limiting the pH and drying temperature of the residual aqueous medium, a supported catalyst having a desired average pore diameter can be obtained without lowering the activity or strength.
【００３０】本発明の乾燥処理は、ロータリーキルン等
の連続式装置や気流乾燥機、通気バンド乾燥機、ターボ
嫌型乾燥機、流動乾燥機等の回分式装置により行える。
乾燥処理に使用する流体は、例えば、圧縮空気、加熱空
気、不活性ガス等が挙げられる。酸化物担体に残存する
水媒体の平均蒸発速度は、通常、乾燥温度や乾燥に使用
する流体流量により制御することができる。乾燥処理の
圧力は、特に制限はないが、通常大気圧下で行われる。The drying treatment of the present invention can be performed by a continuous apparatus such as a rotary kiln or a batch apparatus such as a flash dryer, a ventilation band dryer, a turbo-type dryer or a fluidized dryer.
Examples of the fluid used for the drying treatment include compressed air, heated air, and an inert gas. The average evaporation rate of the aqueous medium remaining on the oxide carrier can usually be controlled by the drying temperature and the flow rate of the fluid used for drying. Although the pressure of the drying treatment is not particularly limited, it is usually performed under atmospheric pressure.
【００３１】本発明では、担持触媒製造時の平均細孔直
径増加率（％、以下ＰＤ増加率と記すことがある）を、 １００×触媒平均細孔直径／担体平均細孔直径−１００ なる式で定義し、触媒製造時の全細孔容積減少率（％、
以下ＰＶ減少率と記すことがある）を、 １００−１００×触媒全細孔容積／担体全細孔容積 なる式で定義する。本発明の方法では、ＰＶ減少率より
もＰＤ増加率を選択的に大きくすることができる。ＰＤ
増加率は、通常２０％以上であり、好ましくは２５％以
上、より好ましくは３０％以上である。ＰＤ増加率の上
限は通常約５００％である。増加率が前記の範囲より小
さいと、同一の酸化物担体から任意の平均細孔直径を有
する触媒を得ることは難しい。ＰＤ増加率を変えること
により、同一の酸化物担体から異なる平均細孔直径を有
する担持触媒が製造でき、逆に異なる酸化物担体から同
一の平均細孔直径を有する担持触媒が製造できる。ＰＶ
減少率は通常０〜２０％である。In the present invention, the rate of increase in average pore diameter (%, sometimes referred to as PD increase rate) during the production of a supported catalyst is expressed by the formula: 100 × average pore diameter of catalyst / average pore diameter of carrier−100. Defined as the total pore volume reduction rate (%,
Hereinafter, this may be referred to as a PV reduction rate) is defined by an equation of 100-100 × total pore volume of catalyst / total pore volume of support. According to the method of the present invention, the PD increase rate can be selectively made larger than the PV decrease rate. PD
The rate of increase is usually at least 20%, preferably at least 25%, more preferably at least 30%. The upper limit of the PD increase rate is usually about 500%. If the rate of increase is smaller than the above range, it is difficult to obtain a catalyst having an arbitrary average pore diameter from the same oxide carrier. By changing the PD increase rate, a supported catalyst having a different average pore diameter can be produced from the same oxide carrier, and a supported catalyst having the same average pore diameter can be produced from a different oxide carrier. PV
The reduction rate is usually 0 to 20%.
【００３２】本発明の方法により製造された担持触媒
は、１０〜３００μｍ、好ましくは３０〜２００μｍの
メジアン径、０．３〜１．５ｍｌ／ｇ、好ましくは０．
５〜１．０ｍｌ／ｇの全細孔容積、８〜４０ｎｍ、好ま
しくは１０〜３０ｎｍの平均細孔直径、５０ｍ2／ｇ以
上、好ましくは１００〜２５０ｍ2／ｇのＢＥＴ比表面
積を有する。更に、本発明の担持触媒は、細孔容積−細
孔直径分布曲線において、細孔直径が１０ｎｍ以上、好
ましくは１０〜８０ｎｍ、より好ましくは１５〜６０ｎ
ｍの領域に細孔容積のピークを有する細孔分布により特
徴づけられる。また、細孔容積−細孔直径分布曲線にお
いて、細孔直径が１０ｎｍ以上である領域の全領域に対
する面積割合が７５％以上であるのが好ましい。The supported catalyst produced by the process of the present invention has a median diameter of 10 to 300 μm, preferably 30 to 200 μm, 0.3 to 1.5 ml / g, preferably 0.1 to 1.5 ml / g.
Total pore volume of 5~1.0ml / g, 8~40nm, preferably having an average pore diameter of 10 to 30 nm, 50 m 2 / g or more, preferably has a BET specific surface area of 100 to 250 m 2 / g. Further, the supported catalyst of the present invention has a pore volume-pore diameter distribution curve in which the pore diameter is 10 nm or more, preferably 10 to 80 nm, more preferably 15 to 60 n.
It is characterized by a pore distribution with a pore volume peak in the region of m. Further, in the pore volume-pore diameter distribution curve, the area ratio of the region where the pore diameter is 10 nm or more to the entire region is preferably 75% or more.
【００３３】本発明で製造された担持触媒は、種々の化
学反応に適用される。適用される化学反応は、有機化合
物の接触水素化反応が好ましい。例えば、アントラキノ
ン法による過酸化水素の製造方法におけるアントラキノ
ン類の水素化触媒として用いられる。The supported catalyst produced according to the present invention is applicable to various chemical reactions. The applied chemical reaction is preferably a catalytic hydrogenation reaction of an organic compound. For example, it is used as a hydrogenation catalyst for anthraquinones in a method for producing hydrogen peroxide by the anthraquinone method.
【００３４】本発明のアントラキノン類の水素化反応に
おいて使用される担持触媒の量は、プロセスの状況に応
じて適切な濃度範囲に制御され、作動溶液に対して通常
５〜７０ｇ／ｌで用いられる。アントラキノン類として
は、エチルアントラキノン、ｔ−ブチルアントラキノ
ン、アミルアントラキノンなどのアルキルアントラキノ
ン；エチルテトラヒドロアントラキノン、ｔ−ブチルテ
トラヒドロアントラキノン、アミルテトラヒドロアント
ラキノンなどのアルキルテトラヒドロアントラキノン；
及びこれらの混合物が好ましい。アルキルアントラキノ
ンとアルキルテトラヒドロアントラキノンは、各々が複
数のアルキルアントラキノンあるいはアルキルテトラヒ
ドラアントラキノンの混合物であってもよい。アルキル
アンラキノンとアルキルテトラヒドロアントラキノンの
混合物を用いる場合、その混合比（モル比）は２：１〜
８：１が好ましく、３：１〜６：１がより好ましい。The amount of the supported catalyst used in the anthraquinone hydrogenation reaction of the present invention is controlled in an appropriate concentration range according to the process conditions, and is usually used at 5 to 70 g / l with respect to the working solution. . Examples of the anthraquinones include alkyl anthraquinones such as ethyl anthraquinone, t-butyl anthraquinone, and amyl anthraquinone; alkyl tetrahydroanthraquinones such as ethyl tetrahydroanthraquinone, t-butyl tetrahydroanthraquinone, and amyl tetrahydroanthraquinone;
And mixtures thereof. The alkylanthraquinone and the alkyltetrahydroanthraquinone may each be a mixture of a plurality of alkylanthraquinones or alkyltetrahydranthraquinones. When a mixture of alkylanlaquinone and alkyltetrahydroanthraquinone is used, the mixing ratio (molar ratio) is 2: 1 to 1
8: 1 is preferable, and 3: 1 to 6: 1 is more preferable.
【００３５】作動溶液中のアルキルアントラキノン類の
濃度は、プロセスの状況に応じて適切な濃度範囲に制御
され、通常は０．４〜１．０ｍｏｌ／ｌである。本発明
において作動溶液を調製するために用いられる溶媒は、
特に限定されるものではないが、好ましい溶媒として
は、芳香族炭化水素と高級アルコールの組み合わせ、芳
香族炭化水素とシクロヘキサノールもしくはアルキルシ
クロヘキサノールのカルボン酸エステルの組み合わせ、
芳香族炭化水素と四置換尿素との組み合わせなどが例示
される。The concentration of the alkylanthraquinones in the working solution is controlled in an appropriate concentration range depending on the process conditions, and is usually from 0.4 to 1.0 mol / l. The solvent used to prepare the working solution in the present invention,
Although not particularly limited, preferred solvents include a combination of an aromatic hydrocarbon and a higher alcohol, a combination of an aromatic hydrocarbon and a carboxylic acid ester of cyclohexanol or alkylcyclohexanol,
Examples include a combination of an aromatic hydrocarbon and a tetra-substituted urea.
【００３６】アントラキノン類の水素化反応は、例え
ば、水素気流下あるいは水素含有ガス雰囲気下、反応温
度１０〜８０℃、反応圧力１００〜５００ｋＰａで５分
〜１時間行われる。担持触媒を除去した後、生成したア
ントラヒドロキノン類を空気などの酸素含有ガスにより
１０〜８０℃で酸化してアントラキノン類に再度転化す
ると同時に過酸化水素を生成させる。生成した過酸化水
素は水により抽出され、作動溶液から分離される。過酸
化水素を分離した後の作動溶液は、再び還元工程に戻さ
れ循環プロセスが形成される。アントラキノン類の水素
化反応に用いる反応器としては、固定床、流動床、機械
撹拌、気泡塔、パイプリアクターなどが例示される。The hydrogenation reaction of anthraquinones is carried out, for example, in a hydrogen stream or a hydrogen-containing gas atmosphere at a reaction temperature of 10 to 80 ° C. and a reaction pressure of 100 to 500 kPa for 5 minutes to 1 hour. After removing the supported catalyst, the generated anthrahydroquinones are oxidized with an oxygen-containing gas such as air at 10 to 80 ° C. to be converted again into anthraquinones and, at the same time, hydrogen peroxide is generated. The produced hydrogen peroxide is extracted by water and separated from the working solution. After separating the hydrogen peroxide, the working solution is returned to the reduction step again to form a circulation process. Examples of the reactor used for the hydrogenation reaction of anthraquinones include a fixed bed, a fluidized bed, mechanical stirring, a bubble column, and a pipe reactor.
【００３７】[0037]
【実施例】本発明を、以下の実施例により更に詳細に説
明するが、本発明はこれらの実施例に限定されるもので
はない。なお、以下の実施例において、各測定は下記の
方法により行った。実施例中、％は特に指定のない限り
重量基準とした。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples, each measurement was performed by the following method. In the examples,% is based on weight unless otherwise specified.
【００３８】（１）比表面積 ＢＥＴ法により測定した。(1) Specific surface area Measured by the BET method.
【００３９】（２）全細孔容積 高速比表面積／細孔分布測定装置（マイクロメリティッ
クス社製ＡＳＡＰ２０００）を用いてガス吸着法により
測定した。(2) Total pore volume The total pore volume was measured by a gas adsorption method using a high-speed specific surface area / pore distribution measuring device (ASAP2000 manufactured by Micromeritics).
【００４０】（３）平均細孔直径 ＢＥＴ比表面積（一点法、相対圧０．１８）と全細孔容
積（一点法、相対圧０．９８）の測定値から下記式より
求めた。 平均細孔直径（ｎｍ）＝４０００×全細孔容積（ｍｌ／
ｇ）／ＢＥＴ比表面積（ｍ2／ｇ）(3) Average pore diameter The average pore diameter was determined from the following equation from the measured values of the BET specific surface area (one-point method, relative pressure 0.18) and the total pore volume (single-point method, relative pressure 0.98). Average pore diameter (nm) = 4000 x total pore volume (ml /
g) / BET specific surface area (m 2 / g)
【００４１】（４）酸化物担体に残存する水媒体のｐＨ 乾燥処理で得られた担持触媒をイオン交換水に０．０５
ｇ／ｍｌの濃度で分散し、８０℃に加熱した後、撹拌し
ながら室温まで冷却して得られた水性分散液をｐＨメー
ターにより測定した。(4) pH of the aqueous medium remaining on the oxide carrier The supported catalyst obtained by the drying treatment was added to ion-exchanged water in 0.05%.
After dispersing at a concentration of g / ml and heating to 80 ° C., the mixture was cooled to room temperature with stirring, and the resulting aqueous dispersion was measured with a pH meter.
【００４２】（５）担持触媒活性の評価 プソイドクメンとジイソブチルカルビノールからなる溶
媒にアミルアントラキノンを溶解した作動溶液を少量の
担持触媒と接触させたときの水素吸収量により担持触媒
の活性を評価した。具体的な試験法を、以下に記した。
１００ｍｌの３つ口フラスコに担持触媒５０．０ｍｇと
２５ｍｌの作動溶液を入れた。作動溶液のアミルアント
ラキノン濃度は０．６ｍｏｌ／ｌであり、プソイドクメ
ン６０容積％とジイソブチルカルビノール４０容積％の
混合溶媒を用いた。フラスコ内を完全密封できる磁力誘
導方式の撹拌機を装着し、フラスコを真空コックで密封
した。次に、フラスコを常圧水素化反応装置に装着し
た。この装置は、フラスコ内での圧力変動を水位で検知
し、リレー式電磁弁を介して水素吸収に見合う分の水素
が計量管から供給される。水素計量管は、ビュレット部
と水貯液部からなり、水素計量管内の水がピストンの役
割をして、フラスコ内圧と大気圧が等しく保たれる。水
素吸収量は、水素計量管内の液面高さの差として測定さ
れる。フラスコを３０℃の水浴に浸し、フラスコ内の排
気と水素導入を３回繰り返した。５分後に撹拌機を作動
させた。水素吸収開始から３０分後までの水素吸収量を
測定した。０℃、１ａｔｍでの水素吸収量に換算し、単
位担持触媒重量当たりの水素吸収速度（ｍｌ／（ｍｉｎ
・ｇ））を求めた。(5) Evaluation of the activity of the supported catalyst The activity of the supported catalyst was evaluated by the amount of hydrogen absorbed when a working solution obtained by dissolving amylanthraquinone in a solvent comprising pseudocumene and diisobutylcarbinol was brought into contact with a small amount of the supported catalyst. The specific test method is described below.
A 100 ml three-necked flask was charged with 50.0 mg of the supported catalyst and 25 ml of working solution. The working solution had an amylanthraquinone concentration of 0.6 mol / l, and a mixed solvent of pseudocumene (60% by volume) and diisobutylcarbinol (40% by volume) was used. A magnetic induction type stirrer capable of completely sealing the inside of the flask was attached, and the flask was sealed with a vacuum cock. Next, the flask was attached to an atmospheric hydrogenation reactor. This device detects pressure fluctuations in the flask at the water level, and supplies hydrogen from the metering pipe through a relay-type solenoid valve in an amount corresponding to hydrogen absorption. The hydrogen metering tube is composed of a burette part and a water storage part, and the water in the hydrogen metering tube acts as a piston so that the internal pressure of the flask and the atmospheric pressure are kept equal. The hydrogen absorption amount is measured as a difference in liquid level in the hydrogen measuring pipe. The flask was immersed in a 30 ° C. water bath, and the evacuation of the flask and introduction of hydrogen were repeated three times. After 5 minutes, the stirrer was turned on. The amount of hydrogen absorption up to 30 minutes after the start of hydrogen absorption was measured. Converted to the hydrogen absorption amount at 0 ° C. and 1 atm, the hydrogen absorption rate per unit supported catalyst weight (ml / (min
G)) was determined.
【００４３】（６）担持触媒の強度評価 強撹拌前後のメジアン径変化率を測定することよって行
った。具体的な試験法を以下に記した。４枚のバッフル
の付いた１ｌ試験器（直径１０ｃｍ、胴長２１ｃｍ、下
部コーン長さ２．５ｃｍ）に担持触媒１５ｇとイオン交
換水０．５ｌを入れた。直径５ｃｍの６枚ディスクター
ビン翼（ディスク：縦１．２ｃｍ×横１．１ｃｍ×幅
０．２ｃｍ）の付いた撹拌機を２０００ｒｐｍで回転さ
せた。撹拌開始１分後と２時間後にスラリーを約５ｍｌ
採取した。レーザー回折式粒度分布測定器（（株）堀場
製作所製ＬＡ−９１０）により、相対屈折率１．１２ｉ
でのメジアン径を測定した。メジアン径変化率（％）＝
（試験１分後のメジアン径−試験２時間後のメジアン
径）／試験１分後のメジアン径を求めた。なお、本発明
の担持触媒のメジアン径変化率は４％以下、好ましくは
２％以下である。(6) Evaluation of Strength of Supported Catalyst The evaluation was performed by measuring the median diameter change rate before and after strong stirring. The specific test method is described below. 15 g of the supported catalyst and 0.5 l of ion-exchanged water were placed in a 1 l tester (diameter 10 cm, trunk length 21 cm, lower cone length 2.5 cm) equipped with four baffles. A stirrer equipped with 6 disk turbine blades having a diameter of 5 cm (disk: 1.2 cm long × 1.1 cm wide × 0.2 cm wide) was rotated at 2000 rpm. Approximately 5 ml of slurry 1 minute and 2 hours after the start of stirring
Collected. A relative refractive index of 1.12i was measured by a laser diffraction particle size distribution analyzer (LA-910, manufactured by Horiba, Ltd.).
Was measured for the median diameter. Median diameter change rate (%) =
(Median diameter one minute after the test-Median diameter two hours after the test) / Median diameter one minute after the test. Incidentally, the median diameter change rate of the supported catalyst of the present invention is 4% or less, preferably 2% or less.
【００４４】（７）細孔容積−細孔直径分布曲線（ｄＶ
／ｄｌｏｇ（Ｄ）曲線） 鷲尾一裕、“ガス吸着法による比表面積／細孔分布測
定”、島津評論、Ｖｏｌ．４８，Ｎｏ．１，ｐｐ３５−
４９（１９９１．６）記載の方法により求めた。すなわ
ち、（２）記載のＡＳＡＰ２０００を用いて求めた吸着
等温線の吸着側でHalsey型ｔ決定式： ｔ(nm)＝3.54×[-5.000/(ln(P/Po)]0.333×10-1 を用い、ＢＪＨ（Barrett−Joyner−Halenda）法で細孔
分布解析を行った。上記式において、ｔは吸着層の厚
み、Ｐは吸着平衡圧、Ｐｏは測定温度（液体窒素の沸
点）でのＮ2飽和蒸気圧を表す。なお、分布曲線は、直
径を対数軸とする片対数グラフで表される。(7) Pore volume-pore diameter distribution curve (dV
/ Dlog (D) curve) Kazuhiro Washio, “Measurement of specific surface area / pore distribution by gas adsorption method”, Shimadzu review, Vol. 48, no. 1, pp35-
49 (1991.6). That is, the Halsey-type t determination equation on the adsorption side of the adsorption isotherm obtained using ASAP2000 described in (2): t (nm) = 3.54 × [-5.000 / (ln (P / Po)] 0.333 × 10 −1 The pore distribution analysis was performed by the BJH (Barrett-Joyner-Halenda) method using the following equation: In the above equation, t is the thickness of the adsorption layer, P is the adsorption equilibrium pressure, and Po is the measurement temperature (boiling point of liquid nitrogen). It represents a N 2 saturated vapor pressure. in addition, the distribution curve is represented by the semi-log plot of a logarithmic axis diameter.
【００４５】実施例１ 富士シリシア化学株式会社製シリカゲル（ＣＡＲｉＡＣ
Ｔ Ｑ−１０）４９ｇを２５％アンモニア水１７０ｍｌ
に懸濁した。この懸濁液を撹拌しながら、２５％アンモ
ニア水３０ｍｌに塩化パラジウム１．６７２ｇを溶解し
た溶液を滴下した。この懸濁液を純水５００ｍｌで洗浄
し、吸引濾過した。１１０℃に恒温乾燥器に入れた。こ
の時の平均蒸発速度は、０．６９ｍｌ／（ｇ・ｈ）であ
った。空気気流下、６００℃で６時間焼成した。次に、
焼成した触媒を水１５０ｍｌに懸濁させ、４％水酸化ナ
トリウム水溶液をｐＨ９．５になるまで加えた。懸濁液
に３７％ホルムアルデヒド水溶液を５ｍｌ加えた。ｐＨ
を９．５に保持したまま、懸濁液の温度を６０℃に上昇
させ、その後６０℃で３０分間撹拌を継続した。懸濁液
を純水５００ｍｌで洗浄し、吸引濾過し、容器に移し
た。１１０℃に恒温乾燥器に入れた。この時、容器の開
口部面積を調節し、酸化物担体に残存する水媒体の平均
蒸発速度を０．４２ｍｌ／（ｇ・ｈ）とした。残存水媒
体のｐＨは９．５であり、残存水媒体の量は酸化物担体
の全細孔容積の０．９５倍であった。得られた触媒量
は、４７．７ｇであった。各測定結果を表１及び２に示
す。また、担持触媒の細孔容積−細孔直径分布曲線を図
１に示す。Example 1 Silica gel (CARiAC, manufactured by Fuji Silysia Chemical Ltd.)
TQ-10) 49 g of 25% ammonia water in 170 ml
Suspended in water. While stirring this suspension, a solution in which 1.672 g of palladium chloride was dissolved in 30 ml of 25% aqueous ammonia was added dropwise. The suspension was washed with 500 ml of pure water and filtered by suction. It was put in a thermostat dryer at 110 ° C. The average evaporation rate at this time was 0.69 ml / (g · h). It was calcined at 600 ° C. for 6 hours in an air stream. next,
The calcined catalyst was suspended in 150 ml of water, and a 4% aqueous sodium hydroxide solution was added until the pH reached 9.5. 5 ml of a 37% aqueous formaldehyde solution was added to the suspension. pH
While maintaining the temperature at 9.5, the temperature of the suspension was raised to 60 ° C., and then stirring was continued at 60 ° C. for 30 minutes. The suspension was washed with 500 ml of pure water, filtered by suction, and transferred to a container. It was put in a thermostat dryer at 110 ° C. At this time, the opening area of the container was adjusted, and the average evaporation rate of the aqueous medium remaining on the oxide carrier was set to 0.42 ml / (gh). The pH of the residual aqueous medium was 9.5, and the amount of the residual aqueous medium was 0.95 times the total pore volume of the oxide carrier. The amount of the obtained catalyst was 47.7 g. Tables 1 and 2 show the measurement results. FIG. 1 shows a pore volume-pore diameter distribution curve of the supported catalyst.
【００４６】実施例２ 容器の開口部面積を調節し、酸化物担体に残存する水媒
体の平均蒸発速度を０．０５６ｍｌ／（ｇ・ｈ）とした
以外は、実施例１と同様の方法で担持触媒を製造した。
各測定結果を表１及び２に示す。また、担持触媒の細孔
容積−細孔直径分布曲線を図２に示す。Example 2 A method similar to that of Example 1 was adopted except that the opening area of the container was adjusted and the average evaporation rate of the aqueous medium remaining in the oxide carrier was 0.056 ml / (g · h). A supported catalyst was produced.
Tables 1 and 2 show the measurement results. FIG. 2 shows a pore volume-pore diameter distribution curve of the supported catalyst.
【００４７】実施例３ 容器の開口部面積を調節し、酸化物担体に残存する水媒
体の平均蒸発速度を０．０４６ｍｌ／（ｇ・ｈ）とし、
残存水媒体のｐＨを７．０とした以外は実施例１と同様
の方法で担持触媒を製造した。各測定結果を表１及び２
に示す。また、担持触媒の細孔容積−細孔直径分布曲線
を図３に示す。Example 3 The opening area of the container was adjusted, and the average evaporation rate of the aqueous medium remaining on the oxide carrier was set to 0.046 ml / (g · h).
A supported catalyst was produced in the same manner as in Example 1 except that the pH of the residual aqueous medium was set to 7.0. Tables 1 and 2 show the results of each measurement.
Shown in FIG. 3 shows a pore volume-pore diameter distribution curve of the supported catalyst.
【００４８】比較例１ 富士シリシア化学株式会社製シリカゲル（ＣＡＲｉＡＣ
Ｔ Ｑ−６）を用い、容器の開口部面積を調節し、酸化
物担体に残存する水媒体の平均蒸発速度を１．５９ｍｌ
／（ｇ・ｈ）とした以外は、実施例１と同様の方法で担
持触媒を製造した。各測定結果を表１及び２に示す。ま
た、担持触媒の細孔容積−細孔直径分布曲線を図４に示
す。Comparative Example 1 Silica gel (CARiAC, manufactured by Fuji Silysia Chemical Ltd.)
Using TQ-6), the opening area of the container was adjusted, and the average evaporation rate of the aqueous medium remaining on the oxide carrier was 1.59 ml.
A supported catalyst was produced in the same manner as in Example 1, except that / (gh) was used. Tables 1 and 2 show the measurement results. FIG. 4 shows a pore volume-pore diameter distribution curve of the supported catalyst.
【００４９】比較例２ 富士シリシア化学株式会社製シリカゲル（ＣＡＲｉＡＣ
Ｔ Ｑ−６）４９ｇを２５％アンモニア水１７０ｍｌに
懸濁した。この懸濁液を撹拌しながら、２５％アンモニ
ア水３０ｍｌに塩化パラジウム１．６７２ｇを溶解した
溶液を滴下した。次いで、この懸濁液を純水５００ｍｌ
で洗浄し、吸引濾過した。１１０℃に恒温乾燥器に入れ
た。この時の平均蒸発速度は、０．６９ｍｌ／（ｇ・
ｈ）であった。空気気流下、６００℃で６時間焼成し
た。焼成した触媒に水３１．５ｍｌを加え良く混合し
た。１１０℃に恒温乾燥器に入れた。この時、容器の開
口部面積を調節し、酸化物担体に残存する水媒体の平均
蒸発速度を０．０４６ｍｌ／（ｇ・ｈ）とした。残存水
媒体のｐＨは、５．０であり、残存水媒体の量は酸化物
担体の全細孔容積の０．８６倍であった。各測定結果を
表１及び２に示す。また、担持触媒の細孔容積−細孔直
径分布曲線を図５に示す。Comparative Example 2 Silica gel manufactured by Fuji Silysia Chemical Ltd. (CARiAC)
49 g of TQ-6) was suspended in 170 ml of 25% aqueous ammonia. While stirring this suspension, a solution in which 1.672 g of palladium chloride was dissolved in 30 ml of 25% aqueous ammonia was added dropwise. Next, this suspension was added to 500 ml of pure water.
And filtered with suction. It was put in a thermostat dryer at 110 ° C. The average evaporation rate at this time was 0.69 ml / (g ·
h). It was calcined at 600 ° C. for 6 hours in an air stream. 31.5 ml of water was added to the calcined catalyst and mixed well. It was put in a thermostat dryer at 110 ° C. At this time, the opening area of the container was adjusted, and the average evaporation rate of the aqueous medium remaining on the oxide carrier was set to 0.046 ml / (gh). The pH of the residual aqueous medium was 5.0, and the amount of the residual aqueous medium was 0.86 times the total pore volume of the oxide carrier. Tables 1 and 2 show the measurement results. FIG. 5 shows a pore volume-pore diameter distribution curve of the supported catalyst.
【００５０】比較例３ 酸化物担体に残存する水媒体のｐＨを１１．１とした以
外は実施例１と同様の方法で担持触媒を製造した。得ら
れた触媒量は、２７．０ｇであった。各測定結果を表１
及び２に示す。また、担持触媒の細孔容積−細孔直径分
布曲線を図６に示す。Comparative Example 3 A supported catalyst was produced in the same manner as in Example 1 except that the pH of the aqueous medium remaining on the oxide carrier was changed to 11.1. The amount of the obtained catalyst was 27.0 g. Table 1 shows the measurement results.
And 2. FIG. 6 shows a pore volume-pore diameter distribution curve of the supported catalyst.
【００５１】 表１ 担 体 還元後の平 共存する水 担持触媒 ＰＤ ＰＶ ＰＤ ＰＶ 均蒸発速度 媒体のｐＨ ＰＤ ＰＶ 増加率 減少率 nm ml/g ml/(g・h) nm ml/g ％ ％ 実施例１ 12.4 0.74 0.42 9.5 15.9 0.70 28 5.4 実施例２ 12.4 0.74 0.056 9.5 27.5 0.67 122 9.5 実施例３ 12.4 0.74 0.046 7.0 17.2 0.70 39 5.4 比較例１ 6.7 0.73 1.59 9.5 7.8 0.68 16 6.8 比較例２ 6.7 0.73 0.046 5.0 8.0 0.67 19 8.2比較例３ 12.4 0.74 0.42 11.1 23.2 1.05 87 -42 ＰＤ：平均細孔直径（ｎｍ）。 ＰＶ：全細孔容積（ｍｌ／ｇ）。 平均蒸発速度：処理開始から０．２５時間後までに蒸発した水容量（ｍｌ）／（ 処理に使用した酸化物担体重量（ｇ）×０．２５時間（ｈ））。 ＰＤ増加率（％）＝１００×担持触媒のＰＤ／酸化物担体のＰＤ−１００。 ＰＶ減少率（％）＝１００−１００×担持触媒のＰＶ／酸化物担体のＰＶ。Table 1 Supports Co-existing water-supported catalyst after reduction PD PV PD PD pH of PV equalization rate medium PD PD increase rate decrease rate nm ml / g ml / (g · h) nm ml / g%% Example 1 12.4 0.74 0.42 9.5 15.9 0.70 28 5.4 Example 2 12.4 0.74 0.056 9.5 27.5 0.67 122 9.5 Example 3 12.4 0.74 0.046 7.0 17.2 0.70 39 5.4 Comparative example 1 6.7 0.73 1.59 9.5 7.8 0.68 16 6.8 Comparative example 2 6.7 0.73 0.046 5.0 8.0 0.67 19 8.2 Comparative Example 3 12.4 0.74 0.42 11.1 23.2 1.05 87 -42 PD: Average pore diameter (nm). PV: total pore volume (ml / g). Average evaporation rate: Water volume (ml) evaporated by 0.25 hours after the start of treatment / (weight of oxide carrier used for treatment (g) × 0.25 hours (h)). PD increase rate (%) = 100 × PD of supported catalyst / PD-100 of oxide support. PV reduction rate (%) = 100−100 × PV of supported catalyst / PV of oxide support.
【００５２】 水素吸収速度：単位担持触媒重量当たりの標準状態にお
ける水素吸収速度。 メジアン径変化率：（試験１分後のメジアン径−試験２
時間後のメジアン径）／試験１分後のメジアン径。[0052] Hydrogen absorption rate: The hydrogen absorption rate in a standard state per unit supported catalyst weight. Median diameter change rate: (Median diameter one minute after test-Test 2
Median diameter after time) / median diameter one minute after test.
【００５３】[0053]
【発明の効果】本発明の担持触媒は、機械的強度に優
れ、細孔容積−細孔直径分布曲線において細孔容積のピ
ークが細孔直径の大きい方に移動した細孔分布を有し、
特に、アントラキノン類の水素化反応に対し高い活性を
示す。また、本発明の製造方法によれば、担持触媒製造
時に、活性や強度を低下させることなく平均細孔直径を
選択的に変化させ、所望の平均細孔直径を有する担持触
媒を得ることができる。また、平均細孔直径が異なる酸
化物担体から同一の平均細孔直径を有する担持触媒を得
ることができ、平均細孔直径が同一の酸化物担体から異
なる平均細孔直径を有する担持触媒を得ることもでき
る。更に、金属化合物の担持ロスを低減することができ
る。The supported catalyst of the present invention has excellent mechanical strength, and has a pore distribution in which the peak of the pore volume moves to the larger pore diameter in the pore volume-pore diameter distribution curve,
In particular, it shows high activity for hydrogenation of anthraquinones. Further, according to the production method of the present invention, during the production of a supported catalyst, the average pore diameter is selectively changed without lowering the activity or the strength, and a supported catalyst having a desired average pore diameter can be obtained. . In addition, a supported catalyst having the same average pore diameter can be obtained from oxide carriers having different average pore diameters, and a supported catalyst having different average pore diameters can be obtained from the same oxide carrier having the same average pore diameter. You can also. Further, the loss of supporting the metal compound can be reduced.
【図１】実施例１で製造した担持触媒の吸着等温線から
求めた細孔容積−細孔直径分布曲線を示すグラフ。FIG. 1 is a graph showing a pore volume-pore diameter distribution curve obtained from an adsorption isotherm of a supported catalyst produced in Example 1.
【図２】実施例２で製造した担持触媒の吸着等温線から
求めた細孔容積−細孔直径分布曲線を示すグラフ。FIG. 2 is a graph showing a pore volume-pore diameter distribution curve obtained from an adsorption isotherm of the supported catalyst produced in Example 2.
【図３】実施例３で製造した担持触媒の吸着等温線から
求めた細孔容積−細孔直径分布曲線を示すグラフ。FIG. 3 is a graph showing a pore volume-pore diameter distribution curve obtained from an adsorption isotherm of the supported catalyst produced in Example 3.
【図４】比較例１で製造した担持触媒の吸着等温線から
求めた細孔容積−細孔直径分布曲線を示すグラフ。FIG. 4 is a graph showing a pore volume-pore diameter distribution curve obtained from an adsorption isotherm of the supported catalyst produced in Comparative Example 1.
【図５】比較例２で製造した担持触媒の吸着等温線から
求めた細孔容積−細孔直径分布曲線を示すグラフ。FIG. 5 is a graph showing a pore volume-pore diameter distribution curve obtained from an adsorption isotherm of the supported catalyst produced in Comparative Example 2.
【図６】比較例３で製造した担持触媒の吸着等温線から
求めた細孔容積−細孔直径分布曲線を示すグラフ。FIG. 6 is a graph showing a pore volume-pore diameter distribution curve obtained from an adsorption isotherm of the supported catalyst produced in Comparative Example 3.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 37/10 Ｂ０１Ｊ 37/10 Ｃ０１Ｂ 15/023 Ｃ０１Ｂ 15/023 Ａ (72)発明者 山岸 健 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京研究所内 (72)発明者 長谷川 浩 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京研究所内 (72)発明者 高橋 香織 東京都葛飾区新宿６丁目１番１号 三菱瓦 斯化学株式会社東京研究所内 Ｆターム(参考） 4G069 AA03 AA08 AA12 AA14 AA15 BA01A BA02A BA02B BA03A BA04A BA05A BB04A BB04B BB06A BB06B BC70A BC71A BC72A BC72B BC75A CB02 CB81 EC13X EC13Y EC18X EC18Y EC26 FA02 FC07 FC08 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 37/10 B01J 37/10 C01B 15/023 C01B 15/023 A (72) Inventor Takeshi Ken Yamagishi Katsushika, Tokyo 6-1-1, Shinjuku-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory (72) Inventor Hiroshi Hasegawa 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory (72) Inventor Takahashi Kaori 6-1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory F-term (reference) 4G069 AA03 AA08 AA12 AA14 AA15 BA01A BA02A BA02B BA03A BA04A BA05A BB04A BB04B BB06A BB06B BC70B EC13Y EC18X EC18Y EC26 FA02 FC07 FC08
Claims (17)
０．１〜１０重量％の金属活性種から本質的になる担持
触媒であって、細孔容積−細孔直径分布曲線において細
孔直径が１０ｎｍ以上の領域に細孔容積のピークが存在
する細孔分布を有し、メジアン径変化率が４％以下であ
ることを特徴とする担持触媒。1. A supported catalyst consisting essentially of an oxide carrier and 0.1 to 10% by weight of a metal active species with respect to the weight of the oxide carrier, the catalyst being fine in a pore volume-pore diameter distribution curve. A supported catalyst having a pore distribution in which a pore volume peak exists in a region having a pore diameter of 10 nm or more, and a median diameter change rate of 4% or less.
細孔容積のピークが存在することを特徴とする請求項１
記載の担持触媒。2. The peak of the pore volume exists in a region having a pore diameter of 10 to 80 nm.
The supported catalyst according to the above.
て、細孔直径が１０ｎｍ以上である領域の全領域に対す
る面積割合が７５％以上であることを特徴とする請求項
１又は２記載の担持触媒。3. The pore volume-pore diameter distribution curve according to claim 1, wherein an area ratio of a region having a pore diameter of 10 nm or more to an entire region is 75% or more. Supported catalyst.
チタニア、ジルコニア、シリカ・アルミナ複合酸化物、
シリカ・チタニア複合酸化物、シリカ・アルミナ・チタ
ニア複合酸化物及びこれらの物理的混合物からなる群よ
り選ばれた少なくとも一の酸化物であり、かつ０．２〜
２．０ｍｌ／ｇの全細孔容積を有することを特徴とする
請求項１〜３のいずれかに記載の担持触媒。4. The method according to claim 1, wherein the oxide carrier is silica, alumina,
Titania, zirconia, silica / alumina composite oxide,
Silica-titania composite oxide, at least one oxide selected from the group consisting of silica-alumina-titania composite oxide and a physical mixture thereof, and 0.2 to 0.2
4. The supported catalyst according to claim 1, having a total pore volume of 2.0 ml / g.
ロジウム化合物、パラジウム化合物及び白金化合物から
なる群より選ばれた少なくとも一の白金族金属化合物由
来であることを特徴とする請求項１〜４のいずれかに記
載の担持触媒。5. The metal active species is a ruthenium compound,
The supported catalyst according to any one of claims 1 to 4, wherein the supported catalyst is derived from at least one platinum group metal compound selected from the group consisting of a rhodium compound, a palladium compound, and a platinum compound.
リカを含み、かつ０．２〜２．０ｍｌ／ｇの全細孔容積
を有することを特徴とする請求項１〜５のいずれかに記
載の担持触媒。6. The oxide carrier according to claim 1, wherein the oxide carrier contains at least amorphous silica and has a total pore volume of 0.2 to 2.0 ml / g. Supported catalyst.
０．１〜１０重量％の金属から本質的になる担持触媒を
製造する方法であり、金属化合物を酸化物担体に担持す
るのと同時に、又は、担持した後に、酸化物担体を水媒
体で接触処理してｐＨ６．０〜１１．０の水媒体を酸化
物担体に存在させる工程と、これに引き続く５０℃以上
の乾燥温度、酸化物担体の重量に対して０．５５ｍｌ／
（ｇ・ｈ）以下の平均蒸発速度で酸化物担体中に残存す
る水媒体を蒸発させる乾燥処理工程を含むことを特徴と
する担持触媒の製造方法。7. A method for producing a supported catalyst consisting essentially of an oxide carrier and 0.1 to 10% by weight of a metal based on the weight of the oxide carrier, wherein the metal compound is supported on the oxide carrier. Simultaneously or after loading, a step of contacting the oxide carrier with an aqueous medium to cause an aqueous medium having a pH of 6.0 to 11.0 to be present in the oxide carrier, and a subsequent drying temperature of 50 ° C. or more, 0.55 ml /
(G · h) A method for producing a supported catalyst, comprising a drying step of evaporating an aqueous medium remaining in an oxide carrier at an average evaporation rate of not more than (g · h).
せることを特徴とする請求項７記載の製造方法。8. The method according to claim 7, wherein the average pore diameter is changed during the production of the supported catalyst.
ことを特徴とする請求項８記載の製造方法。9. The method according to claim 8, wherein the average pore diameter change rate is 20% or more.
ナ、チタニア、ジルコニア、シリカ・アルミナ複合酸化
物、シリカ・チタニア複合酸化物、シリカ・アルミナ・
チタニア複合酸化物及びこれらの物理的混合物からなる
群より選ばれた少なくとも一の酸化物であり、かつ０．
２〜２．０ｍｌ／ｇの全細孔容積を有することを特徴と
する請求項７〜９のいずれかに記載の製造方法。10. The oxide carrier is silica, alumina, titania, zirconia, silica / alumina composite oxide, silica / titania composite oxide, silica / alumina /
At least one oxide selected from the group consisting of titania composite oxides and physical mixtures thereof;
The method according to any of claims 7 to 9, having a total pore volume of 2 to 2.0 ml / g.
シリカを含み、かつ０．２〜２．０ｍｌ／ｇの全細孔容
積を有することを特徴とする請求項７〜１０のいずれか
に記載の製造方法。11. The oxide carrier according to claim 7, wherein the oxide carrier comprises at least amorphous silica and has a total pore volume of 0.2 to 2.0 ml / g. Manufacturing method.
物、ロジウム化合物、パラジウム化合物及び白金化合物
からなる群より選ばれた少なくとも一の白金族金属化合
物であることを特徴とする請求項７〜１１のいずれかに
記載の方法。12. The metal compound according to claim 7, wherein the metal compound is at least one platinum group metal compound selected from the group consisting of a ruthenium compound, a rhodium compound, a palladium compound, and a platinum compound. The method described in.
〜１０．５にすることを特徴とする請求項７〜１２のい
ずれかに記載の方法。13. The pH of the remaining aqueous medium is adjusted to 7.0.
The method according to any one of claims 7 to 12, wherein the value is set to ~ 10.5.
ることを特徴とする請求項７〜１３のいずれかに記載の
方法。14. The method according to claim 7, wherein the drying temperature is 80 ° C. to 150 ° C.
体の全細孔容積に対して０．５〜１．５倍であることを
特徴とする請求項７〜１４のいずれかに記載の方法。15. The method according to claim 7, wherein the amount of the remaining aqueous medium is 0.5 to 1.5 times the total pore volume of the oxide carrier. the method of.
触媒又は請求項７〜１１記載の方法により製造した担持
触媒の存在下で有機化合物を水素化することを特徴とす
る有機化合物を接触水素化する方法。16. An organic compound obtained by hydrogenating an organic compound in the presence of a supported catalyst according to any one of claims 1 to 6 or a supported catalyst produced by the method according to claim 7 to 11. Method of catalytic hydrogenation.
製造方法であって、請求項１〜６のいずれかに記載の担
持触媒又は請求項７〜１５記載の方法により製造した担
持触媒存在下でアントラキノン類の水素化反応を行うこ
とを特徴とする過酸化水素の製造方法。17. A method for producing hydrogen peroxide by the anthraquinone method, wherein the anthraquinone is present in the presence of the supported catalyst according to any one of claims 1 to 6 or the supported catalyst produced by the method according to claims 7 to 15. A method for producing hydrogen peroxide, comprising performing a hydrogenation reaction of hydrogen.
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| CN100342966C (en) * | 2005-09-06 | 2007-10-17 | 南开大学 | Loaded palladium catalyst and preparing method and its use |
| JP2007297248A (en) * | 2006-05-01 | 2007-11-15 | Mitsubishi Gas Chem Co Inc | Activation method for hydrogenation catalyst, and production method for hydrogen peroxide comprising the method |
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| CN100342966C (en) * | 2005-09-06 | 2007-10-17 | 南开大学 | Loaded palladium catalyst and preparing method and its use |
| JP2007297248A (en) * | 2006-05-01 | 2007-11-15 | Mitsubishi Gas Chem Co Inc | Activation method for hydrogenation catalyst, and production method for hydrogen peroxide comprising the method |
| KR100804199B1 (en) | 2006-07-21 | 2008-02-20 | 한국화학연구원 | Synthesis of mesoporous Pt-incorporated titania/silica using platinum precursor as a template |
| JP2009034663A (en) * | 2007-07-11 | 2009-02-19 | Mitsubishi Gas Chem Co Inc | Manufacturing method of regeneration catalyst for working solution used for hydrogen peroxide production |
| WO2016152888A1 (en) * | 2015-03-24 | 2016-09-29 | 千代田化工建設株式会社 | Catalyst for hydrogenating aromatic hydrocarbons, and hydrogenation treatment method in which same is used |
| JP2016179440A (en) * | 2015-03-24 | 2016-10-13 | 千代田化工建設株式会社 | Hydrogenation catalyst for aromatic hydrocarbon and hydrogenation treatment using the same |
| US10745628B2 (en) | 2015-03-24 | 2020-08-18 | Chiyoda Corporation | Hydrogenation catalyst for aromatic hydrocarbon and hydrotreatment method using the catalyst |
| WO2022070674A1 (en) * | 2020-09-29 | 2022-04-07 | 昭和電工株式会社 | Method for producing ethyl acetate production catalyst |
| GB2613281A (en) * | 2020-09-29 | 2023-05-31 | Resonac Corp | Method for producing ethyl acetate production catalyst |
| JP7396511B2 (en) | 2020-09-29 | 2023-12-12 | 株式会社レゾナック | Method for producing catalyst for producing ethyl acetate |
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