KR19990015522A - Catalyst for preparing carboxylic acid ester and preparation method of carboxylic acid ester - Google Patents
Catalyst for preparing carboxylic acid ester and preparation method of carboxylic acid ester Download PDFInfo
- Publication number
- KR19990015522A KR19990015522A KR1019970037664A KR19970037664A KR19990015522A KR 19990015522 A KR19990015522 A KR 19990015522A KR 1019970037664 A KR1019970037664 A KR 1019970037664A KR 19970037664 A KR19970037664 A KR 19970037664A KR 19990015522 A KR19990015522 A KR 19990015522A
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- reaction
- added
- carboxylic acid
- methyl methacrylate
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 271
- 238000002360 preparation method Methods 0.000 title claims description 21
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 title 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 194
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 159
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 50
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011133 lead Substances 0.000 claims description 86
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 84
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 81
- 239000011787 zinc oxide Substances 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229960004279 formaldehyde Drugs 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 89
- 239000000243 solution Substances 0.000 description 77
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 72
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 52
- 239000000203 mixture Substances 0.000 description 44
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 42
- 239000007864 aqueous solution Substances 0.000 description 31
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000010992 reflux Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 24
- 229940046892 lead acetate Drugs 0.000 description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 238000007664 blowing Methods 0.000 description 17
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 15
- 239000000395 magnesium oxide Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000004246 zinc acetate Substances 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 11
- AQBOUNVXZQRXNP-UHFFFAOYSA-L azane;dichloropalladium Chemical compound N.N.N.N.Cl[Pd]Cl AQBOUNVXZQRXNP-UHFFFAOYSA-L 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 230000001172 regenerating effect Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000007774 longterm Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 229910052745 lead 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
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- -1 bismuth acetic acid Bismuth Chemical compound 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 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
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- MLOKPANHZRKTMG-UHFFFAOYSA-N lead(2+);oxygen(2-);tin(4+) Chemical compound [O-2].[O-2].[O-2].[Sn+4].[Pb+2] MLOKPANHZRKTMG-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/50—
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- B01J35/51—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
Abstract
본 발명은 분자상 산소의 존재하에 알데히드와 알코올을 액상으로 반응시킬 때 사용되는 카복실산 에스테르 제조용 촉매로서, 담체로서의 탄산칼슘을 함유하고, 또한 팔라듐, 비스무트, 및 바륨, 철, 아연 및 게르마늄으로 이루어진 그룹으로부터 선택된 1종 이상의 원소를 탄산칼슘에 존재시켜 함유하는 카복실산 에스테르 제조용 촉매에 관한 것이다.The present invention is a catalyst for preparing a carboxylic acid ester used in the liquid phase reaction of an aldehyde with an alcohol in the presence of molecular oxygen, containing calcium carbonate as a carrier, and also a group consisting of palladium, bismuth, and barium, iron, zinc and germanium. The present invention relates to a catalyst for producing a carboxylic acid ester containing at least one element selected from carbonates in calcium carbonate.
Description
본 발명은 알데히드와 알코올로부터 카복실산 에스테르를 1단계로 제조하는 방법 및 이 방법에 사용되는 촉매에 관한 것이다. 특히, 본 발명은 특히 메타크롤레인 또는 아크롤레인으로부터 공업적 가치가 높은 메타크릴산 에스테르 또는 아크릴산 에스테르를 유리하게 제조하는 방법 및 이 방법에 사용되는 촉매에 관한 것이다.The present invention relates to a process for the preparation of carboxylic acid esters from aldehydes and alcohols in one step and to catalysts used in the process. In particular, the present invention relates in particular to a process for the advantageous production of methacrylic esters or acrylic esters of high industrial value from methacrolein or acrolein and the catalyst used in the process.
현재, 카복실산 에스테르인 메타크릴산 에스테르라든지 아크릴산 에스테르를 제조하는 방법으로서는, 알데히드인 메타크롤레인이라든지 아크롤레인을 촉매로 사용하여 기상 접촉 산화시키고, 카복실산인 메타크릴산이라든지 아크릴산을 제조한 후, 알코올과의 에스테르화 반응에 따라서 메타크릴산 에스테르라든지 아크릴산 에스테르를 제조하는 방법이 공업화되어 있다.Currently, as a method for producing methacrylic acid esters or acrylic acid esters, which are carboxylic acid esters, methacrylate or acrolein, which is an aldehyde, is subjected to gas phase contact oxidation, and methacrylic acid or acrylic acid, which is a carboxylic acid, is prepared. According to the esterification reaction, a method of producing methacrylic acid esters or acrylic acid esters has been industrialized.
그러나, 이 제조법에는 산화 공정과 에스테르화 공정의 2단계의 반응이 존재하며, 막대한 제조 설비를 필요로 하는 결점이 있다. 또한, 메타크릴산 에스테르를 제조하는 경우, 메타크롤레인을 산화하여 메타크릴산을 제조하는 산화 공정에 인과 몰리브덴을 주성분으로 하는 헤테로폴리산염계 촉매가 사용되고 있는데, 이 촉매에는 수명이라든지 수율이 불충분하다는 문제가 있다.However, this manufacturing method has a two-step reaction of an oxidation process and an esterification process, and has a drawback in that a huge manufacturing facility is required. In the case of producing methacrylic acid esters, a heteropolyacid catalyst mainly composed of phosphorus and molybdenum is used in the oxidation process of oxidizing methacrolein to produce methacrylic acid, and this catalyst has a problem of insufficient lifetime or yield. have.
그래서, 알데히드와 알코올로부터 액상 반응에 의해 1단계에서 카복실산 에스테르를 고수율로 제조하는 방법이 검토되고 있다. 이러한 방법에 사용되는 촉매로서는 예를 들면, 일본 특허공보 제(소)57-35856호에는 탄산칼슘 담체를 사용한 Pd, Pb계 촉매가, 일본 특허공보 제(평)4-72578호에는 산화아연 담체를 사용한 Pd, Pb계 촉매가, 일본 공개특허공보 제(소)57-50545호 및 일본 특허공보 제(소)61-243044호에는 각종 Pd, Pb계 촉매가, 일본 특허공보 제(소)61-60820호에는 Pd, Bi계 촉매가, 일본 특허공보 제(소)62-7902호 및 일본 공개특허공보 제(평)5-148184호에는 Pd와, Pb 및 Bi 등으로부터 선택된 적어도 1종의 원소로 구성되는 촉매가, 일본 특허공보 제(소)57-35860호에는 Pd, Tl, Hg계 촉매가, 일본 특허공보 제(소)57-19090호에는 Pd, 알칼리 토류금속, Zn, Cd계 촉매가 기재되어 있다.Therefore, a method of producing a carboxylic acid ester in a high yield in one step by liquid phase reaction from aldehyde and alcohol is examined. As a catalyst used in such a method, for example, Japanese Patent Application Laid-Open No. 57-35856 has a Pd and Pb-based catalyst using a calcium carbonate carrier, and Japanese Patent Publication No. Hei 4-72578 has a zinc oxide carrier. Pd and Pb-based catalysts using JP-A-57-50545 and JP-A-61-243044 include various Pd and Pb-based catalysts. -60820, Pd, Bi-based catalyst, Japanese Patent Laid-Open No. 62-7902 and Japanese Patent Laid-Open No. Hei 5-148184 include at least one element selected from Pd, Pb, Bi and the like. The catalyst consisting of Pd, Tl, and Hg type catalyst is disclosed in JP-A-57-35860, and Pd, alkaline earth metal, Zn, Cd-based catalyst is JP-A-57-19090. Is described.
또한, Pd계 촉매는 반응에 장기간 사용하면 Pd가 산화되어 촉매 활성이 저하되므로, 촉매를 재생할 필요가 있다. 촉매를 활성화하는 방법으로서는, 예를 들면, 일본 공개특허공보 제(평)9-38506호에는 Pd-Pb계 촉매를 제조할 때 Pb를 포함하는 물질의 존재하에서 포르말린, 포름산, 히드라진, 메탄올, 분자상 수소를 사용하여 촉매를 활성화하는 방법이 제안되어 있다. 그러나, 이것은 신품의 촉매를 제조할 때 사용하는 방법이고, 반응에 사용하여 활성이 저하한 촉매를 재생하여 사용하는 방법은 아직 알려져 있지 않다.In addition, the Pd-based catalyst needs to be regenerated because the Pd-based catalyst is oxidized when the Pd-based catalyst is used for a long period of time and the catalytic activity is lowered. As a method of activating a catalyst, for example, Japanese Patent Application Laid-Open No. 9-38506 discloses formalin, formic acid, hydrazine, methanol, molecules in the presence of a substance containing Pb when preparing a Pd-Pb catalyst. A method of activating a catalyst using phase hydrogen is proposed. However, this is a method used when producing a new catalyst, and a method of regenerating and using a catalyst whose activity is lowered in the reaction is not known yet.
또한, 상기의 촉매를 사용한 카복실산 에스테르의 제조 방법에서는 반응 속도가 느리고, 수득되는 카복실산 에스테르가 농도가 낮은 알코올 용액으로서 수득되는 포름산메틸 등의 부생성물이 많이 생성되는, 촉매의 수명이 짧고, 수율이 불충분한 등의 문제가 있어, 거듭 개량이 요망된다.Moreover, in the manufacturing method of the carboxylic acid ester using the said catalyst, the reaction speed is slow, and the lifetime of a catalyst is short and the yield which produces | generates many by-products, such as methyl formate obtained as an alcohol solution in which the carboxylic acid ester obtained is low in concentration, is obtained. There are problems such as insufficient, and improvement is desired again and again.
본 발명의 목적은 분자상 산소의 존재하에 알데히드와 알코올을 액상으로 반응시키고, 1단계에서 카복실산 에스테르를 유리하게 제조하기 위한 촉매 및 이 촉매를 사용하는 카복실산 에스테르의 제조방법을 제공하는 데 있다.An object of the present invention is to provide a catalyst for reacting aldehyde and alcohol in the liquid phase in the presence of molecular oxygen in a liquid phase, and advantageously producing a carboxylic acid ester in one step, and a method for producing a carboxylic acid ester using the catalyst.
즉, 본 발명의 촉매는 분자상 산소의 존재하에 알데히드와 알코올을 액상으로 반응시킬 때 사용되는 다음의 (1)∼(4)의 촉매이다;That is, the catalyst of the present invention is the catalyst of the following (1) to (4) used when the aldehyde and the alcohol are reacted in the liquid phase in the presence of molecular oxygen;
(1) 팔라듐, 비스무트, 및 바륨, 철, 아연 및 게르마늄으로 이루어진 그룹으로부터 선택된 적어도 1종의 원소를 탄산칼슘에 존재시켜 이루어지는 카복실산 에스테르 제조용 촉매;(1) Palladium, bismuth and at least one element selected from the group consisting of barium, iron, zinc and germanium in the calcium carbonate catalyst for producing carboxylic acid ester;
(2) 팔라듐, 비스무트, 납, 및 바륨, 철, 아연 및 게르마늄으로 이루어진 그룹으로부터 선택된 적어도 1종의 원소를 탄산칼슘에 존재시켜 이루어지는 카복실산 에스테르 제조용 촉매;(2) Palladium, bismuth, lead, and a catalyst for producing a carboxylic acid ester, wherein at least one element selected from the group consisting of barium, iron, zinc and germanium is present in calcium carbonate;
(3) 팔라듐, 납, 및 크롬, 철, 코발트, 아연 및 은으로 이루어진 그룹으로부터 선택된 적어도 1종의 원소를 탄산칼슘에 존재시켜서 이루어지는 카복실산 에스테르 제조용 촉매;(3) Palladium, lead, and a catalyst for producing a carboxylic acid ester, wherein calcium carbonate is present by at least one element selected from the group consisting of chromium, iron, cobalt, zinc and silver;
(4) 팔라듐, 비스무트, 및 납, 철, 망간, 코발트, 니켈, 구리, 아연, 게르마늄, 바륨 및 텔루르로 이루어진 그룹으로부터 선택된 적어도 1종의 원소를 산화아연에 존재시켜 이루어지는 카복실산 에스테르 제조용 촉매.(4) Palladium, bismuth and at least one element selected from the group consisting of lead, iron, manganese, cobalt, nickel, copper, zinc, germanium, barium and tellurium in a zinc oxide, a catalyst for producing a carboxylic acid ester.
또한 본 발명은 상기 (1)∼(4)의 촉매로부터 선택되는 적어도 1종의 촉매를 사용하여 구성되는 카복실산 에스테르의 제조방법이다.Moreover, this invention is a manufacturing method of the carboxylic acid ester comprised using the at least 1 sort (s) of catalyst chosen from the catalyst of said (1)-(4).
또한, 상기 제조방법에 사용되어 활성이 저하한 촉매를 환원제의 존재하에 0∼100℃의 온도에서 0.1∼50시간 처리한 것을 촉매로서 사용함으로써 이루어지는 상기 카복실산 에스테르의 제조방법이다.Moreover, it is the manufacturing method of the said carboxylic ester formed by using what used for the said manufacturing method the catalyst which reduced activity was 0.1 to 50 hours in the presence of a reducing agent at the temperature of 0-100 degreeC as a catalyst.
본 발명의 카복실산 에스테르 제조용 촉매는 금속 및/또는 금속 화합물이 탄산칼슘 또는 산화아연의 담체상에 담지된 것이다. 또, 이들 촉매에 있어서, 탄산칼슘은 담체로서 사용하고 있지만, 탄산칼슘 자체도 촉매 성분의 일부로서 기능한다. 이하, 본 발명의 카복실산 에스테르 제조용 촉매에 대하여 설명한다.In the catalyst for producing carboxylic acid ester of the present invention, a metal and / or a metal compound is supported on a carrier of calcium carbonate or zinc oxide. In these catalysts, calcium carbonate is used as a carrier, but calcium carbonate itself also functions as part of the catalyst component. Hereinafter, the catalyst for producing carboxylic acid ester of the present invention will be described.
촉매의 제조에 사용되는 금속 및/또는 금속 화합물중에 포함되는 금속 성분의 원료로서는, 팔라듐에 대하여 아세트산팔라듐, 염화팔라듐, 질산팔라듐, 황산팔라듐, 염화팔라듐암모늄, 팔라듐아민 착염 등이, 비스무트에 대하여 아세트산비스무트, 탄산비스무트, 염화비스무트, 질산비스무트, 황산비스무트 등이 사용되며, 납에 대하여 아세트산납, 탄산납, 염화납, 질산납, 황산납, 주석산납, 구연산납 등이 사용되고, 그 밖의 금속에 대해서는 당해 금속의 아세트산염, 탄산염, 질산염, 황산염, 수산염, 염화물, 수산화물 등의 일반적인 금속 화합물이 사용된다.As a raw material of the metal component contained in the metal and / or metal compound used for manufacture of a catalyst, palladium acetate, palladium chloride, palladium nitrate, palladium sulfate, palladium ammonium chloride, palladiumamine complex salt, etc. with bismuth acetic acid Bismuth, bismuth carbonate, bismuth chloride, bismuth nitrate, bismuth sulfate, and the like are used. Lead acetate, lead carbonate, lead chloride, lead nitrate, lead sulfate, lead stannate, lead citrate, and the like are used for the other metals. Common metal compounds such as acetates, carbonates, nitrates, sulfates, oxalates, chlorides and hydroxides of the metals are used.
담체 100중량부에 대한 금속 및/또는 금속 화합물의 담지량은, 금속 원소로 환산하여, 팔라듐이 1∼15중량부, 바람직하게는 3∼13중량부, 비스무트 및 납이 각각 0.1∼15중량부, 바람직하게는 0.5∼12중량부, 다른 금속이 각각 0.1∼7중량부, 바람직하게는 0.3∼5중량부이다.The supported amount of the metal and / or metal compound with respect to 100 parts by weight of the carrier is 1 to 15 parts by weight of palladium, preferably 3 to 13 parts by weight, 0.1 to 15 parts by weight of bismuth and lead, respectively, Preferably 0.5-12 weight part and other metals are 0.1-7 weight part, respectively, Preferably it is 0.3-5 weight part.
본 발명의 촉매는 통상의 방법에 따라서 제조할 수 있다. 일례로서, 팔라듐, 비스무트 및 철을 탄산칼슘에 존재시켜 이루어지는 촉매의 제조법에 대하여 설명한다. 우선 탄산칼슘 분말을 물속에 넣고, 여기에 소정량의 염화팔라듐 용액을 첨가하고, 수득한 혼합물을 교반한다. 이어서, 생성된 현탁액을 포르말린 등의 환원제로 환원시켜 금속 팔라듐을 석출시키고, 여과한 후, 아세트산비스무트 및 질산제2철 수용액에 침지하고, 원하는 바에 따라 재차 환원제로 환원시켜 금속을 석출시키며, 여과한 후, 감압하에서 건조하여 제조한다. 이렇게 하여 제조된 촉매는 통상의 방법에 의해 활성화도 가능하다.The catalyst of the present invention can be prepared according to a conventional method. As an example, a method for producing a catalyst in which palladium, bismuth and iron are present in calcium carbonate will be described. First, the calcium carbonate powder is put in water, a predetermined amount of palladium chloride solution is added thereto, and the obtained mixture is stirred. Subsequently, the resultant suspension is reduced with a reducing agent such as formalin to precipitate metal palladium, and after filtration, it is immersed in bismuth acetate and ferric nitrate aqueous solution, and reduced again with a reducing agent as desired to precipitate the metal, followed by filtration. Then, it is dried and manufactured under reduced pressure. The catalyst prepared in this way can also be activated by a conventional method.
본 발명에서는 이렇게 하여 수득한 촉매를 사용하여 분자상 산소의 존재하에 알데히드와 알코올을 액상으로 반응시켜 카복실산 에스테르를 제조한다. 이하, 본 발명의 카복실산 에스테르의 제조방법에 대하여 설명한다.In the present invention, the carboxylic acid ester is prepared by reacting the aldehyde and the alcohol in the liquid phase in the presence of molecular oxygen using the catalyst thus obtained. Hereinafter, the manufacturing method of the carboxylic acid ester of this invention is demonstrated.
카복실산 에스테르의 원료로서 사용하는 알데히드로서는 예를 들면 아세트알데히드, 프로피온알데히드, 이소부틸알데히드 등의 포화 알데히드; 아크롤레인, 메타크롤레인, 크로톤알데히드 등의 불포화 알데히드; 벤즈알데히드, p-토르알데히드 등의 방향족 알데히드 등을 들 수 있다. 특히, 메타크롤레인, 아크롤레인 및 이들 혼합물은 공업적 가치가 높은 메타크릴산 에스테르 및 아크릴산 에스테르를 제조하는 경우의 출발물질로서 중요하다. 또한, 다른 한쪽의 원료인 알코올로서는 예를 들면 메탄올, 에탄올, 이소프로판올, 아릴 알코올, 메트알릴 알코올 등을 들 수 있다.As an aldehyde used as a raw material of carboxylic acid ester, For example, saturated aldehydes, such as acetaldehyde, a propionaldehyde, an isobutyl aldehyde; Unsaturated aldehydes such as acrolein, methacrolein and crotonaldehyde; Aromatic aldehydes, such as benzaldehyde and p-toraldehyde, etc. are mentioned. In particular, methacrolein, acrolein and their mixtures are important as starting materials for producing methacrylic esters and acrylic esters of high industrial value. Moreover, as alcohol which is another raw material, methanol, ethanol, isopropanol, an aryl alcohol, metallyl alcohol, etc. are mentioned, for example.
반응에 있어서, 알데히드와 알코올의 원료 조합 비율은, 몰 비로 1:100∼1:1이 적당하고, 특히 1:80∼1:3이 바람직하다.In the reaction, the ratio of the raw material combination of aldehyde and alcohol is suitably 1: 100 to 1: 1 in molar ratio, and particularly preferably 1:80 to 1: 3.
반응의 형식은 회분식, 반회분식, 연속식의 어느 것이라도 가능하다. 촉매는 반응액중에 현탁된 상태에서 사용한다. 촉매의 사용량에 특히 한정은 없지만, 반응이 회분식인 경우, 원료 알데히드 100중량부에 대하여 0.1∼20중량부가 적당하고, 특히 0.2∼15중량부가 바람직하다. 또한, 분자상 산소의 공급원으로서는 산소는 물론, 공기, 산소가 풍부한 공기 등을 사용할 수 있다. 통상, 분자상 산소는 반응액에 공기 등의 가스를 불어넣는 것에 의해 공급된다. 또한, 반응액중에는 산화제로서 과산화수소를 존재시켜도 된다.The type of reaction can be any of batch, semibatch, and continuous. The catalyst is used in a suspended state in the reaction solution. Although there is no restriction | limiting in particular in the usage-amount of a catalyst, When reaction is a batch type, 0.1-20 weight part is suitable with respect to 100 weight part of raw material aldehydes, and 0.2-15 weight part is especially preferable. As the source of molecular oxygen, not only oxygen, but also air, oxygen-rich air, and the like can be used. Usually, molecular oxygen is supplied by blowing gas, such as air, into a reaction liquid. In the reaction solution, hydrogen peroxide may be present as the oxidizing agent.
반응은 0∼100℃, 바람직하게는 30∼80℃의 온도 범위에서 수행된다. 통상, 반응은 상압하에서 수행하지만, 가압하 또는 감압하에서 수행해도 된다. 또한, 반응액에는 중합방지제로서 하이드로퀴논, p-메톡시페놀 등을 필요에 따라서 첨가해도 된다.The reaction is carried out in a temperature range of 0 to 100 ° C, preferably 30 to 80 ° C. Usually, the reaction is carried out under normal pressure, but may be carried out under pressure or under reduced pressure. In addition, you may add hydroquinone, p-methoxyphenol, etc. to a reaction liquid as needed as a polymerization inhibitor.
이러한 반응조건에 있어서 사용된 촉매는 사용중에 활성이 서서히 저하한다. 이 때문에, 회분식 반응으로 몇번이나 사용하거나, 연속식으로 장기간 사용한 촉매의 카복실산 에스테르의 수율은 매우 낮아진다.The catalyst used under these reaction conditions gradually decreases in activity during use. For this reason, the yield of the carboxylic acid ester of the catalyst used several times in a batch reaction or used continuously for a long time becomes very low.
본 발명에 있어서는 이와 같이 촉매 활성이 저하된 촉매를 저하된 환원제의 존재하에 처리함으로써 촉매 활성을 재생할 수 있다. 이하, 활성이 저하된 촉매의 재생 방법에 대하여 설명한다.In the present invention, the catalytic activity can be regenerated by treating the catalyst with reduced catalytic activity in the presence of a reduced reducing agent. Hereinafter, the regeneration method of the catalyst with reduced activity is demonstrated.
사용하는 환원제로서는 메탄올, 에탄올, 포르말린, 아세트알데히드, 프로피온알데히드, 이소부틸알데히드, 아크롤레인, 메타크롤레인 및 히드라진으로 이루어진 그룹으로부터 선택된 적어도 1종이다. 재생처리에 사용하는 환원제의 양은 특별히 한정되지는 않지만, 통상은 촉매중의 팔라듐량 100중량부에 대하여 1∼5000중량부, 바람직하게는 10∼4000중량부이다.The reducing agent to be used is at least one selected from the group consisting of methanol, ethanol, formalin, acetaldehyde, propionaldehyde, isobutylaldehyde, acrolein, methacrolein and hydrazine. Although the quantity of the reducing agent used for a regeneration process is not specifically limited, Usually, it is 1-5000 weight part with respect to 100 weight part of palladium amounts in a catalyst, Preferably it is 10-4000 weight part.
촉매는 촉매를 환원제를 포함하는 액상중에 현탁시키고, 0∼100℃, 바람직하게는 20∼80℃의 온도 범위에서 0.1∼50시간, 바람직하게는 0.5∼40시간 동안 처리함으로써 재생된다. 처리는 상압에서 수행할 수도 있지만, 가압하 또는 감압하에서 수행해도 된다. 처리형식은 회분식, 반회분식, 연속식의 어느 것이라도 가능하다. 또한, 이 처리는 질소, 이산화탄소, 헬륨 및 아르곤으로 이루어진 그룹으로부터 선택된 적어도 1종의 가스의 존재하에서 수행할 수 있다.The catalyst is regenerated by suspending the catalyst in a liquid phase containing a reducing agent and treating it for 0.1 to 50 hours, preferably 0.5 to 40 hours in the temperature range of 0 to 100 ° C, preferably 20 to 80 ° C. The treatment may be carried out at normal pressure, but may be carried out under pressure or under reduced pressure. The processing form can be any of batch, semi-batch and continuous. This treatment can also be carried out in the presence of at least one gas selected from the group consisting of nitrogen, carbon dioxide, helium and argon.
재생처리는 카복실산 에스테르를 제조하기 위한 반응기내에서 수행해도 되고, 반응기로부터 촉매를 회수하여 반응기 밖에서 수행해도 된다. 반응기내에서 재생처리를 행하는 경우에는 카복실산 에스테르 제조 반응의 종료후, 환원제를 첨가하여 재생처리를 수행하는 단순한 조작으로 촉매 활성을 회복시킬 수 있다. 그러나, 반응 종료후의 반응액중에 이미 존재하는 미반응 원료가, 상기의 환원제인 경우에는 이것을 환원제로서 사용할 수 있기 때문에, 별도의 환원제를 첨가할 필요가 없는 경우도 있다.The regeneration treatment may be carried out in a reactor for producing carboxylic acid esters, or may be performed outside the reactor by recovering the catalyst from the reactor. When the regeneration treatment is carried out in the reactor, the catalytic activity can be restored by a simple operation of performing the regeneration treatment by adding a reducing agent after the completion of the carboxylic acid ester production reaction. However, when the unreacted raw material which already exists in the reaction liquid after completion | finish of reaction is said reducing agent, since it can be used as a reducing agent, it is not necessary to add another reducing agent.
이하에, 실시예, 참고예 및 비교예를 들어 본 발명의 방법을 더욱 자세히 설명한다. 촉매 조성식에 있어서, 원소기호의 우측 상부 숫자는 담체 100중량부에 담지되어 있는 그 원소의 무게를 중량부로써 나타낸 것이며, “/”의 뒤의 화합물은 담체를 의미한다. 또 분석은 가스 크로마토그래피에 의해 수행한다. 또한, 표중 전화률(%) 및 선택률(%)은 특별한 이유가 없는 한 메타크롤레인의 전화률(%) 및 메타크릴산메틸의 선택률(%)을 의미한다.In the following, examples, reference examples and comparative examples will be described in more detail the method of the present invention. In the catalyst composition formula, the upper right digit of the element symbol indicates the weight of the element carried on 100 parts by weight of the carrier in parts by weight, and the compound after “/” means the carrier. The analysis is also carried out by gas chromatography. In addition, conversion rate (%) and selectivity (%) in a table | surface mean the conversion rate (%) of methacrolein and the selectivity (%) of methyl methacrylate unless there is a special reason.
실시예 1Example 1
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시킨 용액에 탄산칼슘 10g을 첨가하고, 혼합물을 교반하면서 1시간 동안 환류한다. 계속하여, 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여 고형물을 수득한다. 다음에, 질산비스무트 0.46g 및 질산제2철 0.72g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액에 상기 고형물을 첨가하고, 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 10ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.10 g of calcium carbonate is added to a solution of 1.40 g of tetraaminepalladium nitrate dissolved in 20 ml of pure water, and the mixture is refluxed for 1 hour with stirring. Subsequently, after removing water from the mixture, 20 ml of aqueous formalin solution is added, filtered and washed to obtain a solid. Next, the solid is added to a solution in which 0.46 g of bismuth nitrate and 0.72 g of ferric nitrate are dissolved in 40 ml of dilute nitric acid at a 3% concentration, followed by mixing at 60 ° C for 1 hour. 10 ml of formalin aqueous solution was added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2-Fe1/CaCO3 Pd 5 -Bi 2 -Fe 1 / CaCO 3
200ml의 환류기가 부착된 플라스크에, 상기 촉매 2.0g, 메타크롤레인 3.5g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록, 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어 넣으면서 욕온도 70℃에서 4시간 동안 반응을 수행하여 메타크릴산메틸을 합성한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률 75.8%, 메타크릴산메틸의 선택률 97.3%이다.To a flask with 200 ml of reflux was added 2.0 g of the catalyst, 3.5 g of methacrolein and 80 g of methanol. In addition, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute to synthesize methyl methacrylate. . The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 75.8%, and the selectivity of methyl methacrylate was 97.3%.
실시예 2Example 2
아세트산아연 0.34g을 물 20ml에 용해시킨 용액에 5중량% 팔라듐-2중량% 비스무트를 담지한 탄산칼슘 10g(N. E. CHEMCAT사 제품)을 첨가하고 60℃에서 1시간 혼합한다. 혼합물에 포르말린 수용액 5ml를 첨가하고, 여과, 세정한 후 건조하여 다음의 촉매를 수득한다.To a solution in which 0.34 g of zinc acetate was dissolved in 20 ml of water, 10 g of calcium carbonate (manufactured by N. E. CHEMCAT) supporting 5% by weight palladium-2% by weight bismuth was added and mixed at 60 ° C for 1 hour. 5 ml of formalin aqueous solution is added to the mixture, filtered, washed and dried to obtain the following catalyst.
Pd5-Bi2-Zn1/CaCO3 Pd 5 -Bi 2 -Zn 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건에서 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 3Example 3
아세트산아연 대신에 아세트산바륨 0.19g을 사용한 것 이외는 실시예 2와 동일한 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 2 except that 0.19 g of barium acetate was used instead of zinc acetate to obtain the following catalyst.
Pd5-Bi2-Bal/CaCO3 Pd 5 -Bi 2 -Ba l / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응 조건으로 메타크릴산메틸을 합성하고 결과를 표1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 4Example 4
아세트산아연 대신에 산화게르마늄 0.14g을 사용한 것 이외는 실시예 2와 동일한 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 2 except that 0.14 g of germanium oxide was used instead of zinc acetate to obtain the following catalyst.
Pd5-Bi2-Ge1/CaCO3 Pd 5 -Bi 2 -Ge 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 5Example 5
실시예 1에서 제조한 촉매의 양을 3.5g으로 늘린 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the amount of the catalyst prepared in Example 1 was increased to 3.5 g. The results are shown in Table 1.
실시예 6Example 6
200ml의 환류기가 부착된 플라스크에 실시예 1에서 제조한 촉매를 4.0g, 메타크롤레인 7.0g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록, 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 200ml의 속도로 불어넣어면서 욕 온도 70℃에서 4시간 반응을 수행하여 메타크릴산메틸을 합성한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 73.0%, 메타크릴산메틸의 선택률은 96.8%이다.To a flask with 200 ml of reflux was added 4.0 g of the catalyst prepared in Example 1, 7.0 g of methacrolein and 80 g of methanol. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 200 ml per minute to synthesize methyl methacrylate. . The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 73.0%, and the selectivity for methyl methacrylate was 96.8%.
실시예 7Example 7
실시예 1의 촉매를 사용하여, 반응 욕온도를 40℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Using the catalyst of Example 1, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was 40 ° C. The results are shown in Table 1.
실시예 8Example 8
실시예 1의 촉매를 사용하여, 반응 욕온도를 55℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Using the catalyst of Example 1, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was set at 55 ° C. The results are shown in Table 1.
실시예 9Example 9
질산비스무트의 양을 0.70g으로 한 것 이외는 실시예 1과 동일한 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 1 except that the amount of bismuth nitrate was 0.70 g to obtain the next catalyst.
Pd5-Bi3-Fe1/CaCO3 Pd 5 -Bi 3 -Fe 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 10Example 10
테트라아민팔라듐질산염의 양을 2.81g으로, 또한 질산비스무트의 양을 0.93g으로 한 것 이외는 실시예 1과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 1 except that the amount of tetraaminepalladium nitrate was 2.81 g and the amount of bismuth nitrate was 0.93 g, to obtain the following catalyst.
Pd10-Bi4-Fe1/CaCO3 Pd 10 -Bi 4 -Fe 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 11Example 11
실시예 3의 촉매를 사용하여 메타크롤레인 대신에 아크롤레인을 2.80g 사용한 것 이외는 실시예 3과 동일한 반응조건으로 아크릴산메틸을 합성한다. 그 결과를 표1에 나타낸다. 표1 중, 전화률은 아크롤레인의 전화률을, 선택률은 아크릴산메틸의 선택률을 의미한다.Using the catalyst of Example 3, methyl acrylate was synthesized under the same reaction conditions as in Example 3 except that 2.80 g of acrolein was used instead of methacrolein. The results are shown in Table 1. In Table 1, the conversion rate means the conversion rate of acrolein, and the selectivity means the selectivity of methyl acrylate.
실시예 12Example 12
질산비스무트 0.46g 및 아세트산제2철 0.72g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액 대신에 질산비스무트 0.46g, 아세트산연 0.18g 및 질산제2철 0.72g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액을 사용하고, 또한 포르말린 수용액의 사용량을 15ml로 증가한 것 이외는 실시예 1과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.Instead of a solution of 0.46 g of bismuth nitrate and 0.72 g of ferric acetate in 40 ml of diluted 3% nitric acid, 0.46 g of bismuth nitrate, 0.18 g of lead acetate and 0.72 g of ferric nitrate were added to 40 ml of dilute nitric acid 3%. A catalyst was prepared by the same catalyst preparation method as in Example 1 except that the dissolved solution was used and the amount of formalin aqueous solution was increased to 15 ml to obtain the next catalyst.
Pd5-Bi2-Pb1/CaCO3 Pd 5 -Bi 2 -Pb 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 13Example 13
아세트산아연 0.34g을 물 20ml에 용해시킨 용액 대신에, 아세트산아연 0.34g 및 아세트산납 0.18g을 물 50ml에 용해시킨 용액을 사용하고, 또한 포르말린 수용액의 사용량을 10ml로 증가한 것 이외는 실시예 2와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.Instead of a solution in which 0.34 g of zinc acetate was dissolved in 20 ml of water, a solution in which 0.34 g of zinc acetate and 0.18 g of lead acetate was dissolved in 50 ml of water was used, except that the amount of formalin aqueous solution was increased to 10 ml. The catalyst is prepared by the same catalyst preparation method to obtain the following catalyst.
Pd5-Bi2-Pb1-Zn1/CaCO3 Pd 5 -Bi 2 -Pb 1 -Zn 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 14Example 14
아세트산납 대신에 질산납 0.32g을 사용한 것 이외는 실시예 13와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 13 except that 0.32 g of lead nitrate was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Pb2-Zn1/CaCO3 Pd 5 -Bi 2 -Pb 2 -Zn 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 15Example 15
아세트산아연 대신에 아세트산바륨 0.19g을, 또한 아세트산납 대신에 질산납 0.16g을 사용한 것 이외는 실시예 13과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 13 except that 0.19 g of barium acetate instead of zinc acetate and 0.16 g of lead nitrate instead of lead acetate were used to obtain the following catalyst.
Pd5-Bi2-Pb1-Ba1/CaCO3 Pd 5 -Bi 2 -Pb 1 -Ba 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 16Example 16
아세트산아연 대신에 산화게르마늄 0.14g을 사용한 것 이외는 실시예 13과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 13, except that 0.14 g of germanium oxide was used instead of zinc acetate to obtain the following catalyst.
Pd5-Bi2-Pb1-Ge1/CaCO3 Pd 5 -Bi 2 -Pb 1 -Ge 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 17Example 17
실시예 12에서 제조한 촉매의 양을 4.0g으로 늘린 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표1에 나타낸다.Methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the amount of the catalyst prepared in Example 12 was increased to 4.0 g. The results are shown in Table 1 below.
실시예 18Example 18
200ml의 환류기가 부착된 플라스크에 실시예 12에서 제조한 촉매 4.0g, 메타크롤레인 7.0g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록, 0.03규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 200ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행하여 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.To a flask with 200 ml of reflux was added 4.0 g of the catalyst prepared in Example 12, 7.0 g of methacrolein and 80 g of methanol. In addition, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 200 ml per minute to synthesize methyl methacrylate. The results are shown in Table 1.
실시예 19Example 19
실시예 12의 촉매를 사용하여 반응 욕온도를 40℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Using the catalyst of Example 12, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was 40 ° C. The results are shown in Table 1.
실시예 20Example 20
실시예 12의 촉매를 사용하여, 반응 욕온도를 55℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Using the catalyst of Example 12, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was set to 55 ° C. The results are shown in Table 1.
실시예 21Example 21
질산비스무트의 양을 0.70g로 한 것 이외는 실시예 12와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 12 except that the amount of bismuth nitrate was 0.70 g to obtain the next catalyst.
Pd5-Bi3-Pb1-Fe1/CaCO3 Pd 5 -Bi 3 -Pb 1 -Fe 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 22Example 22
테트라아민팔라듐질산염의 양을 2.81g으로, 또한 질산비스무트의 양을 0.93g으로 한 것 이외는 실시예 12와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 12 except that the amount of tetraaminepalladium nitrate was 2.81 g and the amount of bismuth nitrate was 0.93 g, to obtain the following catalyst.
Pd10-Bi4-Pb1-Fe1/CaCO3 Pd 10 -Bi 4 -Pb 1 -Fe 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 23Example 23
실시예 16의 촉매를 사용하여, 메타크롤레인 대신에 아크롤레인을 2.80g 사용한 것 이외는 실시예 16과 동일한 반응조건으로 아크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다. 표중, 전화률은 아크롤레인의 전화률을, 선택률은 아크릴산메틸의 선택률을 의미한다.Using the catalyst of Example 16, methyl acrylate was synthesized under the same reaction conditions as in Example 16 except that 2.80 g of acrolein was used instead of methacrolein. The results are shown in Table 1. In the table, the conversion rate means the conversion rate of acrolein, and the selectivity means the selectivity of methyl acrylate.
실시예 24Example 24
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시킨 용액에 탄산칼슘 10g을 첨가하고, 혼합물을 교반하면서 1시간 환류한다. 계속하여, 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여 고형물을 수득한다. 다음에, 아세트산납 0.18g 및 질산제2철 0.72g을 순수한 물 40m1에 용해시킨 용액에 상기 고형물을 첨가하여, 60℃에서 1시간 혼합하였다. 수득한 혼합물에 포르말린 수용액 15ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.10 g of calcium carbonate is added to a solution of 1.40 g of tetraamine palladium nitrate dissolved in 20 ml of pure water, and the mixture is refluxed for 1 hour with stirring. Subsequently, after removing water from the mixture, 20 ml of aqueous formalin solution is added, filtered and washed to obtain a solid. Next, the solid was added to a solution in which 0.18 g of lead acetate and 0.72 g of ferric nitrate were dissolved in 40 ml of pure water, followed by mixing at 60 ° C for 1 hour. 15 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Pb1-Fe1/CaCO3 Pd 5 -Pb 1 -Fe 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 25Example 25
질산제2철 대신에 질산크롬 0.77g을 사용한 것 이외는 실시예 24와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 24, except that 0.77 g of chromium nitrate was used instead of ferric nitrate to obtain the following catalyst.
Pd5-Pb1-Cr1/CaCO3 Pd 5 -Pb 1 -Cr 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 26Example 26
질산제2철 대신에 아세트산코발트 0.42g를 사용한 것 이외는 실시예 24와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 24, except that 0.42 g of cobalt acetate was used instead of ferric nitrate to obtain the following catalyst.
Pd5-Pb1-Co1/CaCO3 Pd 5 -Pb 1 -Co 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 27Example 27
질산제2철 대신에 아세트산아연 0.34g을 사용한 것 이외는 실시예 24와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 24 except that 0.34 g of zinc acetate was used instead of ferric nitrate to obtain the following catalyst.
Pd5-Pb1-Zn1/CaCO3 Pd 5 -Pb 1 -Zn 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸의 합성을 수행한 결과를 표 1에 나타낸다.Table 1 shows the results of the synthesis of methyl methacrylate under the same reaction conditions as in Example 1 using this catalyst.
실시예 28Example 28
질산제2철 대신에 아세트산을 0.16g 사용한 것 이외는 실시예 24와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 24 except that 0.16 g of acetic acid was used instead of ferric nitrate to obtain the following catalyst.
Pd5-Pb1-Ag1/CaCO3 Pd 5 -Pb 1 -Ag 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 29Example 29
질산제2철 0.72g 및 아세트산아연 0.17g을 물 50ml에 용해시킨 용액에 5중량% 팔라듐-1중량% 납을 함유한 탄산칼슘 10g(N. E. CHEMCAT사 제품)을 첨가하여 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 15ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.To a solution of 0.72 g of ferric nitrate and 0.17 g of zinc acetate in 50 ml of water, 10 g of calcium carbonate (product of NE CHEMCAT) containing 5 wt% palladium-1 wt% lead was added and mixed at 60 ° C. for 1 hour. . 15 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Pb1-Fe1-Zn0. 5/CaCO3 Pd 5 -Pb 1 -Fe 1 -Zn 0.5 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 30Example 30
실시예 24에서 제조한 촉매의 양을 4.0g으로 늘린 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the amount of the catalyst prepared in Example 24 was increased to 4.0 g. The results are shown in Table 1.
실시예 31Example 31
200ml의 환류기가 부착된 플라스크에, 실시예 24에서 제조한 촉매 4.0g, 메타크롤레인 7.0g 및 메탄올 80g을 가한다. 또한, 반응액의 pH가 10.5가 되도록, 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 200ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행하여 메타크릴산메틸을 합성한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 79.8%, 메타크릴산메틸의 선택률은 94.5%이다.To a flask with 200 ml reflux, 4.0 g of the catalyst prepared in Example 24, 7.0 g of methacrolein and 80 g of methanol were added. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 200 ml per minute to synthesize methyl methacrylate. . The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 79.8%, and the selectivity for methyl methacrylate was 94.5%.
실시예 32Example 32
실시예 24의 촉매를 사용하여, 반응 욕온도를 40℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Using the catalyst of Example 24, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was 40 ° C. The results are shown in Table 1.
실시예 33Example 33
실시예 24의 촉매를 사용하여, 반응 욕온도를 55℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Using the catalyst of Example 24, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was set to 55 ° C. The results are shown in Table 1.
실시예 34Example 34
실시예 24에서 아세트산납의 양을 0.37g으로 한 것 이외는 실시예 24와 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 24, except that the amount of lead acetate in Example 24 was 0.37 g, to obtain the following catalyst.
Pd5-Pb2-Fe1/CaCO3 Pd 5 -Pb 2 -Fe 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 35Example 35
실시예 24의 촉매로 메타크롤레인 대신에 아크롤레인을 2.80g 사용한 것 이외는 실시예 1과 동일한 반응조건으로 아크릴산메틸을 합성한다. 그 결과를 표 2에 나타낸다. 표 1중, 전화률은 아크롤레인의 전화률을, 선택률은 아크릴산메틸의 선택률을 의미한다.Methyl acrylate was synthesized under the same reaction conditions as in Example 1 except that 2.80 g of acrolein was used instead of methacrolein as the catalyst of Example 24. The results are shown in Table 2. In Table 1, a conversion rate means the conversion rate of acrolein, and a selectivity means the selectivity of methyl acrylate.
실시예 36Example 36
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시킨 용액에 산화아연 10g을 첨가하고, 혼합물을 교반하면서 1시간 환류한다. 이어서, 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여, 고형물을 수득한다. 다음에, 질산비스무트 0.46g 및 아세트산납 0.18g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액에 상기 고형물을 첨가하고, 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 15ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.10 g of zinc oxide is added to a solution in which 1.40 g of tetraamine palladium nitrate is dissolved in 20 ml of pure water, and the mixture is refluxed for 1 hour with stirring. Subsequently, after removing water from the mixture, 20 ml of formalin aqueous solution is added, filtered and washed to obtain a solid. Next, the solid is added to a solution in which 0.46 g of bismuth nitrate and 0.18 g of lead acetate are dissolved in 40 ml of dilute nitric acid at a concentration of 3%, and mixed at 60 ° C for 1 hour. 15 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2-Pbl/ZnOPd 5 -Bi 2 -Pb l / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 37Example 37
아세트산납 대신에 질산납 0.32g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.32 g of lead nitrate was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Pb2/ZnOPd 5 -Bi 2 -Pb 2 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 38Example 38
아세트산납 대신에 질산제2철 0.72g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.72 g of ferric nitrate was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Fe1/ZnOPd 5 -Bi 2 -Fe 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 39Example 39
아세트산납 대신에 아세트산망간 0.45g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.45 g of manganese acetate was used instead of lead acetate to obtain the next catalyst.
Pd5-Bi2-Mnl/ZnOPd 5 -Bi 2 -Mn l / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 40Example 40
아세트산납 대신에 아세트산코발트 0.42g를 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.42 g of cobalt acetate was used instead of lead acetate to obtain the next catalyst.
Pd5-Bi2-Co1/ZnOPd 5 -Bi 2 -Co 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 41Example 41
아세트산납 대신에 질산니켈 0.50g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 36 except that 0.50 g of nickel nitrate was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Ni1/ZnOPd 5 -Bi 2 -Ni 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 42Example 42
아세트산납 대신에 황산제1구리 0.39g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.39 g of cuprous sulfate was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Cu1/ZnOPd 5 -Bi 2 -Cu 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 43Example 43
아세트산납 대신에 아세트산아연 0.34g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared by the same catalyst preparation method as in Example 36 except that 0.34 g of zinc acetate was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Zn1/ZnOPd 5 -Bi 2 -Zn 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 44Example 44
아세트산납 대신에 이산화게르마늄 0.14g를 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.14 g of germanium dioxide was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Ge1/ZnOPd 5 -Bi 2 -Ge 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 45Example 45
아세트산납 대신에 아세트산바륨 0.19g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.19 g of barium acetate was used instead of lead acetate to obtain the next catalyst.
Pd5-Bi2-Ba1/ZnOPd 5 -Bi 2 -Ba 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 46Example 46
아세트산납 대신에 텔루르산 0.18g을 사용한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that 0.18 g of telluric acid was used instead of lead acetate to obtain the following catalyst.
Pd5-Bi2-Te1/ZnOPd 5 -Bi 2 -Te 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 47Example 47
실시예 36에서 제조한 촉매의 양을 4.0g으로 늘린 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 결과를 표 1에 나타낸다.Methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the amount of the catalyst prepared in Example 36 was increased to 4.0 g. The results are shown in Table 1.
실시예 48Example 48
200ml의 환류기가 부착된 플라스크에 실시예 36에서 제조한 촉매 4.0g, 메타크롤레인 7.0g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록, 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고 공기를 매분 200ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행하여 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.To a flask with 200 ml reflux was added 4.0 g of the catalyst prepared in Example 36, 7.0 g of methacrolein and 80 g of methanol. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 200 ml per minute to synthesize methyl methacrylate. The results are shown in Table 1.
실시예 49Example 49
실시예 36의 촉매를 사용하여, 반응 욕온도를 40℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 결과를 표 1에 나타낸다.Using the catalyst of Example 36, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was 40 ° C. The results are shown in Table 1.
실시예 50Example 50
실시예 36의 촉매를 사용하여, 반응 욕온도를 55℃로 한 것 이외는 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 결과를 표 1에 나타낸다.Using the catalyst of Example 36, methyl methacrylate was synthesized under the same reaction conditions as in Example 1 except that the reaction bath temperature was set to 55 ° C. The results are shown in Table 1.
실시예 51Example 51
실시예 36에서 질산비스무트의 양을 0.70g으로 한 것 이외는 실시예 36과 같은 촉매 제조 방법으로 촉매를 제조하여 다음 촉매를 수득한다.A catalyst was prepared in the same manner as in Example 36, except that the amount of bismuth nitrate was 0.70 g in Example 36, to obtain the following catalyst.
Pd5-Bi3-Pb1/ZnOPd 5 -Bi 3 -Pb 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 52Example 52
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시킨 용액에 산화아연 10g을 첨가하고, 혼합물을 교반하면서 1시간 환류한다. 이어서, 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여 고형물을 수득한다. 다음에, 질산비스무트 0.46g, 아세트산납 0.18g 및 질산제2철 0.72g을 3%농도의 묽은 질산 60ml에 용해시킨 용액에 상기 고형물을 첨가하고, 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 15ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.10 g of zinc oxide is added to a solution in which 1.40 g of tetraamine palladium nitrate is dissolved in 20 ml of pure water, and the mixture is refluxed for 1 hour with stirring. Subsequently, after removing water from the mixture, 20 ml of aqueous formalin solution is added, filtered and washed to obtain a solid. Next, the solid is added to a solution in which 0.46 g of bismuth nitrate, 0.18 g of lead acetate, and 0.72 g of ferric nitrate are dissolved in 60 ml of dilute nitric acid at a 3% concentration, and mixed at 60 ° C for 1 hour. 15 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2-Pb1-Fe1/ZnOPd 5 -Bi 2 -Pb 1 -Fe 1 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
실시예 53Example 53
실시예 36의 촉매로 메타크롤레인 대신에 아크롤레인을 2.80g 사용한 것 이외는 실시예 36과 동일한 반응조건으로 아크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다. 표 중, 전화률은 아크롤레인의 전화률을, 선택률은 아크릴산메틸의 선택률을 의미한다.Methyl acrylate was synthesized under the same reaction conditions as in Example 36, except that 2.80 g of acrolein was used instead of methacrolein as the catalyst of Example 36. The results are shown in Table 1. In the table, the conversion rate means the conversion rate of acrolein, and the selectivity means the selectivity of methyl acrylate.
참고예 1Reference Example 1
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시킨 용액에 탄산칼슘 10g을 첨가하고, 혼합물을 교반하면서 1시간 환류한다. 이어서 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여, 고형물을 수득한다. 다음에, 질산비스무트 0.46g 및 아세트산바륨 0.19g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액에 상기 고형물을 첨가하여, 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 10ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.10 g of calcium carbonate is added to a solution of 1.40 g of tetraamine palladium nitrate dissolved in 20 ml of pure water, and the mixture is refluxed for 1 hour with stirring. Subsequently, after removing water from the mixture, 20 ml of aqueous formalin solution is added, filtered and washed to obtain a solid. Next, the solid is added to a solution in which 0.46 g of bismuth nitrate and 0.19 g of barium acetate are dissolved in 40 ml of dilute nitric acid at a concentration of 3%, and mixed at 60 ° C for 1 hour. 10 ml of formalin aqueous solution was added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2-Ba1/CaCO3 Pd 5 -Bi 2 -Ba 1 / CaCO 3
200ml의 환류기가 부착된 플라스크에, 상기에서 수득한 촉매 2.0g, 메타크롤레인 3.5g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 73.3%, 메타크릴산메틸의 선택률은 96.0%이다. 또한 동일한 반응조건으로 장기간 반복하여 촉매를 연속 사용한 바, 메타크롤레인의 전화률은 56.3%, 메타크릴산메틸의 선택률은 89.1%에까지 저하한다.To a flask with 200 ml of reflux was added 2.0 g of the catalyst obtained above, 3.5 g of methacrolein and 80 g of methanol. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 73.3%, and the selectivity for methyl methacrylate was 96.0%. In addition, when the catalyst was used continuously for a long time under the same reaction conditions, the conversion rate of methacrolein decreased to 56.3% and the selectivity of methyl methacrylate to 89.1%.
실시예 54Example 54
200ml의 환류기가 부착된 플라스크중의, 참고예 1에서 장기간 반복 반응을 수행하고 활성이 저하된 촉매 2.0g에 메탄올 80g을 첨가하며, 질소를 매분 10ml의 속도로 불어넣으면서 욕온도 70℃에서 1시간 교반처리한다. 냉각후, 또한 메타크롤레인 3.5g를 첨가하고, 참고예 1과 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 73.3%, 메타크릴산메틸의 선택률은 96.6%이었다.In a flask with a reflux reactor of 200 ml, a long-term repeated reaction was carried out in Reference Example 1, and 80 g of methanol was added to 2.0 g of the deteriorated catalyst, and nitrogen was blown at a rate of 10 ml per minute for 1 hour at a bath temperature of 70 ° C. Stir. After cooling, 3.5 g of methacrolein was further added, and the reaction was carried out under the same conditions as in Reference Example 1. The conversion rate of methacrolein was 73.3%, and the selectivity of methyl methacrylate was 96.6%.
실시예 55Example 55
참고예 1에서 장기간 반복 반응을 수행하여 활성이 저하된 촉매를 회수하고, 회수촉매 2.0g를 200ml의 환류기가 부착된 플라스크에 가하며, 여기에 포르말린 수용액 10ml를 첨가하고, 질소의 존재하에 30℃에서 1시간 교반처리한다. 이어서, 여과, 세정한 후 건조하여 재생처리제 또는 촉매를 수득하였다.In Reference Example 1, a long-term repeated reaction was carried out to recover a catalyst having reduced activity, and 2.0 g of the recovered catalyst was added to a flask equipped with a 200 ml reflux reactor, and 10 ml of formalin aqueous solution was added thereto at 30 ° C in the presence of nitrogen. Stir for 1 hour. Then, filtered, washed and dried to obtain a regenerating agent or catalyst.
200ml의 환류기가 부착된 플라스크에, 상기의 재생처리제나 촉매 2.0g, 메타크롤레인 3.5g 및 메탄올 80g을 가한다. 반응액의 pH가 10.5가 되도록 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 73.1%, 메타크릴산메틸의 선택률은 96.2%이다.To the flask with a 200 ml reflux group, 2.0 g of the above regenerating agent or catalyst, 3.5 g of methacrolein and 80 g of methanol are added. A 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 73.1%, and the selectivity for methyl methacrylate was 96.2%.
실시예 56Example 56
포르말린 수용액 10ml 대신에 아세트알데히드 수용액 10ml를 사용하여, 20℃에서 2시간 처리한 것 이외는 실시예 55와 같은 조건으로, 촉매의 재생처리, 반응을 수행한 바, 메타크롤레인의 전화률은 72.9%, 메타크릴산메틸의 선택률은 95.7%이다.10 ml of acetaldehyde aqueous solution was used instead of 10 ml of formalin aqueous solution, and the regeneration treatment and reaction of the catalyst were carried out under the same conditions as in Example 55 except that the conversion rate of methacrolein was 72.9. % And the selectivity of methyl methacrylate are 95.7%.
실시예 57Example 57
포르말린 수용액 10ml 대신에 메타크롤레인 1g과 메탄올 50g의 혼합액를 사용하여, 공기의 존재하에 40℃에서 1시간 처리한 것 이외는 실시예 55와 같은 조건으로 촉매의 재생처리, 반응을 수행한 바, 메타크롤레인의 전화률은 73.5%, 메타크릴산메틸의 선택률은 95.9%이다.Using a mixture of 1 g of methacrolein and 50 g of methanol instead of 10 ml of formalin aqueous solution, the catalyst was regenerated and reacted under the same conditions as in Example 55 except that the mixture was treated at 40 ° C. for 1 hour in the presence of air. The conversion rate of crawllane is 73.5%, and the selectivity of methyl methacrylate is 95.9%.
실시예 58Example 58
포르말린 수용액 10ml 대신에 에탄올 20ml를 사용하여, 용량비 1 대 1의 질소와 이산화탄소의 혼합가스를 매분 10ml의 속도로 불어넣으면서 욕온도 70℃에서 1시간 처리한 것 이외는 실시예 55와 같은 조건으로 촉매의 재생처리, 반응을 수행한 바, 메타크롤레인의 전화률은 73.5%, 메타크릴산메틸의 선택률은 96.1%이다.20 ml of ethanol was used instead of 10 ml of formalin aqueous solution, and the catalyst was treated under the same conditions as in Example 55 except that a mixed gas of nitrogen and carbon dioxide having a capacity ratio of 1 to 1 was blown at a rate of 10 ml per minute for 1 hour at a bath temperature of 70 ° C. When the regeneration treatment and the reaction were carried out, the conversion rate of methacrolein was 73.5%, and the selectivity of methyl methacrylate was 96.1%.
실시예 59Example 59
포르말린 수용액 10ml 대신에 히드라진 수용액 10ml를 사용하여, 이산화탄소 가스 존재하 40℃에서 1시간 처리한 것 이외는 실시예 55와 같은 조건으로 촉매의 재생처리, 반응을 수행한 바, 메타크롤레인의 전화률은 73.8%, 메타크릴산메틸의 선택률은 96.4%이다.10 ml of aqueous hydrazine solution was used instead of 10 ml of formalin aqueous solution, and the catalyst was regenerated and reacted under the same conditions as in Example 55 except that the reaction was carried out at 40 ° C. for 1 hour in the presence of carbon dioxide gas. Silver 73.8%, the selectivity of methyl methacrylate is 96.4%.
실시예 60Example 60
포르말린 수용액 10ml 대신에 이소부틸알데히드 10ml를 사용하여, 헬륨 존재하 40℃에서 1시간 처리한 것 이외는 실시예 55와 같은 조건으로 촉매의 재생처리, 반응을 수행한 바, 메타크롤레인의 전화률은 72.0%, 메타크릴산메틸의 선택률은 96.1%이다.10 ml of isobutylaldehyde was used instead of 10 ml of formalin aqueous solution, and the catalyst was regenerated and reacted under the same conditions as in Example 55 except that the treatment was carried out at 40 ° C. for 1 hour in the presence of helium. 72.0% of silver and selectivity of methyl methacrylate were 96.1%.
실시예 61Example 61
포르말린 수용액 10ml 대신에 아크롤레인 1g과 메탄올 30g의 혼합액를 사용하여, 공기의 존재하에 40℃에서 1시간 처리한 것 이외는 실시예 55와 같은 조건으로 촉매의 재생처리, 반응을 수행한 바, 메타크롤레인의 전화률은 72.5%, 메타크릴산메틸의 선택률은 95.5%이다.Using a mixture of 1 g of acrolein and 30 g of methanol instead of 10 ml of formalin aqueous solution, the catalyst was regenerated and reacted under the same conditions as in Example 55 except that the mixture was treated at 40 ° C. for 1 hour in the presence of air. The conversion rate of is 72.5%, the selectivity of methyl methacrylate is 95.5%.
참고예 2Reference Example 2
200ml의 환류 냉각기가 부착된 플라스크에, 테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시켜 혼합하고, 이것에 산화아연 10g을 첨가하고, 혼합물을 교반하면서 환류한다. 이어서, 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여 고형물을 수득한다. 다음에 질산비스무트 0.46g, 아세트산납 0.18g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액에 상기 고형물을 첨가하고 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 15ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.In a flask with a 200 ml reflux condenser, 1.40 g of tetraamine palladium nitrate was dissolved in 20 ml of pure water, mixed, 10 g of zinc oxide was added thereto, and the mixture was refluxed with stirring. Subsequently, after removing water from the mixture, 20 ml of aqueous formalin solution is added, filtered and washed to obtain a solid. Next, the solid was added to a solution in which 0.46 g of bismuth nitrate and 0.18 g of lead acetate were dissolved in 40 ml of diluted nitric acid at a concentration of 3%, and mixed at 60 ° C for 1 hour. 15 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2-Pb1/ZnOPd 5 -Bi 2 -Pb 1 / ZnO
이 촉매를 사용하여 참고예 1과 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 76.9%, 메타크릴산메틸의 선택률은 96.8%이다. 또한 동일한 반응조건으로 장기간 반복하여 촉매를 연속 사용한 바, 메타크롤레인의 전화률은 62.8%, 메타크릴산메틸의 선택률은 87.6%에까지 저하된다.When the reaction was carried out using the catalyst under the same conditions as in Reference Example 1, the conversion of methacrolein was 76.9%, and the selectivity of methyl methacrylate was 96.8%. In addition, when the catalyst was used continuously for a long time under the same reaction conditions, the conversion rate of methacrolein decreased to 62.8% and the selectivity of methyl methacrylate to 87.6%.
실시예 62Example 62
200ml의 환류기가 부착된 플라스크 속에서, 참고예 2에서 장기간 반복반응을 수행하여 활성이 저하된 촉매 2.0g에 메탄올 80g을 첨가하고, 질소를 매분 10ml의 속도로 불어넣으면서 욕온도 50℃에서 1시간 교반 처리한다. 냉각후, 또한 메타크롤레인 3.5g를 첨가하고, 참고예 1과 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 77.3%, 메타크릴산메틸의 선택률은 96.7%이다.In a flask equipped with a 200 ml reflux reactor, 80 g of methanol was added to 2.0 g of the deteriorated catalyst by performing a repeated reaction in Reference Example 2 for 1 hour at a temperature of 50 ° C. while blowing nitrogen at a rate of 10 ml per minute. Stir treatment. After cooling, 3.5 g of methacrolein was further added, and the reaction was carried out under the same conditions as in Reference Example 1. The conversion rate of methacrolein was 77.3%, and the selectivity of methyl methacrylate was 96.7%.
실시예 63Example 63
참고예 2에서 장기간 반복하여 반응을 수행하여 활성이 저하된 촉매를 회수하고, 회수촉매 2.0g를 200ml의 환류기가 부착된 플라스크에 가하고, 이것에 히드라진 수용액 10ml를 첨가하고, 아르곤 가스의 존재하에 40℃에서 1시간 교반 처리한다. 이어서, 여과, 세정한 후 건조하여 재생 촉매를 수득한다.In Reference Example 2, the reaction was repeatedly carried out for a long time to recover the deteriorated catalyst, and 2.0 g of the recovered catalyst was added to a flask equipped with a 200 ml reflux reactor, and 10 ml of an aqueous hydrazine solution was added thereto, and in the presence of argon gas, 40 Stirring is performed at 1 ° C. for 1 hour. Subsequently, it is filtered, washed and dried to obtain a regenerated catalyst.
200ml의 환류기가 부착된 플라스크에, 상기 재생 처리제 또는 촉매 2.0g, 메타크롤레인 3.5g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록, 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하여, 공기를 매분 100ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 76.7%, 메타크릴산메틸의 선택률은 96.5%이다.To a flask with 200 ml of reflux is added 2.0 g of the regeneration agent or catalyst, 3.5 g of methacrolein and 80 g of methanol. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 76.7%, and the selectivity for methyl methacrylate was 96.5%.
참고예 3Reference Example 3
아세트산아연 0.34g을 순수한 물 50ml에 용해시킨 용액에, Pd5-Pb1/CaCO3(N. E. CHEMCAT(주) 제품)를 10g을 첨가하고, 혼합물을 60℃에서 1시간 혼합한다. 수득한 혼합물을 포르말린 수용액 10ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.To a solution of 0.34 g of zinc acetate dissolved in 50 ml of pure water, 10 g of Pd 5 -Pb 1 / CaCO 3 (manufactured by NE CHEMCAT Co., Ltd.) is added, and the mixture is mixed at 60 ° C for 1 hour. 10 ml of formalin aqueous solution is added, the obtained mixture is filtered, washed, and dried to obtain the next catalyst.
Pd5-Pb1-Zn1/CaCO3 Pd 5 -Pb 1 -Zn 1 / CaCO 3
참고예 2와 동일한 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 80.6%, 메타크릴산메틸의 선택률은 95.3%이다. 또한 동일한 반응조건으로 장기간 반복하여 촉매를 연속 사용한 바, 메타크롤레인의 전화률은 66.4%, 메타크릴산메틸의 선택률은 89.7%에까지 저하된다.When the reaction was carried out under the same conditions as in Reference Example 2, the conversion rate of methacrolein was 80.6%, and the selectivity of methyl methacrylate was 95.3%. In addition, when the catalyst was used continuously for a long time under the same reaction conditions, the conversion rate of methacrolein decreased to 66.4% and the selectivity of methyl methacrylate to 89.7%.
실시예 64Example 64
200ml의 환류기가 부착된 플라스크속에서, 참고예 3에서 장기간 반복하여 반응을 수행하여 활성이 저하된 촉매 2.0g에 메탄올 80g을 첨가하고, 질소를 매분 20ml의 속도로 불어넣으면서 욕온도 40℃에서 1시간 교반처리한다. 냉각후, 또한 메타크롤레인 3.5g를 첨가하고, 참고예 1과 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 80.7%, 메타크릴산메틸의 선택률은 95.0%이다.In a flask equipped with a 200 ml reflux reactor, the reaction was repeated for a long time in Reference Example 3 to add 80 g of methanol to 2.0 g of the deteriorated catalyst, and 1 at a bath temperature of 40 ° C. while blowing nitrogen at a rate of 20 ml per minute. Stir for time. After cooling, 3.5 g of methacrolein was further added, and the reaction was carried out under the same conditions as in Reference Example 1. The conversion rate of methacrolein was 80.7%, and the selectivity of methyl methacrylate was 95.0%.
실시예 65Example 65
참고예 3에서 장기간 반복하여 반응을 수행하여 활성이 저하된 촉매를 회수하고, 회수촉매 2.0g을 200ml의 환류기가 부착된 플라스크에 가하고, 이것에 포르말린 수용액 10ml를 첨가하여, 질소의 존재하에 30℃에서 1시간 교반 처리한다. 이어서 여과, 세정한 후 건조하여 재생 촉매를 수득한다.In Reference Example 3, the reaction was repeatedly carried out for a long time to recover the deteriorated catalyst, and 2.0 g of the recovered catalyst was added to a flask equipped with a 200 ml reflux group, and 10 ml of formalin aqueous solution was added thereto, and 30 ° C in the presence of nitrogen. The mixture is stirred for 1 hour. Subsequently, it is filtered, washed and dried to obtain a regenerated catalyst.
200ml의 환류기가 부착된 플라스크에 상기 재생처리제 또는 촉매 2.0g, 메타크롤레인 3.5g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어넣으면서 욕 온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 80.5%, 메타크릴산메틸의 선택률은 95.6%이다.To a flask with 200 ml of reflux is added 2.0 g of the regenerating agent or catalyst, 3.5 g of methacrolein and 80 g of methanol. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 80.5%, and the selectivity for methyl methacrylate was 95.6%.
참고예 4Reference Example 4
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시킨 용액에 탄산칼슘 10g을 첨가하고, 혼합물을 교반하면서 환류한다. 이어서, 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여 고형물을 수득한다. 다음에 질산비스무트 0.46g과 질산제2철 0.72g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액에 상기 고형물을 첨가하여 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 10ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.10 g of calcium carbonate is added to a solution of 1.40 g of tetraaminepalladium nitrate dissolved in 20 ml of pure water, and the mixture is refluxed with stirring. Subsequently, after removing water from the mixture, 20 ml of aqueous formalin solution is added, filtered and washed to obtain a solid. Next, the solid was added to a solution in which 0.46 g of bismuth nitrate and 0.72 g of ferric nitrate were dissolved in 40 ml of diluted nitric acid at a 3% concentration, followed by mixing at 60 ° C for 1 hour. 10 ml of formalin aqueous solution was added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2-Fe1/CaCO3 Pd 5 -Bi 2 -Fe 1 / CaCO 3
이 촉매를 사용하여 참고예 1과 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 75.8%, 메타크릴산메틸의 선택률은 97.3%이다. 또한 동일한 반응조건으로 장기간 반복하여 촉매를 연속 사용한 바, 메타크롤레인의 전화률은 60.5%, 메타크릴산메틸의 선택률은 92.7%에까지 저하된다.When the reaction was carried out using the catalyst under the same conditions as in Reference Example 1, the conversion rate of methacrolein was 75.8%, and the selectivity of methyl methacrylate was 97.3%. In addition, when the catalyst was used continuously for a long time under the same reaction conditions, the conversion rate of methacrolein decreased to 60.5% and the selectivity of methyl methacrylate to 92.7%.
실시예 66Example 66
200ml의 환류기가 부착된 플라스크 속에서, 참고예 4에서 장기간 반복 반응을 수행하여 활성이 저하된 촉매 2.0g에 메탄올 80g을 첨가하고, 질소를 매분 20ml의 속도로 불어넣으면서 욕 온도 70℃에서 1시간 교반 처리한다. 냉각후, 또한 메타크롤레인 3.5g을 첨가하고, 참고예 1과 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 75.6%, 메타크릴산메틸의 선택률은 97.5%이었다.In a flask equipped with a 200 ml reflux group, 80 g of methanol was added to 2.0 g of the deteriorated catalyst by performing a long-term repeated reaction in Reference Example 4, and nitrogen was blown at a rate of 20 ml per minute for 1 hour at a bath temperature of 70 ° C. Stir treatment. After cooling, 3.5 g of methacrolein was further added, and the reaction was carried out under the same conditions as in Reference Example 1. The conversion rate of methacrolein was 75.6%, and the selectivity of methyl methacrylate was 97.5%.
실시예 67Example 67
참고예 4에서 장기간 반복하여 반응을 수행하여 활성이 저하된 촉매를 회수하고, 회수촉매 2.0g을 200ml의 환류기가 부착된 플라스크에 투입하고, 이것에 포르말린 수용액 10ml을 첨가하고, 질소의 존재하에 30℃에서 1시간 교반 처리한다. 이어서 여과, 세정한 후 건조하여 재생처리제 또는 촉매를 수득한다.In Reference Example 4, the reaction was repeatedly carried out for a long time to recover the deteriorated catalyst, 2.0 g of the recovered catalyst was added to a flask equipped with a 200 ml reflux reactor, and 10 ml of formalin aqueous solution was added thereto, and in the presence of nitrogen, 30 Stirring is performed at 1 ° C. for 1 hour. Subsequently, it is filtered, washed and dried to obtain a regenerating agent or catalyst.
200ml의 환류기가 부착된 플라스크에, 상기 재생처리제 또는 촉매 2.0g, 메타크롤레인 3.5g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 75.1%, 메타크릴산메틸의 선택률은 97.3%이다.To a flask equipped with 200 ml of reflux, 2.0 g of the regenerating agent or catalyst, 3.5 g of methacrolein and 80 g of methanol are added. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 75.1%, and the selectivity for methyl methacrylate was 97.3%.
참고예 5Reference Example 5
아세트산아연 0.34g 및 질산제2철 0.72g을 순수한 물 70ml에 용해시킨 용액에, Pd5-Pb1/CaCO3(N. E. CHEMCAT(주) 제품)를 10g을 첨가하고, 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 20ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.To a solution in which 0.34 g of zinc acetate and 0.72 g of ferric nitrate were dissolved in 70 ml of pure water, 10 g of Pd 5 -Pb 1 / CaCO 3 (manufactured by NE CHEMCAT) was added and mixed at 60 ° C for 1 hour. . 20 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Pb1-Fe1-Zn1/CaCO3 Pd 5 -Pb 1 -Fe 1 -Zn 1 / CaCO 3
이 촉매를 사용하여 참고예 1과 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 83.5%, 메타크릴산메틸의 선택률은 95.0%이다. 또한 동일한 반응조건으로 장기간 반복하여 촉매를 연속 사용한 바, 메타크롤레인의 전화률은 68.3%, 메타크릴산메틸의 선택률은 90.1%에까지 저하된다.When the reaction was carried out using the catalyst under the same conditions as in Reference Example 1, the conversion rate of methacrolein was 83.5%, and the selectivity of methyl methacrylate was 95.0%. In addition, when the catalyst was used continuously for a long time under the same reaction conditions, the conversion rate of methacrolein decreased to 68.3%, and the selectivity of methyl methacrylate to 90.1%.
실시예 68Example 68
200ml의 환류기가 부착된 플라스크 속에서, 참고예 5에서 장기간 반복하여 반응을 수행하여 활성이 저하된 촉매 2.0g에, 메탄올 80g을 첨가하고, 질소를 매분 20ml의 속도로 불어넣으면서 욕온도 50℃에서 1시간 교반 처리한다. 냉각후, 또한 메타크롤레인 3.5g을 첨가하고, 참고예 1와 같은 조건으로 반응을 수행한 바, 메타크롤레인의 전화률은 84.0%, 메타크릴산메틸의 선택률은 94.5%이다.In a flask equipped with a 200 ml reflux reactor, the reaction was repeatedly carried out for a long time in Reference Example 5 to add 80 g of methanol to 2.0 g of the deteriorated catalyst, and at a bath temperature of 50 ° C. while blowing nitrogen at a rate of 20 ml per minute. Stir treatment for 1 hour. After cooling, 3.5 g of methacrolein was further added, and the reaction was carried out under the same conditions as in Reference Example 1. The conversion rate of methacrolein was 84.0%, and the selectivity of methyl methacrylate was 94.5%.
실시예 69Example 69
참고예 5에서 장기간 반복 반응을 수행하여 활성이 저하된 촉매를 회수하고, 회수촉매 2.0g을 200ml의 환류기가 부착된 플라스크에 가하고, 이것에 포르말린 수용액 10ml를 첨가하고, 질소의 존재하에 30℃에서 1시간 교반 처리한다. 이어서, 여과, 세정한 후 건조하여 재생처리제 또는 촉매를 수득한다.In Reference Example 5, a long-term repeated reaction was carried out to recover the deteriorated catalyst, and 2.0 g of the recovered catalyst was added to a flask equipped with a 200 ml reflux reactor, and 10 ml of formalin aqueous solution was added thereto at 30 ° C in the presence of nitrogen. Stir treatment for 1 hour. Then, filtered, washed and dried to obtain a regenerating agent or catalyst.
200ml의 환류기가 부착된 플라스크에, 상기 재생처리제 또는 촉매 2.0g, 메타크롤레인 3.5g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어넣으면서 욕 온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 메타크롤레인의 전화률은 83.3%, 메타크릴산메틸의 선택률은 94.9%이다.To a flask equipped with 200 ml of reflux, 2.0 g of the regenerating agent or catalyst, 3.5 g of methacrolein and 80 g of methanol are added. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of methacrolein was 83.3%, and the selectivity for methyl methacrylate was 94.9%.
참고예 6Reference Example 6
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시키고, 이것에 탄산칼슘 10g을 첨가하고, 혼합물을 교반하면서 환류한다. 이어서 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여 고형물을 수득한다. 다음에, 아세트산납 0.18g 및 질산제2철 0.72g을 순수한 물 40ml에 용해시킨 용액에 상기 고형물을 첨가하여 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 15ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.1.40 g of tetraamine palladium nitrate is dissolved in 20 ml of pure water, to which 10 g of calcium carbonate is added, and the mixture is refluxed with stirring. Subsequently, after removing water from the mixture, 20 ml of formalin aqueous solution is added, filtered and washed to obtain a solid. Next, the solid was added to a solution in which 0.18 g of lead acetate and 0.72 g of ferric nitrate were dissolved in 40 ml of pure water, followed by mixing at 60 ° C for 1 hour. 15 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Pb1-Fe1/CaCO3 Pd 5 -Pb 1 -Fe 1 / CaCO 3
200ml의 환류기가 부착된 플라스크에 상기 촉매 2.0g, 아크롤레인 2.80g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록, 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 아크롤레인의 전화률은 85.0%, 아크릴산메틸의 선택률은 95.7%이다. 또한 동일한 반응조건으로 장기간 반복하여 촉매를 연속 사용한 바, 아크롤레인의 전화률은 69.9%, 아크릴산메틸의 선택률은 89.3%에까지 저하된다.2.0 g of the catalyst, 2.80 g of acrolein and 80 g of methanol are added to a flask with 200 ml of reflux. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of acrolein was 85.0%, and the selectivity of methyl acrylate was 95.7%. In addition, when the catalyst was used continuously for a long time under the same reaction conditions, the conversion rate of acrolein decreased to 69.9% and the selectivity of methyl acrylate to 89.3%.
실시예 70Example 70
200ml의 환류기가 부착된 플라스크 속에서, 참고예 6에서 장기간 반복 반응을 수행하여 활성이 저하된 촉매 2.0g에, 메탄올 80g을 첨가하고, 질소를 매분 20ml의 속도로 불어넣으면서 욕온도 70℃에서 1시간 교반 처리한다. 냉각후, 또한 아크롤레인 2.8g을 첨가하고, 참고예 1과 같은 조건으로 반응을 수행한 바, 아크롤레인의 전화률은 85.3%, 아크릴산메틸의 선택율은 95.5%이다.In a flask equipped with a 200 ml reflux reactor, 80 g of methanol was added to 2.0 g of a catalyst whose activity was lowered by performing a long-term repeated reaction in Reference Example 6, and nitrogen was blown at a rate of 20 ml per minute, at a bath temperature of 70 ° C. Stirring time. After cooling, 2.8 g of acrolein was further added, and the reaction was carried out under the same conditions as in Reference Example 1. The conversion rate of acrolein was 85.3%, and the selectivity of methyl acrylate was 95.5%.
실시예 71Example 71
참고예 6에서 장기간 반복하여 반응을 수행하여 활성이 저하된 촉매를 회수하고, 회수촉매 2.0g을 200ml의 환류기가 부착된 플라스크에 가하고, 이것에 포르말린 수용액 10ml를 첨가하고, 질소의 존재하에 30℃에서 1시간 교반한다. 이어서, 여과, 세정한 후 건조하여 재생촉매를 수득한다.In Reference Example 6, the reaction was repeatedly carried out for a long time to recover the deteriorated catalyst, and 2.0 g of the recovered catalyst was added to a flask equipped with a 200 ml reflux reactor, and 10 ml of formalin aqueous solution was added thereto, and 30 ° C in the presence of nitrogen. Stir for 1 hour. Subsequently, it is filtered, washed and dried to obtain a regeneration catalyst.
200ml의 환류기가 부착된 플라스크에, 상기 재생처리제 또는 촉매 2.0g, 아크롤레인 2.8g 및 메탄올 80g을 가한다. 또한 반응액의 pH가 10.5가 되도록 0.03 규정 NaOH 메탄올 용액을 반응액에 첨가하고, 공기를 매분 100ml의 속도로 불어넣으면서 욕온도 70℃에서 4시간 반응을 수행한다. 반응 생성물을 수거하여 분석한 결과, 아크롤레인의 전화률은 84.9%, 아크릴산메틸의 선택률은 95.6%이다.To a flask equipped with 200 ml of reflux, 2.0 g of the regenerating agent or catalyst, 2.8 g of acrolein and 80 g of methanol are added. Further, 0.03 NaOH methanol solution was added to the reaction solution so that the pH of the reaction solution was 10.5, and the reaction was carried out at a bath temperature of 70 ° C. for 4 hours while blowing air at a rate of 100 ml per minute. The reaction product was collected and analyzed. As a result, the conversion rate of acrolein was 84.9%, and the selectivity of methyl acrylate was 95.6%.
비교예 1Comparative Example 1
Pd5-Bi2/CaCO3(N. E. CHEMCAT(주) 제품)를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Md methacrylate was synthesized under the same reaction conditions as in Example 1 using Pd 5 -Bi 2 / CaCO 3 (manufactured by NE CHEMCAT Co., Ltd.). The results are shown in Table 1.
비교예 2Comparative Example 2
담체로서 산화마그네슘을 사용한 것 이외는 실시예 1과 같은 촉매 제조 방법에 의해 다음 촉매를 수득한다.The following catalyst was obtained by the same catalyst preparation method as in Example 1 except that magnesium oxide was used as the carrier.
Pd5-Bi2-Fe1/MgOPd 5 -Bi 2 -Fe 1 / MgO
이 촉매를 사용하여 실시예 1과 같은 조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타내지만, 일반적으로 담체라고 불려지는 산화마그네슘을 사용하면 선택률이 대폭 저하됨을 알 수 있다.Using this catalyst, methyl methacrylate was synthesized under the same conditions as in Example 1. Although the result is shown in Table 1, when using magnesium oxide generally called a carrier, it turns out that a selectivity falls significantly.
비교예 3Comparative Example 3
실시예 13에 따라서 아연이 없는 촉매를 다음 순서로 제조한다. 아세트산납 0.18g을 물 50ml에 용해시킨 용액에, Pd5- Bi2/CaCO3(N. E. CHEMCAT(주) 제품) 10g을 첨가하고, 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 10ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.According to Example 13, a zinc free catalyst was prepared in the following order. To a solution of 0.18 g of lead acetate dissolved in 50 ml of water, 10 g of Pd 5 -Bi 2 / CaCO 3 (manufactured by NE CHEMCAT) is added and mixed at 60 ° C for 1 hour. 10 ml of formalin aqueous solution was added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2-Pb1/CaCO3 Pd 5 -Bi 2 -Pb 1 / CaCO 3
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1.
비교예 4Comparative Example 4
담체로서 산화마그네슘을 사용한 것 이외는 실시예 12와 같은 촉매 제조 방법에 의해 다음 촉매를 수득한다.The following catalyst was obtained by the same catalyst preparation method as in Example 12 except that magnesium oxide was used as the carrier.
Pd5-Bi2-Pb1-Fe1/MgOPd 5 -Bi 2 -Pb 1 -Fe 1 / MgO
이 촉매를 사용하여 실시예 1과 같은 조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타내지만, 상기의 경우도 산화마그네슘을 사용하면 선택률이 대폭 저하됨을 알 수 있다.Using this catalyst, methyl methacrylate was synthesized under the same conditions as in Example 1. The results are shown in Table 1, but in the above case, it can be seen that the use of magnesium oxide significantly reduces the selectivity.
비교예 5Comparative Example 5
Pd5-Pb1/CaCO3(N. E. CHEMCAT(주) 제품)를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타낸다.Methyl methacrylate was synthesized under the same reaction conditions as in Example 1 using Pd 5 -Pb 1 / CaCO 3 (manufactured by NE CHEMCAT Co., Ltd.). The results are shown in Table 1.
비교예 6Comparative Example 6
Pd5-Pb1-Fe1/MgO를 제조하여, 실시예 1과 같은 조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타내지만, 일반적으로 담체라고 불려지는 산화마그네슘을 사용하면 선택률이 대폭 저하됨을 알 수 있다.Pd 5 -Pb 1 -Fe 1 / MgO was prepared, and methyl methacrylate was synthesized under the same conditions as in Example 1. Although the result is shown in Table 1, when using magnesium oxide generally called a carrier, it turns out that a selectivity falls significantly.
비교예 7Comparative Example 7
테트라아민팔라듐질산염 1.40g을 순수한 물 20ml에 용해시킨 용액에 산화아연 10g을 첨가하고, 혼합물을 교반하면서 1시간 환류한다. 이어서, 혼합물로부터 수분을 제거한 후 포르말린 수용액 20ml를 첨가하고, 여과, 세정하여 고형물을 수득한다. 다음에, 질산비스무트 0.46g을 3% 농도의 묽은 질산 40ml에 용해시킨 용액에 상기 고형물을 첨가하고, 60℃에서 1시간 혼합한다. 수득한 혼합물에 포르말린 수용액 15ml를 첨가하고, 여과, 세정한 후 건조하여 다음 촉매를 수득한다.10 g of zinc oxide is added to a solution in which 1.40 g of tetraamine palladium nitrate is dissolved in 20 ml of pure water, and the mixture is refluxed for 1 hour with stirring. Subsequently, after removing water from the mixture, 20 ml of aqueous formalin solution is added, filtered and washed to obtain a solid. Next, the solid is added to a solution in which 0.46 g of bismuth nitrate is dissolved in 40 ml of dilute nitric acid at a concentration of 3%, and mixed at 60 ° C for 1 hour. 15 ml of formalin aqueous solution is added to the obtained mixture, filtered, washed and dried to obtain the next catalyst.
Pd5-Bi2/ZnOPd 5 -Bi 2 / ZnO
이 촉매를 사용하여 실시예 1과 동일한 반응조건으로 메타크릴산메틸을 합성하고 결과를 표 1에 나타낸다. 팔라듐과 비스무트만을 담지한 촉매에서는 선택률이 저하된다.Using this catalyst, methyl methacrylate was synthesized under the same reaction conditions as in Example 1, and the results are shown in Table 1. Selectivity decreases with the catalyst which only supports palladium and bismuth.
비교예 8Comparative Example 8
실시예 36과 같은 방법에 의해 다음 촉매를 수득한다.By the same method as in Example 36, the following catalyst was obtained.
Pd5-Bi2-Pb1/MgOPd 5 -Bi 2 -Pb 1 / MgO
이 촉매를 사용하여 실시예 1과 같은 조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타냈지만, 산화마그네슘을 담체로서 사용하면 선택률이 대폭 저하됨을 알 수 있다.Using this catalyst, methyl methacrylate was synthesized under the same conditions as in Example 1. Although the result is shown in Table 1, when magnesium oxide is used as a support | carrier, it turns out that a selectivity falls significantly.
비교예 9Comparative Example 9
실시예 36과 같은 방법에 의해 다음 촉매를 수득하였다.By the same method as in Example 36, the following catalyst was obtained.
Pd5-Bi2-Pb1/ZrO2 Pd 5 -Bi 2 -Pb 1 / ZrO 2
이 촉매를 사용하여 실시예 1과 같은 조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타냈지만, 산화지르코늄을 담체로서 사용하면 선택률이 대폭으로 저하됨을 알 수 있다.Using this catalyst, methyl methacrylate was synthesized under the same conditions as in Example 1. Although the result was shown in Table 1, when a zirconium oxide is used as a support | carrier, it turns out that a selectivity falls significantly.
비교예 10Comparative Example 10
실시예 36과 같은 방법에 의해 다음 촉매를 수득한다.By the same method as in Example 36, the following catalyst was obtained.
Pd5-Bi2-Pb1/TiO2 Pd 5 -Bi 2 -Pb 1 / TiO 2
이 촉매를 사용하여 실시예 1과 같은 조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타냈지만, 이산화티타늄을 담체로서 사용하면 선택률이 대폭 저하됨을 알 수 있다.Using this catalyst, methyl methacrylate was synthesized under the same conditions as in Example 1. Although the result was shown in Table 1, when titanium dioxide is used as a support | carrier, it turns out that a selectivity falls significantly.
비교예 11Comparative Example 11
실시예 36과 같은 방법에 의해 다음 촉매를 수득한다.By the same method as in Example 36, the following catalyst was obtained.
Pd5-Bi2-Pb1/MgCO3 Pd 5 -Bi 2 -Pb 1 / MgCO 3
이 촉매를 사용하여 실시예 1과 같은 조건으로 메타크릴산메틸을 합성한다. 그 결과를 표 1에 나타냈지만, 탄산마그네슘을 담체로서 사용하면 전화률과 선택률이 대폭 저하됨을 알 수 있다.Using this catalyst, methyl methacrylate was synthesized under the same conditions as in Example 1. Although the result is shown in Table 1, when magnesium carbonate is used as a support | carrier, it turns out that a conversion rate and selectivity fall significantly.
분자상 산소의 존재하에 알데히드와 알코올을 액상으로 반응시킬 때 사용되는 유용한 카복실산 에스테르 제조용 촉매를 제공한다.Provided are catalysts for preparing useful carboxylic esters which are used when reacting aldehydes and alcohols in the liquid phase in the presence of molecular oxygen.
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