JPWO2014163080A1 - シクロヘキサノン化合物の製造方法 - Google Patents
シクロヘキサノン化合物の製造方法 Download PDFInfo
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- JPWO2014163080A1 JPWO2014163080A1 JP2015510097A JP2015510097A JPWO2014163080A1 JP WO2014163080 A1 JPWO2014163080 A1 JP WO2014163080A1 JP 2015510097 A JP2015510097 A JP 2015510097A JP 2015510097 A JP2015510097 A JP 2015510097A JP WO2014163080 A1 JPWO2014163080 A1 JP WO2014163080A1
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- Prior art keywords
- compound
- cyclohexanone
- phenol
- nitrogen
- nitrogen compound
- 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.)
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexyloxide Natural products O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 title claims abstract description 189
- -1 cyclohexanone compound Chemical class 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 89
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 89
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 15
- 150000002390 heteroarenes Chemical class 0.000 claims abstract description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 93
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 229910052757 nitrogen Inorganic materials 0.000 claims description 39
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000003512 tertiary amines Chemical group 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229940126062 Compound A Drugs 0.000 claims description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 150000001412 amines Chemical group 0.000 description 21
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 8
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 8
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 4
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 4
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- JLYNSPSTPQAEAX-UHFFFAOYSA-N 4-cyclohexylcyclohexan-1-one Chemical compound C1CC(=O)CCC1C1CCCCC1 JLYNSPSTPQAEAX-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
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- 230000005494 condensation Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
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- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
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- 238000005259 measurement Methods 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N methylguanidine Chemical compound CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
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- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 238000009825 accumulation Methods 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- WTYGAUXICFETTC-UHFFFAOYSA-N cyclobarbital Chemical compound C=1CCCCC=1C1(CC)C(=O)NC(=O)NC1=O WTYGAUXICFETTC-UHFFFAOYSA-N 0.000 description 1
- 229960004138 cyclobarbital Drugs 0.000 description 1
- JHIVVAPYMSGYDF-PTQBSOBMSA-N cyclohexanone Chemical class O=[13C]1CCCCC1 JHIVVAPYMSGYDF-PTQBSOBMSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
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- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- LWIPGCTWFZCIKX-UHFFFAOYSA-N n-ethyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCC LWIPGCTWFZCIKX-UHFFFAOYSA-N 0.000 description 1
- YIADEKZPUNJEJT-UHFFFAOYSA-N n-ethyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCC YIADEKZPUNJEJT-UHFFFAOYSA-N 0.000 description 1
- OMEMQVZNTDHENJ-UHFFFAOYSA-N n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC OMEMQVZNTDHENJ-UHFFFAOYSA-N 0.000 description 1
- SZEGKVHRCLBFKJ-UHFFFAOYSA-N n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNC SZEGKVHRCLBFKJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
本発明においては、担体に担持されたパラジウム触媒が水素付加反応用の触媒として使用される(以下の説明では、当該触媒を単に「パラジウム担持触媒」と呼ぶ場合がある)。
本発明においては、気相でフェノールの水素付加反応を行うに際して、パラジム担持触媒に加えて、アンモニア、アミン化合物およびヘテロ芳香族化合物から選択される少なくとも1種の窒素化合物の共存下で水素付加反応を進めることを特徴としている。シクロヘキサノンの製造に従来用いられてきたアルカリ金属および/またはアルカリ土類金属化合物は、それらを触媒に担持させて用いる必要があるが、本願における窒素化合物は担持を必要とせず、簡便な方法で触媒表面の酸性を制御できるため有用である。
(1)液状窒素化合物と接触処理したパラジウム担持触媒を、フェノールの水素付加反応触媒として用いる方法。窒素化合物が液状の場合は溶媒を用いることなくそのまま接触させることができ、また粘稠液体や固体の場合は適宜溶媒に溶解させた溶液の形態で使用してもよい。
(2)ガス状の窒素化合物と接触処理したパラジウム担持触媒を、フェノールの水素付加反応触媒として用いる方法。ガス状アミンをパラジウム担持触媒に接触させる方法としては、固定床反応器に充填した触媒に、操作条件における沸点以上に加熱することによりガス化させた窒素化合物を流通させる方法が好ましい。この際、ガス状アミンは、例えば窒素、メタン、エタンなどの不活性ガスと共に供給しても構わない。
(3)フェノールの水素付加反応を行いながら、同時に窒素化合物を連続的に反応器に供給する方法。この場合、窒素化合物は、水素付加反応条件下において、ガス状であることが望ましい。窒素化合物は原料フェノール中に溶解した状態で、または独立して反応器に供給してもよい。独立して反応器に供給する場合は、無溶媒または適宜の溶媒に溶解させた溶液のどちらの状態でもよい。窒素化合物の供給量に特に制限はないが、フェノールのフィード量を100重量%とすると、0.005〜10重量%の範囲が好ましく、0.005〜0.05重量%の範囲がより好ましく、0.01〜0.05重量%の範囲がさらにより好ましい。これより小さい範囲では、触媒性能を改善するのに十分な効果が得られないことがある。また、これより大きい範囲では、生成するシクロヘキサノンとの分離にかかるコストが大きくなることがある。
本発明のシクロヘキサノンの製造方法では、通常はパラジウム担持触媒と窒素化合物の共存下で、反応器にフェノールと水素との混合物をガス状で供給し、気相にて水素付加反応を行う。
フェノールの水素付加反応は、大きな発熱を伴う反応である為、反応の進行に伴い、反応熱を連続的に除去する必要があり、また、本発明においては、固定床触媒上で気相にて反応を行わせるという特徴上、熱交換器と反応器が一体となった多管式反応器またはラジアルフロー型反応器を使用することが好ましい。
図1に示した反応装置を用い、下記の様な方法でフェノールの水素付加反応を行った。図1の反応装置は、供給配管1,2、触媒を充填した固定床型反応器3、気液分離槽4から成る設備を有している。供給配管1から水素あるいは窒素5を、供給配管2からフェノールあるいはアミン6を、反応器3に連続的に供給した。フェノールおよびアミンはポンプにて供給した。
装置名:GC-2010(島津製作所製)
キャリピラリーカラム:TC-WAX(GL Science製、内径0.32mm×長さ60m)
キャリアガス:窒素(1.4mL/min)
測定温度条件:100℃から5℃/分で昇温させ、240℃に達した後12分間保持して終了とした。
FID検出器温度:240℃
注入量:1.0μL
(反応液中に含まれる成分の定量)
絶対検量線法によりフェノール、シクロヘキサノン、シクロヘキサノール、シクロヘキシルシクロヘキサノン、シクロヘキサンおよびベンゼンについてのGC検量線を予め作成しておく。これらの情報と、前記GC測定結果とから常法により、反応液中に含まれる各成分の含有量を定量した。
反応管内には、0.5重量%パラジウムアルミナペレット(NEケムキャット社製:HD−101)を4.0g充填し、触媒充填層8とした。触媒充填層の上部及び下部には、直径2〜4mmのガラスビーズをそれぞれ60g及び15gを充填し(触媒充填層7、9)、各境界には触媒と混合しないようにSUS製の網を敷いた。
アミンをジエチルアミンとしたこと以外は、実施例1と同様にしてフェノールの水素付加反応を行った。フェノール転化率の経時変化を表1および図2、さらにフェノール流通後1.5時間後のフェノール転化率および各成分の選択率を表2に記す。
アミンをn−ブチルアミンとしたこと以外は、実施例1と同様にして、フェノールの水素付加反応を行った。フェノール転化率の経時変化を表1および図2、さらにフェノール流通後1.5時間後のフェノール転化率および各成分の選択率を表2に記す。
アミンをピリジンとしたこと以外は、実施例1と同様にして、フェノールの水素付加反応を行った。フェノール転化率の経時変化を表1および図2、さらにフェノール流通後1.5時間後のフェノール転化率および各成分の選択率を表2に記す。
アミン前処理操作を行わなかったこと以外は、実施例1と同様にして、フェノールの水素付加反応を行った。フェノール転化率の経時変化を表1および図2に記す。
水素供給量を2.9NL/hr、フェノール供給量を4.0g/hr(水素/フェノールのモル比=4、WHSV=1.0h-1)とした以外は、比較例1と同様にして、フェノールの水素付加反応を行った。フェノール転化率の経時変化を表1および図2、さらにフェノール流通後1.5時間後のフェノール転化率および各成分の選択率を表2に記す。
0.5重量%パラジウムアルミナペレット4.0gを、0.5重量%カリウム・0.5重量%パラジウムアルミナペレット5.0gとしたこと以外は、実施例1と同様にして、フェノールの水素付加反応を行った。フェノール流通後11時間後のフェノール転化率および各成分の選択率を表3に記す。
0.5重量%パラジウムアルミナペレットを、0.5重量%カリウム・0.5重量%パラジウムアルミナペレットとし、トリエチルアミンを、30重量%トリメチルアミン水溶液としたこと以外は、実施例1と同様にして、フェノールの水素付加反応を行った。フェノール流通後3.5時間後のフェノール転化率および各成分の選択率を表3に記す。
2・・・供給配管
3・・・反応器
4・・・気液分離器
5・・・水素あるいは窒素
6・・・フェノールあるいはアミン
7・・・ガラスビーズ層
8・・・触媒充填層
9・・・ガラスビーズ層
10・・・ベントガス
11・・・熱媒体
12・・・冷媒体
13・・・反応生成物(反応液)
Claims (14)
- 担体に担持されたパラジウム触媒の存在下で、気相にてフェノール化合物の水素付加反応を行い対応するシクロヘキサノン化合物を得る方法において、アンモニア、アミン化合物およびヘテロ芳香族化合物から選択される少なくとも1種の窒素化合物の共存下で該水素付加反応を進めることを特徴とするシクロヘキサノン化合物の製造方法。
- 担体に担持されたパラジウム触媒の存在下で、気相にてフェノールの水素付加反応を行いシクロヘキサノンを得る方法において、アンモニア、アミン化合物およびヘテロ芳香族化合物から選択される少なくとも1種の窒素化合物の共存下で該水素付加反応を進めることを特徴とするシクロヘキサノンの製造方法。
- 前記窒素化合物が、窒素原子に水素原子が結合した構造を有さないことを特徴とする請求項2に記載のシクロヘキサノンの製造方法。
- 前記窒素化合物が、第三級アミン構造を有するアミン化合物であることを特徴とする請求項3に記載のシクロヘキサノンの製造方法。
- 前記窒素化合物が、水素原子、炭素原子および窒素原子のみから構成されることを特徴とする請求項4に記載のシクロヘキサノンの製造方法。
- 前記窒素化合物が、水素付加反応前に前記パラジウム触媒との接触により触媒表面上に付着された前記窒素化合物であることを特徴とする請求項2〜5のいずれか一項に記載のシクロヘキサノンの製造方法。
- 前記窒素化合物が、原料フェノールとともに添加される前記窒素化合物であることを特徴とする請求項2〜5のいずれか一項に記載のシクロヘキサノンの製造方法。
- 前記窒素化合物の供給量が、フェノールのフィード量を100重量%とすると、0.005〜0.05重量%である請求項7に記載のシクロヘキサノンの製造方法。
- 前記窒素化合物の供給量が、フェノールのフィード量を100重量%とすると、0.01〜0.05重量%である請求項7に記載のシクロヘキサノンの製造方法。
- 前記担体が多孔質アルミナであることを特徴とする請求項2〜9のいずれか一項に記載のシクロヘキサノンの製造方法。
- 前記担体に担持されたパラジウム触媒が、さらにリチウム、ナトリウム、カリウム、マグネシウム、カルシウム、バリウムから選択される少なくとも1種の金属元素を含む請求項2〜10のいずれか一項に記載のシクロヘキサノンの製造方法。
- 水存在下で反応を行うことを特徴とする請求項2〜11のいずれか一項に記載のシクロヘキサノンの製造方法。
- 請求項2〜12のいずれか一項に記載の製造方法により製造されたシクロヘキサノンを用いることを特徴とするカプロラクタムの製造方法。
- 担体に担持されたパラジウム触媒に、アンモニア、アミン化合物およびヘテロ芳香族化合物から選択される少なくとも1種の窒素化合物を接触させることにより得られる、表面に前記窒素化合物が付着した触媒。
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JP (1) | JP6129298B2 (ja) |
KR (1) | KR20150126044A (ja) |
CN (1) | CN105073700A (ja) |
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WO2016075047A1 (en) * | 2014-11-10 | 2016-05-19 | Cap Iii B.V. | Process for the production of cyclohexanone from phenol |
TWI646076B (zh) | 2016-09-09 | 2019-01-01 | 中國石油化學工業開發股份有限公司 | 酚氫化反應生成環己酮之方法 |
EP3363541B1 (de) | 2017-02-17 | 2020-06-17 | Justus-Liebig-Universität Gießen | Katalysatormischung und verfahren zur selektiven oxidation von organischen substraten mit sauerstoff |
US10611705B2 (en) | 2017-05-03 | 2020-04-07 | Exxonmobil Chemical Patents Inc. | Process for conversion of acyclic C5 compounds to cyclic C5 compounds and formulated catalyst compositions used therein |
WO2018204036A1 (en) * | 2017-05-03 | 2018-11-08 | Exxonmobil Chemical Patents Inc. | Process for conversion of acyclic c5 compounds to cyclic c5 compounds and formulated catalyst compositions used therein |
CN108816223B (zh) * | 2018-07-09 | 2021-08-20 | 江苏凌飞科技股份有限公司 | 一种制备壬基环己醇聚氧乙烯醚用的催化剂及其制备方法 |
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TW201446720A (zh) | 2014-12-16 |
TWI596084B (zh) | 2017-08-21 |
JP6129298B2 (ja) | 2017-05-17 |
US20160046553A1 (en) | 2016-02-18 |
KR20150126044A (ko) | 2015-11-10 |
US9481625B2 (en) | 2016-11-01 |
EP2982663A4 (en) | 2017-01-11 |
SG11201508263WA (en) | 2015-11-27 |
EP2982663A1 (en) | 2016-02-10 |
WO2014163080A1 (ja) | 2014-10-09 |
CN105073700A (zh) | 2015-11-18 |
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