JP2022112398A - Method for producing hexamethylene diamine - Google Patents
Method for producing hexamethylene diamine Download PDFInfo
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- JP2022112398A JP2022112398A JP2021008235A JP2021008235A JP2022112398A JP 2022112398 A JP2022112398 A JP 2022112398A JP 2021008235 A JP2021008235 A JP 2021008235A JP 2021008235 A JP2021008235 A JP 2021008235A JP 2022112398 A JP2022112398 A JP 2022112398A
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- hexamethylenediamine
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- raw material
- hexanediol
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 77
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000011949 solid catalyst Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- SUTWPJHCRAITLU-UHFFFAOYSA-N 6-aminohexan-1-ol Chemical compound NCCCCCCO SUTWPJHCRAITLU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 117
- 239000007788 liquid Substances 0.000 claims description 49
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 88
- 229910021529 ammonia Inorganic materials 0.000 abstract description 44
- 239000004480 active ingredient Substances 0.000 abstract description 6
- 230000000737 periodic effect Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 description 78
- 229910052739 hydrogen Inorganic materials 0.000 description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 56
- 238000002360 preparation method Methods 0.000 description 49
- 239000002904 solvent Substances 0.000 description 47
- 239000000203 mixture Substances 0.000 description 44
- 239000003054 catalyst Substances 0.000 description 40
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 38
- 229910052707 ruthenium Inorganic materials 0.000 description 26
- 238000011156 evaluation Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- 229910052697 platinum Inorganic materials 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 229910052759 nickel Inorganic materials 0.000 description 19
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 238000005576 amination reaction Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 7
- 229910052741 iridium Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 238000011088 calibration curve Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 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 4
- 238000001556 precipitation Methods 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical class CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QEDCEMKTASAIQH-UHFFFAOYSA-O azanium;platinum;nitrate Chemical compound [NH4+].[Pt].[O-][N+]([O-])=O QEDCEMKTASAIQH-UHFFFAOYSA-O 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、ヘキサメチレンジアミンの製造方法に関する。 The present invention relates to a method for producing hexamethylenediamine.
ヘキサメチレンジアミンはナイロン原料として非常に有用なモノマーであり、主要な製造方法のひとつとして１，６－ヘキサンジオールのアミノ化反応が挙げられる。効率よくヘキサメチレンジアミンを製造するため、本アミノ化反応を促進する種々の触媒系が開発されてきた。 Hexamethylenediamine is a very useful monomer as a raw material for nylon, and one of the main production methods is the amination reaction of 1,6-hexanediol. In order to efficiently produce hexamethylenediamine, various catalyst systems have been developed to promote this amination reaction.
特許文献１～５では、固体触媒により１，６－ヘキサンジオールをヘキサメチレンジアミンへと変換する技術が開示されている。また、特許文献１及び２ではラネーニッケル触媒を、特許文献３ではコバルトロッド触媒を、特許文献４はルテニウムを活性種とした金属担持触媒を、特許文献５はレニウムを触媒活性種とした合金担持触媒を使用した技術である。 Patent Documents 1 to 5 disclose techniques for converting 1,6-hexanediol to hexamethylenediamine using a solid catalyst. In addition, Patent Documents 1 and 2 are Raney nickel catalysts, Patent Document 3 is a cobalt rod catalyst, Patent Document 4 is a metal-supported catalyst with ruthenium as an active species, and Patent Document 5 is an alloy-supported catalyst with rhenium as a catalytically active species. It is a technique using
１，６－ヘキサンジオールのアミノ化反応系においては、例えば、ヘキサメチレンイミンや重合物（以下、「アミノ化副生物」という）が副生する。これらのアミノ化副生物をヘキサメチレンジアミンへと転化することができれば、反応系全体のヘキサメチレンジアミン収率を向上させることができるため、アミノ化副生物をヘキサメチレンジアミンへと転化する技術が求められる。さらに、上記のアミノ化副生物転化反応と１，６－ヘキサンジオールからヘキサメチレンジアミンへの転化反応とを同時に促進する、つまり、１，６－ヘキサンジオールとアミノ化副生物の混合原料よりヘキサメチレンジアミンを得る技術を開発することが効率的なヘキサメチレンジアミン製造を実現する鍵となる。 In the amination reaction system of 1,6-hexanediol, for example, hexamethyleneimine and polymers (hereinafter referred to as "amination by-products") are by-produced. If these amination by-products can be converted to hexamethylenediamine, the hexamethylenediamine yield of the entire reaction system can be improved. be done. Furthermore, the conversion reaction of the amination by-product and the conversion reaction of 1,6-hexanediol to hexamethylenediamine are simultaneously promoted, that is, the mixed raw material of 1,6-hexanediol and the amination by-product is converted to hexamethylene Developing a technology to obtain diamine is the key to realizing efficient production of hexamethylenediamine.
特許文献１、２及び３では、活性の低い非担持型の卑金属触媒を機能させるため、いずれも１３ＭＰａ以上の高圧下で当該反応を実施している。 In Patent Documents 1, 2, and 3, the reaction is carried out under a high pressure of 13 MPa or higher in order to allow a non-supported base metal catalyst with low activity to function.
一方、特許文献４及び５では担持触媒を用いた技術が検討されているが、これらの触媒を用いたヘキサメチレンジアミンを得る反応において、アミノ化副生物の原料利用については検討されていない。 On the other hand, Patent Documents 4 and 5 discuss techniques using supported catalysts, but do not discuss the use of amination by-products as raw materials in the reaction to obtain hexamethylenediamine using these catalysts.
そこで、本発明は、固体触媒により穏和な条件下で、高い選択率でヘキサメチレンジアミンを与える製造方法を提供することを目的とする。 Accordingly, an object of the present invention is to provide a production method that provides hexamethylenediamine with high selectivity under mild conditions using a solid catalyst.
本発明者らは、本発明の課題を達成するために鋭意検討した結果、特定の固体触媒を用い、且つ、（ｉ）ヘキサメチレンイミン、又は（ｉｉ）特定の縮合体を少なくとも含む原料を用いることで、取り扱いが容易かつ安定な触媒により穏和な条件下で、高い選択率でヘキサメチレンジアミンが得られることを見出した。 The present inventors have made intensive studies to achieve the object of the present invention, and found that a specific solid catalyst is used and (i) hexamethyleneimine or (ii) a raw material containing at least a specific condensate is used. As a result, it was found that hexamethylenediamine can be obtained with high selectivity under mild conditions with an easy-to-handle and stable catalyst.
即ち、本発明は以下の通りである。
［１］
周期表の第８族、第９族、第１０族及び第１１族元素の中から選ばれた１種類以上の金属元素を含む活性成分と担体とを含む固体触媒の存在下で、下記（ｉ）及び（ｉｉ）から選ばれた一種類以上を含む原料とアンモニアとを反応させることを含むヘキサメチレンジアミンの製造方法。
（ｉ）ヘキサメチレンイミン
（ｉｉ）ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン、及び１，６－ヘキサンジオールからなる群から選ばれた１種以上の化合物の縮合体
［２］
前記原料が１，６－ヘキサンジオール、６－アミノヘキサノール、及びヘキサメチレンジアミンからなる群から選ばれた１種類以上の化合物を更に含む［１］に記載のヘキサメチレンジアミンの製造方法。
［３］
前記原料を供給することを含む［１］又は［２］に記載のヘキサメチレンジアミンの製造方法。
［４］
前記原料が前記反応させることにより得られた反応液を精製して得られた回収液を含む［１］～［３］のいずれかに記載のヘキサメチレンジアミンの製造方法。
［５］
前記固体触媒の活性成分が、第８族、第９族、第１０族及び第１１族元素の中から選ばれた２種類以上の金属元素を含む［１］～［４］のいずれかに記載のヘキサメチレンジアミンの製造方法。
［６］
前記固体触媒の活性成分が白金族元素と鉄族元素のそれぞれから１種類以上の金属を含む［１］～［５］のいずれかに記載のヘキサメチレンジアミンの製造方法。
That is, the present invention is as follows.
[1]
The following (i ) and (ii).
(i) hexamethyleneimine (ii) condensates of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol [2]
The method for producing hexamethylenediamine according to [1], wherein the raw material further contains one or more compounds selected from the group consisting of 1,6-hexanediol, 6-aminohexanol, and hexamethylenediamine.
[3]
The method for producing hexamethylenediamine according to [1] or [2], including supplying the raw material.
[4]
The method for producing hexamethylenediamine according to any one of [1] to [3], wherein the raw material contains a recovered liquid obtained by purifying the reaction liquid obtained by the reaction.
[5]
Any one of [1] to [4], wherein the active component of the solid catalyst contains two or more metal elements selected from Group 8, Group 9, Group 10 and Group 11 elements. A method for producing hexamethylenediamine.
[6]
The method for producing hexamethylenediamine according to any one of [1] to [5], wherein the active component of the solid catalyst contains one or more metals from each of platinum group elements and iron group elements.
本発明によれば、固体触媒により穏和な条件下で、高い選択率でヘキサメチレンジアミンを選択的に製造することができる。 According to the present invention, hexamethylenediamine can be selectively produced with high selectivity under mild conditions using a solid catalyst.
本発明について、以下具体的に説明する。なお、本発明は以下の実施の形態（本実施形態）に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 The present invention will be specifically described below. The present invention is not limited to the following embodiment (this embodiment), and various modifications can be made within the scope of the gist thereof.
［ヘキサメチレンジアミンの製造方法］
本実施形態のヘキサメチレンジアミンの製造方法は、周期表の第８族、第９族、第１０族及び第１１族元素の中から選ばれた１種類以上の金属元素を含む活性成分と担体で構成された触媒（以下、単に「固体触媒」ともいう。）の存在下で、下記（ｉ）及び（ｉｉ）から選ばれた一種類以上を含む原料とアンモニアとを反応させること（以下、「反応工程」ともいう）を含む。
（ｉ）ヘキサメチレンイミン
（ｉｉ）ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン、及び１，６－ヘキサンジオールからなる群から選ばれた１種以上の化合物の縮合体
[Method for producing hexamethylenediamine]
In the method for producing hexamethylenediamine of the present embodiment, an active ingredient containing one or more metal elements selected from the elements of Groups 8, 9, 10 and 11 of the periodic table and a carrier are used. Reacting a raw material containing one or more selected from the following (i) and (ii) with ammonia in the presence of a structured catalyst (hereinafter also simply referred to as a "solid catalyst") (hereinafter referred to as " Also referred to as "reaction step").
(i) hexamethyleneimine (ii) condensates of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol
本実施形態では、（ｉ）ヘキサメチレンイミン、又は（ｉｉ）特定の縮合体を少なくとも含む原料を用いることで特定の固体触媒により穏和な条件下で、高い選択率でヘキサメチレンジアミンが得られる。なお、高い選択率が得られる要因は、特定の固体触媒の存在下、アミノ化副生物の系内濃度を大きくすることでアミノ化副生物からヘキサメチレンジアミンへの変換反応の反応速度を向上させ、ヘキサメチレンジアミンのアミノ化副生物への変換反応を抑えるためと考えられるが、要因はこれに限定されない。 In the present embodiment, (i) hexamethyleneimine or (ii) a raw material containing at least a specific condensate is used to obtain hexamethylenediamine with high selectivity under mild conditions using a specific solid catalyst. The reason why the high selectivity is obtained is that the reaction rate of the conversion reaction from the amination by-product to hexamethylenediamine is improved by increasing the concentration of the amination by-product in the system in the presence of a specific solid catalyst. , to suppress the conversion reaction of hexamethylenediamine to an amination by-product, but the factors are not limited to this.
［１］反応工程
反応工程は、固体触媒の存在下で、（ｉ）ヘキサメチレンイミン、又は（ｉｉ）特定の縮合体を含む原料とアンモニアとを反応させる工程である。本実施形態の反応工程は、回分式、半回分式、連続式等の慣用の方法により行うことができる。本実施形態のヘキサメチレンジアミンの製造方法は、上述の原料を供給すること（以下「供給工程」ともいう）を含んでいてもよい。また、本実施形態のヘキサメチレンジアミンの製造方法はヘキサメチレンジアミンを精製すること（以下「分離工程」ともいう）を含んでもよい。分離工程における方法としては、例えば、濃縮、蒸留、抽出、晶析、再結晶等の分離方法や、これらを組み合わせた分離方法が用いられる。
[1] Reaction step The reaction step is a step of reacting (i) hexamethyleneimine or (ii) a raw material containing a specific condensate with ammonia in the presence of a solid catalyst. The reaction process of this embodiment can be carried out by a conventional method such as a batch system, a semi-batch system, or a continuous system. The method for producing hexamethylenediamine according to the present embodiment may include supplying the raw materials described above (hereinafter also referred to as "supplying step"). Further, the method for producing hexamethylenediamine of the present embodiment may include purifying hexamethylenediamine (hereinafter also referred to as "separation step"). As a method in the separation step, for example, a separation method such as concentration, distillation, extraction, crystallization, recrystallization, or a combination of these methods is used.
［２］原料
本実施形態におけるヘキサメチレンジアミンの原料は、下記（ｉ）及び（ｉｉ）から選ばれた一種類以上を含む原料を含む。
（ｉ）ヘキサメチレンイミン
（ｉｉ）ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン、及び１，６－ヘキサンジオールからなる群から選ばれた１種以上の化合物の縮合体
[2] Raw Material The raw material of hexamethylenediamine in the present embodiment includes a raw material containing one or more selected from the following (i) and (ii).
(i) hexamethyleneimine (ii) condensates of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol
上述の（ｉ）ヘキサメチレンイミン、及び（ｉｉ）特定の縮合体は、１，６－ヘキサンジオールのアミノ化反応により得られるアミノ化副生物に含まれることがある。（ｉｉ）の縮合体としては、上述の化合物からアンモニア又は水の脱離をともなって生成される多量体が挙げられる。 (i) Hexamethyleneimine and (ii) certain condensates described above may be included in the amination by-products obtained from the amination reaction of 1,6-hexanediol. Condensates of (ii) include multimers produced from the above-mentioned compounds upon elimination of ammonia or water.
本実施形態で用いられる追加の原料としては、例えば、１，６－ヘキサンジオール、６－アミノヘキサノール、ヘキサメチレンジアミンなどが挙げられる。また、特に限定するわけではないが、収率に優れる観点から、原料が固体触媒による反応工程より得られた反応液を精製して得られた回収液を含むことが好ましい。 Additional raw materials used in this embodiment include, for example, 1,6-hexanediol, 6-aminohexanol, hexamethylenediamine, and the like. Although not particularly limited, it is preferable that the raw material contains a recovered liquid obtained by purifying a reaction liquid obtained from a reaction step using a solid catalyst from the viewpoint of excellent yield.
アンモニアの添加量は、反応速度及び安全性に優れる観点から、例えば、原料に対して、２～５００当量であることが好ましく、２～１５０当量であることがより好ましく、２～１００当量であることが更に好ましい。 The amount of ammonia to be added is preferably 2 to 500 equivalents, more preferably 2 to 150 equivalents, more preferably 2 to 100 equivalents, relative to the starting material, from the viewpoint of excellent reaction rate and safety. is more preferred.
［３］固体触媒
本実施形態のヘキサメチレンジアミンの製造方法においては、固体触媒を使用する。固体触媒は、周期表の第８族、第９族、第１０族及び第１１族元素の中から選ばれた１種類以上の金属元素を含む活性成分と担体とを含む。これらの固体触媒は、穏和な条件下で、且つ、高い選択率でヘキサメチレンジアミンを与える。
[3] Solid catalyst A solid catalyst is used in the method for producing hexamethylenediamine of the present embodiment. The solid catalyst comprises an active component containing one or more metal elements selected from the elements of Groups 8, 9, 10 and 11 of the periodic table, and a carrier. These solid catalysts give hexamethylenediamine with high selectivity under mild conditions.
活性成分とは、触媒調製工程によって担体上に新たに担持された元素を示す。担体にもとより含まれる元素と活性成分が同種の元素の場合も、触媒調製工程によって担持された部分を活性成分とする。 The active component indicates an element newly loaded on the carrier by the catalyst preparation process. Even when the element originally contained in the carrier and the active component are of the same type, the part supported by the catalyst preparation process is regarded as the active component.
活性成分として含まれる金属元素は第８族、第９族、第１０族及び第１１族元素の中から選ばれた１種類以上の金属元素である。活性成分は、金属カチオン、金属錯体及びナノ粒子等の状態で触媒担体に固定化され、この中でも、触媒活性に優れる観点から、ナノ粒子であることが好ましい。 The metal element contained as an active ingredient is one or more metal elements selected from Group 8, Group 9, Group 10 and Group 11 elements. The active ingredient is immobilized on the catalyst carrier in the form of metal cations, metal complexes, nanoparticles, or the like. Among these, nanoparticles are preferred from the viewpoint of excellent catalytic activity.
活性成分は、目的物であるヘキサメチレンジアミンへの選択性に優れる観点から、第８族、第９族、第１０族及び第１１族元素の中から選ばれた２種類以上の金属元素を含むことが好ましい。この中でも、選択性に優れる観点から、白金族元素（ルテニウム、ロジウム、イリジウム、パラジウム、及び白金）と、鉄族元素（鉄、ニッケル、コバルト）のそれぞれから１種類以上の金属元素を含むことがより好ましい。 The active ingredient contains two or more metal elements selected from group 8, group 9, group 10 and group 11 elements from the viewpoint of excellent selectivity to the target hexamethylenediamine. is preferred. Among these, from the viewpoint of excellent selectivity, it is possible to contain one or more metal elements from each of platinum group elements (ruthenium, rhodium, iridium, palladium, and platinum) and iron group elements (iron, nickel, and cobalt). more preferred.
活性成分の含有量は、担体の重量に対して、好ましくは０．５～５０ｗｔ％であり、触媒活性に優れる観点から、より好ましくは１～４０ｗｔ％である。
なお、金属元素の含有量については、担体の重量を１００ｗｔ％とした場合の各金属のｗｔ％を示している。例えば、１０ｗｔ％Ｍ1＊５ｗｔ％Ｍ2／担体と表記される触媒は、Ｍ1：Ｍ2：担体＝１０：５：１００の重量比を有する。
また、固体触媒における金属元素等の含有量は蛍光Ｘ線装置を使用した検量線法で測定する。蛍光Ｘ線装置としては、例えば、リガク社製「ＺＳＸＰｒｉｍｕｓＩＩ」が用いられる。
The content of the active ingredient is preferably 0.5 to 50 wt%, more preferably 1 to 40 wt%, based on the weight of the carrier, from the viewpoint of excellent catalytic activity.
The content of the metal element indicates wt% of each metal when the weight of the support is 100 wt%. For example, a catalyst denoted as 10 wt % M 1 *5 wt % M 2 /support has a weight ratio of M 1 :M 2 :support=10:5:100.
Also, the content of metal elements and the like in the solid catalyst is measured by a calibration curve method using a fluorescent X-ray device. As the fluorescent X-ray device, for example, "ZSX Primus II" manufactured by Rigaku Corporation is used.
担体としては、例えば、金属酸化物や炭素質担体から任意のものを使用することができる。このような担体としては、例えば、酸化チタン、酸化セリウム、酸化ランタン、酸化ジルコニウム、酸化マグネシウム、酸化モリブデン、酸化ニオブ、酸化コバルト、酸化ニッケル、酸化亜鉛、酸化カルシウム、酸化バリウム、窒化チタン、アルミナ、シリカ、ゼオライト、シリカアルミナ、イットリア安定化ジルコニア、セリア－ジルコニア固溶体、酸化ランタン－ジルコニア固溶体、ヒドロキシアパタイト、ハイドロタルサイト、有機ポリマー、活性炭などが挙げられ、この中でも、触媒活性に優れる観点から、酸化チタン、酸化ランタン、酸化セリウム、酸化ニオブ、酸化ジルコニウム、酸化マグネシウム、アルミナ、イットリア安定化ジルコニア、セリア－ジルコニア固溶体、酸化ランタン－ジルコニア固溶体が好ましく、酸化チタン、酸化ジルコニウム、アルミナ、イットリア安定化ジルコニア、セリア－ジルコニア固溶体、酸化ランタン－ジルコニア固溶体がより好ましい。 As the carrier, for example, any metal oxide or carbonaceous carrier can be used. Examples of such carriers include titanium oxide, cerium oxide, lanthanum oxide, zirconium oxide, magnesium oxide, molybdenum oxide, niobium oxide, cobalt oxide, nickel oxide, zinc oxide, calcium oxide, barium oxide, titanium nitride, alumina, Silica, zeolite, silica-alumina, yttria-stabilized zirconia, ceria-zirconia solid solution, lanthanum oxide-zirconia solid solution, hydroxyapatite, hydrotalcite, organic polymer, activated carbon, etc. Among them, from the viewpoint of excellent catalytic activity, oxidation Titanium, lanthanum oxide, cerium oxide, niobium oxide, zirconium oxide, magnesium oxide, alumina, yttria-stabilized zirconia, ceria-zirconia solid solution, lanthanum oxide-zirconia solid solution are preferred, titanium oxide, zirconium oxide, alumina, yttria-stabilized zirconia, A ceria-zirconia solid solution and a lanthanum oxide-zirconia solid solution are more preferable.
固体触媒は、公知の方法で調製してもよい。金属の触媒担体への担持方法としては、特に限定するわけではないが、例えば、析出沈殿法、含浸法、イオン交換法などが適用可能である。 A solid catalyst may be prepared by a known method. Although the method for supporting the metal on the catalyst carrier is not particularly limited, for example, a precipitation precipitation method, an impregnation method, an ion exchange method, and the like can be applied.
［４］還元処理工程
本実施形態のヘキサメチレンジアミンの製造方法は、反応工程の前に、好ましくは、固体触媒の還元処理をすること（以下、「還元処理工程」ともいう）を含む。固体触媒は、大気下で安定であるため、還元などの前処理を行わずに反応に用いることができるが、触媒安定性に優れる観点から、反応前に還元処理を行い、還元処理の後に固体触媒を酸素に曝露することなく反応工程に用いることが好ましい。「還元処理」とは、触媒調製の後、固体触媒を還元剤により処理することをいう。還元処理工程における還元剤は、例えば、水素、金属水素化物、アンモニア、尿素、一酸化炭素などが挙げられるが、触媒活性に優れる観点から、水素を使用することが好ましい。
[4] Reduction treatment step The method for producing hexamethylenediamine of the present embodiment preferably includes subjecting the solid catalyst to reduction treatment (hereinafter also referred to as "reduction treatment step") before the reaction step. Since the solid catalyst is stable in the atmosphere, it can be used in the reaction without pretreatment such as reduction. It is preferred to use the catalyst in the reaction step without exposure to oxygen. “Reduction treatment” refers to treatment of the solid catalyst with a reducing agent after preparation of the catalyst. Examples of the reducing agent in the reduction treatment step include hydrogen, metal hydrides, ammonia, urea, and carbon monoxide. Hydrogen is preferably used from the viewpoint of excellent catalytic activity.
［５］反応生成物
本実施形態のヘキサメチレンジアミンの製造方法は、反応工程によりヘキサメチレンジアミンを含む反応混合物を得ることができる。
[5] Reaction product In the method for producing hexamethylenediamine of the present embodiment, a reaction mixture containing hexamethylenediamine can be obtained by the reaction step.
［６］反応条件
固体触媒の使用量としては、反応後の固体触媒の分離性に優れる観点から、例えば、１，６－ヘキサンジオール１００質量部に対して５～１０００質量部であることが好ましく、１０～７５０質量部であることがより好ましく、２０～５００質量部であることが更に好ましい。
[6] Reaction conditions The amount of the solid catalyst used is preferably, for example, 5 to 1000 parts by mass with respect to 100 parts by mass of 1,6-hexanediol, from the viewpoint of excellent separation of the solid catalyst after the reaction. , more preferably 10 to 750 parts by mass, even more preferably 20 to 500 parts by mass.
反応温度としては、例えば、０～３００℃であることが好ましく、５０～２７０℃であることがより好ましく、１２０～２５０℃であることが更に好ましい。 The reaction temperature is, for example, preferably 0 to 300°C, more preferably 50 to 270°C, even more preferably 120 to 250°C.
反応全圧としては、反応速度及び安全性に優れる観点から、好ましくは１０ＭＰａＧ以下（例えば、０．１～１０．０ＭＰａＧ）、より好ましくは０．５～７．５ＭＰａＧ、特に好ましくは０．５～５．０ＭＰａＧである。 The total reaction pressure is preferably 10 MPaG or less (eg, 0.1 to 10.0 MPaG), more preferably 0.5 to 7.5 MPaG, particularly preferably 0.5 to 0.5 MPaG, from the viewpoint of excellent reaction rate and safety. 5.0 MPaG.
［７］水素圧力
本実施形態のヘキサメチレンジアミンの製造方法においては、例えば、原子効率に優れる観点から、水素非共存下で行うことが好ましい。ただし、水素共存下においても実施することができ、水素の圧力としては、反応速度及び安全性に優れる観点から、例えば、絶対圧力表示で、０～１０．０ＭＰａであることが好ましく、０～５．０ＭＰａであることがより好ましく、０～１．０ＭＰａであることが更に好ましい。
[7] Hydrogen Pressure In the method for producing hexamethylenediamine of the present embodiment, it is preferable to carry out in the absence of hydrogen from the viewpoint of, for example, excellent atomic efficiency. However, it can also be carried out in the presence of hydrogen, and the pressure of hydrogen is, for example, from the viewpoint of excellent reaction rate and safety, in terms of absolute pressure, preferably 0 to 10.0 MPa, and 0 to 5. 0 MPa, more preferably 0 to 1.0 MPa.
［８］溶媒
本実施形態のヘキサメチレンジアミンの製造方法では、例えば、反応工程においてアンモニア分子を溶解する溶媒を使用することが好ましい。このような溶媒としては、例えば、水、炭化水素系溶媒（例えば、トルエン、ベンゼン、キシレン、ペンタン、ヘキサン、デカン）、エーテル系溶媒（例えば、テトラヒドロフラン、ジオキサン、ジメトキシエタン）、アルコール系溶媒（エチレングリコール、エタノール、メタノール、ｔ－ブタノール）、アミド系溶媒（ジメチルアセトアミド、アセトアミド、ジメチルホルムアミド、Ｎ－メチルピロリドン）、ハロゲン系溶媒（ジクロロエタン、ジクロロメタン、クロロホルム、四塩化炭素、トリフルオロトルエン）などが挙げられる。
[8] Solvent In the method for producing hexamethylenediamine of the present embodiment, for example, it is preferable to use a solvent that dissolves ammonia molecules in the reaction step. Examples of such solvents include water, hydrocarbon solvents (e.g., toluene, benzene, xylene, pentane, hexane, decane), ether solvents (e.g., tetrahydrofuran, dioxane, dimethoxyethane), alcohol solvents (e.g., ethylene glycol, ethanol, methanol, t-butanol), amide solvents (dimethylacetamide, acetamide, dimethylformamide, N-methylpyrrolidone), halogen solvents (dichloroethane, dichloromethane, chloroform, carbon tetrachloride, trifluorotoluene), etc. be done.
溶媒量（溶媒の添加量）は、気体アンモニアの吸収効率に優れる観点から、反応系内のアンモニアを溶解させる十分な量が好ましく、例えば、原料１００質量部に対して、５０質量部以上であり、好ましくは１００～１００００質量部、より好ましくは１００～２５００質量部である。 The amount of solvent (the amount of solvent added) is preferably a sufficient amount to dissolve ammonia in the reaction system from the viewpoint of excellent absorption efficiency of gaseous ammonia, for example, 50 parts by mass or more with respect to 100 parts by mass of the raw material. , preferably 100 to 10,000 parts by mass, more preferably 100 to 2,500 parts by mass.
以下に実施例を示して、本発明をより詳細に説明するが、本発明は以下に記載の実施例によって制限されるものではない。なお、以下の表中では１，６－ヘキサンジオールをＨＤＬ、ヘキサメチレンジアミンをＨＭＤ、ヘキサメチレンイミンをＨＭＩ、６－アミノヘキサノールをＡＨＬとそれぞれ略記した。 EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples described below. In the following tables, 1,6-hexanediol is abbreviated as HDL, hexamethylenediamine as HMD, hexamethyleneimine as HMI, and 6-aminohexanol as AHL.
（蛍光Ｘ線分析）
装置：リガク社製、蛍光Ｘ線分析装置（ＺＳＸＰｒｉｍｕｓＩＩ）
条件：検量線法
・各触媒調製時に使用したａｃａｃ錯体、塩化物、又は硝酸塩などを標準物質として用い、各触媒調製時に使用した担体と混合し、標準試料を作成した。前記標準試料を用いて、蛍光Ｘ線分析を行い、検量線を作成した。
・検量線作成用の標準試料は、実施例および比較例に記載する各触媒の上限を超える濃度範囲となるように調製した。
(Fluorescent X-ray analysis)
Apparatus: Fluorescent X-ray analyzer (ZSX Primus II) manufactured by Rigaku
Conditions: Calibration curve method Using acac complexes, chlorides, nitrates, etc. used in the preparation of each catalyst as standard substances, they were mixed with the carrier used in the preparation of each catalyst to prepare standard samples. Using the standard sample, fluorescent X-ray analysis was performed to prepare a calibration curve.
- A standard sample for creating a calibration curve was prepared so that the concentration range exceeded the upper limit of each catalyst described in Examples and Comparative Examples.
（ＧＣ分析）
装置 島津製作所製 ＧＣ－２０１０ｐｌｕｓ
カラム ＣＰ－Ｖｏｌａｍｉｎｅ
条件 インジェクション温度：２００℃、ディテクション温度：３００℃
キャリアガス：窒素（カラム流量７０．８ｍｌ／ｍｉｎ、ＳＰ比５０）
昇温速度：８０℃～（１５℃／ｍｉｎ）～１５０℃（３１分保持）～
（１０℃／ｍｉｎ）～２１０℃（３．３分保持）～
（１５℃／ｍｉｎ）～２９０℃（２．７分保持）
内標 アニソール
(GC analysis)
Device Shimadzu GC-2010plus
Column CP-Volamine
Conditions injection temperature: 200°C, detection temperature: 300°C
Carrier gas: nitrogen (column flow rate 70.8 ml/min, SP ratio 50)
Heating rate: 80°C ~ (15°C/min) ~ 150°C (holding for 31 minutes) ~
(10°C/min) ~ 210°C (held for 3.3 minutes) ~
(15°C/min) to 290°C (held for 2.7 minutes)
Internal standard Anisole
［実施例１］
触媒調製：塩化白金酸と硝酸コバルト六水和物を水溶媒に溶解させた後、ジルコニア担体（第一稀元素化学工業社製品 ＲＣ－１００）に含浸法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を得た。触媒の金属担持量は蛍光Ｘ線装置を使用した検量線法で測定した。
[Example 1]
Catalyst preparation: After dissolving chloroplatinic acid and cobalt nitrate hexahydrate in an aqueous solvent, the solution was supported on a zirconia carrier (product of Daiichi Kigenso Kagaku Kogyo RC-100) by an impregnation method. The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was collected under air to obtain 10 wt% Co*2.5 wt% Pt/ZrO 2 . The amount of metal supported on the catalyst was measured by a calibration curve method using a fluorescent X-ray device.
回収液の調製：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール２．０ｇ、アンモニアを１，６－ヘキサンジオールに対して６４当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。この時、ヘキサメチレンジアミンの収率は３０ｍｏｌ％、選択率は３９ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。ここでは、回収液よりヘキサメチレンイミンを除去しないことが好ましいが、ヘキサメチレンイミンはヘキサメチレンジアミンと比較して沸点が低いため、蒸留により除去される。 Preparation of recovered liquid: 1.0 g of 10 wt % Co*2.5 wt % Pt/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180° C. under hydrogen of 1 MPaG and water solvent. Then, 2.0 g of 1,6-hexanediol and 64 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at 1.0 MPa at room temperature, and reaction was carried out at 180° C. for 2 hours. At this time, the yield of hexamethylenediamine was 30 mol %, and the selectivity was 39 mol %. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction. Here, it is preferable not to remove hexamethyleneimine from the recovered liquid, but since hexamethyleneimine has a lower boiling point than hexamethylenediamine, it is removed by distillation.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理工程を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表１の組成の原料と、当該原料に対して６４．９当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。生成物の収率はガスクロマトグラフィーを使用して内部標準法で測定した。表１に得られた反応後の組成を示した。本実施例では、５４ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率４０ｍｏｌ％、選択率７４ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Pt/ZrO 2 was added to a pressure-resistant reactor, and a reduction treatment step was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Thereafter, a raw material having the composition shown in Table 1 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 64.9 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 2 hours. Product yields were determined by internal standard method using gas chromatography. Table 1 shows the composition after the reaction obtained. In this example, 54 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 40 mol % and a selectivity of 74 mol %.
［実施例２］
回収液の調製：実施例１の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。
[Example 2]
Preparation of recovered liquid: By distilling the reaction liquid of Example 1, a recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表１の組成の原料と、当該原料に対して６７．３当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表１に得られた反応後の組成を示した。本実施例では、５１ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率４１ｍｏｌ％、選択率８０ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Pt/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under 1 MPaG of hydrogen and water solvent. Then, a raw material having the composition shown in Table 1 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 67.3 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 2 hours. Table 1 shows the composition after the reaction obtained. In this example, 51 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 41 mol % and a selectivity of 80 mol %.
［実施例３］
触媒調製：塩化ルテニウムと硝酸コバルト六水和物を水溶媒に溶解させた後、ジルコニア担体（第一稀元素化学工業社製品 ＲＣ－１００）にアンモニアを使用した析出沈殿法で金属を担持させた。得られた粉末を大気下で回収し、１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を得た。
[Example 3]
Catalyst preparation: After dissolving ruthenium chloride and cobalt nitrate hexahydrate in a water solvent, a metal was supported on a zirconia carrier (product of Daiichi Kigenso Kagaku Kogyo Co., Ltd. RC-100) by a precipitation precipitation method using ammonia. . The obtained powder was collected in the atmosphere to obtain 10 wt% Co*2.5 wt% Ru/ZrO 2 .
回収液の調製：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール２．０ｇ、アンモニアを１，６－ヘキサンジオールに対して３２当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。この時、ヘキサメチレンジアミンの収率は２５ｍｏｌ％、選択率は３１ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 1.0 g of 10 wt % Co*2.5 wt % Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180° C. under hydrogen of 1 MPaG and water solvent. Then, 2.0 g of 1,6-hexanediol and 32 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at 1.0 MPa at room temperature, and reaction was carried out at 180° C. for 2 hours. At this time, the yield of hexamethylenediamine was 25 mol % and the selectivity was 31 mol %. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表２の組成の原料と、当該原料に対して３２．１当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａを充填した後、１８０℃で２時間反応を行った。表２に得られた反応後の組成を示した。本実施例では、４６ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３１ｍｏｌ％、選択率６７ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180° C. under hydrogen of 1 MPaG and water solvent. Thereafter, a raw material having the composition shown in Table 2 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 32.1 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 2 hours. Table 2 shows the composition after the reaction obtained. In this example, 46 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 31 mol % and a selectivity of 67 mol %.
［実施例４］
回収液の調製：実施例３の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。
[Example 4]
Preparation of recovered liquid: By distilling the reaction liquid of Example 3, a recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表２の組成の原料と、当該原料に対して３４．３当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表２に得られた反応後の組成を示した。本実施例では、４２ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３２ｍｏｌ％、選択率７６ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180° C. under hydrogen of 1 MPaG and water solvent. Then, the raw material having the composition shown in Table 2 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 34.3 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 2 hours. Table 2 shows the composition after the reaction obtained. In this example, 42 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 32 mol % and a selectivity of 76 mol %.
［実施例５］
回収液の調製：実施例４の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。
[Example 5]
Preparation of recovered liquid: By distilling the reaction liquid of Example 4, a recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表２の組成の原料と、当該原料に対して３１．３当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表２に得られた反応液組成を示した。本実施例では、４１ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３２ｍｏｌ％、選択率７８ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Then, a raw material having the composition shown in Table 2 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 31.3 equivalents of ammonia with respect to the raw material were put into a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 2 hours. Table 2 shows the composition of the reaction solution obtained. In this example, 41 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 32 mol % and a selectivity of 78 mol %.
［実施例６］
触媒調製：硝酸プラチナアンモニウムと硝酸ニッケル六水和物を水溶媒に溶解させた後、１４ｗｔ％Ｙ安定化ジルコニア担体（第一稀元素化学工業社製品 Ｚ－２８７４）に含侵法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを得た。
[Example 6]
Catalyst preparation: After dissolving platinum ammonium nitrate and nickel nitrate hexahydrate in a water solvent, the solution was supported on a 14 wt% Y-stabilized zirconia carrier (Z-2874, a product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by an impregnation method. . The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was recovered under the atmosphere to obtain 10 wt% Ni*2.5 wt% Pt/YSZ.
回収液の調製：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１６０℃で還元処理を行った。その後、１，６－ヘキサンジオール４．０ｇ、アンモニアを１，６－ヘキサンジオールに対して８．６当量加え、水素を室温で１．０ＭＰａ充填した後、１６０℃で２時間反応を行った。この時、ヘキサメチレンジアミンの収率は１５ｍｏｌ％、選択率は２１ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 2.0 g of 10 wt% Ni*2.5 wt% Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 160°C under hydrogen of 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 8.6 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at room temperature to 1.0 MPa, and reaction was carried out at 160° C. for 2 hours. At this time, the yield of hexamethylenediamine was 15 mol% and the selectivity was 21 mol%. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１６０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表３の組成の原料と、当該原料に対して８．６当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１６０℃で２時間反応を行った。表３に得られた反応液組成を示した。本実施例では、３０ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率１９ｍｏｌ％、選択率６３ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni*2.5 wt % Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 160° C. under hydrogen of 1 MPaG and water solvent. Then, a raw material having the composition shown in Table 3 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 8.6 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 160° C. for 2 hours. Table 3 shows the composition of the reaction solution obtained. In this example, 30 mol % of the starting material was consumed, and hexamethylenediamine was obtained with a yield of 19 mol % and a selectivity of 63 mol %.
［実施例７］
回収液の調製：実施例６の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。
[Example 7]
Preparation of recovered liquid: By distilling the reaction liquid of Example 6, a recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１６０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表３の組成の原料と、当該原料に対して８．４当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１６０℃で２時間反応を行った。表３に得られた反応液組成を示した。本実施例では、３２ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率２０ｍｏｌ％、選択率６３ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni*2.5 wt % Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 160° C. under hydrogen of 1 MPaG and water solvent. Thereafter, a raw material having the composition shown in Table 3 obtained by mixing 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above, and 8.4 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 160° C. for 2 hours. Table 3 shows the composition of the reaction solution obtained. In this example, 32 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 20 mol % and a selectivity of 63 mol %.
［実施例８］
回収液の調製：実施例７の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。
[Example 8]
Preparation of recovered liquid: By distilling the reaction liquid of Example 7, a recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１６０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表３の組成の原料と、当該原料に対して８．６当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１６０℃で２時間反応を行った。表３に得られた反応液組成を示した。本実施例では、２２ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率１９ｍｏｌ％、選択率８６ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni*2.5 wt % Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 160° C. under hydrogen of 1 MPaG and water solvent. Then, a raw material having the composition shown in Table 3 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 8.6 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 160° C. for 2 hours. Table 3 shows the composition of the reaction solution obtained. In this example, 22 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 19 mol % and a selectivity of 86 mol %.
［実施例９］
触媒調製：塩化イリジウムと硝酸ニッケル六水和物を水溶媒に溶解させた後、１４ｗｔ％Ｙ安定化ジルコニア担体（第一稀元素化学工業社製品 Ｚ－２８７４）に含侵法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｉｒ／ＹＳＺを得た。
[Example 9]
Catalyst preparation: After dissolving iridium chloride and nickel nitrate hexahydrate in a water solvent, the solution was supported on a 14 wt% Y-stabilized zirconia carrier (Z-2874, a product of Daiichi Kigenso Kagaku Kogyo Co., Ltd.) by an impregnation method. The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was collected under the atmosphere to obtain 10 wt% Ni*2.5 wt% Ir/YSZ.
回収液の調製：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｉｒ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール４．０ｇ、アンモニアを１，６－ヘキサンジオールに対して３３．２当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。この時、ヘキサメチレンジアミンの収率は２０ｍｏｌ％、選択率は２６ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 2.0 g of 10 wt % Ni*2.5 wt % Ir/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 33.2 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at 1.0 MPa at room temperature, and reaction was carried out at 180° C. for 2 hours. At this time, the yield of hexamethylenediamine was 20 mol % and the selectivity was 26 mol %. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｉｒ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表４の組成の原料と、当該原料に対して３３．２当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表４に得られた反応液組成を示した。本実施例では、４７ｍｏｌ％の原料成分が消費されヘキサメチレンジアミンが収率３３ｍｏｌ％、選択率７０ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni*2.5 wt % Ir/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Thereafter, a raw material having the composition shown in Table 4 obtained by mixing 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above, and 33.2 equivalents of ammonia with respect to the raw material were placed in a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 2 hours. Table 4 shows the composition of the reaction solution obtained. In this example, 47 mol % of raw material components were consumed and hexamethylenediamine was obtained with a yield of 33 mol % and a selectivity of 70 mol %.
［実施例１０］
回収液の調製：実施例９の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。
[Example 10]
Preparation of recovered liquid: By distilling the reaction liquid of Example 9, a recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｉｒ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理工程を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表４の組成の原料と、当該原料に対して３３．６当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表４に得られた反応液組成を示した。本実施例では、４６ｍｏｌ％の原料成分が消費されヘキサメチレンジアミンが収率３６ｍｏｌ％、選択率７８ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni*2.5 wt % Ir/YSZ was added to a pressure-resistant reactor, and a reduction treatment step was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Thereafter, the raw material having the composition shown in Table 4 obtained by mixing 1,6-hexanediol, hexamethyleneimine and the recovered liquid obtained above, and 33.6 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 2 hours. Table 4 shows the composition of the reaction solution obtained. In this example, 46 mol % of raw material components were consumed and hexamethylenediamine was obtained with a yield of 36 mol % and a selectivity of 78 mol %.
［実施例１１］
触媒調製：塩化ルテニウムと塩化白金酸を水溶媒に溶解させた後、ジルコニア担体（第一稀元素化学工業社製品 ＲＣ－１００）に含侵法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、５ｗｔ％Ｒｕ＊５ｗｔ％Ｐｔ／ＺｒＯ2を得た。
[Example 11]
Catalyst preparation: After dissolving ruthenium chloride and chloroplatinic acid in an aqueous solvent, they were supported on a zirconia carrier (product of Daiichi Kigenso Kagaku Kogyo RC-100) by an impregnation method. The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was collected under the atmosphere to obtain 5 wt% Ru*5 wt% Pt/ZrO 2 .
回収液の調製：耐圧反応器に５ｗｔ％Ｒｕ＊５ｗｔ％Ｐｔ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール４．０ｇ、アンモニアを１，６－ヘキサンジオールに対して３３．５当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。この時、ヘキサメチレンジアミンの収率は２２ｍｏｌ％、選択率は２８ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 2.0 g of 5 wt% Ru*5 wt% Pt/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen of 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 33.5 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at 1.0 MPa at room temperature, and reaction was carried out at 180° C. for 2 hours. At this time, the yield of hexamethylenediamine was 22 mol % and the selectivity was 28 mol %. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に５ｗｔ％Ｒｕ＊５ｗｔ％Ｐｔ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表５の組成の原料と、当該原料に対して３３．１当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で４時間反応を行った。表５に得られた反応液組成を示した。本実施例では、４０ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率２５ｍｏｌ％、選択率６３ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 5 wt % Ru*5 wt % Pt/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a starting material having the composition shown in Table 5, and 33.1 equivalents of ammonia with respect to the starting material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 4 hours. Table 5 shows the composition of the reaction solution obtained. In this example, 40 mol % of the starting material was consumed, and hexamethylenediamine was obtained with a yield of 25 mol % and a selectivity of 63 mol %.
［実施例１２］
触媒調製：塩化ルテニウムと塩化金酸を水溶媒に溶解させた後、ジルコニア担体（第一稀元素化学工業社製品 ＲＣ－１００）に含侵法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、５ｗｔ％Ａｕ＊５ｗｔ％Ｒｕ／ＺｒＯ2を得た。
[Example 12]
Catalyst preparation: After dissolving ruthenium chloride and chloroauric acid in a water solvent, they were supported on a zirconia carrier (product of Daiichi Kigenso Kagaku Kogyo RC-100) by an impregnation method. The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was collected under the atmosphere to obtain 5 wt% Au*5 wt% Ru/ZrO 2 .
回収液の調製：耐圧反応器に５ｗｔ％Ａｕ＊５ｗｔ％Ｒｕ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール４．０ｇ、アンモニアを１，６－ヘキサンジオールに対して３３．９当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。この時、ヘキサメチレンジアミンの収率は２１ｍｏｌ％、選択率は２８ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 2.0 g of 5 wt% Au*5 wt% Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen of 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 33.9 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at 1.0 MPa at room temperature, and reaction was carried out at 180° C. for 2 hours. At this time, the yield of hexamethylenediamine was 21 mol % and the selectivity was 28 mol %. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に５ｗｔ％Ａｕ＊５ｗｔ％Ｒｕ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表５の組成の原料と、当該原料に対して３４．３当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で４時間反応を行った。表５に得られた反応液組成を示した。本実施例では、４０ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率２４ｍｏｌ％、選択率６０ｍｏｌ％で得られた。
［実施例１３］
触媒調製：塩化ルテニウムを水溶媒に溶解させた後、ジルコニア担体（第一稀元素化学工業社製品 ＲＣ－１００）に含侵法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、５ｗｔ％Ｒｕ／ＺｒＯ2を得た。
[Example 13]
Catalyst preparation: After dissolving ruthenium chloride in a water solvent, it was supported on a zirconia carrier (product of Daiichi Kigenso Kagaku Kogyo RC-100) by an impregnation method. The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was recovered under air to obtain 5 wt% Ru/ZrO 2 .
回収液の調製：耐圧反応器に５ｗｔ％Ｒｕ／ＺｒＯ2を２．０ｇ、１，６－ヘキサンジオール４．０ｇ、アンモニアを１，６－ヘキサンジオールに対して６５．９当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。この時、ヘキサメチレンジアミンの収率は２６ｍｏｌ％、選択率は３６ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 2.0 g of 5 wt% Ru/ZrO 2 , 4.0 g of 1,6-hexanediol, 65.9 equivalents of ammonia to 1,6-hexanediol were added to a pressure-resistant reactor, and hydrogen was added to room temperature. After charging to 1.0 MPa, reaction was carried out at 180° C. for 2 hours. At this time, the yield of hexamethylenediamine was 26 mol % and the selectivity was 36 mol %. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に５ｗｔ％Ｒｕ／ＺｒＯ2を２．０ｇ、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表６の組成の原料と、当該原料に対して６４．９当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表６に得られた反応液組成を示した。本実施例では、５４ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３３ｍｏｌ％、選択率６１ｍｏｌ％で得られた。 Reaction evaluation: Raw materials having the composition shown in Table 6 obtained by mixing 2.0 g of 5 wt% Ru/ZrO 2 , 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above in a pressure-resistant reactor, A pressure-resistant reactor was charged with 64.9 equivalents of ammonia with respect to the raw material, filled with hydrogen at room temperature to 1.0 MPa, and then reacted at 180° C. for 2 hours. Table 6 shows the composition of the reaction solution obtained. In this example, 54 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 33 mol % and a selectivity of 61 mol %.
［実施例１４］
触媒調製：硝酸ニッケル六水和物を水溶媒に溶解させた後、ジルコニア担体（第一稀元素化学工業社製品 ＲＣ－１００）に含侵法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、１０ｗｔ％Ｎｉ／ＺｒＯ2を得た。
[Example 14]
Catalyst preparation: After dissolving nickel nitrate hexahydrate in a water solvent, it was supported on a zirconia carrier (product of Daiichi Kigenso Kagaku Kogyo RC-100) by an impregnation method. The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was collected under air to obtain 10 wt% Ni/ZrO 2 .
回収液の調製：耐圧反応器に１０ｗｔ％Ｎｉ／ＺｒＯ２を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール４．０ｇ、アンモニアを１，６－ヘキサンジオールに対して６３．１当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で８時間反応を行った。この時、ヘキサメチレンジアミンの収率は２３ｍｏｌ％、選択率は２５ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 2.0 g of 10 wt% Ni/ZrO2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180°C under hydrogen of 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 63.1 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at 1.0 MPa at room temperature, and reaction was carried out at 180° C. for 8 hours. At this time, the yield of hexamethylenediamine was 23 mol % and the selectivity was 25 mol %. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表６の組成の原料と、当該原料に対して６６．３当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で８時間反応を行った。表６に得られた反応液組成を示した。本実施例では、４４ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３３ｍｏｌ％、選択率７５ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Thereafter, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 6, and 66.3 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 8 hours. Table 6 shows the composition of the reaction solution obtained. In this example, 44 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 33 mol % and a selectivity of 75 mol %.
［実施例１５］
触媒調製：硝酸コバルト六水和物を水溶媒に溶解させた後、ジルコニア担体（第一稀元素化学工業社製品 ＲＣ－１００）に含侵法で担持させた。得られた粉末を３００℃で２時間空気焼成した後、水素流通下、３００℃で２時間加熱した。その後、粉末を大気下で回収し、１０ｗｔ％Ｃｏ／ＺｒＯ2を得た。
[Example 15]
Catalyst preparation: After dissolving cobalt nitrate hexahydrate in a water solvent, it was supported on a zirconia carrier (product of Daiichi Kigenso Kagaku Kogyo RC-100) by an impregnation method. The obtained powder was calcined in air at 300° C. for 2 hours, and then heated at 300° C. for 2 hours under hydrogen flow. After that, the powder was collected under air to obtain 10 wt% Co/ZrO2.
回収液の調製：耐圧反応器に１０ｗｔ％Ｃｏ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール４．０ｇ、アンモニアを１，６－ヘキサンジオールに対して６３．１当量加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で８時間反応を行った。この時、ヘキサメチレンジアミンの収率は２５ｍｏｌ％、選択率は２８ｍｏｌ％であった。本反応の反応液を蒸留することにより、水、ヘキサメチレンジアミン、ヘキサメチレンイミンを除去した回収液を得た。 Preparation of recovered liquid: 2.0 g of 10 wt % Co/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Then, 4.0 g of 1,6-hexanediol and 63.1 equivalents of ammonia with respect to 1,6-hexanediol were added, hydrogen was charged at 1.0 MPa at room temperature, and reaction was carried out at 180° C. for 8 hours. At this time, the yield of hexamethylenediamine was 25 mol% and the selectivity was 28 mol%. A recovered liquid from which water, hexamethylenediamine and hexamethyleneimine were removed was obtained by distilling the reaction liquid of this reaction.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミンおよび上記で得た回収液を混合して得られた表６の組成の原料と、当該原料に対して６５．３当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で８時間反応を行った。表６に得られた反応液組成を示した。本実施例では、４０ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３２ｍｏｌ％、選択率８０ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Co/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Thereafter, 1,6-hexanediol, hexamethyleneimine, and the recovered liquid obtained above were mixed to obtain a raw material having the composition shown in Table 6, and 65.3 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. In addition, hydrogen was charged to 1.0 MPa at room temperature, and then the reaction was carried out at 180° C. for 8 hours. Table 6 shows the composition of the reaction solution obtained. In this example, 40 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 32 mol % and a selectivity of 80 mol %.
［実施例１６］
触媒調製：実施例１と同様の調製法で１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を得た。
[Example 16]
Catalyst preparation: 10wt%Co* 2.5wt %Pt/ZrO2 was obtained by the same preparation method as in Example 1.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン重合体（ビスヘキサメチレントリアミン）を混合して得られた表７の組成の原料と、当該原料に対して６４．９当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表７に得られた反応液組成を示した。本実施例では、４９ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３６ｍｏｌ％、選択率７３ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Co*2.5 wt % Pt/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180° C. under hydrogen of 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, 6-aminohexanol, hexamethylenediamine polymer (bishexamethylenetriamine) was mixed with the raw material having the composition shown in Table 7, and 64 0.9 equivalent of ammonia was added to the pressure-resistant reactor, hydrogen was charged at room temperature to 1.0 MPa, and then the reaction was carried out at 180° C. for 2 hours. Table 7 shows the composition of the reaction solution obtained. In this example, 49 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 36 mol % and a selectivity of 73 mol %.
［実施例１７］
触媒調製：実施例６と同様の調製法で１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを得た。
[Example 17]
Catalyst preparation: 10 wt% Ni*2.5 wt% Pt/YSZ was obtained by the same preparation method as in Example 6.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン重合体（ビスヘキサメチレントリアミン）を混合して得られた表７の組成の原料と、当該原料に対して３４．０当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表７に得られた反応液組成を示した。本実施例では、４７ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率３９ｍｏｌ％、選択率８３ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni*2.5 wt % Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, 6-aminohexanol, and hexamethylenediamine polymer (bishexamethylenetriamine) were mixed to obtain raw materials having the composition shown in Table 7, and 34 0 equivalent of ammonia was added to the pressure-resistant reactor, hydrogen was charged at room temperature to 1.0 MPa, and then the reaction was carried out at 180° C. for 2 hours. Table 7 shows the composition of the reaction solution obtained. In this example, 47 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 39 mol % and a selectivity of 83 mol %.
［実施例１８］
触媒調製：実施例９と同様の調製法で１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｉｒ／ＹＳＺを得た。
[Example 18]
Catalyst preparation: 10 wt% Ni*2.5 wt% Ir/YSZ was obtained by the same preparation method as in Example 9.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｉｒ／ＹＳＺを２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１６０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン重合体（ビスヘキサメチレントリアミン）を混合して得られた表７の組成の原料と、当該原料に対して９．１当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１６０℃で２時間反応を行った。表７に得られた反応液組成を示した。本実施例では、３１ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率２１ｍｏｌ％、選択率６８ｍｏｌ％で得られた。 Reaction evaluation: 2.0 g of 10 wt % Ni*2.5 wt % Ir/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 160° C. under hydrogen of 1 MPaG and water solvent. Then, 1,6-hexanediol, hexamethyleneimine, 6-aminohexanol, and hexamethylenediamine polymer (bishexamethylenetriamine) were mixed to obtain raw materials having the composition shown in Table 7, and 9 .1 equivalent of ammonia was added to the pressure-resistant reactor, hydrogen was charged at room temperature to 1.0 MPa, and then the reaction was carried out at 160° C. for 2 hours. Table 7 shows the composition of the reaction solution obtained. In this example, 31 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 21 mol % and a selectivity of 68 mol %.
［実施例１９］
触媒調製：実施例１１と同様の調製法で５ｗｔ％Ｒｕ＊５ｗｔ％Ｐｔ／ＺｒＯ2を得た。
[Example 19]
Catalyst preparation: 5wt%Ru * 5wt%Pt/ZrO2 was obtained by the same preparation method as in Example 11.
反応評価：耐圧反応器に５ｗｔ％Ｒｕ＊５ｗｔ％Ｐｔ／ＺｒＯ2を２．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、１，６－ヘキサンジオール、ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン重合体（ビスヘキサメチレントリアミン）を混合して得られた表７の組成の原料と、当該原料に対して３２．４当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で４時間反応を行った。表７に得られた反応液組成を示した。本実施例では、４３ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率２６ｍｏｌ％、選択率６０ｍｏｌ％で得られた。
［実施例２０］
触媒調製：実施例３と同様の調製法で１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を得た。
[Example 20]
Catalyst preparation: 10wt%Co* 2.5wt %Ru/ZrO2 was obtained by the same preparation method as in Example 3.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、ヘキサメチレンイミンとヘキサメチレンイミンに対して６４．７当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表８に得られた反応液組成を示した。本実施例では、７０ｍｏｌ％の原料成分が消費されヘキサメチレンジアミンが収率４５ｍｏｌ％、選択率６４ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180° C. under hydrogen of 1 MPaG and water solvent. After that, hexamethyleneimine and 64.7 equivalents of ammonia with respect to hexamethyleneimine were added to the pressure-resistant reactor, hydrogen was charged at room temperature to 1.0 MPa, and reaction was carried out at 180° C. for 2 hours. Table 8 shows the composition of the reaction solution obtained. In this example, 70 mol % of raw material components were consumed and hexamethylenediamine was obtained with a yield of 45 mol % and a selectivity of 64 mol %.
［実施例２１］
触媒調製：実施例３と同様の調製法で１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を得た。
[Example 21]
Catalyst preparation: 10wt%Co* 2.5wt %Ru/ZrO2 was obtained by the same preparation method as in Example 3.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、ヘキサメチレンイミンと１，６－ヘキサンジオールとの混合原料と、当該原料に対して６６．２当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表８に得られた反応液組成を示した。本実施例では、７０ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率４３ｍｏｌ％、選択率６１ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was carried out at 180° C. under hydrogen of 1 MPaG and water solvent. After that, a mixed raw material of hexamethyleneimine and 1,6-hexanediol and 66.2 equivalents of ammonia with respect to the raw material were added to a pressure-resistant reactor. for 2 hours. Table 8 shows the composition of the reaction solution obtained. In this example, 70 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 43 mol % and a selectivity of 61 mol %.
［実施例２２］
触媒調製：実施例３と同様の調製法で１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を得た。
[Example 22]
Catalyst preparation: 10wt%Co* 2.5wt %Ru/ZrO2 was obtained by the same preparation method as in Example 3.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、ヘキサメチレンイミンと１，６－ヘキサンジオールとの混合原料と、当該原料に対して６７．４当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表８に得られた反応液組成を示した。本実施例では、６２ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率４６ｍｏｌ％、選択率７４ｍｏｌ％で得られた。
［実施例２３］
触媒調製：実施例３と同様の調製法で１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を得た。
[Example 23]
Catalyst preparation: 10wt%Co* 2.5wt %Ru/ZrO2 was obtained by the same preparation method as in Example 3.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｒｕ／ＺｒＯ2を１．０ｇ加え、水素１０ＭＰａＧ、水溶媒下、１６０℃で還元処理を行った。その後、ヘキサメチレンジアミン重合体（ビスヘキサメチレントリアミン）とヘキサメチレンジアミン重合体に対して３２．５当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１６０℃で２時間反応を行った。表９に得られた反応液組成を示した。本実施例では、２０ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率１３ｍｏｌ％、選択率６５ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Ru/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 160° C. under hydrogen of 10 MPaG and water solvent. After that, a hexamethylenediamine polymer (bishexamethylenetriamine) and 32.5 equivalents of ammonia with respect to the hexamethylenediamine polymer were added to the pressure-resistant reactor, hydrogen was charged at room temperature to 1.0 MPa, and then the reaction was carried out at 160°C. The reaction was carried out for 2 hours. Table 9 shows the composition of the reaction solution obtained. In this example, 20 mol % of the starting material was consumed, and hexamethylenediamine was obtained with a yield of 13 mol % and a selectivity of 65 mol %.
［実施例２４］
触媒調製：実施例１と同様の調製法で１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を得た。
[Example 24]
Catalyst preparation: 10wt%Co* 2.5wt %Pt/ZrO2 was obtained by the same preparation method as in Example 1.
反応評価：耐圧反応器に１０ｗｔ％Ｃｏ＊２．５ｗｔ％Ｐｔ／ＺｒＯ2を１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、ヘキサメチレンジアミン重合体（ビスヘキサメチレントリアミン）とヘキサメチレンジアミン重合体に対して３４．３当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表９に得られた反応液組成を示した。本実施例では、２６ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率１６ｍｏｌ％、選択率６２ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Co*2.5 wt % Pt/ZrO 2 was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under 1 MPaG of hydrogen and water solvent. After that, a hexamethylenediamine polymer (bishexamethylenetriamine) and 34.3 equivalents of ammonia with respect to the hexamethylenediamine polymer were added to the pressure-resistant reactor, hydrogen was charged at room temperature to 1.0 MPa, and then the reaction was carried out at 180°C. The reaction was carried out for 2 hours. Table 9 shows the composition of the reaction solution obtained. In this example, 26 mol % of raw material components were consumed, and hexamethylenediamine was obtained with a yield of 16 mol % and a selectivity of 62 mol %.
［実施例２５］
触媒調製：実施例６と同様の調製法で１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを得た。
[Example 25]
Catalyst preparation: 10 wt% Ni*2.5 wt% Pt/YSZ was obtained by the same preparation method as in Example 6.
反応評価：耐圧反応器に１０ｗｔ％Ｎｉ＊２．５ｗｔ％Ｐｔ／ＹＳＺを１．０ｇ加え、水素１ＭＰａＧ、水溶媒下、１８０℃で還元処理を行った。その後、ヘキサメチレンジアミン重合体（ビスヘキサメチレントリアミン）とヘキサメチレンジアミン重合体に対して３２．５当量のアンモニアとを耐圧反応器に加え、水素を室温で１．０ＭＰａ充填した後、１８０℃で２時間反応を行った。表９に得られた反応液組成を示した。本実施例では、３０ｍｏｌ％の原料成分が消費され、ヘキサメチレンジアミンが収率１８ｍｏｌ％、選択率６０ｍｏｌ％で得られた。 Reaction evaluation: 1.0 g of 10 wt % Ni*2.5 wt % Pt/YSZ was added to a pressure-resistant reactor, and reduction treatment was performed at 180° C. under hydrogen of 1 MPaG and water solvent. After that, a hexamethylenediamine polymer (bishexamethylenetriamine) and 32.5 equivalents of ammonia with respect to the hexamethylenediamine polymer were added to a pressure-resistant reactor, hydrogen was charged at room temperature to 1.0 MPa, and then the reaction was carried out at 180°C. The reaction was carried out for 2 hours. Table 9 shows the composition of the reaction solution obtained. In this example, 30 mol % of the starting material was consumed, and hexamethylenediamine was obtained with a yield of 18 mol % and a selectivity of 60 mol %.
Claims (6)
（ｉ）ヘキサメチレンイミン
（ｉｉ）ヘキサメチレンイミン、６－アミノヘキサノール、ヘキサメチレンジアミン、及び１，６－ヘキサンジオールからなる群から選ばれた１種以上の化合物の縮合体 The following (i ) and (ii).
(i) hexamethyleneimine (ii) condensates of one or more compounds selected from the group consisting of hexamethyleneimine, 6-aminohexanol, hexamethylenediamine, and 1,6-hexanediol
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