JP3313993B2 - Method for producing carboxylic acid ester - Google Patents
Method for producing carboxylic acid esterInfo
- Publication number
- JP3313993B2 JP3313993B2 JP33315296A JP33315296A JP3313993B2 JP 3313993 B2 JP3313993 B2 JP 3313993B2 JP 33315296 A JP33315296 A JP 33315296A JP 33315296 A JP33315296 A JP 33315296A JP 3313993 B2 JP3313993 B2 JP 3313993B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- catalyst
- magnesia
- silica
- benzaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims description 57
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 37
- 239000000395 magnesium oxide Substances 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 8
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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
- 239000007791 liquid phase 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 group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical group [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 claims 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 58
- 238000006243 chemical reaction Methods 0.000 description 48
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 29
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 28
- 238000002474 experimental method Methods 0.000 description 18
- 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 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229940095102 methyl benzoate Drugs 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 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 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 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 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- -1 saturated aliphatic aldehydes Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- AYPZCTCULRIASE-ZVGUSBNCSA-L [Pb+2].C([C@H](O)[C@@H](O)C(=O)[O-])(=O)[O-] Chemical compound [Pb+2].C([C@H](O)[C@@H](O)C(=O)[O-])(=O)[O-] AYPZCTCULRIASE-ZVGUSBNCSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$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
- 238000007664 blowing Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012051 hydrophobic carrier Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229940046892 lead acetate Drugs 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
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 1
- YOJAHJGBFDPSDI-UHFFFAOYSA-N methyl 4-nitrobenzoate Chemical compound COC(=O)C1=CC=C([N+]([O-])=O)C=C1 YOJAHJGBFDPSDI-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 1
- 150000003901 oxalic acid esters Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 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
- 238000010992 reflux Methods 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、アルデヒドとアル
コールから対応するカルボン酸エステルを液相、一段で
製造する方法に関する。The present invention relates to a process for producing a corresponding carboxylic acid ester from an aldehyde and an alcohol in a liquid phase in one step.
【０００２】[0002]
【従来の技術】アルデヒドとアルコールから一段でカル
ボン酸エステルを製造する方法は公知であり、高収率で
得る方法についていくつか検討されている。特公昭５７
−３５８５６号公報、特公平４−７２５７８号公報、特
開昭５７−５０５４５号公報等にパラジウム、鉛系触媒
が、特開昭６１−２４３０４４号公報にパラジウム、テ
ルル系触媒が、特公昭５７−３５８６０号公報にパラジ
ウム、タリウム、水銀系触媒が、特公昭５７−１９０９
０号公報にパラジウム、アルカリ土類金属、亜鉛、カド
ミウム系触媒が、特公昭６１−６０８２０号公報、特公
昭６２−７９０２号公報、特開平５−１４８１８４号公
報等にパラジウム、ビスマス系触媒を用いる方法が提案
されている。2. Description of the Related Art A method for producing a carboxylic acid ester from an aldehyde and an alcohol in one step is known, and several methods for obtaining a high yield thereof have been studied. Tokiko 57
JP-A-35856, JP-B-4-72578, JP-A-57-50545 and the like disclose palladium and lead-based catalysts. No. 35860 discloses a palladium, thallium and mercury-based catalyst.
No. 0 uses palladium, alkaline earth metal, zinc, and cadmium-based catalysts. A method has been proposed.
【０００３】一方、触媒担体に関しても反応成績を向上
させるため改良研究が行われている。特公昭５７−３５
８５６号公報、特公昭５７−３５８６０号公報には触媒
担体として炭酸カルシウムを使用した例が、特公平４−
４６６１８号公報には酸化亜鉛−アルミナ、チタニア−
酸化ランタン、酸化亜鉛−チタニアを触媒担体に用いる
例が、特公平４−７２５７８号公報には酸化亜鉛を触媒
担体に用いる例が、特開昭５７−５０９４２号公報には
比表面積が７０ｍ2 ／ｇ以下の担体を用いる例が、特開
平５−１４８１８４号公報には疎水性担体を用いる例が
開示されている。[0003] On the other hand, improvement research has been conducted on catalyst carriers in order to improve the reaction results. Tokiko 57-35
JP-A-856 and JP-B-57-35860 disclose examples using calcium carbonate as a catalyst carrier.
No. 46618 discloses zinc oxide-alumina, titania-
An example in which lanthanum oxide and zinc oxide-titania are used as a catalyst carrier is disclosed in Japanese Patent Publication No. 4-72578, and an example in which zinc oxide is used as a catalyst carrier, and a specific surface area of 70 m 2 / For example, Japanese Patent Application Laid-Open No. 5-148184 discloses an example using a hydrophobic carrier.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、アル
デヒドとアルコールから一段でカルボン酸エステルを有
利に製造するための活性および目的生成物の選択性の優
れた新規な触媒を用いる製造法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a carboxylic acid ester from an aldehyde and an alcohol in one step by using a novel catalyst having excellent activity and selectivity of a desired product. To provide.
【０００５】[0005]
【課題を解決するための手段】本発明は、分子状酸素の
存在下にアルデヒドとアルコールを液相で反応させてカ
ルボン酸エステルを製造するに当り、パラジウム、Ｘお
よびＹ（Ｘはビスマスおよび／または鉛、Ｙはクロム、
鉄、コバルト、亜鉛および銀からなる群より選ばれた少
なくとも１種の元素）を含有し、これらの成分を平均粒
径が２０〜１５０μｍのシリカ−マグネシアに担持して
なる触媒を用いることを特徴とするカルボン酸エステル
の製造法にある。SUMMARY OF THE INVENTION The present invention provides a method for producing a carboxylic acid ester by reacting an aldehyde and an alcohol in a liquid phase in the presence of molecular oxygen. Or lead, Y is chrome,
At least one element selected from the group consisting of iron, cobalt, zinc and silver), and using a catalyst comprising these components supported on silica-magnesia having an average particle size of 20 to 150 μm. In the method for producing a carboxylic acid ester.
【０００６】[0006]
【発明の実施の形態】本発明の原料に用いられるアルデ
ヒドとしては、ベンズアルデヒド、メチルベンズアルデ
ヒド、ニトロベンズアルデヒドなどの芳香族アルデヒ
ド、アセトアルデヒド、プロピオンアルデヒド、イソブ
チルアルデヒド等の飽和脂肪族アルデヒド、アクロレイ
ン、メタクロレイン、クロトンアルデヒド等の不飽和脂
肪族アルデヒドである。BEST MODE FOR CARRYING OUT THE INVENTION The aldehyde used in the raw material of the present invention includes aromatic aldehydes such as benzaldehyde, methylbenzaldehyde and nitrobenzaldehyde, saturated aliphatic aldehydes such as acetaldehyde, propionaldehyde and isobutyraldehyde, acrolein, methacrolein, and the like. It is an unsaturated aliphatic aldehyde such as crotonaldehyde.
【０００７】また、一方の反応原料であるアルコールと
しては、メタノール、エタノール、イソプロパノール、
アリルアルコール、メタリルアルコールなどが挙げられ
る。[0007] On the other hand, alcohols as one of the reaction raw materials include methanol, ethanol, isopropanol, and the like.
Examples include allyl alcohol and methallyl alcohol.
【０００８】本発明で使用する触媒は、シリカ−マグネ
シア担体上にパラジウムが存在することが必須であり、
これに加えてさらに、ビスマスおよび／または鉛の元素
（Ｘ）と、クロム、鉄、コバルト、亜鉛および銀からな
る群より選ばれた少なくとも１種の元素（Ｙ）とが平均
粒径が２０〜１５０μｍのシリカ−マグネシア担体上に
存在してなる触媒である。In the catalyst used in the present invention, it is essential that palladium is present on a silica-magnesia carrier.
In addition, the element (X) of bismuth and / or lead and at least one element (Y) selected from the group consisting of chromium, iron, cobalt, zinc and silver have an average particle size of 20 to It is a catalyst which is present on a 150 μm silica-magnesia carrier.
【０００９】用いる担体の平均粒径は２０〜１５０μｍ
の範囲内の必要がある。平均粒径が２０μｍ未満の担体
を用いると反応後、目的生成物と触媒を分離することが
困難となる場合がある。また、平均粒径が１５０μｍを
超える担体を用いると触媒の反応活性が低下し、目的生
成物の収率が低くなる場合がある。The average particle size of the carrier used is 20 to 150 μm.
Need to be within the range. If a carrier having an average particle size of less than 20 μm is used, it may be difficult to separate the target product from the catalyst after the reaction. When a carrier having an average particle size of more than 150 μm is used, the reaction activity of the catalyst may be reduced, and the yield of the target product may be reduced.
【００１０】本発明における金属化合物のシリカ−マグ
ネシアへの担持量は、シリカ−マグネシアに対して、パ
ラジウムは１〜１５重量％、好ましくは３〜１３重量
％、前記Ｘは０．１〜１５重量％、好ましくは０．５〜
１２重量％、前記Ｙは０．１〜１５重量％、好ましくは
０．３〜１２重量％である。In the present invention, the amount of the metal compound supported on silica-magnesia is 1 to 15% by weight, preferably 3 to 13% by weight, and the X is 0.1 to 15% by weight based on silica-magnesia. %, Preferably 0.5 to
Y is 0.1 to 15% by weight, preferably 0.3 to 12% by weight.
【００１１】本発明で使用する触媒を構成する元素の原
料化合物としては、パラジウムの原料として、酢酸パラ
ジウム、塩化パラジウム、硝酸パラジウム、塩化パラジ
ウムアンモニウム、パラジウムアンミン錯塩などが、ビ
スマスの原料としては、酢酸ビスマス、炭酸ビスマス、
塩化ビスマス、硝酸ビスマス、硫酸ビスマスなどが、鉛
の原料としては、酢酸鉛、炭酸鉛、塩化鉛、硝酸鉛、硫
酸鉛、酒石酸鉛、クエン酸鉛などが、その他の金属の原
料としては、酢酸塩、硝酸塩、硫酸塩、シュウ酸塩、塩
化物、水酸化物などの一般的な金属化合物が使用でき
る。The raw material compounds of the elements constituting the catalyst used in the present invention include palladium raw materials such as palladium acetate, palladium chloride, palladium nitrate, palladium ammonium chloride, and palladium ammine complex salts. Bismuth, bismuth carbonate,
Bismuth chloride, bismuth nitrate, bismuth sulfate, etc. are used as the raw materials for lead, such as lead acetate, lead carbonate, lead chloride, lead nitrate, lead sulfate, lead tartrate, and lead citrate. Common metal compounds such as salts, nitrates, sulfates, oxalates, chlorides and hydroxides can be used.
【００１２】触媒は常法に従って調製することができ
る。一例として、シリカ−マグネシア上にパラジウム、
ビスマスおよび鉄を担持させた触媒の調製法につき説明
すると、塩化パラジウム、硝酸ビスマスおよび硝酸を水
に入れ加熱して溶解させる。ついで該水溶液にシリカ−
マグネシア粉末を加えた後ホルマリン等の還元剤を添加
し、加熱しながら撹拌する。所定時間処理した後、濾過
し、得られた固形物を硝酸第二鉄の水溶液に浸漬した
後、所望により再度還元剤で還元して金属を析出させ、
濾過した後、乾燥して調製することができる。また、こ
のようにして調製した触媒は、常法に従って活性化する
こともできる。The catalyst can be prepared according to a conventional method. As an example, palladium on silica-magnesia,
A method for preparing a catalyst supporting bismuth and iron will be described. Palladium chloride, bismuth nitrate and nitric acid are put in water and dissolved by heating. Then, the aqueous solution
After adding the magnesia powder, a reducing agent such as formalin is added, and the mixture is stirred while heating. After treatment for a predetermined time, filtration, after immersing the obtained solid in an aqueous solution of ferric nitrate, if necessary, reducing again with a reducing agent to precipitate a metal,
After filtration, it can be prepared by drying. The catalyst thus prepared can be activated according to a conventional method.
【００１３】本発明の反応におけるアルデヒドの供給量
とアルコールの供給量との比率は、モル比として１：１
００〜１：１が適当であり、特に１：８０〜１：３が好
ましい。The ratio of the supply amount of the aldehyde to the supply amount of the alcohol in the reaction of the present invention is 1: 1 as a molar ratio.
The ratio is preferably from 00 to 1: 1 and particularly preferably from 1:80 to 1: 3.
【００１４】反応は液相で、触媒は懸濁状態で用いる。
反応形式は回分式、半回分式、連続式のいずれも採用で
きる。また、反応に必要な分子状酸素源には空気、酸素
富化した空気、酸素などが用いられる。このとき酸化剤
として反応液中に過酸化水素などを加えてもよい。The reaction is performed in a liquid phase, and the catalyst is used in a suspended state.
The reaction system can be any of a batch system, a semi-batch system, and a continuous system. Air, oxygen-enriched air, oxygen and the like are used as a molecular oxygen source necessary for the reaction. At this time, hydrogen peroxide or the like may be added to the reaction solution as an oxidizing agent.
【００１５】反応温度は、０〜１００℃、好ましくは３
０〜８０℃で実施される。反応は常圧で行えるが、加圧
下で行ってもよい。[0015] The reaction temperature is 0 to 100 ° C, preferably 3 to 100 ° C.
Performed at 0-80 ° C. The reaction can be performed under normal pressure, but may be performed under pressure.
【００１６】[0016]
【実施例】以下、本発明を実施例、比較例を掲げてさら
に詳しく説明する。説明中シリカ−マグネシアへの金属
化合物の担持量は、シリカ−マグネシアに対する重量％
を意味する。なお、分析はガスクロマトグラフィーによ
り行った。The present invention will be described in more detail with reference to examples and comparative examples. In the description, the amount of the metal compound supported on silica-magnesia is expressed as a percentage by weight based on silica-magnesia.
Means The analysis was performed by gas chromatography.
【００１７】［実施例１］塩化パラジウム０．８５ｇ、
硝酸ビスマス０．４６ｇおよび６０重量％硝酸水溶液５
ｇを純水５０ｍｌに加熱溶解し、これに平均粒径１００
μｍのシリカ−マグネシア粉末１０ｇを加え撹拌した。
ついで５重量％水酸化ナトリウムおよび５重量％ホルマ
リン含有水溶液５０ｍｌを添加し、７０℃で３０分間撹
拌した後、濾過、水洗した（固形物Ａ）。次に、硝酸第
二鉄０．７２ｇを純水４０ｍｌに溶解した溶液に固形物
Ａを加え撹拌した。ついで５重量％ホルマリン水溶液２
０ｍｌを加え、濾過、水洗した後、乾燥し、５重量％パ
ラジウム−２重量％ビスマス−１重量％鉄を担持したシ
リカ−マグネシア触媒を得た。Example 1 0.85 g of palladium chloride
0.46 g of bismuth nitrate and 60 wt% nitric acid aqueous solution 5
g in 50 ml of pure water by heating.
10 g of silica-magnesia powder of μm was added and stirred.
Then, 50 ml of an aqueous solution containing 5% by weight of sodium hydroxide and 5% by weight of formalin was added, and the mixture was stirred at 70 ° C. for 30 minutes, then filtered and washed with water (solid A). Next, solid A was added to a solution of 0.72 g of ferric nitrate dissolved in 40 ml of pure water, and the mixture was stirred. Next, a 5% by weight aqueous solution of formalin 2
After adding 0 ml, filtering, washing with water and drying, a silica-magnesia catalyst supporting 5% by weight of palladium, 2% by weight of bismuth and 1% by weight of iron was obtained.
【００１８】３００ｍｌの還流器付きフラスコに、上記
触媒２ｇ、ベンズアルデヒド４．３ｇおよびメタノール
８０ｇを添加した。空気を毎分１００ｍｌの流量で吹き
込みながら、５０℃で２時間反応させた。反応生成物を
捕集し分析した結果、ベンズアルデヒドの転化率は９
３．３％で、ベンズアルデヒドを基準とした安息香酸メ
チルの選択率は９５．２％であった。To a 300 ml flask equipped with a reflux condenser were added 2 g of the above catalyst, 4.3 g of benzaldehyde and 80 g of methanol. The reaction was carried out at 50 ° C. for 2 hours while blowing air at a flow rate of 100 ml / min. As a result of collecting and analyzing the reaction products, the conversion of benzaldehyde was 9%.
At 3.3%, the selectivity for methyl benzoate based on benzaldehyde was 95.2%.
【００１９】［実施例２］実施例１において硝酸第二鉄
の代りに酢酸コバルト０．４２ｇを使用した以外は実施
例１と同じ方法で触媒を調製し、５重量％パラジウム−
２重量％ビスマス−１重量％コバルトを担持したシリカ
−マグネシア触媒を得た。この触媒を用い実施例１と同
じ反応条件で実験を行ったところ、ベンズアルデヒドの
転化率は９２．３％で、ベンズアルデヒドを基準とした
安息香酸メチルの選択率は９４．０％であった。Example 2 A catalyst was prepared in the same manner as in Example 1 except that 0.42 g of cobalt acetate was used instead of ferric nitrate.
A silica-magnesia catalyst carrying 2% by weight bismuth-1% by weight cobalt was obtained. When an experiment was conducted using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 92.3%, and the selectivity of methyl benzoate based on benzaldehyde was 94.0%.
【００２０】［実施例３］実施例１において硝酸第二鉄
の代りに酢酸亜鉛０．３４ｇを使用した以外は実施例１
と同じ方法で触媒を調製し、５重量％パラジウム−２重
量％ビスマス−１重量％亜鉛を担持したシリカ−マグネ
シア触媒を得た。この触媒を用い実施例１と同じ反応条
件で実験を行ったところ、ベンズアルデヒドの転化率は
９１．０％で、ベンズアルデヒドを基準とした安息香酸
メチルの選択率は９３．３％であった。Example 3 Example 1 was repeated except that 0.34 g of zinc acetate was used in place of ferric nitrate.
A catalyst was prepared in the same manner as described above to obtain a silica-magnesia catalyst supporting 5% by weight of palladium-2% by weight of bismuth-1% by weight of zinc. When an experiment was conducted using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 91.0%, and the selectivity of methyl benzoate based on benzaldehyde was 93.3%.
【００２１】［実施例４］塩化パラジウム０．８５ｇ、
硝酸鉛０．１６ｇおよび６０重量％硝酸水溶液２ｇを純
水５０ｍｌに加熱溶解し、これに平均粒径１００μｍの
シリカ−マグネシア粉末１０ｇを加え撹拌した。ついで
５重量％水酸化ナトリウムおよび５重量％ホルマリン含
有水溶液５０ｍｌを添加し、８０℃で３０分間撹拌した
後、濾過、水洗した（固形物Ｂ）。次に、硝酸クロム
０．７７ｇを純水４０ｍｌに溶解した溶液に固形物Ｂを
加え撹拌した。ついで５重量％ホルマリン水溶液２０ｍ
ｌを加え、濾過、水洗した後、乾燥し、５重量％パラジ
ウム−１重量％鉛−１重量％クロムを担持したシリカ−
マグネシア触媒を得た。この触媒を用い実施例１と同じ
反応条件で実験を行ったところ、ベンズアルデヒドの転
化率は９０．２％で、ベンズアルデヒドを基準とした安
息香酸メチルの選択率は９２．７％であった。Example 4 0.85 g of palladium chloride,
0.16 g of lead nitrate and 2 g of a 60% by weight nitric acid aqueous solution were dissolved by heating in 50 ml of pure water, and 10 g of silica-magnesia powder having an average particle diameter of 100 μm was added thereto and stirred. Then, 50 ml of an aqueous solution containing 5% by weight of sodium hydroxide and 5% by weight of formalin was added, and the mixture was stirred at 80 ° C. for 30 minutes, and then filtered and washed with water (solid B). Next, solid B was added to a solution of 0.77 g of chromium nitrate dissolved in 40 ml of pure water, and the mixture was stirred. Then, a 5% by weight aqueous solution of formalin 20 m
l, filtered, washed with water, dried, and dried with 5% by weight palladium-1% by weight lead-1% by weight chromium-supported silica.
A magnesia catalyst was obtained. When an experiment was conducted using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 90.2% and the selectivity of methyl benzoate based on benzaldehyde was 92.7%.
【００２２】［実施例５］実施例４において硝酸クロム
の代りに酢酸銀０．１６ｇを使用した以外は実施例４と
同じ方法で触媒を調製し、５重量％パラジウム−１重量
％鉛−１重量％銀を担持したシリカ−マグネシア触媒を
得た。この触媒を用いて実施例１と同じ反応条件で実験
を行ったところ、ベンズアルデヒドの転化率は８９．７
％で、ベンズアルデヒドを基準とした安息香酸メチルの
選択率は９２．１％であった。Example 5 A catalyst was prepared in the same manner as in Example 4 except that 0.16 g of silver acetate was used instead of chromium nitrate, and 5% by weight of palladium-1% by weight of lead-1 A silica-magnesia catalyst supporting silver by weight was obtained. When an experiment was carried out using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 89.7.
%, The selectivity for methyl benzoate based on benzaldehyde was 92.1%.
【００２３】［実施例６］実施例４において硝酸クロム
の代りに硝酸第二鉄０．７２ｇを使用した以外は実施例
４と同じ方法で触媒を調製し、５重量％パラジウム−１
重量％鉛−１重量％鉄を担持したシリカ−マグネシア触
媒を得た。この触媒を用いて実施例１と同じ反応条件で
実験を行ったところ、ベンズアルデヒドの転化率は９
０．２％で、ベンズアルデヒドを基準とした安息香酸メ
チルの選択率は９０．８％であった。Example 6 A catalyst was prepared in the same manner as in Example 4 except that 0.72 g of ferric nitrate was used instead of chromium nitrate.
There was obtained a silica-magnesia catalyst supporting 1% by weight of lead and 1% by weight of iron. When an experiment was carried out using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 9%.
At 0.2%, the selectivity for methyl benzoate based on benzaldehyde was 90.8%.
【００２４】［実施例７］実施例４において硝酸クロム
の代りに酢酸亜鉛０．３４ｇを使用した以外は実施例４
と同じ方法で触媒を調製し、５重量％パラジウム−１重
量％鉛−１重量％亜鉛を担持したシリカ−マグネシア触
媒を得た。この触媒を用いて実施例１と同じ反応条件で
実験を行ったところ、ベンズアルデヒドの転化率は８
８．９％で、ベンズアルデヒドを基準とした安息香酸メ
チルの選択率は９０．３％であった。Example 7 Example 4 was repeated except that 0.34 g of zinc acetate was used instead of chromium nitrate.
A catalyst was prepared in the same manner as described above to obtain a silica-magnesia catalyst supporting 5% by weight of palladium-1% by weight of lead-1% by weight of zinc. When an experiment was conducted using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 8%.
At 8.9%, the selectivity for methyl benzoate based on benzaldehyde was 90.3%.
【００２５】［実施例８］実施例４において硝酸クロム
の代りに硝酸第二鉄０．７２ｇおよび酢酸亜鉛０．１７
を使用した以外は実施例４と同じ方法で触媒を調製し、
５重量％パラジウム−１重量％鉛−１重量％鉄−０．５
重量％亜鉛を担持したシリカ−マグネシア触媒を得た。
この触媒を用いて実施例１と同じ反応条件で実験を行っ
たところ、ベンズアルデヒドの転化率は９０．１％で、
ベンズアルデヒドを基準とした安息香酸メチルの選択率
は９３．５％であった。Example 8 In Example 4, 0.72 g of ferric nitrate and 0.17 of zinc acetate were used instead of chromium nitrate.
A catalyst was prepared in the same manner as in Example 4 except that
5% by weight palladium-1% by weight lead-1% by weight iron-0.5
There was obtained a silica-magnesia catalyst supporting weight% zinc.
When an experiment was conducted using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 90.1%.
The selectivity for methyl benzoate based on benzaldehyde was 93.5%.
【００２６】［実施例９］塩化パラジウム０．８５ｇ、
硝酸鉛０．１６ｇ、硝酸ビスマス０．４６ｇおよび６０
重量％硝酸水溶液５ｇを純水５０ｍｌに加熱溶解し、こ
れに平均粒径１００μｍのシリカ−マグネシア粉末１０
ｇを加え撹拌した。ついで５重量％水酸化ナトリウムお
よび５重量％ホルマリン含有水溶液８０ｍｌを添加し、
７０℃で３０分間撹拌した後、濾過、水洗した（固形物
Ｃ）。硝酸第二鉄０．７２ｇを純水４０ｍｌに溶解した
溶液に固形物Ｃを加え撹拌した。ついで５重量％ホルマ
リン水溶液２０ｍｌを加え、濾過、水洗した後、乾燥
し、５重量％パラジウム−２重量％ビスマス−１重量％
鉛−１重量％鉄を担持したシリカ−マグネシア触媒を得
た。この触媒を用いて実施例１と同じ反応条件で実験を
行ったところ、ベンズアルデヒドの転化率は９４．３％
で、ベンズアルデヒドを基準とした安息香酸メチルの選
択率は９５．８％であった。Example 9 0.85 g of palladium chloride
0.16 g lead nitrate, 0.46 g bismuth nitrate and 60
A 5% by weight aqueous solution of nitric acid was heated and dissolved in 50 ml of pure water.
g was added and stirred. Then, 80 ml of an aqueous solution containing 5% by weight of sodium hydroxide and 5% by weight of formalin was added,
After stirring at 70 ° C. for 30 minutes, the mixture was filtered and washed with water (solid C). Solid C was added to a solution of 0.72 g of ferric nitrate dissolved in 40 ml of pure water, followed by stirring. Then, 20 ml of a 5% by weight formalin aqueous solution was added, filtered, washed with water, dried, and dried at 5% by weight palladium-2% by weight bismuth-1% by weight
A silica-magnesia catalyst supporting lead-1 wt% iron was obtained. When an experiment was carried out under the same reaction conditions as in Example 1 using this catalyst, the conversion of benzaldehyde was 94.3%.
The selectivity for methyl benzoate based on benzaldehyde was 95.8%.
【００２７】［実施例１０］実施例９において硝酸第二
鉄の代りに酢酸亜鉛０．３４ｇを、および平均粒径が５
０μｍのシリカ−マグネシア粉末を使用した以外は実施
例９と同じ方法で触媒を調製し、５重量％パラジウム−
２重量％ビスマス−１重量％鉛−１重量％亜鉛を担持し
たシリカ−マグネシア触媒を得た。この触媒を用いて実
施例１と同じ反応条件で実験を行ったところ、ベンズア
ルデヒドの転化率は９３．３％で、ベンズアルデヒドを
基準とした安息香酸メチルの選択率は９４．５％であっ
た。Example 10 In Example 9, 0.34 g of zinc acetate was used instead of ferric nitrate, and the average particle size was 5%.
A catalyst was prepared in the same manner as in Example 9 except that silica-magnesia powder of 0 μm was used.
A silica-magnesia catalyst carrying 2% by weight bismuth-1% by weight lead-1% by weight zinc was obtained. When an experiment was carried out using this catalyst under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 93.3%, and the selectivity of methyl benzoate based on benzaldehyde was 94.5%.
【００２８】[0028]
【００２９】［実施例１２］実施例１で調製した触媒を
用い、アルデヒドとしてｐ−メチルベンズアルデヒドを
５．０２ｇ用いた以外は実施例１と同じ反応条件で実験
を行ったところ、ｐ−メチルベンズアルデヒドの転化率
は９７．８％で、ｐ−メチルベンズアルデヒドを基準と
したｐ−メチル安息香酸メチルの選択率は９３．７％で
あった。Example 12 An experiment was carried out under the same reaction conditions as in Example 1 except that the catalyst prepared in Example 1 was used and 5.02 g of p-methylbenzaldehyde was used as the aldehyde. Was 97.8% and the selectivity for methyl p-methylbenzoate based on p-methylbenzaldehyde was 93.7%.
【００３０】［実施例１３］実施例１で調製した触媒を
用い、アルデヒドとしてｐ−ニトロベンズアルデヒドを
６．４１ｇ用いた以外は実施例１と同じ反応条件で実験
を行ったところ、ｐ−ニトロベンズアルデヒドの転化率
は６９．０％で、ｐ−ニトロベンズアルデヒドを基準と
したｐ−ニトロ安息香酸メチルの選択率は９０．８％で
あった。Example 13 An experiment was conducted under the same reaction conditions as in Example 1 except that the catalyst prepared in Example 1 was used and 6.41 g of p-nitrobenzaldehyde was used as the aldehyde. Was 69.0% and the selectivity for methyl p-nitrobenzoate based on p-nitrobenzaldehyde was 90.8%.
【００３１】［実施例１４］実施例１で調製した触媒を
用い、アルデヒドとしてメタクロレインを２．８７ｇ用
い、反応時間を４時間とした以外は実施例１と同じ反応
条件で実験を行ったところ、メタクロレインの転化率は
８８．０％で、メタクロレインを基準としたメタクリル
酸メチルの選択率は９６．８％であった。Example 14 An experiment was performed under the same reaction conditions as in Example 1 except that the catalyst prepared in Example 1 was used, 2.87 g of methacrolein was used as the aldehyde, and the reaction time was 4 hours. And the conversion of methacrolein was 88.0%, and the selectivity of methyl methacrylate based on methacrolein was 96.8%.
【００３２】［実施例１５］実施例２で調製した触媒を
用い、アルデヒドとしてメタクロレインを２．８７ｇ用
い、反応時間を４時間とした以外は実施例１と同じ反応
条件で実験を行ったところ、メタクロレインの転化率は
８５．０％で、メタクロレインを基準としたメタクリル
酸メチルの選択率は９５．７％であった。Example 15 An experiment was conducted under the same reaction conditions as in Example 1 except that the catalyst prepared in Example 2 was used, 2.87 g of methacrolein was used as the aldehyde, and the reaction time was 4 hours. The conversion of methacrolein was 85.0%, and the selectivity of methyl methacrylate based on methacrolein was 95.7%.
【００３３】［実施例１６］実施例１で調製した触媒を
用い、アルデヒドとしてアクロレインを２．３ｇ用い、
反応時間を４時間とした以外は実施例１と同じ反応条件
で実験を行ったところ、アクロレインの転化率は９５．
０％で、アクロレインを基準としたアクリル酸メチルの
選択率は９６．３％であった。Example 16 Using the catalyst prepared in Example 1, 2.3 g of acrolein as an aldehyde was used.
The experiment was carried out under the same reaction conditions as in Example 1 except that the reaction time was changed to 4 hours, and the conversion of acrolein was 95.
At 0%, the selectivity for methyl acrylate based on acrolein was 96.3%.
【００３４】［比較例１］実施例１において硝酸第二鉄
を用いずに実施例１と同じ方法で調製して得た、５重量
％パラジウム−２重量％ビスマスを担持したシリカ−マ
グネシア触媒を用い、実施例１と同じ反応条件で実験を
行ったところ、ベンズアルデヒドの転化率は９３．７％
で、ベンズアルデヒドを基準とした安息香酸メチルの選
択率は８５．１％であった。Comparative Example 1 A silica-magnesia catalyst carrying 5% by weight of palladium and 2% by weight of bismuth and prepared by the same method as in Example 1 without using ferric nitrate was used. When the experiment was carried out under the same reaction conditions as in Example 1, the conversion of benzaldehyde was 93.7%.
The selectivity for methyl benzoate based on benzaldehyde was 85.1%.
【００３５】［比較例２］実施例１においてシリカ−マ
グネシアの代りに平均粒径５０μｍのマグネシア粉末を
用いた点以外は実施例１と同じ方法で触媒を調製して得
た、５重量％パラジウム−２重量％ビスマス−１重量％
鉄を担持したマグネシア触媒を用い、実施例１と同じ反
応条件で実験を行ったところ、ベンズアルデヒドの転化
率は８６．３％で、ベンズアルデヒドを基準とした安息
香酸メチルの選択率は８７．９％であった。Comparative Example 2 5% by weight of palladium obtained by preparing a catalyst in the same manner as in Example 1 except that magnesia powder having an average particle size of 50 μm was used instead of silica-magnesia in Example 1 -2% by weight bismuth-1% by weight
When an experiment was carried out under the same reaction conditions as in Example 1 using a magnesia catalyst supporting iron, the conversion of benzaldehyde was 86.3%, and the selectivity of methyl benzoate based on benzaldehyde was 87.9%. Met.
【００３６】［比較例３］実施例１において平均粒径１
００μｍのシリカ−マグネシアの代りに平均粒径０．５
μｍのシリカ−マグネシア粉末を用いた点以外は実施例
１と同じ方法で触媒を調製して得た、５重量％パラジウ
ム−２重量％ビスマス−１重量％鉄を担持したシリカ−
マグネシア触媒を用い、実施例１と同じ反応条件で実験
を行ったところ、ベンズアルデヒドの転化率は９３．９
％で、ベンズアルデヒドを基準とした安息香酸メチルの
選択率は９３．５％であったが、反応終了後の反応液か
ら濾過によって触媒を分離することが極めて困難であっ
た。Comparative Example 3 The average particle size of Example 1 was 1
Average particle size 0.5 instead of 00 μm silica-magnesia
5% by weight of palladium-2% by weight of bismuth-1% by weight of iron-supported silica obtained by preparing a catalyst in the same manner as in Example 1 except that a μm silica-magnesia powder was used.
When an experiment was carried out under the same reaction conditions as in Example 1 using a magnesia catalyst, the conversion of benzaldehyde was 93.9.
%, The selectivity of methyl benzoate based on benzaldehyde was 93.5%, but it was extremely difficult to separate the catalyst from the reaction solution after the reaction by filtration.
【００３７】［比較例４］比較例３においてシリカ−マ
グネシアとして平均粒径２５０μｍのものを用いた以外
は比較例３と同様に実験を行ったところ、ベンズアルデ
ヒドの転化率５８．０％、ベンズアルデヒドを基準とし
た安息香酸メチルの選択率は７９．５％であった。Comparative Example 4 An experiment was performed in the same manner as in Comparative Example 3 except that silica-magnesia having an average particle size of 250 μm was used as the silica-magnesia. The conversion of benzaldehyde was 58.0%, and The standard selectivity for methyl benzoate was 79.5%.
【００３８】[0038]
【００３９】[0039]
【発明の効果】本発明の方法によれば、アルデヒドとア
ルコールから一段でカルボン酸エステルを活性および選
択性よく製造することができる。According to the method of the present invention, a carboxylic acid ester can be produced from an aldehyde and an alcohol in one step with good activity and selectivity.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ０１Ｊ 23/89 Ｃ０７Ｃ 69/00 Ｃ０７Ｂ 61/00 ３００ 69/54 Ｃ０７Ｃ 69/00 69/78 69/54 201/12 69/78 205/57 201/12 Ｂ０１Ｊ 23/64 １０１Ｚ 205/57 １０３ (56)参考文献 特開 平９−52044（ＪＰ，Ａ) 特開 昭58−198442（ＪＰ，Ａ) 特開 昭57−50942（ＪＰ，Ａ) 特開 昭53−68718（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 67/39 C07C 69/00 C07C 69/54 C07C 69/78 C07C 201/12 C07C 205/57 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI B01J 23/89 C07C 69/00 C07B 61/00 300 69/54 C07C 69/00 69/78 69/54 201/12 69/78 205/57 201/12 B01J 23/64 101Z 205/57 103 (56) References JP-A-9-52044 (JP, A) JP-A-58-198442 (JP, A) JP-A-57-50942 (JP) (A) JP-A-53-68718 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 67/39 C07C 69/00 C07C 69/54 C07C 69/78 C07C 201/12 C07C 205/57
Claims (1)
コールを液相で反応させてカルボン酸エステルを製造す
るに当り、パラジウム、ＸおよびＹ（Ｘはビスマスおよ
び／または鉛、Ｙはクロム、鉄、コバルト、亜鉛および
銀からなる群より選ばれた少なくとも１種の元素）を含
有し、これらの成分を平均粒径が２０〜１５０μｍのシ
リカ−マグネシアに担持してなる触媒を用いることを特
徴とするカルボン酸エステルの製造法。In producing a carboxylic acid ester by reacting an aldehyde and an alcohol in the liquid phase in the presence of molecular oxygen, palladium, X and Y (X is bismuth and / or lead, Y is chromium, iron , At least one element selected from the group consisting of cobalt, zinc and silver), and using a catalyst comprising these components supported on silica-magnesia having an average particle size of 20 to 150 μm. A method for producing a carboxylic acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33315296A JP3313993B2 (en) | 1996-11-29 | 1996-11-29 | Method for producing carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33315296A JP3313993B2 (en) | 1996-11-29 | 1996-11-29 | Method for producing carboxylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10158214A JPH10158214A (en) | 1998-06-16 |
| JP3313993B2 true JP3313993B2 (en) | 2002-08-12 |
Family
ID=18262880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33315296A Expired - Lifetime JP3313993B2 (en) | 1996-11-29 | 1996-11-29 | Method for producing carboxylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3313993B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4631230B2 (en) * | 2001-08-03 | 2011-02-16 | マツダ株式会社 | Exhaust gas purification catalyst |
| TW201512168A (en) * | 2013-07-29 | 2015-04-01 | Rohm & Haas | Oxidative esterification process |
| TW201509900A (en) * | 2013-07-29 | 2015-03-16 | Rohm & Haas | Oxidative esterification process |
| WO2016069225A1 (en) * | 2014-10-31 | 2016-05-06 | Rohm And Haas Company | Oxidative esterification process for making methyl methacrylate |
-
1996
- 1996-11-29 JP JP33315296A patent/JP3313993B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10158214A (en) | 1998-06-16 |
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