JPH1028865A - Improved preparation method of catalyst for production of carboxylic acid ester - Google Patents
Improved preparation method of catalyst for production of carboxylic acid esterInfo
- Publication number
- JPH1028865A JPH1028865A JP8189609A JP18960996A JPH1028865A JP H1028865 A JPH1028865 A JP H1028865A JP 8189609 A JP8189609 A JP 8189609A JP 18960996 A JP18960996 A JP 18960996A JP H1028865 A JPH1028865 A JP H1028865A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- palladium
- catalyst
- supported
- reaction
- 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 107
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 title abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 247
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 115
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 32
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 21
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 16
- 150000001299 aldehydes Chemical class 0.000 claims description 33
- -1 alkali metal salt Chemical class 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical group CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 25
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 15
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 abstract description 47
- 239000000243 solution Substances 0.000 abstract description 23
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- 239000011133 lead Substances 0.000 description 145
- 238000006243 chemical reaction Methods 0.000 description 72
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 40
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 30
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 19
- 239000006227 byproduct Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 230000007547 defect Effects 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- 229910001882 dioxygen Inorganic materials 0.000 description 8
- 229940046892 lead acetate Drugs 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 150000002941 palladium compounds Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- DGPIGKCOQYBCJH-UHFFFAOYSA-M sodium;acetic acid;hydroxide Chemical compound O.[Na+].CC([O-])=O DGPIGKCOQYBCJH-UHFFFAOYSA-M 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 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
- 230000008901 benefit Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 101500021165 Aplysia californica Myomodulin-A Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- YNKMHABLMGIIFX-UHFFFAOYSA-N benzaldehyde;methane Chemical compound C.O=CC1=CC=CC=C1 YNKMHABLMGIIFX-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルデヒドとアル
コール及び分子状酸素からカルボン酸エステルを製造す
る際に使用する触媒の製造方法に関する。The present invention relates to a method for producing a catalyst used in producing a carboxylic acid ester from an aldehyde, an alcohol and molecular oxygen.
【０００２】[0002]
【従来の技術】工業的に有用なメタクリル酸メチル（以
下、ＭＭＡという。）又はアクリル酸メチルを製造する
方法としてメタクロレインからメタクリル酸を製造し、
さらにＭＭＡに変換する直酸法と呼ばれる製法が既に工
業化されている。しかしながら、メタクロレインを酸化
しメタクリル酸とする工程の収率は長年にわたる触媒改
良により８０％台前半まで改善されてきているが依然と
して低く改良の余地が大きい。また使用されるヘテロポ
リ酸触媒は、熱的安定性にもともと難点があり、反応温
度条件下で分解が徐々に進行する。耐熱性を向上させる
ための触媒改良が報じられているものの、工業触媒とし
ては触媒寿命が未だ不十分といわれる。BACKGROUND ART As a method for producing industrially useful methyl methacrylate (hereinafter referred to as MMA) or methyl acrylate, methacrylic acid is produced from methacrolein,
Further, a production method called a direct acid method for converting into MMA has already been industrialized. However, although the yield of the process of oxidizing methacrolein to methacrylic acid has been improved to the lower 80% level by the catalyst improvement over many years, it is still low and there is much room for improvement. Further, the heteropolyacid catalyst to be used originally has a problem in thermal stability, and the decomposition gradually proceeds under the reaction temperature conditions. Although improvement of the catalyst for improving heat resistance has been reported, it is said that the catalyst life is still insufficient as an industrial catalyst.
【０００３】一方、メタクロレイン又はアクロレインを
メタノールと分子状酸素と反応させて一挙にメタクリル
酸メチル又はアクリル酸メチルを製造する新しいルート
が近時脚光をあびている。メタクロレイン又はアクロレ
インをメタノール中で分子状酸素と反応させることによ
って行われ、パラジウムを含む触媒の存在が必須であ
る。On the other hand, a new route for producing methyl methacrylate or methyl acrylate by reacting methacrolein or acrolein with methanol and molecular oxygen has recently been in the spotlight. It is carried out by reacting methacrolein or acrolein with molecular oxygen in methanol, and the presence of a catalyst containing palladium is essential.
【０００４】従来、この製法はアルデヒドの分解反応を
併発して炭化水素や炭酸ガスが生成し、目的とするカル
ボン酸エステルの収率が低く、またカルボン酸エステル
の生成反応と並行してアルコール自身の酸化による異種
のアルデヒドおよびそのアルデヒドから異種のカルボン
酸エステル（例えば、アルコールとしてメタノールを用
いた場合は蟻酸メチル、エタノールの場合は酢酸エチ
ル）が副生し、アルコール基準の選択性も悪かった。し
かも触媒活性を長期にわたり維持できないという欠点も
あった。特に工業的実用価値の高いメタクロレインやア
クロレインなどのα・β−不飽和アルデヒドを出発原料
とした場合には、これら反応中間体の安定性が一段と低
いため反応中に多量の炭酸ガスやオレフィン（メタクロ
レインの場合はプロピレン）などの分解生成物が発生
し、実用化レベルにはほど遠かった。本発明者らは、特
公昭５７−０３５８５６号、特公昭５７−０３５８５７
号、特公昭５７−０３５８５９号の各公報でパラジウ
ム、鉛を含む触媒系を提案し、メタクロレイン又はアク
ロレインを基準とした当該メチルエステルへの選択率を
大幅に改善し、９０％を超える高い値となることを示し
ているが、反応温度は高々５０℃までであった。引き続
き、特公昭６２−００７９０２号公報ではパラジウムと
鉛とが簡単な整数比で結合した金属間化合物を含む触媒
を提案し、メタクロレイン又はアクロレインの分解反応
がほぼ完全に抑止され、かつ触媒活性も長期間失われる
ことがない触媒系であることを示した。これら新しい触
媒系を使用する新製法は前記した通り収率改善及び触媒
寿命改善に頭打ちの感のある直酸法に比べ工程が短いな
どの利点もあり、工業的に有用なポリマー原料の新しい
製法として工業化が待ち望まれている。Heretofore, in this production method, hydrocarbons and carbon dioxide gas have been produced in combination with the decomposition reaction of the aldehyde, and the yield of the desired carboxylic acid ester has been low. A different aldehyde and a different carboxylic acid ester (for example, methyl formate when methanol is used as an alcohol, and ethyl acetate when ethanol is used) are by-produced from the aldehyde, resulting in poor selectivity on the basis of alcohol. In addition, there is a disadvantage that the catalyst activity cannot be maintained for a long time. In particular, when α / β-unsaturated aldehydes such as methacrolein and acrolein, which have high industrial practical value, are used as starting materials, the stability of these reaction intermediates is much lower, so that a large amount of carbon dioxide or olefin ( Decomposition products such as propylene in the case of methacrolein) were generated, which was far from practical use. The present inventors have disclosed JP-B-57-035856 and JP-B-57-035857.
And Japanese Patent Publication No. 57-035859 propose a catalyst system containing palladium and lead, greatly improving the selectivity to the methyl ester based on methacrolein or acrolein, and having a high value exceeding 90%. The reaction temperature was up to 50 ° C. at most. Subsequently, Japanese Patent Publication No. 62-007902 proposes a catalyst containing an intermetallic compound in which palladium and lead are combined at a simple integer ratio, whereby the decomposition reaction of methacrolein or acrolein is almost completely inhibited, and the catalytic activity is also reduced. It was shown that the catalyst system was not lost for a long time. As described above, the new production method using these new catalyst systems has the advantage that the process is shorter than that of the direct acid method, which has a feeling that the yield and catalyst life have reached a plateau, and thus a new production method of industrially useful polymer raw materials. Industrialization has been awaited.
【０００５】しかしながら、工業的実施を前提として経
済的に有利な反応条件である６０℃以上の高温で本反応
を実施すると、前記触媒系ではＭＭＡ選択率の低下及び
アルコール自身の酸化による蟻酸メチルの副生量が急激
する。即ち、特公昭６２−００７９０２号公報は９０％
を超える高いＭＭＡ選択率が得られ、しかも蟻酸メチル
は０．０３〜０．０６モル／モルＭＭＡと僅かし生成し
ないことを例示しているが、これらはアルデヒド濃度が
１０％以下でしかも反応温度も４０〜６０℃という穏和
な条件で実施されたものである。これらの条件では生成
するＭＭＡ濃度が低いため未反応メタノールのリサイク
ル量が多く、その結果蒸気使用量が増大し経済性を悪化
させている。しかも生産性が低く反応器も大きい。経済
性改善のためにはアルデヒド濃度及び反応温度を可及的
に高めることが望ましく、特公平５−０６９８１３号公
報ではメタクロレイン濃度２０％、反応温度８０℃での
反応例が示されている。ところがこのような高いメタク
ロレイン濃度及び高い反応温度条件になると９０％を超
える高いＭＭＡ選択率は得られない。しかも蟻酸メチル
が０．０９２３モル／モルＭＭＡと倍増する。さらにメ
タクロレイン濃度を３０％を越えるより過酷な条件にす
ると、アルデヒドの分解反応が起こりやすくなりＭＭＡ
の選択率がさらに悪化することが、本発明者らの検討で
明らかになった。However, if this reaction is carried out at a high temperature of 60 ° C. or higher, which is an economically advantageous reaction condition on the premise of industrial practice, the catalyst system reduces MMA selectivity and produces methyl formate due to oxidation of the alcohol itself. The amount of by-products increases rapidly. That is, Japanese Patent Publication No. 62-007902 discloses 90%
MMA selectivity exceeding 0.2% was obtained, and methyl formate was little formed at 0.03-0.06 mol / mol MMA. Was carried out under a mild condition of 40 to 60 ° C. Under these conditions, the amount of unreacted methanol recycled is large due to the low concentration of MMA produced, resulting in an increase in the amount of steam used and a decrease in economic efficiency. Moreover, the productivity is low and the reactor is large. To improve the economy, it is desirable to increase the aldehyde concentration and the reaction temperature as much as possible. Japanese Patent Publication No. 5-069813 discloses a reaction example at a methacrolein concentration of 20% and a reaction temperature of 80 ° C. However, under such high methacrolein concentration and high reaction temperature conditions, a high MMA selectivity exceeding 90% cannot be obtained. Moreover, methyl formate doubles to 0.0923 mol / mol MMA. Further, when the methacrolein concentration is set to a more severe condition exceeding 30%, an aldehyde decomposition reaction is likely to occur, and MMA
It has been clarified in the study of the present inventors that the selectivity of is further deteriorated.
【０００６】経済性改善のため、高温、高アルデヒド濃
度下で９０％を超える高いＭＭＡ選択率及び蟻酸メチル
副生の少ない触媒系の出現が待たれていた。[0006] In order to improve economical efficiency, a catalyst system having a high MMA selectivity of more than 90% at high temperature and high aldehyde concentration and a low amount of methyl formate by-product has been expected.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、アルデヒド
とアルコールをパラジウム及び鉛を含む触媒と反応させ
てカルボン酸エステルを製造するに際し、アルデヒドの
濃度および反応温度を高めて経済性を改善した反応条件
においても、カルボン酸エステルの選択率が高くしかも
蟻酸メチルなどのアルコール由来の副生物の少ない触媒
を製造する方法を提供するものである。SUMMARY OF THE INVENTION The present invention relates to a method for producing a carboxylic acid ester by reacting an aldehyde and an alcohol with a catalyst containing palladium and lead, wherein the concentration and reaction temperature of the aldehyde are increased to improve the economic efficiency. An object of the present invention is to provide a method for producing a catalyst having a high selectivity for a carboxylate ester and a small amount of alcohol-derived by-products such as methyl formate even under conditions.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、このよう
な現状に鑑み、カルボン酸エステル選択率が高くしかも
蟻酸メチルなどのアルコール由来の副生物の少ない触媒
を開発すべくパラジウム、鉛を含む触媒系につき鋭意研
究し、本発明を完成した。即ち、本発明は以下のとおり
である。 １． 酸素の存在下でアルデヒドとアルコールを反応さ
せてカルボン酸エステルを製造する際に用いるパラジウ
ム／鉛含有担持触媒の製造方法において、パラジウム／
鉛担持組成比が原子比で３／０以上３／１．３未満の触
媒前駆体を、パラジウム／鉛原子比で３／０．７〜３／
１．３の担持組成比を有するパラジウム／鉛担持触媒を
得るのに必要な量の鉛化合物が存在する水溶液またはメ
タノール溶液中でホルマリン、蟻酸、ヒドラジンまたは
分子状水素で還元することを特徴とするパラジウム／鉛
含有担持触媒の製造方法。 ２． 低級脂肪酸、低級脂肪酸のアルカリ金属塩または
低級脂肪酸のアルカリ土類金属塩を共存させて行う上記
１のパラジウム／鉛含有担持触媒の製造方法。 ３． パラジウム／鉛含有担持触媒のパラジウム／鉛の
担持組成比が原子比で３／０．７〜３／１．３であり、
パラジウム／鉛金属間化合物の（１１１）面のＸ線回折
角（２θ）が３８．５５〜３８．７０である上記１のパ
ラジウム／鉛含有担持触媒の製造方法。 ４． アルデヒドがメタクロレイン、アクロレインまた
はこれらの混合物であり、アルコールがメタノールであ
る上記１のパラジウム／鉛含有担持触媒の製造方法。In view of such circumstances, the present inventors have developed palladium and lead to develop a catalyst having a high carboxylate ester selectivity and a small amount of alcohol-derived by-products such as methyl formate. The present inventors have intensively studied the catalyst system including the catalyst and completed the present invention. That is, the present invention is as follows. 1. In the method for producing a supported palladium / lead-containing catalyst used in producing a carboxylic acid ester by reacting an aldehyde and an alcohol in the presence of oxygen,
A catalyst precursor having a lead carrying composition ratio of 3/0 or more and less than 3 / 1.3 in atomic ratio is converted into a palladium / lead atomic ratio of 3 / 0.7 to 3 /
Reduction with formalin, formic acid, hydrazine or molecular hydrogen in an aqueous solution or methanol solution in which the amount of lead compound required to obtain a palladium / lead supported catalyst having a supported composition ratio of 1.3 is present. A method for producing a supported catalyst containing palladium / lead. 2. The method for producing a supported palladium / lead-containing catalyst according to 1 above, wherein the catalyst is a coexistence of a lower fatty acid, an alkali metal salt of a lower fatty acid, or an alkaline earth metal salt of a lower fatty acid. 3. The supported composition ratio of palladium / lead of the supported catalyst containing palladium / lead is 3 / 0.7 to 3 / 1.3 in atomic ratio,
The method for producing a supported palladium / lead-containing catalyst according to 1 above, wherein the (111) plane of the palladium / lead intermetallic compound has an X-ray diffraction angle (2θ) of 38.5 to 38.70. 4. The method for producing a supported palladium / lead-containing catalyst according to 1 above, wherein the aldehyde is methacrolein, acrolein or a mixture thereof, and the alcohol is methanol.
【０００９】以下、本発明につき詳細に説明する。本発
明者らは、特公昭６２−００７９０２号公報で提案し
た、パラジウムと鉛が簡単な整数比で結合した金属間化
合物種である原子比３／１のＰｂ3 Ｐｂ1 種に注目し、
Ｐｂ3 Ｐｂ1 が担持されてなる担持触媒の製造について
より緻密な研究を進めた。その結果、特公昭６２−００
７９０２号公報記載の調製法で得られるパラジウム、鉛
を含む担持触媒は、触媒種としてＰｂ3 Ｐｂ1 金属間化
合物を含むものの純度が低く、しかもパラジウム／鉛金
属間化合物の結晶格子に欠陥等が多く残る触媒であるこ
とが明らかとなった。特に、鉛の担持量を、Ｐｂ3 Ｐｂ
1 金属間化合物のパラジウム／鉛の量論組成である原子
比３／１で調製した触媒は、結晶格子の欠陥が一段と増
加し、経済的に有利な条件である高温、高アルデヒド濃
度条件では、ＭＭＡ選択率が却って低くなる触媒である
ことも本発明者らにより明らかとなった。Hereinafter, the present invention will be described in detail. Departure
The authors proposed in Japanese Patent Publication No. 62-007902.
In addition, palladium and lead are combined at a simple integer ratio
Pb with an atomic ratio of 3/1, which is a compound speciesThreePb1Focus on the seeds,
PbThreePb1Of supported catalyst on which is supported
We conducted more detailed research. As a result,
Palladium and lead obtained by the preparation method described in JP 7902
Supported catalyst containing Pb as a catalyst speciesThreePb1Intermetallic
Low purity of compound containing, and palladium / lead gold
The catalyst must have many defects in the crystal lattice of the intergeneric compound.
It became clear. In particular, when the amount of supported lead is PbThreePb
1An atom that is a stoichiometric composition of palladium / lead in the intermetallic compound
In the catalyst prepared at a ratio of 3/1, defects in the crystal lattice were further increased.
In addition, high temperature and high aldehyde concentration which are economically favorable conditions
Under low temperature conditions, the MMA selectivity is rather low.
This has also been made clear by the present inventors.
【００１０】さらに研究を進めた結果、特公昭６２−０
０７９０２号公報に記載の通常の調製法では、高純度で
高品位なＰｂ3 Ｐｂ1 金属間化合物が担持されてなる触
媒は得られず、本発明で提案するところの触媒製造方法
により、結晶格子に欠陥の少ない高品位なＰｂ3 Ｐｂ1
金属間化合物を高純度で含む担持触媒が得られることを
見出した。得られた触媒は、前記したような高いアルデ
ヒド濃度及び高い反応温度の過酷な反応条件であっても
高いＭＭＡ選択率を示すことも本発明者等は明らかにし
た。As a result of further research, the Japanese Patent Publication No. 62-0
In the ordinary preparation method described in Japanese Patent Application Laid-Open No. 07902/1995, a high-purity and high-grade Pb 3 Pb 1 intermetallic compound-supported catalyst cannot be obtained, and the catalyst production method proposed in the present invention provides a crystal lattice. High quality Pb 3 Pb 1 with few defects
It has been found that a supported catalyst containing an intermetallic compound with high purity can be obtained. The present inventors have also found that the obtained catalyst shows high MMA selectivity even under the severe reaction conditions of the high aldehyde concentration and the high reaction temperature as described above.
【００１１】本発明において用いる、パラジウム／鉛担
持組成比が原子比で３／０以上３／１．３未満の触媒前
駆体は、公知の調製法で準備することができる。代表的
な触媒調製法について説明すれば、パラジウム及び鉛が
担持されてなる触媒前駆体は、塩化パラジウムなどの可
溶性のパラジウム化合物、及び可溶性の鉛化合物を、パ
ラジウム／鉛比が原子比で３／０以上３／１．３未満と
なるように溶解させた水溶液に担体を加温含浸させ、パ
ラジウム、鉛を担持するなどの公知の方法で準備するこ
とができる。この場合、パラジウムを担持する前に鉛を
担持しておいてもよいし、上記説明のようにパラジウ
ム、鉛を同時に担持してもよい。あるいはパラジウムを
担持した後、鉛を担持しても構わないため種々の製法が
可能である。The catalyst precursor used in the present invention having a palladium / lead carrying composition ratio of 3/0 or more and less than 3 / 1.3 by atomic ratio can be prepared by a known preparation method. Explaining a typical catalyst preparation method, a catalyst precursor in which palladium and lead are supported is prepared by mixing a soluble palladium compound such as palladium chloride and a soluble lead compound with a palladium / lead ratio of 3 / atomic ratio. The carrier can be prepared by a known method such as heating and impregnating a carrier with an aqueous solution dissolved so as to be 0 or more and less than 3 / 1.3, and carrying palladium and lead. In this case, lead may be loaded before loading palladium, or palladium and lead may be loaded simultaneously as described above. Alternatively, since lead may be supported after supporting palladium, various production methods are possible.
【００１２】触媒前駆体中に含まれる触媒成分としてパ
ラジウム、鉛の他に異種元素として、例えば水銀、タリ
ウム、ビスマス、テルル、ニッケル、クロム、コバル
ト、インジウム、タンタル、銅、亜鉛、ジルコニウム、
ハフニウム、タングステン、マンガン、銀、レニウム、
アンチモン、スズ、ロジウム、ルテニウム、イリジウ
ム、白金、金、チタン、アルミニウム、硼素、珪素など
を含んでいてもよい。これらの異種元素は通常、５重量
％を超えない範囲で、好ましくは１重量％を超えない範
囲で含むことができる。さらにはアルカリ金属化合物お
よびアルカリ土類金属化合物から選ばれた少なくとも一
員を含むものは反応活性が高くなるなどの利点がある。
アルカリ金属、アルカリ土類金属は通常０．０１〜３０
重量％、好ましくは０．０１〜５重量％の範囲から選ば
れる。これらの異種元素あるいはアルカリ金属およびア
ルカリ土類金属化合物などは結晶格子間に少量、侵入し
たり、または結晶格子金属の一部と置換していてもよ
い。また、アルカリ金属および／又はアルカリ土類金属
化合物は触媒前駆体調製時にパラジウム化合物あるいは
鉛化合物を含む溶液に加えておき担体に吸着あるいは付
着させてもよいし、あらかじめこれらを担持した担体を
利用して触媒前駆体を調製することもできる。また、反
応条件下に反応系に添加することも可能である。In addition to palladium and lead as catalyst components contained in the catalyst precursor, other elements such as mercury, thallium, bismuth, tellurium, nickel, chromium, cobalt, indium, tantalum, copper, zinc, zirconium,
Hafnium, tungsten, manganese, silver, rhenium,
It may contain antimony, tin, rhodium, ruthenium, iridium, platinum, gold, titanium, aluminum, boron, silicon and the like. These different elements can be contained usually in a range not exceeding 5% by weight, preferably in a range not exceeding 1% by weight. Further, a compound containing at least one member selected from an alkali metal compound and an alkaline earth metal compound has an advantage that the reaction activity is increased.
Alkali metal and alkaline earth metal are usually 0.01 to 30.
% By weight, preferably in the range of 0.01 to 5% by weight. These dissimilar elements or alkali metal and alkaline earth metal compounds may penetrate the crystal lattice in a small amount, or may be substituted with a part of the crystal lattice metal. Further, the alkali metal and / or alkaline earth metal compound may be added to a solution containing a palladium compound or a lead compound at the time of preparing the catalyst precursor, and may be adsorbed or adhered to the carrier. To prepare a catalyst precursor. It is also possible to add to the reaction system under the reaction conditions.
【００１３】触媒前駆体調製のために用いられるパラジ
ウム化合物あるいは鉛化合物は、例えば蟻酸塩、酢酸塩
などの有機酸塩、硫酸塩、塩酸塩、硝酸塩などの無機酸
塩、アンミン錯体、ベンゾニトリル錯体などの有機金属
錯体、酸化物、水酸化物などのなかから適宜選ばれる
が、パラジウム化合物としては塩化パラジウム、酢酸パ
ラジウムなどが、鉛化合物としては硝酸鉛、酢酸鉛など
が好適である。またアルカリ金属化合物、アルカリ土類
金属化合物についても有機酸塩、無機酸塩、水酸化物な
どから選ばれる。The palladium compound or lead compound used for preparing the catalyst precursor includes, for example, organic acid salts such as formate and acetate, inorganic acid salts such as sulfate, hydrochloride and nitrate, ammine complex and benzonitrile complex. The organic compound is appropriately selected from organometallic complexes, oxides, hydroxides, and the like. Palladium compounds, palladium acetate, and the like are preferable as the palladium compound, and lead nitrate, lead acetate, and the like are preferable as the lead compound. The alkali metal compound and alkaline earth metal compound are also selected from organic acid salts, inorganic acid salts, hydroxides and the like.
【００１４】担体は活性炭、シリカ、アルミナ、シリカ
アルミナ、ゼオライト、マグネシア、水酸化マグネシウ
ム、チタニア、炭酸カルシウム、活性炭などから広く選
ぶことができる。担体へのパラジウム担持量は特に限定
はないが担体１００重量部に対して通常０．１〜２０重
量部、好ましくは１〜１０重量部である。鉛の担持量も
特に限定はなく担体１００重量部に対して通常０．１〜
２０重量部、好ましくは１〜１０重量部であるが、パラ
ジウム、鉛の各担持量よりも、むしろパラジウム／鉛の
担持組成比（原子比）が重要である。即ち、本発明にお
いて触媒前駆体のパラジウム／鉛組成比は原子比で３／
０以上３／１．３未満の範囲から選ばれる。好ましくは
３／０〜３／１．０、特に好ましくは３／０〜３／０．
７の範囲から選ばれる。本発明の触媒は、これら触媒前
駆体を、パラジウム／鉛原子比で３／０．７〜３／１．
３の担持組成比を有するパラジウム／鉛担持触媒を得る
のに必要な量の鉛化合物が存在する水溶液もしくはメタ
ノール溶液中でホルマリン、蟻酸、ヒドラジンもしくは
分子状水素で還元することで得られ、最終的に３／０．
７〜３／１．３のパラジウム／鉛担持組成比を有する触
媒を得る。本発明においては、触媒前駆体を鉛化合物が
存在する水溶液もしくはメタノール溶液中でホルマリ
ン、蟻酸、ヒドラジンもしくは分子状水素で還元するこ
とが必要である。The carrier can be widely selected from activated carbon, silica, alumina, silica alumina, zeolite, magnesia, magnesium hydroxide, titania, calcium carbonate, activated carbon and the like. The amount of palladium supported on the carrier is not particularly limited, but is usually 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the carrier. The amount of lead carried is not particularly limited either, and is usually 0.1 to 100 parts by weight of the carrier.
The amount is 20 parts by weight, preferably 1 to 10 parts by weight. However, the supported palladium / lead composition ratio (atomic ratio) is more important than the supported amounts of palladium and lead. That is, in the present invention, the palladium / lead composition ratio of the catalyst precursor is 3 / atomic ratio.
It is selected from the range of 0 or more and less than 3 / 1.3. Preferably 3/0 to 3 / 1.0, particularly preferably 3/0 to 3/0.
7 range. The catalyst of the present invention comprises these catalyst precursors in a palladium / lead atomic ratio of 3 / 0.7 to 3/1.
The catalyst is obtained by reduction with formalin, formic acid, hydrazine or molecular hydrogen in an aqueous solution or a methanol solution in which an amount of lead compound required to obtain a palladium / lead supported catalyst having a supported composition ratio of 3 is obtained. 3/0.
A catalyst having a palladium / lead carrying composition ratio of 7 to 3 / 1.3 is obtained. In the present invention, it is necessary to reduce the catalyst precursor with formalin, formic acid, hydrazine or molecular hydrogen in an aqueous solution or a methanol solution containing a lead compound.
【００１５】以下、パラジウム／鉛担持組成比が原子比
で３／０以上３／１．３未満の触媒前駆体から本発明の
触媒を得る方法につき説明する。前述の触媒前駆体を水
もしくはメタノールに分散加温しながら、パラジウム／
鉛原子比で３／０．７〜３／１．３の担持組成比を有す
るパラジウム／鉛担持触媒を得るのに必要な量の鉛化合
物が存在する水溶液もしくはメタノール溶液中でホルマ
リン、蟻酸、ヒドラジンもしくは分子状水素で還元す
る。A method for obtaining the catalyst of the present invention from a catalyst precursor having a palladium / lead carrying composition ratio of 3/0 or more and less than 3 / 1.3 in atomic ratio will be described below. While dispersing and heating the above-mentioned catalyst precursor in water or methanol, palladium /
Formalin, formic acid, hydrazine in an aqueous solution or a methanol solution containing an amount of a lead compound required to obtain a palladium / lead supported catalyst having a supported composition ratio of 3 / 0.7 to 3 / 1.3 in terms of a lead atom ratio. Alternatively, it is reduced with molecular hydrogen.
【００１６】当該条件で安定な溶剤であれば水、メタノ
ール以外の不活性な溶剤を選ぶこともできるが、実用的
には水、又はメタノールを選ぶのが好ましい。還元剤と
してホルマリン、蟻酸、ヒドラジン、もしくは分子状水
素を使用する。ホルマリン、ヒドラジン、蟻酸の場合は
ホルマリン、ヒドラジン、蟻酸含有溶液を触媒前駆体分
散溶液に添加するだけでよい。また分子状水素による還
元処理は、純粋な水素ガス又は窒素、メタン等の不活性
なガスで希釈された水素濃度０．１容量％以上の水素含
有ガスを常圧ないしは数十気圧、好ましくは常圧ないし
数気圧の圧力条件で触媒前駆体分散溶液に吹き込んで行
われる。ホルマリン、蟻酸、ヒドラジン、もしくは分子
状水素の使用量は一般的にはパラジウム担持量に対し
０．５〜１００倍モル、実用的には２〜１０倍モルが使
用される。また、この量を越えても特に問題はない。ま
た、還元剤と同時に苛性ソーダなどのアルカリを加えて
おくと還元がより容易に進行する。通常、還元剤に対し
１／１００〜等モル程度を加える。As long as the solvent is stable under the above conditions, an inert solvent other than water and methanol can be selected, but practically, water or methanol is preferably selected. Formalin, formic acid, hydrazine, or molecular hydrogen is used as a reducing agent. In the case of formalin, hydrazine and formic acid, it is only necessary to add a solution containing formalin, hydrazine and formic acid to the catalyst precursor dispersion. In the reduction treatment with molecular hydrogen, a hydrogen-containing gas having a hydrogen concentration of 0.1% by volume or more diluted with pure hydrogen gas or an inert gas such as nitrogen or methane is subjected to normal pressure or several tens atmospheres, preferably normal pressure. This is carried out by blowing into the catalyst precursor dispersion solution under pressure conditions of several to several atmospheres. The amount of formalin, formic acid, hydrazine, or molecular hydrogen used is generally 0.5 to 100 times, and practically 2 to 10 times, the molar amount of the supported palladium. There is no particular problem if the amount exceeds this amount. If an alkali such as caustic soda is added at the same time as the reducing agent, the reduction proceeds more easily. Usually, about 1/100 to equimolar amount is added to the reducing agent.
【００１７】還元の際には鉛を含む物質を共存させる。
通常、鉛を含む物質を触媒前駆体を分散させた水もしく
はメタノール中に加えるのが一般的である。鉛を含む物
質を添加する際には、鉛イオンとして溶解するものであ
れば特に制限はない。その一例として蟻酸塩、酢酸塩な
どの有機酸塩、硫酸塩、塩酸塩、硝酸塩などの無機酸
塩、アセチルアセトナート錯体、エチレンジアミンテト
ラアセテート錯体などの有機金属錯体、酸化物、水酸化
などがあげられるが、溶解度の高い硝酸鉛、酢酸鉛など
が好適である。At the time of reduction, a substance containing lead coexists.
Usually, a substance containing lead is generally added to water or methanol in which a catalyst precursor is dispersed. When adding a substance containing lead, there is no particular limitation as long as it dissolves as lead ions. Examples thereof include organic acid salts such as formate and acetate, inorganic acid salts such as sulfate, hydrochloride and nitrate, organic metal complexes such as acetylacetonate complex and ethylenediaminetetraacetate complex, oxides, and hydroxides. However, lead nitrate, lead acetate and the like having high solubility are preferred.
【００１８】溶解する鉛イオン濃度としては、少なくと
も３０ｐｐｍ以上が必要であり、好ましくは３００ｐｐ
ｍ以上、さらに好ましくは１０００ｐｐｍ以上である。
加える鉛化合物の量は対象となる触媒前駆体に担持され
ている鉛量により異なる。一般的には触媒前駆体に担持
されているパラジウム量を基準に、触媒前駆体に担持さ
れている鉛量と溶液中の鉛量を合わせてパラジウム／鉛
原子比で３／０．７〜３／１．３となるのに必要な量の
鉛化合物を加えて水溶液又はメタノール溶液を調製し、
該水溶液又はメタノール溶液に触媒前駆体を分散させ還
元を行う。The concentration of dissolved lead ions must be at least 30 ppm, preferably 300 pp.
m or more, more preferably 1000 ppm or more.
The amount of the lead compound to be added depends on the amount of lead supported on the target catalyst precursor. Generally, based on the amount of palladium supported on the catalyst precursor, the amount of lead supported on the catalyst precursor and the amount of lead in the solution are combined to form a palladium / lead atomic ratio of 3 / 0.7 to 3. Aqueous solution or methanol solution is prepared by adding an amount of lead compound necessary to obtain
The catalyst precursor is dispersed in the aqueous solution or methanol solution to perform reduction.
【００１９】上記鉛化合物は還元操作を始める前に加え
ておいてもよいし、還元操作中に連続的に又は間欠的に
加えることもできる。触媒前駆体のパラジウム／鉛比が
既に３／０．７以上３／１．３未満の範囲にある場合に
も、パラジウム／鉛原子比が最終的に３／１．３を越え
ない範囲で鉛化合物を添加して、前記してきた如く還元
する必要がある。The above-mentioned lead compound may be added before starting the reduction operation, or may be added continuously or intermittently during the reduction operation. Even when the palladium / lead ratio of the catalyst precursor is already in the range of 3 / 0.7 or more and less than 3 / 1.3, the lead must be in the range where the palladium / lead atomic ratio does not finally exceed 3 / 1.3. Compounds need to be added and reduced as described above.
【００２０】触媒前駆体を還元する際にプロピオンン
酸、酢酸、酪酸、マレイン酸等の低級脂肪酸を系に加え
ながら還元することもできる。加える低級脂肪酸の量は
担持パラジウムを基準に０．１〜３０倍モル程度加え
る。より好ましくは１〜１５倍モルの範囲から選ぶ。実
用的には入手容易な酢酸を選ぶのが好ましい。これら低
級脂肪酸は還元剤と同時に加えてもよいが、還元剤添加
前に加えるとより効果的である。これら低級脂肪酸の添
加はパラジウム及び鉛が担持されてなる触媒前駆体に適
用する際に特に効果的である。When the catalyst precursor is reduced, the reduction can be carried out while adding a lower fatty acid such as propionic acid, acetic acid, butyric acid or maleic acid to the system. The amount of the lower fatty acid to be added is about 0.1 to 30 times mol based on the supported palladium. More preferably, it is selected from the range of 1 to 15 times mol. Practically, it is preferable to select acetic acid which is easily available. These lower fatty acids may be added simultaneously with the reducing agent, but it is more effective to add them before adding the reducing agent. The addition of these lower fatty acids is particularly effective when applied to a catalyst precursor on which palladium and lead are supported.
【００２１】さらに好ましくは低級脂肪酸のアルカリ金
属塩、アルカリ土類金属塩を添加することであり、これ
らの金属塩を添加することで、得られるＰｂ3 Ｐｂ1 金
属間化合物の格子欠陥がより少なくなり、きわめて高品
位のＰｂ3 Ｐｂ1 金属間化合物が担持されてなる触媒が
得られることを本発明者らは見いだした。この効果はパ
ラジウムが担持されてなる触媒前駆体、パラジウム及び
鉛が担持されてなる触媒前駆体いずれに対しても効果的
である。低級脂肪酸のアルカリ金属塩、アルカリ土類金
属塩は担持パラジウムを基準に０．１〜３０倍モル程度
加える。より好ましくは１〜１５倍モルの範囲から選
ぶ。低級脂肪酸のアルカリ金属塩、アルカリ土類金属塩
としては酢酸ナトリウム、酢酸マグネシウムなどが好ま
しい。如何なる理由により高品位のＰｂ3 Ｐｂ1 が得ら
れるのか未だ理由は不明であるが、アルカリカチオンあ
るいはアルカリ土類カチオンの働きにより、鉛イオンが
選択的にＰｄ／Ｐｂ化合物の格子欠陥部に相互作用する
のを助けているものと推察している。More preferably, an alkali metal salt or an alkaline earth metal salt of a lower fatty acid is added, and by adding these metal salts, the resulting Pb 3 Pb 1 intermetallic compound has less lattice defects. The present inventors have found that a catalyst in which an extremely high-quality Pb 3 Pb 1 intermetallic compound is supported can be obtained. This effect is effective for both a catalyst precursor on which palladium is supported and a catalyst precursor on which palladium and lead are supported. The alkali metal salt or alkaline earth metal salt of a lower fatty acid is added in an amount of about 0.1 to 30 moles based on the supported palladium. More preferably, it is selected from the range of 1 to 15 times mol. As the alkali metal salt or alkaline earth metal salt of a lower fatty acid, sodium acetate, magnesium acetate and the like are preferable. The reason why high-quality Pb 3 Pb 1 can be obtained is not yet known, but the action of alkali cations or alkaline earth cations causes lead ions to selectively interact with lattice defects in the Pd / Pb compound. I guess it is helping to do that.
【００２２】また、これら低級脂肪酸、低級脂肪酸のア
ルカリ金属塩および／又はアルカリ土類金属塩を添加す
る場合で、触媒前駆体のパラジウム／鉛比が既に３／
０．７以上３／１．３未満の範囲にある場合には、水溶
液またはメタノール溶液中に溶解した鉛が存在すること
から、鉛化合物を添加することなく、還元することが可
能である。When the lower fatty acid and the alkali metal salt and / or alkaline earth metal salt of the lower fatty acid are added, the palladium / lead ratio of the catalyst precursor is already 3/3.
When it is in a range of 0.7 or more and less than 3 / 1.3, since lead dissolved in an aqueous solution or a methanol solution is present, reduction can be performed without adding a lead compound.
【００２３】還元操作は室温〜２００℃の温度で行うこ
とができる。液相に保つために必要な圧力をかけてお
く。好ましくは４０〜１６０℃、常圧から数気圧の条件
で行う。還元処理時間は触媒種、処理条件により変わる
ため決めがたいが、数分〜１００時間である。数時間以
内に処理が完了するように条件を設定するのが好都合で
ある。また、得られる触媒のパラジウム／鉛金属間化合
物の（１１１）面のＸ線回折角を測定すれば処理完了を
容易に判断できる。The reduction operation can be performed at a temperature from room temperature to 200 ° C. Apply the necessary pressure to maintain the liquid phase. Preferably, it is carried out at 40 to 160 ° C. and normal pressure to several atmospheres. The reduction processing time is difficult to determine because it varies depending on the type of the catalyst and the processing conditions, but is several minutes to 100 hours. It is convenient to set conditions so that the process is completed within a few hours. The completion of the treatment can be easily determined by measuring the X-ray diffraction angle of the (111) plane of the palladium / lead intermetallic compound of the obtained catalyst.
【００２４】還元に使用する反応器は特に制限はなく、
通常の攪拌槽型反応器で行える。以上、説明してきた還
元処理を触媒前駆体に施すことで、パラジウム／鉛の担
持組成比が原子比で３／０．７〜３／１．３であって、
かつパラジウム／鉛化合物の（１１１）面のＸ線回折角
（２θ）が３８．５５〜３８．７０である、格子欠陥の
少ない、高品位なＰｄ3 Ｐｄ1 化合物からなる高純度の
担持触媒を得ることができる。さらに好ましいのはパラ
ジウム金属（３ｄ（３／２）＋３ｄ（５／２））／鉛金
属（４ｆ（７／２）×１．７５）のＸ線光電子スペクト
ル強度比が１／０．２〜１／０．７である。The reactor used for the reduction is not particularly limited.
It can be performed in a usual stirred tank type reactor. By performing the reduction treatment described above on the catalyst precursor, the supported composition ratio of palladium / lead is 3 / 0.7 to 3 / 1.3 in atomic ratio,
A high-purity supported catalyst composed of a high-quality Pd 3 Pd 1 compound having a small lattice defect and an X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead compound of 38.55 to 38.70 is provided. Obtainable. More preferably, the X-ray photoelectron spectrum intensity ratio of palladium metal (3d (3/2) + 3d (5/2)) / lead metal (4f (7/2) × 1.75) is 1 / 0.2-1. /0.7.
【００２５】パラジウム／鉛化合物の（１１１）面のＸ
線回折角（２θ）が３８．５５未満の触媒ではアルコー
ル基準の収率の低下が著しく、例えば蟻酸メチルの生成
が増加する。３８．７０を越えるとアルデヒドの分解が
顕著となり、アルデヒド基準の収率が低下する。また、
担持鉛量が原子比で１．３を超えると蟻酸メチルの生成
が顕著となり、０．７未満ではアルデヒドの分解による
ＭＭＡ選択率の低下が大きい。本発明の製造法により得
られる触媒はアルデヒド基準、及びアルコール基準の収
率がともに改善される。X of the (111) plane of the palladium / lead compound
With a catalyst having a line diffraction angle (2θ) of less than 38.55, the yield on an alcohol basis is significantly reduced, and for example, the production of methyl formate increases. If it exceeds 38.70, the decomposition of aldehyde becomes remarkable, and the yield based on aldehyde decreases. Also,
When the amount of supported lead exceeds 1.3 in terms of atomic ratio, the formation of methyl formate becomes remarkable, and when the amount is less than 0.7, the decrease in MMA selectivity due to the decomposition of aldehyde is large. The catalyst obtained by the production method of the present invention has improved aldehyde-based and alcohol-based yields.
【００２６】本発明の方法により、パラジウム／鉛の担
持組成比（原子比）が３／０．７〜３／１．３と３／１
に近づけた触媒であって、過剰の鉛を含まず、しかも、
格子欠陥のないＰｄ3 Ｐｂ1 を高純度で含む担持触媒を
得ることを可能にした。原理的には触媒への鉛担持量を
可及的にパラジウム／鉛原子比で３／１の触媒を得るこ
とが可能である。公知の製法では、前記したとおりパラ
ジウム／鉛原子比が３／１に近い組成で調製した触媒は
ＭＭＡ選択率が低かった。本発明の方法により、従来不
可能とされてきたパラジウム／鉛原子比が３／１の触媒
に活性化することが可能となった。ＭＭＡ選択率の改善
は勿論のこと、蟻酸メチルなどのアルコール由来の副生
も極めて少ない触媒が得られ、しかも触媒中に鉛を含む
不純物が少ないためプロセス排水中への鉛の流出のない
触媒となることが期待でき、排水中の鉛を無害化するた
めの処理コストが不要となるなどの利点があり、工業的
に実施する際にはきわめて重要である。According to the method of the present invention, the supported composition ratio (atomic ratio) of palladium / lead is 3 / 0.7 to 3 / 1.3 and 3/1.
, A catalyst that does not contain excess lead,
This has made it possible to obtain a supported catalyst containing Pd 3 Pb 1 with high purity without lattice defects. In principle, it is possible to obtain a catalyst having a palladium / lead atomic ratio of 3/1 as much as possible with respect to the amount of lead carried on the catalyst. According to a known production method, as described above, a catalyst prepared with a composition in which the palladium / lead atomic ratio is close to 3/1 has a low MMA selectivity. According to the method of the present invention, it has become possible to activate a catalyst having an atomic ratio of palladium / lead of 3/1, which has heretofore been impossible. Not only the MMA selectivity is improved, but also a catalyst with very little by-products derived from alcohols such as methyl formate is obtained. In addition, the catalyst contains no lead-containing impurities and has no lead outflow into process wastewater. This is advantageous in that it does not require a treatment cost for detoxifying lead in wastewater, and is extremely important when industrially implemented.
【００２７】如何なる理由により、パラジウムが担持さ
れてなる触媒前駆体、パラジウム及び鉛が担持されてな
る触媒前駆体を、鉛を含む物質の存在する条件で、低級
脂肪酸、低級脂肪酸のアルカリ金属塩もしくはアルカリ
土類金属塩を共存させながらホルマリン、蟻酸、ヒドラ
ジンもしくは分子状水素で還元処理するだけのきわめて
簡便な方法で、結晶格子に欠陥の少ない高品位なＰｂ3
Ｐｂ1金属間化合物を、高純度で含む担持触媒が得られ
るのか未だ詳細は不明であるが、本発明者らの推察する
ところによると、第一に該条件で触媒上に形成される活
性水素が重要な役割を果たしており、この活性水素の働
きにより、パラジウム／鉛金属間化合物が活性化され、
欠陥の少ない構造への変化を容易にしていること、また
第二に共存する鉛イオンが活性化を進行させているこ
と、第三にアルカリカチオンあるいはアルカリ土類カチ
オンの働きにより鉛イオンが選択的にＰｄ／Ｐｂ化合物
の格子欠陥部に相互作用を助けるのに重要な役割を演じ
ているものと推察される。For any reason, a catalyst precursor comprising palladium and a catalyst precursor comprising palladium and lead may be converted to a lower fatty acid, an alkali metal salt of a lower fatty acid or an alkali metal salt of a lower fatty acid in the presence of a substance containing lead. A very simple method of reducing with formalin, formic acid, hydrazine or molecular hydrogen while coexisting with an alkaline earth metal salt. High-quality Pb 3 with few defects in the crystal lattice.
It is not yet known whether a supported catalyst containing Pb 1 intermetallic compound can be obtained with high purity, but it is presumed by the present inventors that, first, active hydrogen formed on the catalyst under the conditions Plays an important role, and the action of this active hydrogen activates the palladium / lead intermetallic compound,
Facilitating the change to a structure with few defects, Secondly, activation of coexisting lead ions, and Third, selective selection of lead ions by the action of alkali cations or alkaline earth cations It is presumed that it plays an important role in assisting the interaction with the lattice defect of the Pd / Pb compound.
【００２８】本発明の触媒製造法で得られるパラジウム
／鉛含有担持触媒は、アルデヒドをアルコール及び分子
状酸素と反応させてカルボン酸エステルを製造する反応
に好適に使用することができる。触媒の使用量は、反応
原料の種類、触媒の組成や調製法、反応条件、反応形式
などによって大巾に変更することができ、特に限定はな
いが、触媒をスラリー状態で反応させる場合には反応液
１リットル中に０．０４〜０．５ｋｇ使用するのが好ま
しい。The palladium / lead-containing supported catalyst obtained by the catalyst production method of the present invention can be suitably used in the reaction for producing a carboxylic acid ester by reacting an aldehyde with an alcohol and molecular oxygen. The amount of the catalyst used can be largely changed depending on the type of the reaction raw materials, the composition and preparation method of the catalyst, the reaction conditions, the reaction type, etc., but is not particularly limited, but when the catalyst is reacted in a slurry state, It is preferable to use 0.04 to 0.5 kg per liter of the reaction solution.
【００２９】本発明においてカルボン酸エステル製造反
応に使用するアルデヒドとしては、例えば、ホルムアル
デヒド、アセトアルデヒド、プロピオンアルデヒド、イ
ソブチルアルデヒド、グリオキサールなどの脂肪族飽和
アルデヒド、アクロレイン、メタクロレイン、クロトン
アルデヒドなどの脂肪族α・β−不飽和アルデヒド、ベ
ンズアルデヒド、トリルアルデヒド、ベンジルアルデヒ
ド、フタルアルデヒドなどの芳香族アルデヒド並びにこ
れらアルデヒドの誘導体などがあげられる。これらのア
ルデヒドは単独もしくは任意の二種以上の混合物として
用いることができる。The aldehyde used in the carboxylic acid ester production reaction in the present invention includes, for example, aliphatic saturated aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde and glyoxal, and aliphatic α such as acrolein, methacrolein and crotonaldehyde. -Aromatic aldehydes such as β-unsaturated aldehyde, benzaldehyde, tolylaldehyde, benzylaldehyde, and phthalaldehyde, and derivatives of these aldehydes. These aldehydes can be used alone or as a mixture of two or more kinds.
【００３０】カルボン酸エステル製造反応に使用するア
ルコールとしては、例えば、メタノール、エタノール、
イソプロパノール、オクタノールなどの脂肪族飽和アル
コール、エチレングリコール、ブタンジオールなどのジ
オール、アリルアルコール、メタリルアルコールなどの
脂肪族不飽和アルコール、ベンジルアルコールなどの芳
香族アルコールなどがあげられる。これらのアルコール
は単独もしくは任意の二種以上の混合物として用いるこ
とができる。The alcohol used in the carboxylic acid ester production reaction includes, for example, methanol, ethanol,
Examples include aliphatic saturated alcohols such as isopropanol and octanol, diols such as ethylene glycol and butanediol, aliphatic unsaturated alcohols such as allyl alcohol and methallyl alcohol, and aromatic alcohols such as benzyl alcohol. These alcohols can be used alone or as a mixture of two or more kinds.
【００３１】カルボン酸エステルを製造する反応におけ
るアルデヒドとアルコールとの使用量比には特に限定は
なく、例えばアルデヒド／アルコールのモル比で１０〜
１／１０００のような広い範囲で実施できるが、一般的
には１／２〜１／５０の範囲で実施される。特に、本発
明の触媒を使用すれば従来の触媒以上にアルデヒド濃度
を高めることが可能であり、重量％であらわすならば３
０〜６０重量％もの高濃度の反応でも工業的に実施でき
る。There is no particular limitation on the ratio of the aldehyde and the alcohol used in the reaction for producing the carboxylic acid ester.
Although it can be performed in a wide range such as 1/1000, it is generally performed in a range of 1/2 to 1/50. In particular, the use of the catalyst of the present invention makes it possible to increase the aldehyde concentration more than the conventional catalyst.
Even reactions as high as 0 to 60% by weight can be carried out industrially.
【００３２】カルボン酸エステル製造反応は気相反応、
液相反応、潅液反応などの任意の従来公知の方法で実施
できる。例えば液相で実施する際には気泡塔反応器、ド
ラフトチューブ型反応器、撹拌槽反応器などの任意の反
応器形式によることができる。カルボン酸エステルの製
造反応に使用する酸素は分子状酸素、すなわち酸素ガス
自体又は酸素ガスを反応に不活性な希釈剤、例えば窒
素、炭酸ガスなどで希釈した混合ガスの形とすることが
でき、空気を用いることもできる。また、本反応を連続
的に実施する際には鉛を含む物質を反応器に加えながら
反応を行うことで触媒の劣化を抑制できる。このとき、
反応器出口側の酸素分圧を０．８ｋｇ／ｃｍ2 以下とす
ることで反応器に供給する原料液中の鉛濃度を少量にし
て触媒の劣化を抑制できる。反応させるアルデヒド種、
アルコール種などの反応原料、反応条件もしくは反応器
形式などにより鉛の添加量、反応器出口の酸素分圧は特
定の値に決めがたいが、実用的には反応器出口の酸素分
圧を０．０２〜０．８ｋｇ／ｃｍ2 に管理し、反応器に
添加する鉛濃度は０．１〜２０００ｐｐｍの範囲で反応
を行う。酸素条件にあわせて鉛量を決定して反応器に供
給することで触媒の状態を反応中も安定に維持すること
ができる。添加する鉛量が多い場合には、排水中の鉛を
無害化するための処理コストが高くなったり、また反応
副生物の蟻酸メチルの量が多くなるなど好ましくないた
め、反応器出口側の酸素分圧は０．４ｋｇ／ｃｍ2 以下
として供給する鉛量を減らすのが好ましい。更に好まし
くは０．２ｋｇ／ｃｍ2 以下にすることもできるが反応
に必要な酸素を確保せねば酸素不足になり原料アルデヒ
ドの転化率が低下したり、不都合な副生物が生成するた
めこれらの悪影響がでない範囲で選べばよい。The carboxylic acid ester production reaction is a gas phase reaction,
It can be carried out by any conventionally known method such as a liquid phase reaction and a perfusion solution. For example, when the reaction is carried out in the liquid phase, any reactor type such as a bubble column reactor, a draft tube reactor, a stirred tank reactor, etc. can be used. The oxygen used in the production reaction of the carboxylic acid ester can be in the form of molecular oxygen, that is, oxygen gas itself or a mixed gas obtained by diluting oxygen gas with a diluent inert to the reaction, such as nitrogen or carbon dioxide gas, Air can also be used. When the present reaction is continuously performed, the deterioration of the catalyst can be suppressed by performing the reaction while adding a substance containing lead to the reactor. At this time,
By setting the oxygen partial pressure at the reactor outlet side to 0.8 kg / cm 2 or less, the lead concentration in the raw material liquid supplied to the reactor can be reduced to suppress the deterioration of the catalyst. Aldehyde species to react,
The amount of lead added and the oxygen partial pressure at the outlet of the reactor are difficult to determine to specific values depending on the reaction raw materials such as alcohol species, reaction conditions or the reactor type, but practically, the oxygen partial pressure at the reactor outlet is set to 0. The reaction is controlled at 0.02 to 0.8 kg / cm 2 and the concentration of lead added to the reactor is in the range of 0.1 to 2000 ppm. By determining the amount of lead in accordance with the oxygen conditions and supplying it to the reactor, the state of the catalyst can be stably maintained even during the reaction. If the amount of lead to be added is large, the treatment cost for detoxifying the lead in the wastewater increases, and the amount of methyl formate, a by-product of the reaction, becomes unfavorable. It is preferable to reduce the amount of lead supplied by setting the partial pressure to 0.4 kg / cm 2 or less. More preferably, the pressure can be reduced to 0.2 kg / cm 2 or less. However, if the oxygen required for the reaction is not ensured, the oxygen becomes insufficient and the conversion rate of the raw material aldehyde is reduced, or undesired by-products are formed. You can choose within the range that is not.
【００３３】反応圧力は減圧から加圧下の任意の広い圧
力範囲で実施することができるが、通常は０．５〜２０
ｋｇ／ｃｍ2 の圧力で実施される。反応器流出ガスの酸
素濃度が爆発範囲（８％）を越えないように全圧を設定
するとよい。カルボン酸エステルの製造反応は、反応系
にアルカリ金属もしくはアルカリ土類金属の化合物（例
えば、酸化物、水酸化物、炭酸塩、カルボン酸塩など）
を添加して反応系のｐＨを６〜９に保持することが好ま
しい。特にｐＨを６以上にすることで触媒中の鉛成分の
溶解を防ぐ効果がある。これらのアルカリ金属もしくは
アルカリ土類金属の化合物は単独もしくは二種以上組み
合わせて使用することができる。The reaction can be carried out in a wide range of pressure from reduced pressure to increased pressure.
It is performed at a pressure of kg / cm 2 . The total pressure is preferably set so that the oxygen concentration of the gas discharged from the reactor does not exceed the explosion range (8%). In the production reaction of the carboxylic acid ester, a compound of an alkali metal or an alkaline earth metal (eg, oxide, hydroxide, carbonate, carboxylate, etc.) is added to the reaction system.
Is preferably added to maintain the pH of the reaction system at 6 to 9. In particular, setting the pH to 6 or more has an effect of preventing dissolution of the lead component in the catalyst. These alkali metal or alkaline earth metal compounds can be used alone or in combination of two or more.
【００３４】カルボン酸エステルの製造反応は、１００
℃以上の高温でも実施できるが、好ましくは３０〜１０
０℃である。反応時間は特に限定されるものではなく、
設定した条件により異なるので一義的には決められない
が、通常１〜２０時間である。The production reaction of the carboxylic acid ester is 100
C. or higher, preferably 30 to 10
0 ° C. The reaction time is not particularly limited,
Since it differs depending on the set conditions, it cannot be uniquely determined, but is usually 1 to 20 hours.
【００３５】[0035]
【発明の実施の形態】以下に実施例、比較例を用いて本
発明をさらに詳細に説明する。なお、実施例等で用いる
圧力は絶対圧力で表示し、ｋｇ／ｃｍ2 で示すことにす
る。 ＜参考製造例１＞シリカゾル水溶液としての日産化学社
製スノーテックスＮ−３０（ＳｉＯ2 分：３０重量％）
に硝酸アルミニウム、硝酸マグネシウムをそれぞれＡｌ
／Ｓｉ＋Ａｌ＝１０モル％、Ｍｇ／Ｓｉ＋Ｍｇ＝１０モ
ル％となるように加え溶解させた後、１３０℃の温度に
設定した噴霧乾燥機で噴霧乾燥して平均粒子系６０μｍ
の球状担体を得た。３００℃、ついで６００℃で焼成し
た後、これを担体として塩化パラジウムを担体１００重
量部当たりパラジウム分として５．０重量部となるよう
に担持して触媒前駆体（Ｐｄ５．０／Ｍｇ、Ａｌ−Ｓｉ
Ｏ2 と表記する。）を得た。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to Examples and Comparative Examples. The pressure used in the examples and the like is expressed as an absolute pressure and is expressed in kg / cm 2 . <Reference Production Example 1> Snowtex N-30 manufactured by Nissan Chemical Co., Ltd. as an aqueous silica sol solution (SiO 2 content: 30% by weight)
Aluminum nitrate and magnesium nitrate to Al
/ Si + Al = 10 mol%, Mg / Si + Mg = 10 mol%, and then dissolved, and then spray-dried with a spray dryer set at a temperature of 130 ° C. to obtain an average particle size of 60 μm.
Was obtained. After calcining at 300 ° C. and then at 600 ° C., palladium chloride was used as a carrier to support 5.0 parts by weight of palladium per 100 parts by weight of the carrier, and the catalyst precursor (Pd5.0 / Mg, Al— Si
Expressed as O 2 . ) Got.
【００３６】[0036]
【実施例１】参考製造例１の触媒前駆体２ｋｇ、酢酸ナ
トリウム１水和物を６重量％含む水２０リットル、触媒
前駆体担持パラジウムを基準にパラジウム／鉛＝３／
１．２７原子比相当の酢酸鉛、そして触媒担持パラジウ
ムを基準にホルマリン／パラジウム＝１０モル比のホル
マリンを３０リットルオートクレーブに仕込み、触媒前
駆体をかき混ぜながら９０℃で１時間還元処理を実施し
た。得られた触媒のＰｄ／Ｐｂの担持組成比（原子比）
は３／１．２５、パラジウム／鉛金属間化合物の（１１
１）面のＸ線回折角（２θ）は３８．６０１度であり、
パラジウム金属（３ｄ）／鉛金属（４ｆ）のＸ線光電子
スペクトルの強度比は１／０．４９であった。EXAMPLE 1 2 kg of the catalyst precursor of Reference Production Example 1, 20 liters of water containing 6% by weight of sodium acetate monohydrate, palladium / lead = 3 /
A 30 liter autoclave was charged with 1.27 atomic ratio of lead acetate and formalin at a formalin / palladium = 10 molar ratio based on the catalyst-supported palladium, and reduced at 90 ° C. for 1 hour while stirring the catalyst precursor. Pd / Pb loading composition ratio (atomic ratio) of the obtained catalyst
Is 3 / 1.25, the (11) of the palladium / lead intermetallic compound
1) The X-ray diffraction angle (2θ) of the plane is 38.601 degrees,
The intensity ratio of the X-ray photoelectron spectrum of palladium metal (3d) / lead metal (4f) was 1 / 0.49.
【００３７】得られた触媒２４０ｇを触媒分離器を備
え、液相部が１．２リットルの外部循環型ステンレス製
気泡塔反応器に仕込み反応を実施した。酢酸鉛を供給原
料液中の鉛濃度が２０ｐｐｍとなるように加えた３６．
７重量％のメタクロレイン／メタノール溶液を０．５４
リットル／ｈｒ、ＮａＯＨ／メタノール溶液を０．０６
リットル／ｈｒ連続的に供給し、反応温度８０℃、反応
圧力５ｋｇ／ｃｍ2 で出口酸素濃度が４．０％（酸素分
圧０．２０ｋｇ／ｃｍ2 相当）となるように空気量を調
整しながら反応器に空気を供給し、１０時間反応を行っ
た。反応液のｐＨは７．１となるように反応器に供給す
るＮａＯＨ濃度をコントロールした。反応生成物を分析
したところ、メタクロレイン転化率は６１．８％、メタ
クリル酸メチル選択率は９１．８％であり、副生物とし
てプロピレンが選択率１．２％、蟻酸メチルが０．０４
６モル／モルＭＭＡ生成していた。 ＜Ｐｄ／Ｐｂ化合物の（１１１）面のＸ線回折角度の測
定＞測定は理学製ＲＡＤ−ＲＡを使用して通常の粉末Ｘ
線回折の測定手順に従い、ＣｕＫα１線（１．５４０５
９８１Å）を用いて、担持触媒パラジウム／鉛金属間化
合物の（１１１）面の回折角２θを測定した。測定は特
に高精度に行わねばならない。例えばNational Institu
te of Standards & Technologyが標準参照物質660とし
て定めるところのＬａＢ6化合物の（１１１）面、（２
００）面を測定し、それぞれの値を３７．４４１、４
３．５０６となるように規準化する。これにより測定精
度が高く再現性のよい結果が得られる。A 240 g portion of the obtained catalyst was charged into an externally circulating stainless steel bubble column reactor equipped with a catalyst separator and having a liquid phase of 1.2 liters, and the reaction was carried out. 36. Lead acetate was added so that the lead concentration in the feedstock liquid was 20 ppm.
0.54% by weight of a 7% by weight methacrolein / methanol solution
Liter / hr, NaOH / methanol solution 0.06
Liters / hr were continuously fed, the reaction temperature 80 ° C., a reaction pressure 5 kg / cm 2 outlet oxygen concentration is 4.0% (the oxygen partial pressure of 0.20 kg / cm 2 equivalent) and so as to adjust the amount of air While supplying air to the reactor, the reaction was performed for 10 hours. The NaOH concentration supplied to the reactor was controlled so that the pH of the reaction solution was 7.1. When the reaction product was analyzed, the conversion of methacrolein was 61.8%, the selectivity for methyl methacrylate was 91.8%, the selectivity was 1.2% for propylene as a by-product, and 0.04% for methyl formate.
6 mol / mol MMA was produced. <Measurement of X-ray diffraction angle of (111) plane of Pd / Pb compound> Measurement was performed using RAD-RA manufactured by Rigaku Co., Ltd.
According to the measurement procedure of X-ray diffraction, CuKα1 ray (1.5405
981 °), the diffraction angle 2θ of the (111) plane of the supported palladium / lead intermetallic compound was measured. The measurement must be performed with particularly high precision. For example, National Institu
(111) face of the LaB 6 compound as defined by the te of Standards & Technology as the standard reference substance 660, (2
00) plane was measured, and the respective values were 37.441, 4
It is standardized to be 3.506. As a result, a result with high measurement accuracy and good reproducibility can be obtained.
【００３８】触媒は１６０℃で真空排気し、３時間処理
することで低分子の吸着／吸蔵成分を除去した後、測定
する。 ＜Ｘ線光電子スペクトルの測定＞測定はＶＧ製ＥＳＣＡ
ＬＡＢ−２００−Ｘを使用して行った。図２に示す如
く、ピーク分離処理した後各ピークの面積を求め、パラ
ジウム金属（３ｄ（３／２）＋３ｄ（５／２））／鉛金
属（４ｆ（７／２）×１．７５）の面積比及び、パラジ
ウム金属（３ｄ（３／２）＋３ｄ（５／２））／有電荷
性鉛（４ｆ（７／２）＋４ｆ（５／２））の面積比を求
め、これをピーク強度比とした。The catalyst is evacuated at 160 ° C. and treated for 3 hours to remove low molecular adsorbed / occluded components and then measured. <Measurement of X-ray photoelectron spectrum> The measurement was performed by ESCA manufactured by VG.
Performed using LAB-200-X. As shown in FIG. 2, after the peak separation process, the area of each peak was determined, and the ratio of palladium metal (3d (3/2) + 3d (5/2)) / lead metal (4f (7/2) × 1.75) was obtained. The area ratio and the area ratio of palladium metal (3d (3/2) + 3d (5/2)) / charged lead (4f (7/2) + 4f (5/2)) were determined, and this was calculated as the peak intensity ratio. And
【００３９】図１、図２にそれぞれパラジウム（３
ｄ）、鉛（４ｆ）の測定例を示す。FIGS. 1 and 2 show palladium (3
d) shows a measurement example of lead (4f).
【００４０】[0040]
【比較例１】参考製造例１で使用した担体に塩化パラジ
ウム、硝酸鉛を担体１００重量部当たりそれぞれパラジ
ウム、鉛分として５．０重量部、４．２重量部となるよ
うに同時に担持した触媒前駆体（Ｐｄ５．０Ｐｂ４．２
／Ｍｇ、Ａｌ−ＳｉＯ2 と表記する。）を得た。この触
媒前駆体と触媒前駆体担持パラジウムを基準にホルマリ
ン／パラジウム＝１０モル比のホルマリンを３０リット
ルオートクレーブに仕込み、触媒前駆体をかき混ぜなが
ら９０℃で１時間還元処理を実施した。得られた触媒の
Ｐｄ／Ｐｂの担持組成比（原子比）は３／１．２５、パ
ラジウム／鉛金属間化合物の（１１１）面のＸ線回折角
（２θ）は３８．８９１度であり、パラジウム金属（３
ｄ）／鉛金属（４ｆ）のＸ線光電子スペクトルの強度比
は１／０．４９であった。Comparative Example 1 A catalyst in which palladium chloride and lead nitrate were simultaneously supported on the carrier used in Reference Production Example 1 so that palladium and lead were 5.0 parts by weight and 4.2 parts by weight, respectively, per 100 parts by weight of the carrier. Precursor (Pd5.0Pb4.2
/ Mg, expressed as Al-SiO 2. ) Got. A 30-liter autoclave was charged with formalin in a formalin / palladium = 10 molar ratio based on the catalyst precursor and the catalyst-supported palladium, and a reduction treatment was performed at 90 ° C. for 1 hour while stirring the catalyst precursor. The Pd / Pb supported composition ratio (atomic ratio) of the obtained catalyst was 3 / 1.25, and the X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead intermetallic compound was 38.891 degrees. Palladium metal (3
The intensity ratio of the X-ray photoelectron spectrum of d) / lead metal (4f) was 1 / 0.49.
【００４１】得られた触媒を実施例１と同一の装置、操
作条件で反応を行い反応生成物を分析したところ、メタ
クロレイン転化率は５８．２％、メタクリル酸メチル選
択率は８４．６％であり、副生物としてプロピレンが選
択率６．３％、蟻酸メチルが０．１７８モル／モルＭＭ
Ａ生成していた。The obtained catalyst was reacted under the same apparatus and operating conditions as in Example 1 and the reaction product was analyzed. The conversion of methacrolein was 58.2% and the selectivity of methyl methacrylate was 84.6%. Propylene as a by-product, selectivity 6.3%, methyl formate 0.178 mol / mol MM
A had been generated.
【００４２】[0042]
【比較例２】酢酸鉛量を触媒前駆体担持パラジウムを基
準にパラジウム／鉛＝３／１．９５原子比相当としたほ
かは実施例１と全く同様にして参考製造例１の触媒前駆
体から触媒を調製した。得られた触媒のＰｄ／Ｐｂ担持
組成比（原子比）は３／１．９２、パラジウム／鉛金属
間化合物の（１１１）面のＸ線回折角（２θ）は３８．
６２３度であり、パラジウム金属（３ｄ）／鉛金属（４
ｆ）のＸ線光電子スペクトルの強度比は１／１．２３で
あった。また、得られた触媒を実施例１と同一の装置、
操作条件で反応を行い、応生成物を分析したところ、メ
タクロレイン転化率は５７．８％、メタクリル酸メチル
選択率は８７．３％であり、副生物としてプロピレンが
選択率１．９％、蟻酸メチルが０．２１３モル／モルＭ
ＭＡ生成していた。Comparative Example 2 The same procedure as in Example 1 was repeated except that the amount of lead acetate was changed to an atomic ratio of palladium / lead = 3 / 1.95 based on the palladium supported on the catalyst precursor. A catalyst was prepared. The Pd / Pb carrying composition ratio (atomic ratio) of the obtained catalyst was 3 / 1.92, and the X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead intermetallic compound was 38.
623 degrees, and palladium metal (3d) / lead metal (4
The intensity ratio of the X-ray photoelectron spectrum of f) was 1 / 1.23. Further, the obtained catalyst was used in the same apparatus as in Example 1,
The reaction was performed under the operating conditions, and the reaction product was analyzed. The conversion of methacrolein was 57.8%, the selectivity of methyl methacrylate was 87.3%, and the selectivity of propylene as a by-product was 1.9%. 0.213 mol / mol M of methyl formate
MA was generated.
【００４３】[0043]
【比較例３】酢酸鉛量を触媒前駆体担持パラジウムを基
準にパラジウム／鉛＝３／１．５５原子比相当としたこ
と、及び酢酸ナトリウム１水和物を使用しなかった他は
実施例１と全く同様にして参考製造例１の触媒前駆体か
ら触媒を調製した。得られた触媒のＰｄ／Ｐｂ担持組成
比（原子比）は３／１．５８、パラジウム／鉛金属間化
合物の（１１１）面のＸ線回折角（２θ）は３８．７５
０度であり、パラジウム金属（３ｄ）／鉛金属（４ｆ）
のＸ線光電子スペクトルの強度比は１／０．７５であっ
た。また、得られた触媒を実施例１と同一の装置、操作
条件で反応を行い、応生成物を分析したところ、メタク
ロレイン転化率は５７．８％、メタクリル酸メチル選択
率は８５．３％であり、副生物としてプロピレンが選択
率５．１％、蟻酸メチルが０．１２９モル／モルＭＭＡ
生成していた。Comparative Example 3 Example 1 was repeated except that the amount of lead acetate was equivalent to a palladium / lead = 3 / 1.55 atomic ratio based on palladium supported on a catalyst precursor, and that sodium acetate monohydrate was not used. A catalyst was prepared from the catalyst precursor of Reference Production Example 1 in exactly the same manner as in Example 1. The Pd / Pb carrying composition ratio (atomic ratio) of the obtained catalyst was 3 / 1.58, and the X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead intermetallic compound was 38.75.
0 degree, palladium metal (3d) / lead metal (4f)
The intensity ratio of the X-ray photoelectron spectrum was 1 / 0.75. The obtained catalyst was reacted under the same apparatus and operating conditions as in Example 1, and the reaction product was analyzed. The conversion of methacrolein was 57.8% and the selectivity of methyl methacrylate was 85.3%. Propylene as a by-product, selectivity 5.1%, methyl formate 0.129 mol / mol MMA
Had been generated.
【００４４】[0044]
【実施例２】参考製造例１の触媒前駆体２ｋｇ、触媒担
持パラジウムを基準にパラジウム／鉛＝３／１．１９原
子比相当の硝酸鉛、及び酢酸ナトリウム１水和物を６重
量％含む水２０リットルを３０リットルのオートクレー
ブに仕込み、２００℃に加温し触媒前駆体をかき混ぜな
がら１時間、窒素で希釈した２％水素ガスを５Ｎリット
ル／分で吹き込み触媒前駆体を還元した。得られた触媒
のＰｄ／Ｐｂ担持組成比（原子比）は３／１．１８、パ
ラジウム／鉛金属間化合物の（１１１）面のＸ線回折角
（２θ）は３８．６９７度であり、パラジウム金属（３
ｄ）／鉛金属（４ｆ）のＸ線光電子スペクトルの強度比
は１／０．７２であった。得られた触媒を実施例１と同
一の装置、操作条件で反応を行い反応生成物を分析した
ところ、メタクロレイン転化率は５５．２％、メタクリ
ル酸メチル選択率は８８．６％であり、副生物としてプ
ロピレンが選択率２．３％、蟻酸メチルが０．１０４モ
ル／モルＭＭＡ生成していた。 ＜参考製造例２＞富士シリシア社製シリカゲル（商品
名：キャリアクト１０）１００重量部に塩化パラジウ
ム、酢酸鉛、酢酸カリウムをそれぞれパラジウム分、鉛
分、カリウム分として５．０重量部、２．１３重量部、
２．０重量部担持した触媒前駆体を得た。得られた触媒
前駆体のＰｄ／Ｐｂ原子比は３／０．６６であった。EXAMPLE 2 2 kg of the catalyst precursor of Reference Production Example 1, water containing lead nitrate equivalent to an atomic ratio of palladium / lead = 3 / 1.19 based on palladium supported on catalyst, and water containing 6% by weight of sodium acetate monohydrate Twenty liters were charged into a 30 liter autoclave, heated to 200 ° C., and agitated with the catalyst precursor for 1 hour while blowing 2% hydrogen gas diluted with nitrogen at 5 N liter / min to reduce the catalyst precursor. The Pd / Pb carrying composition ratio (atomic ratio) of the obtained catalyst was 3 / 1.18, the X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead intermetallic compound was 38.697 degrees, and the palladium Metal (3
The intensity ratio of the X-ray photoelectron spectrum of d) / lead metal (4f) was 1 / 0.72. The obtained catalyst was reacted under the same apparatus and operating conditions as in Example 1 and the reaction product was analyzed. The conversion of methacrolein was 55.2% and the selectivity of methyl methacrylate was 88.6%. As a by-product, propylene was formed at a selectivity of 2.3% and methyl formate was produced at 0.104 mol / mol MMA. <Reference Production Example 2> 5.0 parts by weight of palladium chloride, lead acetate, and potassium acetate as palladium, lead, and potassium, respectively, in 100 parts by weight of silica gel (trade name: Caracto 10) manufactured by Fuji Silysia Ltd. 13 parts by weight,
A catalyst precursor supporting 2.0 parts by weight was obtained. The Pd / Pb atomic ratio of the obtained catalyst precursor was 3 / 0.66.
【００４５】[0045]
【実施例３〜７】参考製造例２の触媒前駆体を実施例３
〜７の還元操作を施して得られた触媒のＰｄ／Ｐｂ原子
比、パラジウム／鉛化合物の（１１１）面のＸ線回折角
（２θ）、パラジウム金属（３ｄ）／鉛金属（４ｆ）の
Ｘ線光電子スペクトルの強度比及び反応成績を表１にま
とめた。比較のため実施例１と同一の装置及び反応条件
で反応を行った。Examples 3 to 7 The catalyst precursor of Reference Production Example 2 was used in Example 3.
, The Pd / Pb atomic ratio of the catalyst obtained by performing the reduction operations of Nos. 7 to 7, the X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead compound, and the X of the palladium metal (3d) / lead metal (4f). Table 1 shows the intensity ratio of the linear photoelectron spectrum and the reaction results. For comparison, the reaction was carried out using the same apparatus and reaction conditions as in Example 1.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【実施例８】比較例１の触媒前駆体を２ｋｇ及び酢酸ナ
トリウムを１０重量％含む水溶液２０リットルを内容積
３０リットルのオートクレーブに仕込み、９０℃で１時
間攪拌した。水溶液を分析したとこころ７５０重量ｐｐ
ｍの鉛イオンが溶解していた。ついで触媒前駆体担持パ
ラジウムを基準にホルマリン／パラジウム＝５モル比の
ホルマリンを追加して９０℃で１時間還元処理を実施し
た。得られた触媒のＰｄ／Ｐｂ担持組成比（原子比）は
３／１．２７、パラジウム／鉛金属間化合物の（１１
１）面のＸ線回折角（２θ）は３８．６１０度であり、
パラジウム金属（３ｄ）／鉛金属（４ｆ）のＸ線光電子
スペクトルの強度比は１／０．３９であった。Example 8 An autoclave having an internal volume of 30 liters was charged with 20 liters of an aqueous solution containing 2 kg of the catalyst precursor of Comparative Example 1 and 10% by weight of sodium acetate, and stirred at 90 ° C. for 1 hour. When the aqueous solution was analyzed, the weight was 750 wt pp.
m lead ions were dissolved. Subsequently, formalin was added in a molar ratio of formalin / palladium = 5 based on the catalyst-supported palladium, and a reduction treatment was performed at 90 ° C. for 1 hour. The Pd / Pb carrying composition ratio (atomic ratio) of the obtained catalyst was 3 / 1.27, and the palladium / lead intermetallic compound (11
1) The X-ray diffraction angle (2θ) of the surface is 38.610 degrees,
The intensity ratio of the X-ray photoelectron spectrum of palladium metal (3d) / lead metal (4f) was 1 / 0.39.
【００４８】実施例１で用いた触媒分離器を備え、液相
部が１．２Ｌの外部循環型ステンレス製気泡塔反応器を
直列に２基連結し、活性化処理を終えた触媒２４０ｇを
仕込み反応を実施した。第一段目の反応器に酢酸鉛を供
給原料液中の鉛濃度が２０ｐｐｍとなるように溶かした
３６．７重量％のメタクロレイン／メタノール溶液を
０．５４リットル／ｈｒ、ＮａＯＨ／メタノール溶液を
０．０６リットル／ｈｒ連続的に供給し、反応温度８０
℃、反応圧力５ｋｇ／ｃｍ2 で出口酸素濃度が４．０％
（酸素分圧０．２０ｋｇ／ｃｍ2 相当）となるように空
気量を調整しながら反応器に空気を供給して反応を行っ
た。触媒懸濁液は液固分離して触媒は反応器に戻し反応
液のみを第二段反応器にＮａＯＨ／メタノール溶液０．
０６リットル／ｈｒと共に送り、第一段反応器の流出ガ
スは第二段反応器に通気する一方、第二段反応器の出口
酸素濃度が２．２％（酸素分圧０．１１ｋｇ／ｃｍ2 相
当）となるように不足分の空気を第二段反応器に追加し
反応温度８０℃、反応圧力４．６ｋｇ／ｃｍ2 で反応を
行った。また、第一段反応器、第二段反応器ともに反応
液のｐＨが７．１となるように反応器に供給するＮａＯ
Ｈ濃度をコントロールした。反応生成物を分析したとこ
ろ、メタクロレイン転化率は８４．９％、メタクリル酸
メチル選択率は９１．４％であり副生物としてプロピレ
ンが選択率１．１％、蟻酸メチルが０．０４５モル／モ
ルＭＭＡ生成していた。The catalyst separator used in Example 1 was provided, and two externally circulating stainless steel bubble column reactors having a liquid phase of 1.2 L were connected in series, and 240 g of the activated catalyst was charged. The reaction was performed. 0.54 l / hr of a 36.7% by weight methacrolein / methanol solution obtained by dissolving lead acetate in the first stage reactor so that the lead concentration in the feedstock solution becomes 20 ppm, and NaOH / methanol solution 0.06 liter / hr continuously, reaction temperature 80
At a reaction pressure of 5 kg / cm 2 and an outlet oxygen concentration of 4.0%
The reaction was performed by supplying air to the reactor while adjusting the amount of air so that the oxygen partial pressure became 0.20 kg / cm 2 . The catalyst suspension was separated into liquid and solid, and the catalyst was returned to the reactor.
And the effluent gas of the first-stage reactor is passed through the second-stage reactor while the oxygen concentration at the outlet of the second-stage reactor is 2.2% (oxygen partial pressure 0.11 kg / cm 2). Insufficient air was added to the second-stage reactor so that the reaction temperature reached 80 ° C. and the reaction pressure was 4.6 kg / cm 2 . In addition, NaO supplied to the first-stage reactor and the second-stage reactor so that the reaction solution has a pH of 7.1 is supplied to the reactor.
The H concentration was controlled. When the reaction product was analyzed, the conversion of methacrolein was 84.9%, the selectivity for methyl methacrylate was 91.4%, and the selectivity was 1.1% for propylene as a by-product and 0.045 mol / m for methyl formate. Molar MMA was formed.
【００４９】[0049]
【実施例９】富士シリシア社製シリカゲル（商品名：キ
ャリアクト１０）１００重量部に、パラジウムアンミン
錯体を利用してパラジウムを５．０重量部担持して触媒
前駆体を得た。この触媒前駆体を実施例１と同様の酢酸
ナトリウム共存下でホルマリン還元する際に鉛分として
３．９３重量部、タリウム分として０．１１重量部が共
存する条件下で還元処理した。得られた触媒（Ｐｄ５．
０Ｐｂ３．９３Ｔｌ０．１１／ＳｉＯ2 と表記する。）
のＰｄ／Ｐｂ担持組成（原子比）は３／１．２１、パラ
ジウム／鉛金属間化合物の（１１１）面のＸ線回折角
（２θ）は３８．６２０度であり、パラジウム金属（３
ｄ）／鉛金属（４ｆ）のＸ線光電子スペクトルの強度比
は１／０．４７であった。Example 9 5.0 parts by weight of palladium was supported on 100 parts by weight of silica gel manufactured by Fuji Silysia Ltd. (trade name: Caracto 10) using a palladium ammine complex to obtain a catalyst precursor. This catalyst precursor was subjected to formalin reduction in the presence of sodium acetate in the same manner as in Example 1 under a condition in which 3.93 parts by weight of lead and 0.11 part by weight of thallium were present. The resulting catalyst (Pd5.
Referred to as 0Pb3.93Tl0.11 / SiO 2. )
Has a Pd / Pb supporting composition (atomic ratio) of 3 / 1.21, an X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead intermetallic compound is 38.620 degrees, and the palladium metal (3
The intensity ratio of the X-ray photoelectron spectrum of d) / lead metal (4f) was 1 / 0.47.
【００５０】実施例１と同一容量をもつ攪拌槽型反応器
に活性化を終えた触媒２００ｇを仕込み反応器に供給す
る鉛濃度を１０ｐｐｍとした以外は実施例１と同一の操
作条件で反応を行った。反応生成物を分析したところ、
メタクロレイン転化率は６２．４％、メタクリル酸メチ
ル選択率は９１．２％であり副生物としてプロピレンが
選択率１．２％、蟻酸メチルが０．０４２モル／モルＭ
ＭＡ生成していた。The reaction was carried out under the same operating conditions as in Example 1 except that 200 g of the activated catalyst was charged into a stirred tank reactor having the same capacity as in Example 1 and the lead concentration supplied to the reactor was 10 ppm. went. When the reaction product was analyzed,
The conversion of methacrolein is 62.4%, the selectivity of methyl methacrylate is 91.2%, propylene as by-products is 1.2%, and methyl formate is 0.042 mol / mol M.
MA was generated.
【００５１】[0051]
【実施例１０】Ｐｄ５．０Ｍｇ２．０／Ａｌ2 Ｏ3 の組
成をもつ触媒前駆体を実施例１と同様の酢酸ナトリウム
共存下でホルマリン還元する際に鉛、ビスマスを共存さ
せた。Ｐｄ５．０Ｐｂ４．０Ｂｉ０．２３Ｍｇ２．０／
Ａｌ2 Ｏ3 の組成をもつ触媒が得られ、Ｐｄ／Ｐｂ原子
比は３／１．２４、パラジウム／鉛化合物の（１１１）
面のＸ線回折角（２θ）は３８．６１２度であり、パラ
ジウム金属（３ｄ）／鉛金属（４ｆ）のＸ線光電子スペ
クトルの強度比は１／０．５２であった。Example 10 When a catalyst precursor having a composition of Pd5.0Mg2.0 / Al 2 O 3 was formalin-reduced in the presence of sodium acetate as in Example 1, lead and bismuth were allowed to coexist. Pd5.0Pb4.0Bi0.23Mg2.0 /
A catalyst having the composition of Al 2 O 3 was obtained, the Pd / Pb atomic ratio was 3 / 1.24, and the (111) palladium / lead compound
The X-ray diffraction angle (2θ) of the surface was 38.612 degrees, and the intensity ratio of the X-ray photoelectron spectrum of palladium metal (3d) / lead metal (4f) was 1 / 0.52.
【００５２】実施例１０と同一の装置及び同一の操作条
件で反応を行い反応生成物を分析したところ、メタクロ
レイン転化率は６０．３％、メタクリル酸メチル選択率
は９０．５％であり副生物としてプロピレンが選択率
１．２％、蟻酸メチルが０．０５２モル／モルＭＭＡ生
成していた。The reaction was carried out in the same apparatus and under the same operating conditions as in Example 10, and the reaction product was analyzed. The conversion of methacrolein was 60.3%, and the selectivity for methyl methacrylate was 90.5%. Propylene was selected as a living thing at a selectivity of 1.2%, and methyl formate was produced at 0.052 mol / mol MMA.
【００５３】[0053]
【実施例１１】実施例８の得られた触媒を用いて、メタ
クロレインにかえてアクロレインを反応させた以外は実
施例８と同様の操作及び反応条件で反応を行い、反応生
成物を分析したところアクロレイン転化率は５８．４
％、アクリル酸メチル選択率は９２．４％であり副生物
としてエチレンが選択率１．０％、蟻酸メチルが０．０
４２モル／モルＭＡ生成していた。Example 11 Using the catalyst obtained in Example 8, a reaction was carried out under the same operation and reaction conditions as in Example 8 except that acrolein was reacted instead of methacrolein, and the reaction product was analyzed. However, the conversion of acrolein was 58.4.
%, Methyl acrylate selectivity was 92.4%, ethylene as a by-product was 1.0% selectivity, and methyl formate was 0.0%.
42 mol / mol MA was produced.
【００５４】[0054]
【発明の効果】アルデヒドとアルコールを分子状酸素と
反応させてカルボン酸エステルを製造するに際し、アル
デヒドの濃度及び反応温度を高めて経済性を改善した反
応条件においても、アルデヒドおよびアルコール基準の
収率を同時に改善する触媒を得ることができる。According to the present invention, in producing a carboxylic acid ester by reacting an aldehyde and an alcohol with molecular oxygen, the yield based on the aldehyde and the alcohol can be obtained even under the reaction conditions in which the concentration and reaction temperature of the aldehyde are increased to improve the economic efficiency. Can be obtained at the same time.
【図１】Ｐｄ（３ｄ）のＸ線光電子スペクトル例を示す
スペクトル図である。FIG. 1 is a spectrum diagram showing an example of an X-ray photoelectron spectrum of Pd (3d).
【図２】Ｐｂ（４ｆ）のＸ線光電子スペクトル及びカー
ブフィッティング結果を示すスペクトル図である。FIG. 2 is a spectrum diagram showing an X-ray photoelectron spectrum of Pb (4f) and a result of curve fitting.
１ Ｐｂ4f7/2(Ｐｂ0) ２ Ｐｂ4f5/2(Ｐｂ0) ３ Ｐｂ4f7/2(Ｐｂox) ４ Ｐｂ4f5/2(Ｐｂox) ５ Ｓｉ2sのＸ線サテライト（ＭｇＫα3) ６ Ｓｉ2sのＸ線サテライト（ＭｇＫα4)1 Pb4f 7/2 (Pb 0 ) 2 Pb 4f 5/2 (Pb 0 ) 3 Pb 4f 7/2 (Pb ox ) 4 Pb 4f 5/2 (Pb ox ) 5 X-ray satellite of Si2s (MgKα 3 ) 6 X of Si2s Wire satellite (MgKα 4 )
Claims (4)
を反応させてカルボン酸エステルを製造する際に用いる
パラジウム／鉛含有担持触媒の製造方法において、パラ
ジウム／鉛担持組成比が原子比で３／０以上３／１．３
未満の触媒前駆体を、パラジウム／鉛原子比で３／０．
７〜３／１．３の担持組成比を有するパラジウム／鉛担
持触媒を得るのに必要な量の鉛化合物が存在する水溶液
またはメタノール溶液中でホルマリン、蟻酸、ヒドラジ
ンまたは分子状水素で還元することを特徴とするパラジ
ウム／鉛含有担持触媒の製造方法。1. A method for producing a supported palladium / lead-containing catalyst used in producing a carboxylic acid ester by reacting an aldehyde and an alcohol in the presence of oxygen, wherein the palladium / lead-supported composition ratio is 3/0 in atomic ratio. 3 / 1.3
Less than 3/0. Palladium / lead atomic ratio.
Reduction with formalin, formic acid, hydrazine or molecular hydrogen in an aqueous or methanol solution in which the lead compound is present in an amount necessary to obtain a palladium / lead supported catalyst having a supported composition ratio of 7 to 3 / 1.3. A method for producing a supported catalyst containing palladium / lead, characterized by comprising:
塩または低級脂肪酸のアルカリ土類金属塩を共存させて
行う請求項１記載のパラジウム／鉛含有担持触媒の製造
方法。2. The process for producing a supported palladium / lead-containing catalyst according to claim 1, which is carried out in the presence of a lower fatty acid, an alkali metal salt of a lower fatty acid or an alkaline earth metal salt of a lower fatty acid.
ム／鉛の担持組成比が原子比で３／０．７〜３／１．３
であり、パラジウム／鉛金属間化合物の（１１１）面の
Ｘ線回折角（２θ）が３８．５５〜３８．７０である請
求項１記載のパラジウム／鉛含有担持触媒の製造方法。3. The supported palladium / lead composition ratio of the supported palladium / lead-containing catalyst is from 3 / 0.7 to 3 / 1.3 in atomic ratio.
The method for producing a supported palladium / lead-containing catalyst according to claim 1, wherein the X-ray diffraction angle (2θ) of the (111) plane of the palladium / lead intermetallic compound is 38.55 to 38.70.
インまたはこれらの混合物であり、アルコールがメタノ
ールである請求項１記載のパラジウム／鉛含有担持触媒
の製造方法。4. The method according to claim 1, wherein the aldehyde is methacrolein, acrolein or a mixture thereof, and the alcohol is methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18960996A JP3556397B2 (en) | 1996-07-18 | 1996-07-18 | Improved method for producing catalyst for carboxylic acid ester production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18960996A JP3556397B2 (en) | 1996-07-18 | 1996-07-18 | Improved method for producing catalyst for carboxylic acid ester production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1028865A true JPH1028865A (en) | 1998-02-03 |
| JP3556397B2 JP3556397B2 (en) | 2004-08-18 |
Family
ID=16244179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18960996A Expired - Lifetime JP3556397B2 (en) | 1996-07-18 | 1996-07-18 | Improved method for producing catalyst for carboxylic acid ester production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3556397B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002098558A1 (en) * | 2001-06-04 | 2002-12-12 | Nippon Shokubai Co., Ltd. | Catalyst for carboxylic ester production and process for producing carboxylic ester |
| JP2003024782A (en) * | 2001-07-16 | 2003-01-28 | Asahi Kasei Corp | Carboxylic acid ester producing catalyst excellent in activity |
| JP2003053188A (en) * | 2001-06-04 | 2003-02-25 | Nippon Shokubai Co Ltd | Metallic particle carrying and supporting body method of manufacturing carboxylate |
| JP2003093876A (en) * | 2001-09-26 | 2003-04-02 | Nippon Shokubai Co Ltd | Catalyst for synthesizing carboxylate and manufacturing method for carboxylate |
| JP2006224091A (en) * | 2005-01-18 | 2006-08-31 | Showa Denko Kk | Production and use of supported catalyst |
| JP2007275854A (en) * | 2006-04-12 | 2007-10-25 | Asahi Kasei Chemicals Corp | Carboxylate production catalyst excellent in reaction stability and method for producing carboxylate |
| JP2007301501A (en) * | 2006-05-12 | 2007-11-22 | Asahi Kasei Chemicals Corp | Gold-deposited particle containing aluminum and silica and method for producing carboxylate by using the same |
| WO2021044983A1 (en) * | 2019-09-06 | 2021-03-11 | Ａｇｃ株式会社 | Method for producing hydrofluoroolefin |
-
1996
- 1996-07-18 JP JP18960996A patent/JP3556397B2/en not_active Expired - Lifetime
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002098558A1 (en) * | 2001-06-04 | 2002-12-12 | Nippon Shokubai Co., Ltd. | Catalyst for carboxylic ester production and process for producing carboxylic ester |
| JP2003053188A (en) * | 2001-06-04 | 2003-02-25 | Nippon Shokubai Co Ltd | Metallic particle carrying and supporting body method of manufacturing carboxylate |
| US7326806B2 (en) | 2001-06-04 | 2008-02-05 | Nippon Shokubai Co., Ltd. | Catalyst for the preparation of carboxylic esters and method for producing carboxylic esters |
| JP2003024782A (en) * | 2001-07-16 | 2003-01-28 | Asahi Kasei Corp | Carboxylic acid ester producing catalyst excellent in activity |
| JP4626931B2 (en) * | 2001-07-16 | 2011-02-09 | 旭化成ケミカルズ株式会社 | Carboxylate production catalyst with excellent activity |
| JP2003093876A (en) * | 2001-09-26 | 2003-04-02 | Nippon Shokubai Co Ltd | Catalyst for synthesizing carboxylate and manufacturing method for carboxylate |
| JP2006224091A (en) * | 2005-01-18 | 2006-08-31 | Showa Denko Kk | Production and use of supported catalyst |
| JP2007275854A (en) * | 2006-04-12 | 2007-10-25 | Asahi Kasei Chemicals Corp | Carboxylate production catalyst excellent in reaction stability and method for producing carboxylate |
| JP2007301501A (en) * | 2006-05-12 | 2007-11-22 | Asahi Kasei Chemicals Corp | Gold-deposited particle containing aluminum and silica and method for producing carboxylate by using the same |
| WO2021044983A1 (en) * | 2019-09-06 | 2021-03-11 | Ａｇｃ株式会社 | Method for producing hydrofluoroolefin |
| CN114341086A (en) * | 2019-09-06 | 2022-04-12 | Ａｇｃ株式会社 | Process for producing hydrofluoroolefin |
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