JP5659860B2 - Palladium-containing catalyst for hydrogenating nitrile compound and method for hydrogenating nitrile compound using the catalyst - Google Patents
Palladium-containing catalyst for hydrogenating nitrile compound and method for hydrogenating nitrile compound using the catalyst Download PDFInfo
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- JP5659860B2 JP5659860B2 JP2011042011A JP2011042011A JP5659860B2 JP 5659860 B2 JP5659860 B2 JP 5659860B2 JP 2011042011 A JP2011042011 A JP 2011042011A JP 2011042011 A JP2011042011 A JP 2011042011A JP 5659860 B2 JP5659860 B2 JP 5659860B2
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- palladium
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- gold
- nitrile compound
- alumina
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 146
- 239000003054 catalyst Substances 0.000 title claims description 75
- 229910052763 palladium Inorganic materials 0.000 title claims description 72
- -1 nitrile compound Chemical class 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 27
- 239000010931 gold Substances 0.000 claims description 35
- 229910052737 gold Inorganic materials 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims description 29
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 description 34
- 150000003141 primary amines Chemical class 0.000 description 34
- 239000012266 salt solution Substances 0.000 description 30
- 229910044991 metal oxide Inorganic materials 0.000 description 21
- 150000004706 metal oxides Chemical class 0.000 description 21
- 150000002940 palladium Chemical class 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 13
- 229910000510 noble metal Inorganic materials 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002941 palladium compounds Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- 150000002344 gold compounds Chemical class 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 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 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product 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
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940080262 sodium tetrachloroaurate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N Valeric acid Natural products CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明はニトリル化合物から第一級アミンを高選択率で製造するためのパラジウム含有触媒およびニトリル化合物の水素化方法に関する。 The present invention relates to a palladium-containing catalyst and a method for hydrogenating a nitrile compound for producing a primary amine from a nitrile compound with high selectivity.
第一級アミンは、有機溶剤、医薬、農薬、及び合成樹脂原料としての用途を有し、工業的に極めて重要な物質である。故に、有機ニトリル化合物の接触水素化による第一級アミンへの変換反応は、種々のアミンを製造する手法として古くより用いられている重要な反応である。この反応は、通常、種々の金属触媒（Co、Ni、Rh、Pd、Pt等）を用いて、多くの場合液相中にて行なわれており、例えば、ナイロンの原料として重要な化合物であるヘキサメチレンジアミンの製造は、Co触媒またはNi触媒を使用してアジポニトリルの水素化により製造されている。 Primary amines are industrially extremely important substances that have uses as organic solvents, pharmaceuticals, agricultural chemicals, and synthetic resin raw materials. Therefore, the conversion reaction to the primary amine by catalytic hydrogenation of an organic nitrile compound is an important reaction that has been used for a long time as a technique for producing various amines. This reaction is usually carried out in a liquid phase using various metal catalysts (Co, Ni, Rh, Pd, Pt, etc.), and is an important compound as a raw material for nylon, for example. Hexamethylenediamine is produced by hydrogenation of adiponitrile using a Co catalyst or Ni catalyst.
しかしながら、有機ニトリル化合物の水素化では、第一級アミンの生成に伴って、対応する第二級アミン及び第三級アミンも容易に生成することが知られている。これら第二級アミン及び第三級アミンは下記式に示すようにして生成する。即ち、有機ニトリル化合物が水素化されて生成するアルドイミンに第一アミンが反応して、アンモニアが脱離するとアゾメチンが生成する。アゾメチンは水素化されて第二級アミンとなる。また、第二級アミン自身もアルドイミン中間体に付加することができ、これにより第三級アミンが生成する。 However, it is known that in the hydrogenation of an organic nitrile compound, the corresponding secondary amine and tertiary amine are easily generated with the generation of the primary amine. These secondary amines and tertiary amines are produced as shown in the following formula. That is, azomethine is produced when primary amine reacts with aldoimine produced by hydrogenation of an organic nitrile compound and ammonia is eliminated. Azomethine is hydrogenated to a secondary amine. Secondary amines themselves can also be added to the aldoimine intermediate, thereby producing a tertiary amine.
生成するアミンの割合は触媒、pH、温度、圧力、溶媒などの反応条件によって大きく異なり、第一級アミンを選択的に得るためには触媒及び反応条件の選択が重要となる。一般に、第一級アミンを主に得るためには、アンモニア等の強アルカリ剤、あるいは塩酸等の強酸の共存下で、高温高圧条件で反応を行なう必要がある。 The proportion of amine produced varies greatly depending on the reaction conditions such as the catalyst, pH, temperature, pressure, and solvent, and selection of the catalyst and reaction conditions is important in order to selectively obtain primary amines. In general, in order to mainly obtain primary amines, it is necessary to carry out the reaction under high-temperature and high-pressure conditions in the presence of a strong alkaline agent such as ammonia or a strong acid such as hydrochloric acid.
例えば、特許文献１では、アジポニトリルの水素化によるヘキサメチレンジアミンの製造において、アンモニア共存下でラネーコバルト触媒を用いて水素圧6.9〜21 MPa(=68〜207 atm)、反応温度120℃で行なわれる製造方法が開示されている。 For example, in Patent Document 1, the production of hexamethylenediamine by hydrogenation of adiponitrile is carried out using a Raney cobalt catalyst in the presence of ammonia at a hydrogen pressure of 6.9 to 21 MPa (= 68 to 207 atm) and a reaction temperature of 120 ° C. A manufacturing method is disclosed.
特許文献２または３では、アンモニア共存下でラネーニッケル触媒あるいは他の金属元素がドープされたラネーニッケル触媒を用いてニトリルの水素化が行われている。 In Patent Document 2 or 3, nitrile hydrogenation is performed using a Raney nickel catalyst or a Raney nickel catalyst doped with another metal element in the presence of ammonia.
さらに、近年では、アルカリ金属炭酸塩あるいはアルカリ金属炭酸水素塩で変性せしめたラネーニッケル触媒を用いることで、アンモニア非共存下で水素圧1 MPa(=9.9 atm)、反応温度125℃の条件でラウロニトリルから対応する第一級アミンを選択的に合成する製造例も報告されている（特許文献４）。 Furthermore, in recent years, by using a Raney nickel catalyst modified with alkali metal carbonate or alkali metal bicarbonate, lauronitrile is used under the conditions of hydrogen pressure 1 MPa (= 9.9 atm) and reaction temperature 125 ° C in the absence of ammonia. A production example for selectively synthesizing a corresponding primary amine from the above has also been reported (Patent Document 4).
また、第二級アミンおよび第三級アミンの生成反応が比較的起こりにくい芳香環に直接シアノ基が結合したニトリル化合物に関しては、塩化アンモニウムおよびアンモニアの存在下でラネーニッケル触媒を用いて、水素圧0.88 MPa(=8.7 atm)、反応温度40℃という比較的穏和な条件下で対応する第一級アミンを選択的に与える反応例も報告されている(特許文献５)。 In addition, regarding a nitrile compound in which a cyano group is directly bonded to an aromatic ring in which secondary amine and tertiary amine formation reactions are relatively unlikely, a Raney nickel catalyst is used in the presence of ammonium chloride and ammonia, and a hydrogen pressure of 0.88 is used. A reaction example in which a corresponding primary amine is selectively given under a relatively mild condition of MPa (= 8.7 atm) and a reaction temperature of 40 ° C. has been reported (Patent Document 5).
従来から知られている有機ニトリル化合物の水素化による第一級アミンへの選択的変換は、第二級アミンおよび第三級アミンの生成を抑制するために、多くの場合、高温高圧条件、アンモニアの共存といった過酷な反応条件を要する。そのため、製造に使用する設備には高温高圧条件に耐え得る材質の反応容器を使用する必要があり、また、安全面での厳重な対策が不可欠である。さらには、従前の方法で広く用いられているコバルト触媒またはニッケル触媒は、空気雰囲気下で極めて不安定であり、触媒の取扱いが困難である点も課題の一つであるといえる。これに対して、空気雰囲気下で安定に取り扱うことができる固体触媒を用いて、常温常圧に近い穏和な反応条件で該反応を実施できれば、工業的に有用である。 In order to suppress the formation of secondary and tertiary amines, the selective conversion of conventionally known organic nitrile compounds to primary amines by hydrogenation often involves high temperature and high pressure conditions, ammonia. Requires harsh reaction conditions such as coexistence of Therefore, it is necessary to use a reaction vessel made of a material that can withstand high-temperature and high-pressure conditions for the equipment used for manufacturing, and strict measures in terms of safety are indispensable. Furthermore, it can be said that the cobalt catalyst or nickel catalyst widely used in the conventional method is extremely unstable in an air atmosphere, and it is difficult to handle the catalyst. On the other hand, it is industrially useful if the reaction can be carried out under mild reaction conditions close to normal temperature and pressure using a solid catalyst that can be handled stably in an air atmosphere.
従って、本発明の目的は、ニトリル化合物の水素化反応に用いた場合に、常温常圧に近
い穏和な条件下で高い原料転化率と優れた第一級アミンへの選択性とを示し、且つ空気雰
囲気下で安定に取り扱うことができるパラジウム含有触媒および該触媒を用いたニトリル化合物の水素化方法を提供することにある。
Therefore, the object of the present invention is to provide a high raw material conversion rate and excellent selectivity to a primary amine under mild conditions close to normal temperature and normal pressure when used in a hydrogenation reaction of a nitrile compound, and to provide a hydrogenation how nitrile compound using a palladium-containing catalyst and the catalyst which can be handled stably in air atmosphere.
本発明者らは鋭意検討した結果、下記の触媒および水素化方法により上記の目的を達成することができることを見出し、本発明を完成するに至った。
即ち、本発明は第一に、アルミナと、該アルミナに担持されたパラジウムとを有してなり、該アルミナに担持された金を更に含み、脂肪族ニトリル化合物から脂肪族第一級アミンを得ることのできるニトリル化合物水素化用触媒を提供する。
本発明は第二に、上記触媒の存在下、脂肪族ニトリル化合物を水素雰囲気中にて湿式で水素化し、脂肪族第一級アミンを得ることを含むニトリル化合物の水素化方法を提供する。
As a result of intensive studies, the present inventors have found that the above object can be achieved by the following catalyst and hydrogenation method, and have completed the present invention.
That is, the present invention first, and alumina, will have the palladium supported on the alumina, further saw including a gold supported on the alumina, the aliphatic primary amine from an aliphatic nitrile compound It provides nitrile compound hydrogenation catalyst which can give Rukoto.
The present invention is the second, the presence of the catalyst, the aliphatic nitrile compound is hydrogenated in a wet C. in a hydrogen atmosphere, to provide a process for hydrogenating nitrile compounds containing Rukoto give aliphatic primary amine.
本発明のパラジウム含有触媒によれば、穏和な反応条件の下、高い転化率かつ優れた選択性でニトリル化合物から第一級アミンを製造することができる。本発明のパラジウム含有触媒は、パラジウムに加えて金が担持されていると、より高い選択性を発揮しやすい。本発明のパラジウム含有触媒は空気雰囲気下で安定であり、取り扱いが容易である。 According to the palladium-containing catalyst of the present invention, a primary amine can be produced from a nitrile compound with a high conversion rate and excellent selectivity under mild reaction conditions. The palladium-containing catalyst of the present invention tends to exhibit higher selectivity when gold is supported in addition to palladium. The palladium-containing catalyst of the present invention is stable in an air atmosphere and easy to handle.
本明細書において、ニトリル化合物の転化率とは、水素化反応において基質として使用した全ニトリル化合物に対する、該反応で消費されたニトリル化合物のモル比をいい、第一級アミンの選択率とは、全反応生成物における第一級アミンのモル比をいう。 In the present specification, the conversion rate of the nitrile compound refers to the molar ratio of the nitrile compound consumed in the reaction to the total nitrile compound used as a substrate in the hydrogenation reaction, and the selectivity of the primary amine is Refers to the molar ratio of primary amine in the total reaction product.
本発明のパラジウム含有触媒(以下、「本発明の触媒」と略すこともある。)は、ニトリル化合物から第一級アミンを高選択率で得ることのできるニトリル化合物水素化用触媒である。本発明において「第一級アミンを高選択率で得る」とは、第一級アミンを、通常、６５〜１００％、好ましくは７０〜１００％、より好ましくは７５〜１００％、更により好ましくは８０〜１００％、特に好ましくは８５〜１００％の選択率で得ることを意味する。 The palladium-containing catalyst of the present invention (hereinafter sometimes abbreviated as “the catalyst of the present invention”) is a nitrile compound hydrogenation catalyst capable of obtaining a primary amine from a nitrile compound with high selectivity. In the present invention, “obtaining a primary amine with high selectivity” means that the primary amine is usually 65 to 100%, preferably 70 to 100%, more preferably 75 to 100%, and still more preferably. It means to obtain with a selectivity of 80 to 100%, particularly preferably 85 to 100%.
［担体］
本発明の触媒において、金属酸化物は担体として用いられるものであり、例えば、ジル
コニア、チタニア、セリア、シリカ、マグネシア、アルミナが挙げられ、好ましくはアル
ミナである。
[Carrier]
In the catalyst of the present invention, the metal oxide is used as a support, and examples thereof include zirconia, titania, ceria, silica, magnesia, and alumina, and preferably alumina .
金属酸化物の比表面積は300m2/g以下が好ましく、50〜200m2/gが特に好ましい。なお、本明細書において、比表面積はＢＥＴ法で測定した値である。 The specific surface area of the metal oxide is preferably 300 m 2 / g or less, particularly preferably 50 to 200 m 2 / g. In the present specification, the specific surface area is a value measured by the BET method.
金属酸化物の粒径は、特に限定されないが、メジアン径が0.5〜500μmの範囲であることが好ましく、10〜100μmが特に好ましい。本明細書において、メジアン径はレーザー散乱法により測定した体積基準の値である。 The particle diameter of the metal oxide is not particularly limited, but the median diameter is preferably in the range of 0.5 to 500 μm, particularly preferably 10 to 100 μm. In this specification, the median diameter is a volume-based value measured by a laser scattering method.
［触媒成分］
本発明の触媒が金を含む場合には、パラジウムの担持量を該触媒が金を含まない場合に比べてほぼ半減させても、第一級アミンへの選択性を該触媒が金を含まない場合と同等レベルに維持することが容易である。よって、該触媒においてパラジウムの担持量は、該触媒が金を含む場合には、好ましくは３重量％以上（例えば、３〜３０重量％）、より好ましくは５重量％以上（例えば、５〜３０重量％）である。
該担持量が上記範囲内であると、本発明の触媒を用いて脂肪族ニトリル化合物から脂肪族第一級アミンを高選択率で得ることが容易である。
[Catalyst component]
When the catalysts of the present invention comprises gold, also the carried amount of palladium almost reduced by half as compared with the case where the catalyst does not contain gold, said catalyst contains a gold selectivity to primary amine It is easy to maintain at the same level as when there is not. Therefore, the supported amount of palladium in the catalyst is preferably 3% by weight or more (for example, 3 to 30% by weight), more preferably 5% by weight or more (for example, 5 to 30%) when the catalyst contains gold. % By weight).
When the carried weight is in the above range, it is easy to obtain the aliphatic primary amine from an aliphatic nitrile compound using the catalyst of the present invention with high selectivity.
本発明の触媒に含まれるパラジウムの比表面積は、副反応の抑制の観点から、好ましくは４０ｍ２／ｇ以上２２０ｍ２／ｇ以下、より好ましくは５０ｍ２／ｇ以上２００ｍ２／ｇ以下、更により好ましくは５０ｍ２／ｇ以上１８０ｍ２／ｇ以下である。パラジウムの比表面積が前記範囲内であると、得られる触媒による反応速度および選択性が向上しやすい。 From the viewpoint of suppressing side reactions, the specific surface area of palladium contained in the catalyst of the present invention is preferably 40 m 2 / g or more and 220 m 2 / g or less, more preferably 50 m 2 / g or more and 200 m 2 / g or less, and even more. preferably is 50 m 2 / g or more 180 m 2 / g or less. When the specific surface area of palladium is within the above range, the reaction rate and selectivity of the obtained catalyst are likely to be improved.
上記のとおりにパラジウムの比表面積を制御する方法としては、本発明の実施例に記載の還元方法の他、焼成工程を加え温度を制御する方法、焼成時の雰囲気の還元性または酸化性を制御する方法、パラジウム塩溶液またはパラジウム塩溶液と金塩溶液を金属コロイド状にする方法、パラジウム原料またはパラジウム原料と金原料としてパラジウムの有機化合物またはパラジウムの有機化合物と金の有機化合物を用いる方法、還元処理工程の時間を調整して金属原子の凝集度合いを制御する方法、パラジウム塩溶液またはパラジウム塩溶液と金塩溶液のｐＨを調整して金属成分の凝集度合いを制御する方法、パラジウム塩溶液またはパラジウム塩溶液と金塩溶液の熟成時間を調整して金属成分の凝集度合いを制御する方法、担体である金属酸化物の表面積を大きくして金属成分の分散性を向上させてパラジウムの比表面積を大きくする方法、担体である金属酸化物の表面積を小さくして金属成分の分散を抑制してパラジウムの比表面積を小さくする方法、スラリー中の金属酸化物成分の濃度を調整する方法、還元剤の濃度を調整する方法、還元剤および貴金属塩溶液（即ち、パラジウム塩溶液またはパラジウム塩溶液と金塩溶液）の一方または両方の投入速度を調整して貴金属粒子（即ち、パラジウム粒子またはパラジウム粒子と金粒子）の成長を制御する方法などが挙げられる。 As described above, as a method for controlling the specific surface area of palladium, in addition to the reduction method described in the examples of the present invention, a method of controlling the temperature by adding a calcination step, the reducibility or oxidizability of the atmosphere during calcination is controlled. A palladium salt solution or a palladium salt solution and a gold salt solution in a metal colloid, a palladium raw material or a palladium organic compound as a gold raw material or a method using a palladium organic compound and a gold organic compound as a raw material, reduction A method for controlling the degree of aggregation of metal atoms by adjusting the processing time, a method for controlling the degree of aggregation of metal components by adjusting the pH of palladium salt solution or palladium salt solution and gold salt solution, palladium salt solution or palladium Method for controlling the degree of aggregation of metal components by adjusting the aging time of salt solution and gold salt solution, metal acid as carrier To increase the specific surface area of palladium by increasing the surface area of the product to improve the dispersibility of the metal component, and to reduce the surface area of the metal oxide as the carrier and to suppress the dispersion of the metal component to reduce the specific surface area of palladium One of the method of reducing, the method of adjusting the concentration of the metal oxide component in the slurry, the method of adjusting the concentration of the reducing agent, the reducing agent and the noble metal salt solution (ie, palladium salt solution or palladium salt solution and gold salt solution) Alternatively, a method of controlling the growth of noble metal particles (that is, palladium particles or palladium particles and gold particles) by adjusting both charging speeds may be used.
本発明の触媒に含まれるパラジウムの粒子径は２．３ｎｍ以上であることが好ましく、２．８ｎｍ以上であることがより好ましい。パラジウムの粒子径は一酸化炭素吸着量の測定データより算出することができる。なお、パラジウムの粒子径の上限は１０ｎｍ程度であることが好ましい。パラジウムの粒子径の上限が１０ｎｍ程度であれば、得られる触媒による反応速度および選択性が向上しやすい。 The particle diameter of palladium contained in the catalyst of the present invention is preferably 2.3 nm or more, and more preferably 2.8 nm or more. The particle diameter of palladium can be calculated from the measurement data of the carbon monoxide adsorption amount. The upper limit of the palladium particle diameter is preferably about 10 nm. If the upper limit of the palladium particle diameter is about 10 nm, the reaction rate and selectivity of the resulting catalyst are likely to be improved.
本発明の触媒の一酸化炭素吸着量は、パラジウム１ｇ当たり５０ｍｌ以下であることが好ましく、より好ましくは４５ｍｌ以下、更に好ましくは４０ｍｌ以下である。 The amount of carbon monoxide adsorbed on the catalyst of the present invention is preferably 50 ml or less per gram of palladium, more preferably 45 ml or less, still more preferably 40 ml or less.
本発明の触媒は、金属酸化物に担持された金を更に含むことが好ましい。これにより、第一級アミンへの選択性が飛躍的に向上するため、パラジウムの節約に有効であり、効果的に省資源化を図ることができる。触媒中のパラジウム1モルに対する金のモル数、即ち、金とパラジウムのモル比は0.005〜1が好ましく、0.01〜0.5がより好ましく、0.05〜0.2が特に好ましい。 The catalyst of the present invention preferably further contains gold supported on a metal oxide. Thereby, since selectivity to primary amines is dramatically improved, it is effective in saving palladium, and resource saving can be effectively achieved. The number of moles of gold relative to 1 mole of palladium in the catalyst, that is, the mole ratio of gold and palladium is preferably 0.005 to 1, more preferably 0.01 to 0.5, and particularly preferably 0.05 to 0.2.
[触媒の調製方法]
金属酸化物へのパラジウムもしくはパラジウムと金の固定は、該金属酸化物にパラジウムもしくはパラジウムと金を含む溶液を接触させることにより行うことができる。
[Catalyst preparation method]
The palladium or palladium and gold can be fixed to the metal oxide by bringing the metal oxide into contact with a solution containing palladium or palladium and gold.
具体的には、本発明の触媒は、例えば、パラジウム化合物もしくはパラジウム化合物と金化合物を溶媒に溶解して得た溶液を、金属酸化物の懸濁液中に、投入量および投入時間を調整して投入し、パラジウム化合物もしくはパラジウム化合物と金化合物を吸着または含浸することにより得ることができる。パラジウムもしくはパラジウムと金を上記の吸着または含浸などの方法で金属酸化物に担持した触媒に対しては、必要に応じて還元処理を実施してもよい。湿式で還元する場合には、メタノール、ホルムアルデヒド、蟻酸などの還元剤のほか、ガス状水素を用いることができる。乾式で還元する場合にはガス状水素を用いて行うが、水素ガスを窒素等の不活性ガスで希釈して使用することも可能である。こうして、パラジウムもしくはパラジウムと金が金属酸化物に固定されたパラジウム含有触媒が得られる。パラジウムと金を金属酸化物への固定は、おのおの独立して行なってもよいが、同時に行うことが好ましい。 Specifically, the catalyst of the present invention is prepared by, for example, adjusting a charging amount and a charging time of a solution obtained by dissolving a palladium compound or a palladium compound and a gold compound in a solvent in a suspension of a metal oxide. And adsorbed or impregnated with a palladium compound or a palladium compound and a gold compound. For the catalyst in which palladium or palladium and gold are supported on the metal oxide by the above-described adsorption or impregnation method, reduction treatment may be performed as necessary. In the case of reducing in a wet manner, gaseous hydrogen can be used in addition to a reducing agent such as methanol, formaldehyde, formic acid or the like. When the reduction is performed in a dry manner, gaseous hydrogen is used, but it is also possible to dilute the hydrogen gas with an inert gas such as nitrogen. Thus, a palladium-containing catalyst in which palladium or palladium and gold are fixed to the metal oxide is obtained. Fixing of palladium and gold to the metal oxide may be performed independently, but is preferably performed at the same time.
また、本発明の触媒の調製方法において還元処理を行う場合には、金属酸化物と貴金属塩溶液との混合物中に還元剤を投入する方法、貴金属塩溶液と還元剤との混合物中に金属酸化物を投入する方法、還元剤と金属酸化物の懸濁液との混合物中に貴金属塩溶液を投入する方法、金属酸化物の懸濁液と還元剤との混合スラリー中に貴金属塩溶液を投入する方法、貴金属塩溶液と還元剤の一部もしくは全てとを混合して貴金属成分前駆体をつくった後に担体である金属酸化物および残りの還元剤（残存するならば）と混合して該金属酸化物に貴金属粒子を担持させる方法などがある。 Further, when the reduction treatment tone made a catalyst of the present invention, metal method, in admixture with a noble metal salt solution a reducing agent to be introduced into the mixture a reducing agent and a metal oxide and a noble metal salt solution A method of introducing an oxide, a method of introducing a noble metal salt solution into a mixture of a reducing agent and a suspension of a metal oxide, and a noble metal salt solution in a mixed slurry of a suspension of a metal oxide and a reducing agent. A method of charging, mixing a part or all of the noble metal salt solution and the reducing agent to form a noble metal component precursor, and then mixing with the metal oxide as a support and the remaining reducing agent (if remaining) There is a method of supporting noble metal particles on a metal oxide.
また、このような還元処理を行う触媒の調製方法では、未還元の貴金属塩が残っていれば更に還元剤を投入してもよい。更に、これらの製法において担体として使用される金属酸化物には、あらかじめ還元剤もしくは貴金属塩溶液またはその両方の一部もしくは全てを含浸させておいてもよい。
なお、本発明の触媒の調製方法において、貴金属塩溶液の投入順序、投入速度、使用される塩の種類、温度、撹拌速度、ｐＨなどの反応条件は当業者が適宜設定することができるが、最終的に出来上がる触媒におけるパラジウムの比表面積および粒子径は本明細書記載の好ましい範囲になるように調整することが好ましい。
In addition, in the method for preparing a catalyst for performing such a reduction treatment, a reducing agent may be further added if an unreduced noble metal salt remains. Further, the metal oxide used as a support in these production methods may be impregnated with a reducing agent or a noble metal salt solution or a part or all of both in advance.
In the catalyst preparation method of the present invention, the reaction conditions such as the order of addition of the noble metal salt solution, the addition speed, the type of salt used, the temperature, the stirring speed, and the pH can be appropriately set by those skilled in the art. It is preferable to adjust the specific surface area and particle diameter of palladium in the final catalyst to be within the preferable ranges described in the present specification.
触媒調製に用いる溶媒は、パラジウム化合物あるいはパラジウム化合物と金化合物を溶解するものであれば特に制限されないが、これらの化合物が水溶性である場合には水が好ましく、これらの化合物が非水溶性で有機溶媒に可溶である場合には、エタノール、アセトン、クロロホルム等の有機溶媒であって該化合物を溶解するものが好適である。 The solvent used for preparing the catalyst is not particularly limited as long as it dissolves the palladium compound or the palladium compound and the gold compound. However, when these compounds are water-soluble, water is preferable, and these compounds are water-insoluble. In the case of being soluble in an organic solvent, an organic solvent such as ethanol, acetone, chloroform or the like that dissolves the compound is suitable.
パラジウム化合物としては、触媒調製工程に使用する溶媒に可溶性であれば特に限定されないが、例えば、硝酸パラジウム、硫酸パラジウム、テトラアンミンパラジウム塩化物、テトラアンミンパラジウム臭化物、テトラアンミンパラジウム硝酸塩、テトラアンミンパラジウム硫酸塩、塩化パラジウム酸等の水溶性パラジウム化合物；ビス（２，４−ペンタンジオナト）パラジウム、ジクロロ（１，５−シクロオクタジエン）パラジウム、ジクロロビス（トリフェニルホスフィン）パラジウム、テトラキス（トリフェニルホスフィン）パラジウム、トリス（ジベンジリデンアセトン）二パラジウム等の有機溶媒可溶性パラジウム錯体が使用でき、硝酸パラジウム、塩化パラジウム酸、塩化パラジウム酸ナトリウム、ジクロロ（１，５−シクロオクタジエン）パラジウムが好ましい。パラジウム化合物は１種単独で用いても２種以上を併用してもよい。パラジウム塩溶液中のパラジウム濃度は、パラジウム塩が溶媒に完全溶解していれば特に限定されないが、例えば、１〜１０００mmol/Lが挙げられ、５〜１００mmol/Lが好ましい。 The palladium compound is not particularly limited as long as it is soluble in the solvent used in the catalyst preparation step. For example, palladium nitrate, palladium sulfate, tetraammine palladium chloride, tetraammine palladium bromide, tetraammine palladium nitrate, tetraammine palladium sulfate, palladium chloride. Water-soluble palladium compounds such as acids; bis (2,4-pentanedionato) palladium, dichloro (1,5-cyclooctadiene) palladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tris ( Organic solvent soluble palladium complexes such as dibenzylideneacetone) dipalladium can be used, palladium nitrate, chloropalladate, sodium chloropalladate, dichloro (1,5-cyclohexane) Kutajien) palladium is preferable. A palladium compound may be used individually by 1 type, or may use 2 or more types together. The palladium concentration in the palladium salt solution is not particularly limited as long as the palladium salt is completely dissolved in the solvent, and examples thereof include 1 to 1000 mmol / L, and 5 to 100 mmol / L is preferable.
金の化合物としては、触媒調製工程に使用する溶媒に可溶性であれば特に限定されないが、例えば、塩化金（III）、四塩化金酸、四塩化金酸ナトリウムおよびそれらの混合物が使用でき、四塩化金酸、四塩化金酸ナトリウムが好ましい。金化合物は１種単独で用いても２種以上を併用してもよい。金塩溶液中の金濃度は、金塩が溶媒に完全溶解していれば特に限定されないが、例えば、０．１〜１００mmol/Lが挙げられ、０．５〜１０mmol/Lが好ましい。 The gold compound is not particularly limited as long as it is soluble in the solvent used in the catalyst preparation step. For example, gold (III) chloride, tetrachloroauric acid, sodium tetrachloroaurate and a mixture thereof can be used. Chloroauric acid and sodium tetrachloroaurate are preferred. A gold compound may be used individually by 1 type, or may use 2 or more types together. The gold concentration in the gold salt solution is not particularly limited as long as the gold salt is completely dissolved in the solvent, and examples thereof include 0.1 to 100 mmol / L, and preferably 0.5 to 10 mmol / L.
パラジウム塩溶液と金塩溶液とからなる貴金属塩溶液を金属酸化物に含浸させる場合、パラジウム塩溶液と金塩溶液は、おのおの別に金属酸化物に含浸させてもよく、パラジウム塩および金塩の混合溶液として金属酸化物に含浸せてもよい。 When impregnating a metal oxide with a noble metal salt solution comprising a palladium salt solution and a gold salt solution, the palladium salt solution and the gold salt solution may be impregnated separately into the metal oxide, and a mixture of palladium salt and gold salt. The metal oxide may be impregnated as a solution.
[基質]
本発明の触媒による水素化の基質となるニトリル化合物としては、例えば、下記一般式（Ｉ）：
R1-CN （Ｉ）
（式中、R1は非置換もしくは置換のアルキル基または非置換もしくは置換のアリール基を表す。）
で表されるニトリル化合物が挙げられる。ニトリル化合物は１種単独で用いても２種以上を併用してもよい。
[Substrate]
Examples of the nitrile compound serving as a substrate for hydrogenation with the catalyst of the present invention include the following general formula (I):
R 1 -CN (I)
(In the formula, R 1 represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group.)
The nitrile compound represented by these is mentioned. A nitrile compound may be used individually by 1 type, or may use 2 or more types together.
上記R1としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、t−ブチル基、ペンチル基、ヘキシル基、オクチル基等の炭素原子数１〜２０、好ましくは３〜１０のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等の炭素原子数６〜２０のアリール基；これらの基の水素原子の一部又は全部をフッ素、臭素、塩素等のハロゲン原子、水酸基、アミノ基、カルボニル基、オキソ基（即ち、＝Ｏ）、アルコキシ基、アリロキシ基、チオール基等で置換した基、例えば、クロロメチル基、ブロモエチル基、３，３，３−トリフルオロプロピル基、ｐ−クロロフェニル基等が挙げられる。 Examples of R 1 include 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and octyl, preferably 3 to 10 An aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; a halogen atom such as fluorine, bromine or chlorine, or a hydroxyl group, part or all of the hydrogen atoms of these groups A group substituted with an amino group, a carbonyl group, an oxo group (ie, ═O), an alkoxy group, an allyloxy group, a thiol group, such as a chloromethyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group, Examples thereof include a p-chlorophenyl group.
ニトリル化合物は、好ましくは有機ニトリル化合物であり、より好ましくは脂肪族ニトリル化合物である。脂肪族ニトリル化合物としては、例えば、上記一般式（Ｉ）で表されるニトリル化合物であって、R1が非置換または置換のアルキル基であるものが挙げられる。 The nitrile compound is preferably an organic nitrile compound, and more preferably an aliphatic nitrile compound. Examples of the aliphatic nitrile compound include nitrile compounds represented by the above general formula (I), wherein R 1 is an unsubstituted or substituted alkyl group.
[反応生成物]
本発明の触媒による水素化により得られる第一級アミンとしては、例えば、下記一般式（II）：
R1-CH2-NH2 （II）
（式中、R1は前記と同様である。）
で表される第一級アミンが挙げられる。第一級アミンは、用いるニトリル化合物に応じ、１種単独でも２種以上の組み合わせでもよい。
[Reaction product]
Examples of the primary amine obtained by hydrogenation with the catalyst of the present invention include, for example, the following general formula (II):
R 1 -CH 2 -NH 2 (II)
(In the formula, R 1 is the same as described above.)
The primary amine represented by these is mentioned. The primary amine may be used alone or in combination of two or more depending on the nitrile compound used.
用いるニトリル化合物が脂肪族ニトリル化合物である場合には、第一級アミンは脂肪族第一級アミンとなる。脂肪族第一級アミンとしては、例えば、上記一般式（II）で表される第一級アミンであって、R1が非置換または置換のアルキル基であるものが挙げられる。 When the nitrile compound to be used is an aliphatic nitrile compound, the primary amine is an aliphatic primary amine. Examples of the aliphatic primary amine include primary amines represented by the above general formula (II), wherein R 1 is an unsubstituted or substituted alkyl group.
［ニトリル化合物の水素化方法］
本発明の触媒の存在下、脂肪族ニトリル化合物を水素雰囲気中にて湿式で水素化することにより、脂肪族第一級アミンを高選択率で生成させることができる。本発明の水素化方法において、本発明の触媒は１種単独で用いても２種以上を併用してもよい。
Hydrogenation how nitrile compound]
The presence of a catalyst of the present invention, by hydrogenation in the wet in a hydrogen atmosphere aliphatic nitrile compound, it is possible to generate the aliphatic primary amine at a high selectivity. In the hydrogenation method of the present invention, the catalyst of the present invention may be used alone or in combination of two or more.
上記水素化方法において本発明の触媒は、反応物であるニトリル化合物に対して、パラジウムとして、好ましくは0.01〜20モル％、より好ましくは0.1〜10モル％、更により好ましくは0.5〜5モル％の範囲で用いられる。 In the above hydrogenation method, the catalyst of the present invention is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol%, still more preferably 0.5 to 5 mol% as palladium with respect to the nitrile compound as a reactant. It is used in the range.
本明細書において「湿式にて」とは、通常、「溶媒の存在下で」を意味し、好ましくは「溶媒中で」を意味する。上記の水素化に用いる溶媒としては、例えば、テトラヒドロフラン、N,N-ジメチルホルムアミド、メタノール、酢酸などの極性有機溶媒またはこれらの組み合わせが挙げられ、酢酸などのプロトン性溶媒が特に好ましい。溶媒は１種単独で用いても２種以上を併用してもよい。 In the present specification, “in the wet state” usually means “in the presence of a solvent”, preferably “in a solvent”. Examples of the solvent used for the hydrogenation include polar organic solvents such as tetrahydrofuran, N, N-dimethylformamide, methanol, acetic acid, and combinations thereof, and a protic solvent such as acetic acid is particularly preferable. A solvent may be used individually by 1 type, or may use 2 or more types together.
本発明の水素化方法において、水素雰囲気、即ち、分子状水素を含む雰囲気の水素圧は、好ましくは0.10MPa以上1.0MPa未満(1.0atm以上9.9atm未満)、より好ましくは0.10MPa以上0.50MPa以下(1.0atm以上5.0atm以下)、更に好ましくは0.10MPa以上0.20MPa以下(1.0atm以上2.0atm以下)である。水素圧が前記範囲内であると、転化率および第一級アミン選択率が向上しやすく、また、反応系に対する安全対策が不要な場合があり、製造コストを抑えることができる場合がある。なお、反応圧力が１．０ＭＰａ以上の場合、消防法上の高圧ガス設備に該当するため、設備の仕様および設置環境への規制が厳しくなる。 In the hydrogenation method of the present invention, the hydrogen pressure of the hydrogen atmosphere, that is, the atmosphere containing molecular hydrogen, is preferably 0.10 MPa or more and less than 1.0 MPa (1.0 atm or more and less than 9.9 atm), more preferably 0.10 MPa or more and 0.50 MPa or less. (1.0 atm to 5.0 atm), more preferably 0.10 MPa to 0.20 MPa (1.0 atm to 2.0 atm). If the hydrogen pressure is within the above range, the conversion rate and the primary amine selectivity are likely to be improved, and safety measures for the reaction system may be unnecessary, and the production cost may be reduced. When the reaction pressure is 1.0 MPa or more, it corresponds to a high-pressure gas facility in accordance with the Fire Service Act, so that the specification of the facility and the regulations on the installation environment become strict.
また、本発明の水素化方法における水素化の反応温度は、好ましくは20〜100℃、より好ましくは20〜80℃、更に好ましくは20〜60℃である。反応温度が前記範囲内であると、反応速度および第一級アミン選択率が向上しやすく、また、反応系の圧力が増大しにくいので安全性の確保が容易である。 The reaction temperature of the hydrogenation in the hydrogenation process of the present invention is preferably 20 to 100 ° C., more preferably 20 to 80 ° C., more preferably 20 to 60 ° C.. When the reaction temperature is within the above range, the reaction rate and the primary amine selectivity are easily improved, and the pressure in the reaction system is hardly increased, so that it is easy to ensure safety.
以下に、本発明の実施例及び比較例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention and comparative examples are shown below, but the present invention is not limited to these examples.
（１）パラジウム担持アルミナ触媒の調製
純水を用い、担体となるアルミナを分散させて調製した懸濁液に、還元剤を添加して均一な担体懸濁液を得た。別に、塩化パラジウム酸ナトリウムを溶解したパラジウム塩の溶液を調製した。次に前記担体懸濁液にパラジウム塩の溶液を滴下して新たに懸濁液を得た。この懸濁液を60℃に加熱して還元を行った。
こうして、担体であるアルミナの表面にパラジウムの粒子を担持した。
反応液を冷却後、固形物をろ過し洗浄した。その後、乾燥を約70℃の大気中で行い、担体であるアルミナ上にパラジウムを担持した触媒を得た。
本調製ではパラジウムの理論含有量は触媒重量に対して25重量%であり、ICP分析法によるパラジウムの担持比率は触媒重量に対して25重量%であった（実施例１）。
(1) Preparation of palladium-supported alumina catalyst A reducing agent was added to a suspension prepared by dispersing alumina serving as a carrier using pure water to obtain a uniform carrier suspension. Separately, a solution of a palladium salt in which sodium chloropalladate was dissolved was prepared. Next, a palladium salt solution was added dropwise to the carrier suspension to obtain a new suspension. This suspension was heated to 60 ° C. for reduction.
Thus, palladium particles were supported on the surface of alumina as a carrier.
After cooling the reaction solution, the solid was filtered and washed. Thereafter, drying was performed in an atmosphere at about 70 ° C., and a catalyst supporting palladium on alumina as a support was obtained.
In this preparation, the theoretical content of palladium was 25% by weight with respect to the catalyst weight, and the palladium loading ratio by ICP analysis was 25% by weight with respect to the catalyst weight (Example 1).
更に、同担持比率が10重量%（実施例２）または5重量%（比較例１）である触媒も同様に調製した。 Further, a catalyst having the same loading ratio of 10% by weight (Example 2) or 5% by weight (Comparative Example 1) was similarly prepared.
なお、実施例１、実施例２および比較例１において、触媒に含まれるパラジウムの比表面積は、それぞれ１４９、１９８および２３４ｍ２／ｇであった。 In Example 1, Example 2, and Comparative Example 1, the specific surface areas of palladium contained in the catalyst were 149, 198, and 234 m 2 / g, respectively.
（２）パラジウム−金担持アルミナ触媒の調製
純水を用い、担体となるアルミナを分散させて調製した懸濁液に、還元剤を添加して均一な担体懸濁液を得た。別に、塩化パラジウム酸ナトリウムを溶解したパラジウム塩の溶液と、四塩化金酸を溶解した金塩の溶液とを混合し、適宜pHを調整して、パラジウム塩および金塩の混合溶液を調製した。次に前記担体懸濁液にパラジウム塩および金塩の混合溶液を滴下して新たに懸濁液を得た。この懸濁液を60℃に加熱して還元を行った。
こうして、担体であるアルミナの表面にパラジウムおよび金の粒子を担持した。
反応液を冷却後、固形物をろ過し洗浄した。その後、乾燥を約70℃の大気中で行い、担体であるアルミナ上にパラジウム−金を担持した触媒を得た。
本調製ではパラジウムと金との理論量比はモル比で９：１であり、ICP分析法による担持比率は触媒重量に対してパラジウム25重量%および金5重量%であった（実施例３）。
(2) Preparation of palladium-gold supported alumina catalyst Using pure water, a reducing agent was added to a suspension prepared by dispersing alumina serving as a carrier to obtain a uniform carrier suspension. Separately, a palladium salt solution in which sodium chloropalladate was dissolved and a gold salt solution in which tetrachloroauric acid was dissolved were mixed, and the pH was adjusted appropriately to prepare a mixed solution of palladium salt and gold salt. Next, a mixed solution of palladium salt and gold salt was added dropwise to the carrier suspension to obtain a new suspension. This suspension was heated to 60 ° C. for reduction.
Thus, palladium and gold particles were supported on the surface of alumina as a carrier.
After cooling the reaction solution, the solid was filtered and washed. Thereafter, drying was performed in an atmosphere at about 70 ° C., and a catalyst in which palladium-gold was supported on alumina as a carrier was obtained.
In this preparation, the theoretical amount ratio of palladium to gold was 9: 1 in terms of molar ratio, and the loading ratio by ICP analysis was 25% by weight palladium and 5% by weight gold based on the catalyst weight (Example 3). .
更に、同モル比にて、同担持比率がパラジウム10重量%および金2重量%（実施例４）、または、パラジウム5重量%および金1重量%（実施例５）である触媒も同様に調製した。 Further, a catalyst having the same molar ratio and the same loading ratio of 10% by weight of palladium and 2% by weight of gold (Example 4) or 5% by weight of palladium and 1% by weight of gold (Example 5) was also prepared in the same manner. did.
なお、実施例３、４および５において、触媒に含まれるパラジウムの比表面積は、それぞれ６５、１０４および１２０ｍ２／ｇであった。 In Examples 3, 4 and 5, the specific surface areas of palladium contained in the catalyst were 65, 104 and 120 m 2 / g, respectively.
（３）吉草酸ニトリルの水素化反応
オートクレーブに吉草酸ニトリル20 mmolと酢酸50 mLを投入し溶解させた。この溶液にパラジウムに換算して0.2 mmolの触媒を投入し、水素雰囲気下(水素圧0.15 MPa=1.48 atm)、50℃で5時間撹拌して反応を行った。反応後、触媒をろ過分離し、得られたろ液に氷冷下で水酸化ナトリウム溶液を溶液がアルカリ性を示すまで加えた。これにクロロホルムを加えて抽出し、最後に、クロロホルム層に内部標準物質であるニトロベンゼンを適当量添加し、サンプリングした。サンプリング試料をガスクロマトグラフィー(GC)にて分析した。表１に、用いた触媒、転化率および対応する第一級アミンの選択率の測定結果を示す。
(3) Hydrogenation reaction of valeric nitrile 20 mmol of valeric acid nitrile and 50 mL of acetic acid were put into an autoclave and dissolved. To this solution, 0.2 mmol of catalyst in terms of palladium was added, and the reaction was carried out by stirring at 50 ° C. for 5 hours in a hydrogen atmosphere (hydrogen pressure 0.15 MPa = 1.48 atm). After the reaction, the catalyst was separated by filtration, and sodium hydroxide solution was added to the obtained filtrate under ice-cooling until the solution became alkaline. Chloroform was added thereto for extraction, and finally, an appropriate amount of nitrobenzene as an internal standard substance was added to the chloroform layer and sampled. The sampling sample was analyzed by gas chromatography (GC). Table 1 shows the measurement results of the catalyst used, the conversion rate, and the selectivity of the corresponding primary amine.
まず始めに、Pd含有量が25重量%、10重量%または5重量%であるPd/アルミナ触媒を用いて水素化反応を実施した。その結果、いずれの触媒でも基質である吉草酸ニトリルは完全に消費された。一方で、第一級アミンの選択率は、25重量% Pd /アルミナにおいては80%を超える良好な値を示し(実施例1)、10重量% Pd /アルミナにおいては70%を超える良好な値を示したが(実施例2)、5重量% Pd /アルミナでは大幅に低下した(比較例1)。
さらに、30重量%Pd/カーボンを用いて水素化反応を実施したところ、第一級アミンの選択率は5重量％Pd/アルミナ(比較例1)での結果をも下回る低い値を示した(比較例2)。
First, a hydrogenation reaction was performed using a Pd / alumina catalyst having a Pd content of 25% by weight, 10% by weight, or 5% by weight. As a result, valeric nitrile as a substrate was completely consumed by any catalyst. On the other hand, the selectivity for primary amines showed good values above 80% at 25 wt% Pd / alumina (Example 1) and good values above 70% at 10 wt% Pd / alumina. (Example 2), but 5 wt% Pd / alumina significantly decreased (Comparative Example 1).
Furthermore, when the hydrogenation reaction was carried out using 30% by weight Pd / carbon, the selectivity for the primary amine showed a low value lower than the result with 5% by weight Pd / alumina (Comparative Example 1) ( Comparative Example 2).
次に、Pd含有量が25重量%、10重量%または5重量%であり、パラジウムと金とのモル比が９：１であるPd - Au/アルミナ触媒を用いて水素化反応を実施した。その結果、25重量% Pd - 5重量% Au/アルミナでは、第一級アミン選択率は90%という優れた値を示した(実施例3)。この値は、Pd含有量が同等の25重量％Pd/アルミナ(実施例1)に比べ優れている。10重量% Pd - 2重量% Au/アルミナは、Pd含有量が同等の10重量％Pd/アルミナ(実施例2)に比べ優れた第一級アミン選択率を示しただけでなく、Pd含有量が2.5倍の25重量％Pd/アルミナ(実施例1)と同レベルの良好な第一級アミン選択率を示した(実施例4)。5重量% Pd - 1重量% Au/アルミナは、Pd含有量が同等の5重量％Pd/アルミナ(比較例1)に比べ優れた第一級アミン選択率を示しただけでなく、Pd量が2倍の10重量%Pd/アルミナ(実施例2)と同レベルの良好な第一級アミン選択率を示した(実施例5)。
さらに、25重量% Pd - 5重量% Au/カーボンを用いて水素化反応を実施したところ、PdとAuの組成が同等である25重量% Pd - 5重量% Au/アルミナに比べて、第一級アミンの選択率が著しく低下したばかりか、5重量％Pd/アルミナ(比較例1)にも劣る結果を与えた(比較例3)。
Next, a hydrogenation reaction was carried out using a Pd—Au / alumina catalyst having a Pd content of 25% by weight, 10% by weight or 5% by weight and a molar ratio of palladium to gold of 9: 1. As a result, with 25 wt% Pd-5 wt% Au / alumina, the primary amine selectivity showed an excellent value of 90% (Example 3). This value is superior to 25 wt% Pd / alumina (Example 1) having an equivalent Pd content. 10 wt% Pd-2 wt% Au / alumina not only showed superior primary amine selectivity compared to 10 wt% Pd / alumina (Example 2) with the same Pd content, but also Pd content Exhibited 2.5 times as much primary amine selectivity as that of 25% by weight Pd / alumina (Example 1) (Example 4). 5 wt% Pd-1 wt% Au / alumina not only showed superior primary amine selectivity compared to 5 wt% Pd / alumina (Comparative Example 1) with the same Pd content, but also the amount of Pd It showed good primary amine selectivity at the same level as double 10% by weight Pd / alumina (Example 2) (Example 5).
Furthermore, when hydrogenation reaction was carried out using 25 wt% Pd-5 wt% Au / carbon, the first composition compared to 25 wt% Pd-5 wt% Au / alumina with the same composition of Pd and Au. Not only did the selectivity for the secondary amines drop significantly, but also 5 wt% Pd / alumina (Comparative Example 1) gave inferior results (Comparative Example 3).
Claims (5)
前記水素雰囲気の水素圧が０．１０MPa以上１．０MPa未満であり、
前記水素化の反応温度が２０〜１００℃である
脂肪族ニトリル化合物の水素化方法。 The presence of a catalyst according to any one of claims 1-4, the aliphatic nitrile compound is hydrogenated in a wet C. in a hydrogen atmosphere, it comprises Rukoto give aliphatic primary amine,
The hydrogen pressure of the hydrogen atmosphere is 0.10 MPa or more and less than 1.0 MPa,
The hydrogenation reaction temperature is 20-100 ° C.
A method for hydrogenating aliphatic nitrile compounds .
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