JP2889365B2 - Method for producing aldehyde - Google Patents
Method for producing aldehydeInfo
- Publication number
- JP2889365B2 JP2889365B2 JP2312947A JP31294790A JP2889365B2 JP 2889365 B2 JP2889365 B2 JP 2889365B2 JP 2312947 A JP2312947 A JP 2312947A JP 31294790 A JP31294790 A JP 31294790A JP 2889365 B2 JP2889365 B2 JP 2889365B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- catalyst
- ester
- group
- ring
- 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 - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 28
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 16
- 125000005907 alkyl ester group Chemical group 0.000 claims description 15
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004438 BET method Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 29
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 19
- -1 heterocyclic carboxylic acid Chemical class 0.000 description 17
- 150000001299 aldehydes Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000011651 chromium Substances 0.000 description 9
- 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 8
- 150000002148 esters Chemical class 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229960002446 octanoic acid Drugs 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 description 2
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical class O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- CKMXAIVXVKGGFM-UHFFFAOYSA-N p-cumic acid Chemical compound CC(C)C1=CC=C(C(O)=O)C=C1 CKMXAIVXVKGGFM-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- XEZVDURJDFGERA-UHFFFAOYSA-N tricosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCC(O)=O XEZVDURJDFGERA-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- IJVLVRYLIMQVDD-UHFFFAOYSA-N 1,3-thiazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CS1 IJVLVRYLIMQVDD-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- CCFAKBRKTKVJPO-UHFFFAOYSA-N 1-anthroic acid Chemical compound C1=CC=C2C=C3C(C(=O)O)=CC=CC3=CC2=C1 CCFAKBRKTKVJPO-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-N 2,2-diethylpropanedioic acid Chemical compound CCC(CC)(C(O)=O)C(O)=O LTMRRSWNXVJMBA-UHFFFAOYSA-N 0.000 description 1
- RIZUCYSQUWMQLX-UHFFFAOYSA-N 2,3-dimethylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 description 1
- QDAWXRKTSATEOP-UHFFFAOYSA-N 2-acetylbenzoic acid Chemical compound CC(=O)C1=CC=CC=C1C(O)=O QDAWXRKTSATEOP-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- ZKTFZNPTAJIXMK-UHFFFAOYSA-N 2-cyclohexylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1CCCCC1 ZKTFZNPTAJIXMK-UHFFFAOYSA-N 0.000 description 1
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- PKRSYEPBQPFNRB-UHFFFAOYSA-N 2-phenoxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1 PKRSYEPBQPFNRB-UHFFFAOYSA-N 0.000 description 1
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 1
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical group N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical class [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- YNBADRVTZLEFNH-UHFFFAOYSA-N Methyl nicotinate Natural products COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical class [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000002785 azepinyl group Chemical group 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- QOWZHEWZFLTYQP-UHFFFAOYSA-K chromium(3+);triformate Chemical compound [Cr+3].[O-]C=O.[O-]C=O.[O-]C=O QOWZHEWZFLTYQP-UHFFFAOYSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UVLKUUBSZXVVDZ-UHFFFAOYSA-N icos-9-ene Chemical compound CCCCCCCCCCC=CCCCCCCCC UVLKUUBSZXVVDZ-UHFFFAOYSA-N 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- ATYBXHSAIOKLMG-UHFFFAOYSA-N oxepin Chemical group O1C=CC=CC=C1 ATYBXHSAIOKLMG-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- QZZGJDVWLFXDLK-UHFFFAOYSA-N tetracosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(O)=O QZZGJDVWLFXDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical group S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- ADCBRSDRBJKLFK-UHFFFAOYSA-N zinc chromium(3+) oxygen(2-) Chemical compound [O-2].[Cr+3].[O-2].[Zn+2] ADCBRSDRBJKLFK-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は有機合成中間体として価値のあるアルデヒド
の製造方法に関するものである。詳しくはカルボン酸又
はそのアルキルエステルを水素化することによりアルデ
ヒドを製造する方法の改良に関するものである。The present invention relates to a method for producing an aldehyde which is valuable as an intermediate for organic synthesis. More specifically, the present invention relates to an improvement in a method for producing an aldehyde by hydrogenating a carboxylic acid or an alkyl ester thereof.
(従来の技術) アルデヒド類を製造する方法としては従来各種の方法
が報告されている。カルボン酸又はその誘導体を原料と
する最も普通に行われている方法としては、カルボン酸
クロリドを経由する所謂ローゼンムント(Rosenmunt)
還元法が挙げられるが製造コストが高い欠点がある。(Prior Art) Various methods have been reported as methods for producing aldehydes. The most common method using carboxylic acid or a derivative thereof as a raw material is the so-called Rosenmunt via carboxylic acid chloride.
Although a reduction method is mentioned, there is a disadvantage that the production cost is high.
カルボン酸を直接分子状水素で還元することによりア
ルデヒド類を効率よく製造できれば最も好ましいが、こ
の方法は従来極めて困難であるとされていた。即ち、カ
ルボン酸又はその誘導体の水素化反応に関しては、触媒
として酸化イットリウムを用いる方法(米国特許第4328
373号)あるいは酸化アルミニウムを用いる方法(米国
特許第3935265号)等が報告されているが、これらの方
法はアルデヒドの選択性に問題がある。It is most preferable that the aldehydes can be efficiently produced by directly reducing the carboxylic acid with molecular hydrogen, but this method has heretofore been considered extremely difficult. That is, regarding the hydrogenation reaction of a carboxylic acid or a derivative thereof, a method using yttrium oxide as a catalyst (US Pat.
373) or a method using aluminum oxide (US Pat. No. 3,935,265), but these methods have a problem in the selectivity of aldehyde.
本発明者等は先に、酸化ジルコニウムを主成分とする
触媒を用いてカルボン酸又はそのエステルの水素化反応
により対応するアルデヒドを製造する方法について報告
した(例えば特開昭60−152434号、特開昭60−243037
号、特開昭61−115043号)。この方法では、原料として
カルボキシル基に対するα−位の炭素に2個の水素原子
が結合している脂肪族カルボン酸もしくはそのエステル
を用いた場合、脱炭酸縮合反応によりケトン体が副生
し、目的とするアルデヒドの選択性が必ずしも充分とは
言い難かった。また原料として、複素環にN、S、O等
のヘテロ原子を含む複素環式カルボン酸もしくはそのエ
ステルを用いた場合にも、アルデヒドの選択性は不十分
であった。The present inventors have previously reported a method for producing a corresponding aldehyde by hydrogenation of a carboxylic acid or an ester thereof using a catalyst containing zirconium oxide as a main component (for example, JP-A-60-152434, Kaisho 60-243037
No., JP-A-61-115043). In this method, when an aliphatic carboxylic acid having two hydrogen atoms bonded to the carbon at the α-position to the carboxyl group or an ester thereof is used as a raw material, a ketone body is by-produced by a decarboxylation condensation reaction. Is not always sufficient. Also, when a heterocyclic carboxylic acid containing a hetero atom such as N, S, or O in a heterocyclic ring or an ester thereof is used as a raw material, the selectivity of the aldehyde was insufficient.
一方、触媒として酸化亜鉛−酸化クロムを用いて、酢
酸、n−酪酸等の低級脂肪酸のシクロアルキルエステル
を水素化すると、夫々対応するアセトアルデヒド、n−
ブチルアルデヒドが低収率ながら生成することが報告さ
れ(特公昭47−38410号)、また触媒として小量の酸化
クロムを含む酸化鉄を用いて、安息香酸メチル、ピバリ
ン酸等を水素化すると、夫々対応するアルデヒドがある
程度の収率で生成することが報告されているが(欧州特
許第304853号)、これらの触媒では、水素化反応は一応
進行するものの、実用上満足し得る収率は得難く、更に
高性能の触媒の出現が望まれている。On the other hand, when a cycloalkyl ester of a lower fatty acid such as acetic acid or n-butyric acid is hydrogenated using zinc oxide-chromium oxide as a catalyst, the corresponding acetaldehyde, n-
It is reported that butyraldehyde is produced with a low yield (Japanese Patent Publication No. 47-38410), and when hydrogenation of methyl benzoate, pivalic acid, etc. is performed using iron oxide containing a small amount of chromium oxide as a catalyst, It has been reported that the corresponding aldehydes are produced in a certain yield (European Patent No. 304853), but with these catalysts, the hydrogenation reaction proceeds for a while, but a practically satisfactory yield is obtained. It is difficult, and the appearance of a higher performance catalyst is desired.
以上に述べたように、従来の報告によれば、脂肪族、
脂環族、芳香族及び複素環式等の各種のカルボン酸又は
その誘導体を直接水素化することにより、夫々対応する
アルデヒドを効率よく製造するための方法は未だ確立さ
れておらず、触媒活性及び目的物の選択性の向上や触媒
寿命の延長等解決すべき問題が多い。As mentioned above, according to previous reports, aliphatic,
A method for efficiently producing the corresponding aldehyde by directly hydrogenating various carboxylic acids such as alicyclic, aromatic and heterocyclic or derivatives thereof has not yet been established, and the catalytic activity and There are many problems to be solved, such as improvement in selectivity of the target substance and extension of the catalyst life.
(発明が解決しようとする課題) 本発明は上に述べた従来法による問題点を解決し、脂
肪族、脂環族、芳香族及び複素環式等の各種のカルボン
酸又はそれらのアルキルエステルから、直接夫々の対応
するアルデヒドを優れた選択率で製造する方法を提供す
ることを目的とするものである。(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems caused by the conventional methods, and comprises various carboxylic acids such as aliphatic, alicyclic, aromatic, and heterocyclic or alkyl esters thereof. It is an object of the present invention to provide a method for directly producing each corresponding aldehyde with excellent selectivity.
(課題を解決するための手段) 本発明者等は上記の課題を解決するために検討を重ね
た結果、特定の担体に担持された特定の触媒を使用する
ことにより、上記の目的が達成されることを知見し、本
発明に到達したものである。即ち、本発明の要旨は、カ
ルボン酸又はそのアルキルエステルを触媒の存在下分子
状水素により水素化してアルデヒドを製造する方法にお
いて、触媒としてBET法で測定した比表面積が100m2/g以
下の酸化アルミニウム担体に担持した酸化クロムを用い
ることを特徴とするアルデヒドの製造方法に存する。(Means for Solving the Problems) As a result of repeated studies by the present inventors to solve the above problems, the above object has been achieved by using a specific catalyst supported on a specific carrier. That is, they have reached the present invention. That is, the gist of the present invention is to provide a method for producing an aldehyde by hydrogenating a carboxylic acid or an alkyl ester thereof with molecular hydrogen in the presence of a catalyst, wherein the specific surface area measured by the BET method as a catalyst is 100 m 2 / g or less. An aldehyde production method characterized by using chromium oxide supported on an aluminum carrier.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
[原料物質] 本発明の方法に使用される出発原料としては、脂肪族
カルボン酸、脂環族カルボン酸、芳香族カルボン酸及び
複素環式等の種々のカルボン酸又はこれらのアルキルエ
ステル類が挙げられ、特に脂肪族カルボン酸もしくはそ
のアルキルエステル及び脂環族カルボン酸もしくはその
アルキルエステルが好適に使用される。[Raw Materials] Examples of starting materials used in the method of the present invention include various carboxylic acids such as aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids, and heterocyclic compounds, and alkyl esters thereof. In particular, aliphatic carboxylic acids or their alkyl esters and alicyclic carboxylic acids or their alkyl esters are preferably used.
脂肪族カルボン酸としては、例えば、酢酸、プロピオ
ン酸、酪酸、イソ酪酸、ピバリン酸、吉草酸、ヘキサン
酸、ヘプタン酸、オクタン酸、2−エチルヘキサン酸、
ノナン酸、デカン酸、ウンデカン酸、ラウリン酸、トリ
デカン酸、テトラデカン酸、ペンタデカン酸、ヘキサデ
カン酸、ステアリン酸、イソステアリン酸、ノナデカン
酸、トリコサン酸、テトラコサン酸、10−ウンデセン
酸、オレイン酸、11−エイコセン酸等の炭素数2〜24の
飽和又は不飽和の脂肪族モノカルボン酸;蓚酸、マロン
酸、ジエチルマロン酸、琥珀酸、グルタル酸、アジピン
酸、デカン二酸、オクタデカン二酸等の脂肪族ポリカル
ボン酸が挙げられる。As the aliphatic carboxylic acid, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid,
Nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, stearic acid, isostearic acid, nonadecanoic acid, tricosanoic acid, tetracosanoic acid, 10-undecenoic acid, oleic acid, 11-eicosene A saturated or unsaturated aliphatic monocarboxylic acid having 2 to 24 carbon atoms such as an acid; an aliphatic polyacid such as oxalic acid, malonic acid, diethylmalonic acid, succinic acid, glutaric acid, adipic acid, decandioic acid, and octadecandioic acid; Carboxylic acids.
また、脂環族カルボン酸としては、例えばシクロペン
タンカルボン酸、シクロヘキサンカルボン酸、1,4−シ
クロヘキサンジカルボン酸等が挙げられる。これらの脂
肪族カルボン酸及び脂環族カルボン酸は、反応に不活性
な置換基、例えばアリール基、アルコキシ基、N、S、
O等のヘテロ原子を含む複素環基を有していてもよい。
更に、脂肪族カルボン酸及び脂環族カルボン酸のアルキ
ルエステルとしては、例えばメチルエステル、エチルエ
ステル、プロピルエステル、n−ブチルエステル、イソ
ブチルエステル等の炭素数1〜4の低級アルキルエステ
ル類が好ましい。Examples of the alicyclic carboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. These aliphatic carboxylic acids and alicyclic carboxylic acids have a substituent inert to the reaction, for example, an aryl group, an alkoxy group, N, S,
It may have a heterocyclic group containing a hetero atom such as O.
Further, as the alkyl ester of the aliphatic carboxylic acid and the alicyclic carboxylic acid, lower alkyl esters having 1 to 4 carbon atoms such as methyl ester, ethyl ester, propyl ester, n-butyl ester and isobutyl ester are preferable.
本発明の原料に使用される芳香族カルボン酸及びその
アルキルエステルとしては、次の式(1) Ar−(COOR)n ……(1) (式中Rは水素原子又はアルキル基を示し、nは1又
は2の数を示し、ArはCOOR基以外に置換基を有していて
もよいアリール基を示す) で表される化合物が挙げられる。As the aromatic carboxylic acid and its alkyl ester used in the raw material of the present invention, the following formula (1) Ar- (COOR) n (1) (wherein R represents a hydrogen atom or an alkyl group, and Represents a number of 1 or 2, and Ar represents an aryl group which may have a substituent other than a COOR group).
(1)式の化合物において、Arとしてはフェニル基、
ナフチル基、アントリル基等のアリール基が挙げられ
る。またArが有していてもよいCOOR基以外の置換基とし
ては、例えばアルキル基、シクロアルキル基、アルコキ
シ基、アリールオキシ基、ハロゲン原子、ヒドロキシル
基、ホルミル基、アシル基等が挙げられる。更にRとし
ては水素原子の外、例えばメチル基、エチル基、プロピ
ル基、n−ブチル基、イソブチル基等のアルキル基が挙
げられる。(1)式の化合物の具体例としては、例え
ば、安息香酸、トルイル酸、ジメチル安息香酸、シクロ
ヘキシル安息香酸、クミン酸、t−ブチル安息香酸、フ
ェニル安息香酸、アニス酸、フェノキシ安息香酸、クロ
ロ安息香酸、ヒドロキシ安息香酸、アセチル安息香酸、
ナフトエ酸、フタル酸、アントラセンカルボン酸が挙げ
られ、またエステルとしては、上記のカルボン酸のメチ
ルエステル、エチルエステル、プロピルエステル、n−
ブチルエステル、イソブチルエステル等の炭素数1〜4
の低級アルキルエステル類が好ましい。In the compound of the formula (1), Ar is a phenyl group,
And aryl groups such as a naphthyl group and an anthryl group. Examples of the substituent other than the COOR group that Ar may have include an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a halogen atom, a hydroxyl group, a formyl group, and an acyl group. Examples of R further include a hydrogen atom and an alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and an isobutyl group. Specific examples of the compound of the formula (1) include, for example, benzoic acid, toluic acid, dimethylbenzoic acid, cyclohexylbenzoic acid, cumic acid, t-butylbenzoic acid, phenylbenzoic acid, anisic acid, phenoxybenzoic acid, and chlorobenzoic acid Acid, hydroxybenzoic acid, acetylbenzoic acid,
Examples include naphthoic acid, phthalic acid, and anthracene carboxylic acid. Examples of the ester include methyl ester, ethyl ester, propyl ester, and n-
C 1-4 carbon atoms such as butyl ester and isobutyl ester
Lower alkyl esters are preferred.
更に、本発明の原料に使用される複素環式カルボン酸
及びそのエステルは、複素環内に少なくとも1個のN、
S、O等のヘテロ原子を含むカルボン酸もしくはそのエ
ステルであり、複素環の具体例としては、ピロール環、
フラン環、チオフェン環、オキサゾール環、チアゾール
環、オキサゾリン環、イミダゾール環、イミダゾリン
環、ピラゾール環、ピラン環、チオピラン環、ピリジン
環、キノリン環、オキサジン環、チアジン環、ピリミジ
ン環、ピラジン環、トリアジン環、アゼピン環、オキセ
ピン環等が挙げられる。なお、カルボン酸エステル基と
してはメチルエステル、エチルエステル、プロピルエス
テル、n−ブチルエステル、イソブチルエステル等の炭
素数1〜4の低級アルキルエステル類が好ましい。複素
環式カルボン酸及びそのエステルの具体例としては、例
えばニコチン酸、フランカルボン酸、チアゾールカルボ
ン酸及びこれらのアルキルエステル類が挙げられる。Further, the heterocyclic carboxylic acid and its ester used in the raw material of the present invention may have at least one N,
A carboxylic acid containing a hetero atom such as S or O or an ester thereof, and specific examples of the heterocyclic ring include a pyrrole ring,
Furan ring, thiophene ring, oxazole ring, thiazole ring, oxazoline ring, imidazole ring, imidazoline ring, pyrazole ring, pyran ring, thiopyran ring, pyridine ring, quinoline ring, oxazine ring, thiazine ring, pyrimidine ring, pyrazine ring, triazine ring Azepine ring, oxepin ring and the like. The carboxylic acid ester group is preferably a lower alkyl ester having 1 to 4 carbon atoms such as methyl ester, ethyl ester, propyl ester, n-butyl ester, isobutyl ester and the like. Specific examples of the heterocyclic carboxylic acid and its ester include, for example, nicotinic acid, furan carboxylic acid, thiazole carboxylic acid and alkyl esters thereof.
[触 媒] 本発明においては、上記原料物質を水素化する際の触
媒として、BET法により測定した比表面積が100m2/g以下
の酸化アルミニウム担体に担持した酸化クロムを使用す
ることを必須の要件とするものであり、この点が本発明
の重要な特徴である。好ましい酸化アルミニウム担体の
比表面積は1〜80m2/gであり、特に好ましい比表面積は
2〜50m2/gである。なお、以下に記載する比表面積の値
は、全てBET法によって測定した値を指示する。[Catalyst] In the present invention, it is essential to use a chromium oxide supported on an aluminum oxide carrier having a specific surface area of 100 m 2 / g or less as measured by the BET method as a catalyst for hydrogenating the above raw material. This is an important feature of the present invention. The specific surface area of the preferred aluminum oxide support is 1 to 80 m 2 / g, and the particularly preferred specific surface area is 2 to 50 m 2 / g. In addition, the values of the specific surface areas described below all indicate values measured by the BET method.
酸化クロムとしては、市販のクロムの水酸化物、硫酸
塩、硝酸塩、ハロゲン化物;無水クロム酸;重クロム酸
のアンモニウム塩もしくはアルカリ金属塩等の無機塩あ
るいはクロムのギ酸塩、酢酸塩、蓚酸塩等の有機塩を原
料とし、これを熱分解することにより調製されたものが
挙げられるが、被毒作用を呈する不純物を含まない点か
ら、クロムの水酸化物もしくは硝酸塩、無水クロム酸、
重クロム酸のアンモニウム塩又はクロムのギ酸塩、酢酸
塩、蓚酸塩等のような比較的低温で分解しかつ他の被毒
元素を含まない原料を熱分解したものが望ましい。Examples of chromium oxide include commercially available hydroxides, sulfates, nitrates, and halides of chromium; chromic anhydride; inorganic salts such as ammonium salts or alkali metal salts of dichromic acid, and formate, acetate, and oxalate of chromium. Such as an organic salt as a raw material, and those prepared by thermally decomposing, but from the point of containing no impurities exhibiting poisoning, hydroxide or nitrate of chromium, chromic anhydride,
It is desirable to use a material obtained by thermally decomposing a raw material which decomposes at a relatively low temperature and does not contain other poisoning elements, such as ammonium salt of dichromic acid or chromium formate, acetate, oxalate and the like.
一方、酸化アルミニウム担体(以下アルミナ担体とい
う)としては、市販のジブサイト、バイアライト、ベー
マイト、ノルストランダイト、シアスボア、無定形アル
ミナゲル、χ−、ρ−、η−、θ−、γ−、σ−、δ
−、α−アルミナ、あるいはアルミニウムの硫酸塩、硝
酸塩、ハロゲン化物等の無機塩及び酢酸塩、蓚酸塩、ア
ルミニウムのアルコオキシサイド等の有機塩を原料と
し、これらを沈澱法、加熱分解法等により処理して調製
されるが、被毒元素を含まない原料を使用するのが望ま
しい。アルミナ担体は粉末状で用いることもできるが、
適当な形状に成形して使用するのが実用上便利である。
アルミナ担体の比表面積は、その調製方法によって影響
を受けるが、一般的には焼成温度を変えることにより制
御することができる。例えば、表面積が270m2/gのγ−
アルミナを用いた場合には、900℃以上の温度で焼成す
ることにより、比表面積が100m2/g以下のアルミナ担体
を得ることができる。On the other hand, aluminum oxide carriers (hereinafter referred to as alumina carriers) include commercially available gibbsite, vialite, boehmite, norstrandite, sheasbore, amorphous alumina gel, χ-, ρ-, η-, θ-, γ-, σ −, Δ
-, Α-alumina or inorganic salts such as aluminum sulfates, nitrates and halides, and organic salts such as acetates, oxalates, and aluminum alkoxides as raw materials, and these are precipitated by a precipitation method, a thermal decomposition method, or the like. It is prepared by processing, but it is desirable to use raw materials that do not contain poisoning elements. Alumina carrier can be used in powder form,
It is practically convenient to mold and use it in an appropriate shape.
The specific surface area of the alumina support is affected by its preparation method, but can generally be controlled by changing the firing temperature. For example, γ- with a surface area of 270 m 2 / g
When alumina is used, the alumina carrier having a specific surface area of 100 m 2 / g or less can be obtained by firing at a temperature of 900 ° C. or more.
アルミナ担体に酸化クロムを担持させるには、前述の
クロム原料を用い、含浸法、吸着法、混練法、沈着法や
蒸発乾固法等の公知の方法が採用され、次いで400℃〜1
200℃、好ましくは500℃〜1000℃の温度で焼成する。触
媒は周知の方法により成形することができる。例えば、
打錠成形方法、噴霧乾燥後焼成する方法、あるいはクロ
ム化合物及びアルミナ担体に水を加え、要すればバイン
ダーを添加して混練し、押出成形後、乾燥して所定の温
度で焼成する方法等により成形される。To support chromium oxide on the alumina carrier, using the above-described chromium raw material, a known method such as an impregnation method, an adsorption method, a kneading method, a deposition method or an evaporation to dryness method is employed, and then 400 ° C to 1 ° C.
Firing at a temperature of 200 ° C, preferably 500 ° C to 1000 ° C. The catalyst can be formed by a known method. For example,
Tablet compression method, spray drying and firing method, or adding water to chromium compound and alumina carrier, adding binder if necessary, kneading, extrusion molding, drying and firing at a predetermined temperature, etc. Molded.
[水素化反応] カルボン酸又はそのアルキルエステルの分子状水素に
よる水素化反応は、上述の触媒の存在下、気相において
温度200℃〜500℃、好ましくは250℃〜450℃で実施する
のが有利である。反応圧力は常圧でよいが多少の加圧状
態で行うこともできる。[Hydrogenation reaction] The hydrogenation reaction of carboxylic acid or its alkyl ester with molecular hydrogen is carried out in the presence of the above-mentioned catalyst in the gas phase at a temperature of 200 ° C to 500 ° C, preferably 250 ° C to 450 ° C. It is advantageous. The reaction pressure may be normal pressure, but the reaction may be carried out in a slightly pressurized state.
触媒を例えば固体床触媒として用いる場合、原料カル
ボン酸又はそのアルキルエステルの空間速度は、LHSVと
して0.01〜1hr-1程度、好ましくは0.03〜0.5hr-1程度が
適当である。一方、水素の空間速度はGHSVとして100〜2
0,000hr-1程度、好ましくは500〜5,000hr-1程度とする
のが適当である。使用する水素中には、若干の不活性ガ
ス例えば窒素、水蒸気等が含まれていても差し支えな
い。なお、本発明の水素化反応は、固定床方式に限られ
るものでなく、流動床方式等の他の反応方式を採用する
こともできる。When the catalyst is used, for example, as a solid bed catalyst, the space velocity of the starting carboxylic acid or its alkyl ester is about 0.01 to 1 hr -1 as LHSV, preferably about 0.03 to 0.5 hr -1 . On the other hand, the space velocity of hydrogen is 100 ~ 2 as GHSV.
It is appropriate to set it to about 0,000 hr -1 , preferably about 500 to 5,000 hr -1 . The hydrogen used may contain some inert gas such as nitrogen and water vapor. In addition, the hydrogenation reaction of the present invention is not limited to the fixed bed system, and other reaction systems such as a fluidized bed system may be employed.
(実施例) 次に本発明を実施例により、更に詳細に説明するが、
本発明はその要旨を超えない限り、以下の実施例に限定
されるものではない。(Examples) Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist.
実施例1 直径5mm、比表面積2.3m2/gの市販の球状α−アルミナ
担体44.0gに、硝酸クロム・9水塩25.8gを水100mlに溶
解した水溶液を加え、蒸発乾固した後、空気中において
700℃で3時間焼成することにより酸化クロム/α−ア
ルミナ担体触媒(Cr2O3として10重量%)を調製した。Example 1 An aqueous solution obtained by dissolving 25.8 g of chromium nitrate / 9 hydrate in 100 ml of water was added to 44.0 g of a commercially available spherical α-alumina carrier having a diameter of 5 mm and a specific surface area of 2.3 m 2 / g. In
By baking at 700 ° C. for 3 hours, a chromium oxide / α-alumina supported catalyst (10% by weight as Cr 2 O 3 ) was prepared.
上記触媒を用い、n−カプリル酸の水素化反応を常圧
下、酸の空間速度:LHSV=0.11kg/l・Cat・hr、水素の空
間速度:GHSV=1250hr-1の条件で実施した。反応温度380
℃におけるn−カプリル酸の転化率は96.4%であり、n
−カプリルアルデヒドの選択率は95.7%であった。Using the above catalyst, the hydrogenation reaction of n-caprylic acid was carried out under normal pressure under the conditions of acid space velocity: LHSV = 0.11 kg / l · Cat · hr and hydrogen space velocity: GHSV = 1250 hr −1 . Reaction temperature 380
The conversion of n-caprylic acid at 9 ° C. is 96.4%
The selectivity for caprylaldehyde was 95.7%.
実施例2 直径4mm、比表面積273m2/gの市販の球状γ−アルミナ
担体を空気中において1080℃で3時間焼成することによ
り、比表面積が27.3m2/gのアルミナ担体を調製した。焼
成後のアルミナの結晶形は、X線回折によりα・アルミ
ナであることが確認された。Example 2 A commercially available spherical γ-alumina carrier having a diameter of 4 mm and a specific surface area of 273 m 2 / g was calcined in the air at 1080 ° C. for 3 hours to prepare an alumina carrier having a specific surface area of 27.3 m 2 / g. The crystal form of the fired alumina was confirmed to be α-alumina by X-ray diffraction.
実施例1で使用した比表面積2.3m2/gのα−アルミナ
担体の代りに、上記の方法で得た比表面積27.3m2/gのα
−アルミナ担体を使用し、他は実施例1と同様の方法に
より硝酸クロム水溶液と混合して蒸発乾固し、焼成する
ことにより、酸化クロム/α−アルミナ担体触媒(Cr2O
3として10重量%)を調製した。In place of the α-alumina support having a specific surface area of 2.3 m 2 / g used in Example 1, α having a specific surface area of 27.3 m 2 / g obtained by the above method was used.
A chromium oxide / α-alumina carrier catalyst (Cr 2 O) was mixed with an aqueous solution of chromium nitrate, evaporated to dryness, and calcined in the same manner as in Example 1 except for using an alumina carrier.
3 as 10% by weight).
上記触媒を用い、実施例1に示したと同一の条件でn
−カプリル酸の水素化反応を実施したところ、反応温度
380℃におけるn−カプリル酸の転化率は97.4%であ
り、n−カプリルアルデヒドの選択率は94.9%であっ
た。Using the above catalyst, n was obtained under the same conditions as in Example 1.
-When the hydrogenation reaction of caprylic acid was performed, the reaction temperature
The conversion of n-caprylic acid at 380 ° C. was 97.4%, and the selectivity for n-caprylic aldehyde was 94.9%.
実施例3 実施例2で使用した市販の球状γ−アルミナ担体を空
気中において1200℃で3時間焼成することにより、比表
面積が9.2m2/gのアルミナ担体を調製した。Example 3 The commercially available spherical γ-alumina carrier used in Example 2 was calcined in air at 1200 ° C. for 3 hours to prepare an alumina carrier having a specific surface area of 9.2 m 2 / g.
実施例1で使用した比表面積2.3m2/gのアルミナ担体
の代りに、上記の方法で得た比表面積9.2m2/gのアルミ
ナ担体を使用し、他は実施例1と同様の方法により硝酸
クロム水溶液と混合して蒸発乾固し、焼成することによ
り、酸化クロム/α−アルミナ担体触媒(Cr2O3として1
0重量%)を調製した。Instead of the alumina support having a specific surface area of 2.3 m 2 / g used in Example 1, the alumina support having a specific surface area of 9.2 m 2 / g obtained by the above method was used, and the other method was the same as in Example 1. It is mixed with an aqueous solution of chromium nitrate, evaporated to dryness, and calcined to obtain a chromium oxide / α-alumina carrier catalyst (1% as Cr 2 O 3).
0% by weight).
上記触媒を用い、実施例1に示したと同一の条件でn
−カプリル酸の水素化反応を実施したところ、反応温度
380℃におけるn−カプリル酸の転化率は57.0%であ
り、n−カプリルアルデヒドの選択率は95.5%であっ
た。なお、ケトン体等の副生は極めて微量であった。Using the above catalyst, n was obtained under the same conditions as in Example 1.
-When the hydrogenation reaction of caprylic acid was performed, the reaction temperature
The conversion of n-caprylic acid at 380 ° C. was 57.0% and the selectivity for n-caprylic aldehyde was 95.5%. The amount of by-products such as ketone bodies was extremely small.
実施例4〜実施例7 実施例1の方法で調製した酸化クロム/α−アルミナ
担体触媒(Cr2O3として10重量%)を使用し、反応基質
としてピバリン酸、シクロヘキサンカルボン酸、安息香
酸及び3−ニコチン酸メチルを用い、表1に示す条件下
において水素化反応を実施した。その結果を表1に示
す。Examples 4 to 7 Using the chromium oxide / α-alumina carrier catalyst (10% by weight as Cr 2 O 3 ) prepared by the method of Example 1, pivalic acid, cyclohexanecarboxylic acid, benzoic acid and A hydrogenation reaction was carried out using methyl 3-nicotinate under the conditions shown in Table 1. Table 1 shows the results.
比較例1 実施例2で使用した市販の球状γ−アルミナ担体を空
気中において900℃で3時間焼成することにより比表面
積131m2/gのアルミナ担体を調製した。 Comparative Example 1 The commercially available spherical γ-alumina carrier used in Example 2 was calcined in air at 900 ° C. for 3 hours to prepare an alumina carrier having a specific surface area of 131 m 2 / g.
実施例1で用いた比表面積が2.3m2/gのアルミナ担体
の代りに、上記方法で得た比表面積が131m2/gのアルミ
ナ担体を使用し、他は実施例1と同様の方法により硝酸
クロム水溶液と混合して蒸発乾固し、焼成することによ
り酸化クロム/α−アルミナ担体触媒(Cr2O3として10
重量%)を調製した。Instead of the alumina support having a specific surface area of 2.3 m 2 / g used in Example 1, the alumina support having a specific surface area of 131 m 2 / g obtained by the above method was used, and the other method was the same as that in Example 1. It is mixed with an aqueous solution of chromium nitrate, evaporated to dryness, and calcined to obtain a chromium oxide / α-alumina carrier catalyst (10% as Cr 2 O 3).
% By weight).
上記触媒を用い、実施例1に示したと同様の条件でn
−カプリル酸の水素化反応を実施したところ、反応温度
390℃におけるn−カプリル酸の転化率は60.0%であ
り、n−カプリルアルデヒドの選択率は44.7%であっ
た。Using the above catalyst, n was obtained under the same conditions as in Example 1.
-When the hydrogenation reaction of caprylic acid was performed, the reaction temperature
The conversion of n-caprylic acid at 390 ° C. was 60.0% and the selectivity for n-caprylic aldehyde was 44.7%.
(発明の効果) 本発明の方法によれば、上記実施例に具体的に示され
るように、特定の比表面積を有するアルミナ担体に担持
された酸化クロム触媒を使用することにより、種々のカ
ルボン酸及びそれらのエステルから、それぞれ対応する
アルデヒドを優れた選択率で効率よく得ることができ、
これらアルデヒドの工業的製造に寄与するところは大き
い。(Effects of the Invention) According to the method of the present invention, various carboxylic acids can be obtained by using a chromium oxide catalyst supported on an alumina carrier having a specific specific surface area, as specifically shown in the above Examples. And their esters, the corresponding aldehydes can be efficiently obtained with excellent selectivity,
Significant contribution to the industrial production of these aldehydes.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C07C 47/54 C07C 47/54 // C07B 61/00 300 C07B 61/00 300 (58)調査した分野(Int.Cl.6,DB名) C07C 47/02 - 47/54 C07C 45/41 B01J 35/10 B01J 23/26 C07B 61/00 WPI/L(QUESTEL) CA(STN)──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C07C 47/54 C07C 47/54 // C07B 61/00 300 C07B 61/00 300 (58) Investigation field (Int.Cl. 6 C07C 47/02-47/54 C07C 45/41 B01J 35/10 B01J 23/26 C07B 61/00 WPI / L (QUESTEL) CA (STN)
Claims (1)
媒の存在下分子状水素により水素化してアルデヒドを製
造する方法において、触媒としてBET法で測定した比表
面積が100m2/g以下の酸化アルミニウム担体に担持した
酸化クロムを用いることを特徴とするアルデヒドの製造
方法。1. A method for producing an aldehyde by hydrogenating a carboxylic acid or an alkyl ester thereof with molecular hydrogen in the presence of a catalyst, the method comprising the steps of: using an aluminum oxide support having a specific surface area of 100 m 2 / g or less as measured by a BET method as a catalyst. A method for producing an aldehyde, comprising using a supported chromium oxide.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2312947A JP2889365B2 (en) | 1990-11-20 | 1990-11-20 | Method for producing aldehyde |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP2312947A JP2889365B2 (en) | 1990-11-20 | 1990-11-20 | Method for producing aldehyde |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04187654A JPH04187654A (en) | 1992-07-06 |
JP2889365B2 true JP2889365B2 (en) | 1999-05-10 |
Family
ID=18035392
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JP2312947A Expired - Fee Related JP2889365B2 (en) | 1990-11-20 | 1990-11-20 | Method for producing aldehyde |
Country Status (1)
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JP (1) | JP2889365B2 (en) |
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1990
- 1990-11-20 JP JP2312947A patent/JP2889365B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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JPH04187654A (en) | 1992-07-06 |
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