JP2008044874A - Manufacturing method of propanediol - Google Patents
Manufacturing method of propanediol Download PDFInfo
- Publication number
- JP2008044874A JP2008044874A JP2006220919A JP2006220919A JP2008044874A JP 2008044874 A JP2008044874 A JP 2008044874A JP 2006220919 A JP2006220919 A JP 2006220919A JP 2006220919 A JP2006220919 A JP 2006220919A JP 2008044874 A JP2008044874 A JP 2008044874A
- Authority
- JP
- Japan
- Prior art keywords
- propanediol
- acid
- solvent
- glycerin
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 235000011187 glycerol Nutrition 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 42
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 30
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 30
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 27
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000013772 propylene glycol Nutrition 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- -1 cyclic amide compound Chemical class 0.000 claims description 5
- 239000011973 solid acid Substances 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 15
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 150000003950 cyclic amides Chemical class 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- FQMNVNKBWNEVMK-UHFFFAOYSA-J barium(2+);platinum(2+);disulfate Chemical compound [Ba+2].[Pt+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FQMNVNKBWNEVMK-UHFFFAOYSA-J 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JQXKXXSVXKMWCR-UHFFFAOYSA-J calcium;platinum(2+);dicarbonate Chemical compound [Ca+2].[Pt+2].[O-]C([O-])=O.[O-]C([O-])=O JQXKXXSVXKMWCR-UHFFFAOYSA-J 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910003449 rhenium oxide Inorganic materials 0.000 description 2
- XZQYTGKSBZGQMO-UHFFFAOYSA-I rhenium pentachloride Chemical compound Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 1
- MTNKRTXSIXNCAP-UHFFFAOYSA-N 1-(4-butoxyphenyl)-n-[4-[2-[4-[(4-butoxyphenyl)methylideneamino]phenyl]ethyl]phenyl]methanimine Chemical compound C1=CC(OCCCC)=CC=C1C=NC(C=C1)=CC=C1CCC1=CC=C(N=CC=2C=CC(OCCCC)=CC=2)C=C1 MTNKRTXSIXNCAP-UHFFFAOYSA-N 0.000 description 1
- VAOZBWLXMFASGV-UHFFFAOYSA-L 2,2,3,3,4,4-hexafluorobutanoate;rhodium(2+) Chemical compound [Rh+2].[O-]C(=O)C(F)(F)C(F)(F)C(F)F.[O-]C(=O)C(F)(F)C(F)(F)C(F)F VAOZBWLXMFASGV-UHFFFAOYSA-L 0.000 description 1
- AZFHXIBNMPIGOD-UHFFFAOYSA-N 4-hydroxypent-3-en-2-one iridium Chemical compound [Ir].CC(O)=CC(C)=O.CC(O)=CC(C)=O.CC(O)=CC(C)=O AZFHXIBNMPIGOD-UHFFFAOYSA-N 0.000 description 1
- CSCGIFZJZYNKLV-UHFFFAOYSA-J C([O-])([O-])=O.[Ba+2].[Pt+2].C([O-])([O-])=O Chemical compound C([O-])([O-])=O.[Ba+2].[Pt+2].C([O-])([O-])=O CSCGIFZJZYNKLV-UHFFFAOYSA-J 0.000 description 1
- NVOYQERHRHCQMT-UHFFFAOYSA-L C([O-])([O-])=O.[Ca+2].[Rh+3] Chemical compound C([O-])([O-])=O.[Ca+2].[Rh+3] NVOYQERHRHCQMT-UHFFFAOYSA-L 0.000 description 1
- FAZJWINWHGHNNX-UHFFFAOYSA-L C([O-])([O-])=O.[Ca+2].[Ru+3] Chemical compound C([O-])([O-])=O.[Ca+2].[Ru+3] FAZJWINWHGHNNX-UHFFFAOYSA-L 0.000 description 1
- ZSKCYRQOFSOVNM-UHFFFAOYSA-K Cl.Cl[Ir](Cl)Cl Chemical compound Cl.Cl[Ir](Cl)Cl ZSKCYRQOFSOVNM-UHFFFAOYSA-K 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 description 1
- 229910021606 Palladium(II) iodide Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910000566 Platinum-iridium alloy Inorganic materials 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- PNVBTTRFUJULII-UHFFFAOYSA-N [C].[Pt]=S Chemical compound [C].[Pt]=S PNVBTTRFUJULII-UHFFFAOYSA-N 0.000 description 1
- SOBIOYGVHBQDRH-UHFFFAOYSA-N [O-2].[Zr+4].[Pt+2].[O-2].[O-2] Chemical compound [O-2].[Zr+4].[Pt+2].[O-2].[O-2] SOBIOYGVHBQDRH-UHFFFAOYSA-N 0.000 description 1
- JLCHNBRGUPQWKF-UHFFFAOYSA-J [OH-].[C+4].[OH-].[OH-].[OH-] Chemical compound [OH-].[C+4].[OH-].[OH-].[OH-] JLCHNBRGUPQWKF-UHFFFAOYSA-J 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WOSOOWIGVAKGOC-UHFFFAOYSA-N azanylidyneoxidanium;ruthenium(2+);trinitrate Chemical compound [Ru+2].[O+]#N.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WOSOOWIGVAKGOC-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CKWZZRQMNIOWCY-UHFFFAOYSA-N benzonitrile;dihydrochloride Chemical compound Cl.Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 CKWZZRQMNIOWCY-UHFFFAOYSA-N 0.000 description 1
- WAJRCRIROYMRKA-UHFFFAOYSA-L benzonitrile;platinum(2+);dichloride Chemical compound [Cl-].[Cl-].[Pt+2].N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WAJRCRIROYMRKA-UHFFFAOYSA-L 0.000 description 1
- RKNFJIIYAUSTJA-UHFFFAOYSA-N bis(sulfanylidene)platinum Chemical compound S=[Pt]=S RKNFJIIYAUSTJA-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- OMNLCNQUBBRPNW-UHFFFAOYSA-L calcium;iridium(3+);carbonate Chemical compound [Ca+2].[Ir+3].[O-]C([O-])=O OMNLCNQUBBRPNW-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IMXPGQMYBLTHFR-UHFFFAOYSA-L dibromorhodium hydrate Chemical compound O.Br[Rh]Br IMXPGQMYBLTHFR-UHFFFAOYSA-L 0.000 description 1
- YEPXCFHWKVNVAX-UHFFFAOYSA-N dioxoiridium;hydrate Chemical compound O.O=[Ir]=O YEPXCFHWKVNVAX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- DCFICEJAMGURSD-UHFFFAOYSA-L hexanoate;rhodium(2+) Chemical compound [Rh+2].CCCCCC([O-])=O.CCCCCC([O-])=O DCFICEJAMGURSD-UHFFFAOYSA-L 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- DZQBLSOLVRLASG-UHFFFAOYSA-N iridium;methane Chemical compound C.[Ir] DZQBLSOLVRLASG-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XKTGKMXHQPHUOL-UHFFFAOYSA-N nitrosyl chloride;ruthenium(3+);hydrate Chemical compound O.[Ru+3].ClN=O XKTGKMXHQPHUOL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- MBDHJOBKSBYBJB-UHFFFAOYSA-N oxygen(2-) platinum(2+) titanium(4+) Chemical compound [O-2].[Ti+4].[Pt+2].[O-2].[O-2] MBDHJOBKSBYBJB-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- FAUWSVSZYKETJJ-UHFFFAOYSA-N palladium titanium Chemical compound [Ti].[Pd] FAUWSVSZYKETJJ-UHFFFAOYSA-N 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- XDASSWBZWFFNPX-UHFFFAOYSA-N palladium(ii) cyanide Chemical compound [Pd+2].N#[C-].N#[C-] XDASSWBZWFFNPX-UHFFFAOYSA-N 0.000 description 1
- HNNUTDROYPGBMR-UHFFFAOYSA-L palladium(ii) iodide Chemical compound [Pd+2].[I-].[I-] HNNUTDROYPGBMR-UHFFFAOYSA-L 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- INXLGDBFWGBBOC-UHFFFAOYSA-N platinum(2+);dicyanide Chemical compound [Pt+2].N#[C-].N#[C-] INXLGDBFWGBBOC-UHFFFAOYSA-N 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- SNPHNDVOPWUNON-UHFFFAOYSA-J platinum(4+);tetrabromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Pt+4] SNPHNDVOPWUNON-UHFFFAOYSA-J 0.000 description 1
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical class [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 description 1
- KIDPOJWGQRZHFM-UHFFFAOYSA-N platinum;hydrate Chemical compound O.[Pt] KIDPOJWGQRZHFM-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- WXBOMIKEWRRKBB-UHFFFAOYSA-N rhenium(iv) oxide Chemical compound O=[Re]=O WXBOMIKEWRRKBB-UHFFFAOYSA-N 0.000 description 1
- IZVAOCKUNBYXSU-UHFFFAOYSA-J rhenium;tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Re] IZVAOCKUNBYXSU-UHFFFAOYSA-J 0.000 description 1
- YNWSXIWHOSSPCO-UHFFFAOYSA-N rhodium(2+) Chemical compound [Rh+2] YNWSXIWHOSSPCO-UHFFFAOYSA-N 0.000 description 1
- SWJHFWLQASBTNJ-UHFFFAOYSA-L rhodium(2+);2,2,2-trifluoroacetate Chemical compound [Rh+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F SWJHFWLQASBTNJ-UHFFFAOYSA-L 0.000 description 1
- ITDJKCJYYAQMRO-UHFFFAOYSA-L rhodium(2+);diacetate Chemical compound [Rh+2].CC([O-])=O.CC([O-])=O ITDJKCJYYAQMRO-UHFFFAOYSA-L 0.000 description 1
- CDPPVBDJYWOMMV-UHFFFAOYSA-K rhodium(3+);phosphate Chemical compound [Rh+3].[O-]P([O-])([O-])=O CDPPVBDJYWOMMV-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- PMMMCGISKBNZES-UHFFFAOYSA-K ruthenium(3+);tribromide;hydrate Chemical compound O.Br[Ru](Br)Br PMMMCGISKBNZES-UHFFFAOYSA-K 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 description 1
- AQXYDBKYCQZMNH-UHFFFAOYSA-M sulfanide;tris(sulfanylidene)rhenium Chemical compound [SH-].S=[Re](=S)=S.S=[Re](=S)=S AQXYDBKYCQZMNH-UHFFFAOYSA-M 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KVDBPOWBLLYZRG-UHFFFAOYSA-J tetrachloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)(Cl)Cl KVDBPOWBLLYZRG-UHFFFAOYSA-J 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- KBXXFKPVKJZGJG-UHFFFAOYSA-K tribromoiridium;hydrate Chemical compound O.Br[Ir](Br)Br KBXXFKPVKJZGJG-UHFFFAOYSA-K 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- HSSMNYDDDSNUKH-UHFFFAOYSA-K trichlororhodium;hydrate Chemical compound O.Cl[Rh](Cl)Cl HSSMNYDDDSNUKH-UHFFFAOYSA-K 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
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- 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
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
Description
本発明は、プロパンジオールの製造方法に関する。さらに詳しくは、本発明は、グリセリンを原料とし、これを酸、水素化触媒及び必要により溶媒の存在下にて水素化することによって１，３−プロパンジオールの収率の高いプロパンジオールの製造方法に関する。 The present invention relates to a method for producing propanediol. More specifically, the present invention relates to a process for producing propanediol with a high yield of 1,3-propanediol by using glycerin as a raw material and hydrogenating it in the presence of an acid, a hydrogenation catalyst and, if necessary, a solvent. About.
プロパンジオール類は、溶媒、ポリエステル原料として極めて重要である。そのため、従来から、１，２−プロパンジオールについてはプロピレンの部分酸化による製造技術、１，３−プロパンジオールについては、糖の発酵による製造技術が実用化されている。 Propanediols are extremely important as solvents and polyester raw materials. Therefore, conventionally, for 1,2-propanediol, a production technique by partial oxidation of propylene and for 1,3-propanediol, a production technique by fermentation of sugar has been put to practical use.
一方、グリセリンは油脂類のエステル交換反応によるＢＤＦ（バイオディーゼルフューエル）製造の際の副産物として世界的な供給過剰が予想されている物質である（非特許文献１参照）。したがって、グリセリンを原料としたプロパンジオールの製造方法が確立されれば、その産業的な意義は大きいと考えられる。 On the other hand, glycerin is a substance that is expected to be supplied globally as a by-product in the production of BDF (biodiesel fuel) by transesterification of fats and oils (see Non-Patent Document 1). Therefore, if a method for producing propanediol using glycerin as a raw material is established, it is considered that its industrial significance is great.
現在までに知られているグリセリンからのプロパンジオールの製造方法としては、微生物を用いる発酵法（非特許文献２，３参照）と、触媒を用いる水素化分解法（非特許文献４，５及び特許文献１参照）が知られている。
Known methods for producing propanediol from glycerin to date include fermentation methods using microorganisms (see Non-Patent
しかし、発酵法による製造においては、１，３−プロパンジオールの収率が７０％近くに達するという利点はあるが、反応速度が遅いため、巨大な発酵槽が必要となる他、副生成物による阻害のため最終的な水溶液中の生成物濃度が７％程度と低いことから、水や未反応グリセリンから１，３−プロパンジオールを分離、精製するためのコストが大きくなるという問題がある。 However, in the production by the fermentation method, there is an advantage that the yield of 1,3-propanediol reaches nearly 70%. However, since the reaction rate is slow, a huge fermenter is required, and it depends on by-products. Since the final product concentration in the aqueous solution is as low as about 7% due to inhibition, there is a problem that the cost for separating and purifying 1,3-propanediol from water and unreacted glycerin increases.
これに対し、触媒を用いる水素化分解法は、発酵法のように巨大な設備が必要でなく、一般に有機溶媒中で反応が行われるので、生成物の分離精製が容易である点で有利である。しかし、水素化分解法ではその一方で収率が非常に低いという問題がある。例えば、担持ロジウム触媒の場合（非特許文献１参照）、１，３−プロパンジオールの収率は最高４％、１，２−プロパンジオールの収率は最高１５％である。また、担持ルテニウム触媒の場合（非特許文献１参照）、１，３−プロパンジオールの収率は最高０．６％、１，２−プロパンジオールの収率は最高１８％である。また、ルテニウム錯体触媒の場合（特許文献１参照）、１，３−プロパンジオールの収率は４．６％である。
このように、１，３−プロパンジオールは、ポリプロピレンテレフタレート（ＰＰＴ）の原料となるため、グリセリンからの製造が強く要請されているものであるものの、工業的に有利な接触水素化分解による製造方法では、５％以下の収率でしか得られていない。 Thus, since 1,3-propanediol is a raw material for polypropylene terephthalate (PPT), production from glycerin is strongly demanded, but an industrially advantageous production method by catalytic hydrocracking However, it is obtained only in a yield of 5% or less.
本発明は、かかる実状を背景に、余剰産物とされていたグリセリンを原料とし、これを水素化分解法によりプロパンジオール、特に１，３−プロパンジオールをより高収率に製造するためになされたものである。 The present invention has been made in order to produce propanediol, particularly 1,3-propanediol, in a higher yield by hydrocracking the raw material from glycerin, which has been regarded as a surplus product, in the background of the actual situation. Is.
かくして、本発明者は、このような課題に対して、まず通常のオートクレーブを用いて、水素化触媒、酸、及び溶媒からなる触媒系の存在下で、グリセリンを水素化分解させたが、プロパンジオールは少量しか得られず、大部分のグリセリンが回収される結果となった。ところが、同じ原料を用いてガラス内管付きのオートクレーブで反応を行った場合には、ガラス内管とオートクレーブ壁面の間のわずかの隙間に反応後の反応液のかなりの部分が存在しており、驚くべきことに、その反応液中に１，２−プロパンジオール、ｎ−プロパノールとともに、１，３−プロパンジオールが高収率で生成していることが判明した。これは、反応中に溶媒とグリセリン水素化反応生成物、及び水がガラス管外に留去したため、ガラス管内の触媒がスラリー状になり、グリセリンの水素化活性が向上したためと考えられた。本発明はこの知見に基づいて完成させたものであり、溶媒量を少なくしたスラリー触媒系を用いることにより、グリセリンの反応性を向上させるとともに、生成したプロパンジオールと水を連続的に反応系外に抜き出しながらグリセリンを水素化分解させることにより、水による反応阻害とｎ−プロパノールの生成が抑制され、プロパンジオール類が高収率で得られるものと推察される。 Thus, in order to solve such problems, the present inventor first hydrocracked glycerin in the presence of a catalyst system comprising a hydrogenation catalyst, an acid, and a solvent using an ordinary autoclave. Only a small amount of diol was obtained, resulting in the recovery of most of the glycerin. However, when the reaction is carried out in an autoclave with a glass inner tube using the same raw material, a considerable portion of the reaction solution after the reaction exists in a slight gap between the glass inner tube and the autoclave wall surface, Surprisingly, it was found that 1,3-propanediol was produced in a high yield together with 1,2-propanediol and n-propanol in the reaction solution. This was thought to be because the solvent, glycerin hydrogenation reaction product, and water were distilled out of the glass tube during the reaction, so that the catalyst in the glass tube became a slurry and the hydrogenation activity of glycerin was improved. The present invention has been completed based on this finding. By using a slurry catalyst system with a reduced amount of solvent, the reactivity of glycerin is improved and the produced propanediol and water are continuously removed from the reaction system. By hydrocracking glycerin while being extracted, it is surmised that reaction inhibition by water and generation of n-propanol are suppressed, and propanediols can be obtained in high yield.
すなわち、本発明は、下記の製造方法に係るものである。
項１．グリセリンを酸及び水素化触媒の存在下にて水素化することによって１，２−プロパンジオール及び１，３−プロパンジオールの混合物を製造する方法であって、必要により反応系に溶媒を存在させ、酸が常温で固体の酸であり、酸及び水素化触媒の合計重量とグリセリン及び溶媒の合計容量の比が１／１５〜１０ｇ／ｍＬであることを特徴とするプロパンジオールの製造方法。
項２．溶媒が環状アミド化合物である項１に記載の製造方法。
項３．溶媒重量がグリセリン重量に対して０〜２０倍である請求項１又は２に記載の製造方法。
項４．酸が、タングステン酸、タングストリン酸、五酸化バナジウム、γ−アルミナ、ゼオライト及びシリカからなる群から選択される少なくとも１種である項１〜３のいずれかに記載の製造方法。
項５．水素化触媒が活性炭担持白金触媒、活性炭担持ルテニウム触媒、活性炭担持パラジウム触媒、活性炭担持ロジウム触媒及びアルミナ担持白金触媒からなる群から選択される少なくとも１種である項１〜４のいずれかに記載の製造方法。
項６．反応生成物を系外に排出させつつ反応させることを特徴とする項１〜５のいずれかに記載の製造方法。
That is, the present invention relates to the following manufacturing method.
Item 3. The production method according to
Item 4. Item 4. The production method according to any one of
Item 5. Item 5. The hydrogenation catalyst is at least one selected from the group consisting of an activated carbon-supported platinum catalyst, an activated carbon-supported ruthenium catalyst, an activated carbon-supported palladium catalyst, an activated carbon-supported rhodium catalyst, and an alumina-supported platinum catalyst. Production method.
Item 6. Item 6. The production method according to any one of
本発明はさらに下記の製造方法も包含しうる。
項７．項１〜６のいずれかの方法によって製造された混合物から１，３−プロパンジオールを分離することを特徴とする１，３−プロパンジオールの製造方法。
The present invention can further include the following production methods.
Item 7.
グリセリンの水素化分解によるプロパンジオールの製造は公知であり、その反応機構は下記のスキームにより示される。この一段の反応により、１，３−プロパンジオール、１，２−プロパンジオール、及びｎ−プロパノールが生成する。 Production of propanediol by hydrogenolysis of glycerin is known, and the reaction mechanism is shown by the following scheme. This one-step reaction produces 1,3-propanediol, 1,2-propanediol, and n-propanol.
従来のグリセリンを水素化分解してプロパンジオールを製造する方法では水素化分解のためグリセリンに加え常温で固体の酸、水素化触媒及び溶媒が必須であり、これによりプロパンジオールを生成するものであるが、得られる１，３−プロパンジオールの収率は非常に低いものであった。本発明ではこの反応系において、溶媒の量を非常に少量とするか使用しないことを特徴とする。すなわち、本発明では、グリセリン、常温で固体の酸及び水素化触媒、必要に応じてここに溶媒を加え、この際、酸及び水素化触媒の合計重量（ｇ）がグリセリン及び溶媒の合計容量（ｍＬ）の１／１５〜１０倍であることが必須であり、好ましくは１／１５〜３倍である（なお、触媒金属が担体に担持された水素化触媒を使用する場合は、触媒金属重量と担体重量の合計を水素化触媒の重量とする）。液体であるグリセリン及び溶媒、特に溶媒の量を少量とすることによって１，３−プロパンジオールの収率が向上する。さらに、本発明では、溶媒として環状アミドを使用することによって１，３−プロパンジオールの収率が高まる。 In the conventional method for producing propanediol by hydrocracking glycerol, an acid, a hydrogenation catalyst and a solvent which are solid at room temperature in addition to glycerol are essential for hydrocracking, thereby producing propanediol. However, the yield of 1,3-propanediol obtained was very low. The present invention is characterized in that the amount of the solvent is very small or not used in this reaction system. That is, in the present invention, glycerin, an acid that is solid at room temperature and a hydrogenation catalyst, and if necessary, a solvent is added thereto. At this time, the total weight (g) of the acid and the hydrogenation catalyst is the total capacity of glycerin and the solvent ( It is essential that it is 1/15 to 10 times that of mL), preferably 1/15 to 3 times (in the case of using a hydrogenation catalyst in which the catalyst metal is supported on the support, the weight of the catalyst metal And the weight of the carrier is the weight of the hydrogenation catalyst). The yield of 1,3-propanediol is improved by reducing the amount of glycerin and a solvent, particularly a solvent, in a small amount. Furthermore, in the present invention, the yield of 1,3-propanediol is increased by using a cyclic amide as a solvent.
プロパンジオールは、例えば、オートクレーブ内に所定量のグリセリン、酸、水素化触媒、必要に応じて溶媒を仕込み、加熱することによって製造できる。本発明において、溶媒は必須ではないが、少量であれば有用であり、１種単独又は２種以上組み合わせて使用できる。溶媒の例は、環状アミド、スルホラン、ＤＭＳＯ等である。溶媒は、沸点が１５０℃以上のものが好ましく、２５０℃以上のものがより好ましい。好ましい溶媒は環状アミドであり、その例としては、１，３−ジメチルイミダゾリジノン、Ｎ−メチルピロリジノンなどが挙げられる。環状アミドの中でも、環を構成する元素のうちの一つ以上が窒素である環状アミドが好ましい。 Propanediol can be produced, for example, by charging a predetermined amount of glycerin, acid, hydrogenation catalyst and, if necessary, a solvent in an autoclave and heating. In the present invention, a solvent is not essential, but a small amount is useful and can be used alone or in combination of two or more. Examples of the solvent are cyclic amide, sulfolane, DMSO and the like. The solvent preferably has a boiling point of 150 ° C. or higher, more preferably 250 ° C. or higher. A preferred solvent is a cyclic amide, and examples thereof include 1,3-dimethylimidazolidinone and N-methylpyrrolidinone. Among the cyclic amides, cyclic amides in which one or more of the elements constituting the ring are nitrogen are preferable.
上記溶媒の使用量は、グリセリン１重量部に対して０〜２０重量部、好ましくは０．５〜１０重量部、より好ましくは１〜５重量部、よりいっそう好ましくは１〜３重量部である。溶媒が上記の範囲にある場合、プロパンジオール、特に１，３−プロパンジオールの収率の点で有利である。また、上記の範囲ではグリセリン、溶媒、酸及び触媒はスラリー状態になることが多い。 The amount of the solvent used is 0 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, and still more preferably 1 to 3 parts by weight with respect to 1 part by weight of glycerin. . When the solvent is in the above range, it is advantageous in terms of the yield of propanediol, particularly 1,3-propanediol. In the above range, glycerin, solvent, acid and catalyst are often in a slurry state.
本発明において、酸は常温で固体の酸（固体酸）であり、１種単独又は２種以上組み合わせて使用できる。例えば、モリブデン酸、タングステン酸、タングストリン酸、バナジン酸、ニオブ酸などのヘテロポリ酸、五酸化バナジウム、アルミナ、ゼオライト、シリカなどが挙げられる。好ましい酸は、タングステン酸、タングストリン酸である。 In this invention, an acid is a solid acid (solid acid) at normal temperature, and can be used individually by 1 type or in combination of 2 or more types. Examples thereof include heteropolyacids such as molybdic acid, tungstic acid, tungstophosphoric acid, vanadic acid and niobic acid, vanadium pentoxide, alumina, zeolite and silica. Preferred acids are tungstic acid and tungstophosphoric acid.
上記酸の使用量は、グリセリン１重量部に対して０．００１〜５重量部、好ましくは０．０１〜１重量部である。 The amount of the acid used is 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 1 part by weight of glycerin.
本発明において、水素化触媒は、グリセリンを水素化してプロパンジオールを生成する反応を触媒するものであれば１種単独又は２種以上組み合わせて使用できる。水素化触媒としては触媒金属単独でも、触媒金属を担体に担持させたものでも使用できる。水素化触媒としては、例えば、白金、ロジウム、パラジウム、ニッケル、ルテニウム、イリジウム、またはレニウム触媒等の遷移金属触媒が挙げられる。このような触媒としては、白金、ロジウム、パラジウム、ニッケル、ルテニウム、イリジウム、またはレニウム等の金属、これら金属の合金、または、その塩化物、臭化物、ヨウ化物、硝酸塩、硫酸塩、リン酸塩、酸化物、硫化物、硼化物、水酸化物、シアン化物、アセチルアセトネート、酢酸塩、またはトリフルオロ酢酸塩等が挙げられる。より具体的には、白金金属、白金ブラック、白金（ＩＩ）アセチルアセトネート、白金（ＩＩ）ビス（ベンゾニトリル）ジクロリド、白金（ＩＩ）ブロミド、白金（ＩＶ）ブロミド、白金（ＩＩ）クロリド、白金（ＩＶ）クロリド、白金（ＩＩ）シアニド、白金（ＩＩ）ヨージド、酸化（ＩＶ）白金、酸化（ＩＶ）白金水和物、白金ロジウム合金、白金パラジウム合金、白金イリジウム合金、白金（ＩＶ）スルフィド；ロジウム金属、ロジウムブラック、ロジウム（ＩＩ）酢酸塩、ロジウム（ＩＩ）アセチルアセトネート、ロジウム（ＩＩ）ブロミド水和物、ロジウム（ＩＩＩ）クロリド、ロジウム（ＩＩＩ）クロリド水和物、ロジウム（ＩＩ）ヘキサフルオロブタン酸塩、ロジウム（ＩＩ）ヘキサン酸塩、ロジウム（ＩＩＩ）ヨージド水和物、硝酸ロジウム（ＩＩＩ）、酸化ロジウム（ＩＩＩ）、酸化ロジウム（ＩＩＩ）水和物、リン酸ロジウム（ＩＩＩ）、硫酸ロジウム（ＩＩＩ）、ロジウム（ＩＩ）トリフルオロ酢酸塩；パラジウム金属、パラジウムブラック、パラジウム（ＩＩ）酢酸塩、パラジウム（ＩＩ）アセチルアセトネート、パラジウム（ＩＩ）ビス（ベンゾニトリル）ジクロリド、パラジウム（ＩＩ）ブロミド、パラジウム（ＩＩ）クロリド、パラジウム（ＩＩ）シアニド、水酸化パラジウム（ＩＩ）、パラジウム（ＩＩ）ヨージド、硝酸パラジウム（ＩＩ）、硝酸パラジウム（ＩＩ）水和物、酸化パラジウム（ＩＩ）、酸化パラジウム（ＩＩ）水和物、パラジウム（ＩＩ）プロピオン酸塩、硫酸パラジウム（ＩＩ）、パラジウム（ＩＩ）スルフィド、パラジウム（ＩＩ）トリフルオロ酢酸塩；ニッケル金属、ラネーニッケル、硼化ニッケル、酸化ニッケル（ＩＩ）；ルテニウム金属、ルテニウムブラック、ルテニウム（ＩＩＩ）アセチルアセトネート、ルテニウム（ＩＩＩ）ブロミド、ルテニウム（ＩＩＩ）ブロミド水和物、ルテニウム（ＩＩＩ）クロリド、ルテニウム（ＩＩＩ）クロリド水和物、ルテニウム（ＩＩＩ）ヨージド、ルテニウム（ＩＩＩ）ニトロシルクロリド水和物、硝酸ルテニウム（ＩＩＩ）ニトロシル、酸化ルテニウム（ＩＶ）、酸化ルテニウム（ＩＶ）水和物；イリジウム金属、イリジウム（ＩＩＩ）アセチルアセトネート、イリジウム（ＩＩＩ）ブロミド水和物、イリジウム（ＩＩＩ）クロリド、イリジウム（ＩＩＩ）クロリド塩酸塩、イリジウム（ＩＶ）クロリド水和物、酸化イリジウム（ＩＶ）、酸化イリジウム（ＩＶ）水和物；レニウム金属、レニウム（ＩＩＩ）クロリド、レニウム（Ｖ）クロリド、レニウム（ＩＶ）フルオリド、酸化レニウム（ＩＶ）、酸化レニウム（ＶＩ）、酸化レニウム（ＶＩＩ）、レニウム（ＶＩＩ）スルフィド等が挙げられる。好ましくは、酸化白金、酸化パラジウム、プラチナブラック、パラジウムブラック、ラネーニッケル、硼化ニッケル等が挙げられる。 In the present invention, the hydrogenation catalyst can be used singly or in combination of two or more as long as it catalyzes the reaction of hydrogenating glycerin to produce propanediol. As the hydrogenation catalyst, a catalyst metal alone or a catalyst metal supported on a carrier can be used. Examples of the hydrogenation catalyst include transition metal catalysts such as platinum, rhodium, palladium, nickel, ruthenium, iridium, or rhenium catalyst. Such catalysts include metals such as platinum, rhodium, palladium, nickel, ruthenium, iridium or rhenium, alloys of these metals, or their chlorides, bromides, iodides, nitrates, sulfates, phosphates, Examples thereof include oxides, sulfides, borides, hydroxides, cyanides, acetylacetonates, acetates, and trifluoroacetates. More specifically, platinum metal, platinum black, platinum (II) acetylacetonate, platinum (II) bis (benzonitrile) dichloride, platinum (II) bromide, platinum (IV) bromide, platinum (II) chloride, platinum (IV) chloride, platinum (II) cyanide, platinum (II) iodide, oxidized (IV) platinum, oxidized (IV) platinum hydrate, platinum rhodium alloy, platinum palladium alloy, platinum iridium alloy, platinum (IV) sulfide; Rhodium metal, rhodium black, rhodium (II) acetate, rhodium (II) acetylacetonate, rhodium (II) bromide hydrate, rhodium (III) chloride, rhodium (III) chloride hydrate, rhodium (II) hexa Fluorobutanoate, rhodium (II) hexanoate, rhodium (III) iodide hydration Rhodium (III) nitrate, rhodium (III) oxide, rhodium (III) oxide hydrate, rhodium (III) phosphate, rhodium (III) sulfate, rhodium (II) trifluoroacetate; palladium metal, palladium black, Palladium (II) acetate, palladium (II) acetylacetonate, palladium (II) bis (benzonitrile) dichloride, palladium (II) bromide, palladium (II) chloride, palladium (II) cyanide, palladium hydroxide (II) , Palladium (II) iodide, palladium (II) nitrate, palladium (II) nitrate hydrate, palladium (II) oxide, palladium (II) oxide hydrate, palladium (II) propionate, palladium (II) sulfate , Palladium (II) sulfide, palladium II) Trifluoroacetate; nickel metal, Raney nickel, nickel boride, nickel (II) oxide; ruthenium metal, ruthenium black, ruthenium (III) acetylacetonate, ruthenium (III) bromide, ruthenium (III) bromide hydrate , Ruthenium (III) chloride, ruthenium (III) chloride hydrate, ruthenium (III) iodide, ruthenium (III) nitrosyl chloride hydrate, ruthenium (III) nitrosyl nitrate, ruthenium oxide (IV), ruthenium oxide (IV) Hydrate; iridium metal, iridium (III) acetylacetonate, iridium (III) bromide hydrate, iridium (III) chloride, iridium (III) chloride hydrochloride, iridium (IV) chloride hydrate, oxidation Iridium (IV), iridium (IV) oxide hydrate; rhenium metal, rhenium (III) chloride, rhenium (V) chloride, rhenium (IV) fluoride, rhenium (IV) oxide, rhenium oxide (VI), rhenium oxide ( VII), rhenium (VII) sulfide and the like. Preferable examples include platinum oxide, palladium oxide, platinum black, palladium black, Raney nickel, nickel boride and the like.
また、これらの触媒金属は、触媒活性、再現性、保存安定性、操作性、リサイクルの容易さ等の観点から、粉末担体に分散させた形態の触媒として用いることがより好ましい。上記粉末担体としては、例えば炭素、アルミナ、シリカ−アルミナ、シリカ、炭酸バリウム、硫酸バリウム、炭酸カルシウム、酸化チタン、酸化ジルコニウム、ゼオライト等が挙げられる。好ましくは、これら粉末担体に担持された白金、ロジウム、またはパラジウムの金属、合金もしくはその硫化物、または水酸化物等である。 Further, these catalytic metals are more preferably used as a catalyst in a form dispersed in a powder carrier from the viewpoints of catalytic activity, reproducibility, storage stability, operability, ease of recycling, and the like. Examples of the powder carrier include carbon, alumina, silica-alumina, silica, barium carbonate, barium sulfate, calcium carbonate, titanium oxide, zirconium oxide, and zeolite. Preferably, platinum, rhodium or palladium metal, alloy or sulfide thereof, or hydroxide supported on the powder carrier.
担体に担持された水素化触媒として具体的には、例えば白金−炭素、白金（ＩＩ）スルフィド−炭素、白金−アルミナ、白金−シリカーアルミナ、白金−シリカ、白金−炭酸バリウム、白金−硫酸バリウム、白金−炭酸カルシウム、白金−酸化チタン、白金−酸化ジルコニウム、白金−ゼオライト、白金ロジウム合金−炭素、白金パラジウム合金−炭素；ロジウム−炭素、ロジウム−アルミナ、ロジウム−シリカ、ロジウム−炭酸カルシウム；パラジウム−炭素、水酸化パラジウム（ＩＩ）−炭素、パラジウム（ＩＩ）スルフィド−炭素、パラジウム−アルミナ、パラジウム−シリカーアルミナ、パラジウム−シリカ、パラジウム−炭酸バリウム、パラジウム−硫酸バリウム、パラジウム−炭酸カルシウム、パラジウム−酸化チタン、パラジウム−酸化ジルコニウム、パラジウム−ゼオライト、；ルテニウム−炭素、ルテニウム−アルミナ、ルテニウム−シリカ、ルテニウム−炭酸カルシウム；イリジウム−炭素、イリジウム−アルミナ、イリジウム−シリカ、イリジウム−炭酸カルシウム等が挙げられる。好ましくは、パラジウム−炭素、ロジウム−炭素、白金−炭素、パラジウム−アルミナ、白金−アルミナ、パラジウム−炭酸カルシウム、白金−炭酸カルシウム、パラジウム−硫酸バリウム、白金−硫酸バリウム、ルテニウム−炭素、ロジウム−炭素等が挙げられる。 Specific examples of the hydrogenation catalyst supported on the carrier include platinum-carbon, platinum (II) sulfide-carbon, platinum-alumina, platinum-silica-alumina, platinum-silica, platinum-barium carbonate, platinum-barium sulfate. Platinum-calcium carbonate, platinum-titanium oxide, platinum-zirconium oxide, platinum-zeolite, platinum rhodium alloy-carbon, platinum palladium alloy-carbon; rhodium-carbon, rhodium-alumina, rhodium-silica, rhodium-calcium carbonate; palladium -Carbon, palladium (II) hydroxide-carbon, palladium (II) sulfide-carbon, palladium-alumina, palladium-silica-alumina, palladium-silica, palladium-barium carbonate, palladium-barium sulfate, palladium-calcium carbonate, palladium -Titanium oxide, para-dioxide Beam - zirconium oxide, palladium - zeolite; ruthenium - carbon, ruthenium - alumina, ruthenium - silica, ruthenium - calcium carbonate; iridium - carbon, iridium - alumina, iridium - silica, iridium - calcium carbonate. Preferably, palladium-carbon, rhodium-carbon, platinum-carbon, palladium-alumina, platinum-alumina, palladium-calcium carbonate, platinum-calcium carbonate, palladium-barium sulfate, platinum-barium sulfate, ruthenium-carbon, rhodium-carbon Etc.
上記水素化触媒（担体含む）の使用量は、グリセリン１重量部に対して０．０００１重量部〜５重量部、好ましくは０．００１重量部〜１重量部である。 The amount of the hydrogenation catalyst (including carrier) used is 0.0001 to 5 parts by weight, preferably 0.001 to 1 part by weight, based on 1 part by weight of glycerin.
本発明の製造方法において、反応は水素の存在下で行えばよく、水素圧は特に限定されないが、好ましくは１０〜１５０気圧、より好ましくは５０〜１００気圧である。また、反応温度は、好ましくは１００〜３００℃、より好ましくは１６０〜２２０℃であり、反応時間は、好ましくは１〜４８時間、より好ましくは１０〜２４時間である。 In the production method of the present invention, the reaction may be carried out in the presence of hydrogen, and the hydrogen pressure is not particularly limited, but is preferably 10 to 150 atm, more preferably 50 to 100 atm. Moreover, reaction temperature becomes like this. Preferably it is 100-300 degreeC, More preferably, it is 160-220 degreeC, Reaction time becomes like this. Preferably it is 1-48 hours, More preferably, it is 10-24 hours.
本発明の製造方法では、反応中に生成物を連続的に系外に排出して回収することが好ましい。目的物であるプロパンジオールの沸点がグリセリンの沸点より低いため、プロパンジオールを系外に排出することによって、二次生成物であるｎ−プロパノールの生成が抑制され、プロパンジオールの収率が向上するためである。 In the production method of the present invention, it is preferable that the product is continuously discharged out of the system and recovered during the reaction. Since the boiling point of propanediol, which is the target product, is lower than the boiling point of glycerin, the production of n-propanol, which is a secondary product, is suppressed by discharging propanediol out of the system, and the yield of propanediol is improved. Because.
上記のグリセリン、酸、水素化触媒、溶媒を加圧及び加熱可能な反応器に仕込み、加熱することによってプロパンジオールを製造できる。例えばガラス内筒を有するオートクレーブ中に水素化触媒、酸、溶媒及びグリセリンを仕込み、反応条件を例えば水素初圧８０気圧、反応温度１７０℃に設定し、スラリー状の反応物を攪拌しながら所定時間反応させる。反応中に生成物と溶媒の一部はガラス内筒の外側に留出する。この留出により生成物は連続的に反応系外に排出されることとなるが、生成物を反応系外に排出する手段はこれに限定されない。反応後、得られる生成物から所望のプロパンジオールを分離する。反応器の一例を図１に示す。 Propanediol can be produced by charging the glycerin, acid, hydrogenation catalyst, and solvent in a reactor capable of being pressurized and heated and heating. For example, a hydrogenation catalyst, acid, solvent and glycerin are charged into an autoclave having a glass inner cylinder, the reaction conditions are set to, for example, an initial hydrogen pressure of 80 atm and a reaction temperature of 170 ° C., and the slurry-like reactant is stirred for a predetermined time. React. During the reaction, a part of the product and the solvent distills outside the glass inner tube. The product is continuously discharged out of the reaction system by this distillation, but means for discharging the product out of the reaction system is not limited to this. After the reaction, the desired propanediol is separated from the resulting product. An example of the reactor is shown in FIG.
グリセリンの水素化によって生成したプロパンジオールは１，２−プロパンジオールと１，３−プロパンジオールの混合物である。１，２−プロパンジオールと１，３−プロパンジオールとを分離する場合、蒸留、各種クロマトグラフィー分離などの公知の方法により分離精製することができる。 Propanediol produced by hydrogenation of glycerin is a mixture of 1,2-propanediol and 1,3-propanediol. When 1,2-propanediol and 1,3-propanediol are separated, they can be separated and purified by known methods such as distillation and various chromatographic separations.
本発明によれば、グリセリンを水素化触媒により水素化してプロパンジオールを生成する方法において、従来より相対的に非常に高い収率でプロパンジオール、特に１，３−プロパンジオールを製造することができる。 According to the present invention, in a method for producing propanediol by hydrogenating glycerin with a hydrogenation catalyst, it is possible to produce propanediol, particularly 1,3-propanediol, in a relatively high yield compared to conventional methods. .
以下、本発明を実施例等により詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example etc. demonstrate this invention in detail, this invention is not limited to these Examples.
実施例１
縁を外に開いてオートクレーブ内壁との隙間を小さくした試験管様の形状をしたガラス内管を備えた３０ｍＬ容のオートクレーブ中に、グリセリン約３ｍｍｏｌ（０．２１６ｍＬ）、所定量（０、０．５、１、２ｍＬ）の溶媒である１，３−ジメチルイミダゾリジノン（ＤＭＩ）、タングステン酸０．２ｍｍｏｌ（０．０４９ｇ）、活性炭に白金を担持させた触媒０．０３９ｇ（白金０．０１ｍｇ−ａｔｏｍ）を仕込んで、オートクレーブの蓋を閉めた後、水素ガス（室温で８０気圧）加圧下、１７０℃で１８時間反応を行った。オートクレーブ内に生成している１，３−プロパンジオール、１，２−プロパンジオール及びｎ−プロパノールをガスクロマトグラフィーで定量分析し、グリセリンに対する収率を図２に示した。
Example 1
In a 30 mL autoclave equipped with a glass inner tube shaped like a test tube with the edge opened to the outside and the gap with the inner wall of the autoclave being reduced, about 3 mmol (0.216 mL) of glycerin, a predetermined amount (0, 0. 5,1,2 mL) solvent 1,3-dimethylimidazolidinone (DMI), tungstic acid 0.2 mmol (0.049 g), activated carbon supported platinum 0.039 g (platinum 0.01 mg- atom) and the autoclave cover was closed, followed by reaction at 170 ° C. for 18 hours under pressure of hydrogen gas (80 atm at room temperature). 1,3-propanediol, 1,2-propanediol and n-propanol produced in the autoclave were quantitatively analyzed by gas chromatography, and the yield relative to glycerin is shown in FIG.
溶媒０．５ｍＬを用いた場合には、原料グリセリン基準で１，３−プロパンジオール０．７ｍｍｏｌ（２３％）、１，２−プロパンジオール０．６ｍｍｏｌ（１９％）、ｎ−プロパノール０．２ｍｍｏｌ（５％）が生成していた。また、反応溶液を液体クロマトグラフィーにより分析したところ、１．１ｍｍｏｌ（３４％）のグリセリンが未反応であることが分かった。図２から、溶媒を使用しない場合には、ｎ−プロパノールの生成量が増大してグリセリンの回収率が低下（５％）し、溶媒量が１ｍＬより多い場合には、生成物の収率が低下して未反応のグリセリンが多くなることが分かった。 When 0.5 mL of the solvent was used, 1,3-propanediol 0.7 mmol (23%), 1,2-propanediol 0.6 mmol (19%), n-propanol 0.2 mmol (based on the raw material glycerin) 5%) was produced. Moreover, when the reaction solution was analyzed by liquid chromatography, it was found that 1.1 mmol (34%) of glycerin was unreacted. From FIG. 2, when the solvent is not used, the production amount of n-propanol is increased and the recovery rate of glycerin is decreased (5%). When the solvent amount is more than 1 mL, the yield of the product is increased. It was found that the amount of unreacted glycerin decreased and increased.
実施例２
ガラス内管を備えていない３０ｍＬ容のオートクレーブを使用したこと以外は実施例１と同様にしてグリセリンの水素化反応を行い生成物の定量を行った。なお、本例ではガラス内管を利用していないため、生成物は反応系外へ除去されることはない。結果を図３に示す。１，３−プロパンジオールの収率は９〜１５％と従来技術に比べて高かった。図２と図３の比較により、ガラス内管があり生成物が反応系から除去される場合には、ガラス内管がなく生成物が反応系から除去されない場合に比べて、１，３−プロパンジオールの最大収率が１．５倍以上であることが理解できる。生成物を反応系外へ除去することによって収率が向上することが示された。
Example 2
The product was quantified by hydrogenating glycerin in the same manner as in Example 1 except that a 30 mL autoclave without an inner glass tube was used. In this example, since the glass inner tube is not used, the product is not removed out of the reaction system. The results are shown in FIG. The yield of 1,3-propanediol was 9-15% higher than that of the prior art. By comparing FIG. 2 and FIG. 3, when there is a glass inner tube and the product is removed from the reaction system, 1,3-propane is present compared to when there is no glass inner tube and the product is not removed from the reaction system. It can be seen that the maximum yield of diol is 1.5 times or more. It was shown that the yield was improved by removing the product out of the reaction system.
実施例３
溶媒、酸及び触媒を下記表１に示すものに代え、溶媒量を０．５ｍＬとし、触媒金属量を０．０１ｍｇ−ａｔｏｍに統一した（担体込みの触媒量としては７〜３９ｍｇになる）こと以外は実施例１と同様にしてグリセリンの水素化反応を行い生成物の定量を行った。結果を表１に示す。表中、PDOはプロパンジオール、n-Pはｎ−プロパノール、DMIは１，３−ジメチルイミダゾリジノン、NMPはＮ−メチルピロリジノン、H2WO4はタングステン酸を示す。
Example 3
The solvent, acid, and catalyst are replaced with those shown in Table 1 below, the solvent amount is 0.5 mL, and the catalyst metal amount is unified to 0.01 mg-atom (the catalyst amount including the support is 7 to 39 mg). Except for the above, the hydrogenation reaction of glycerin was performed in the same manner as in Example 1 to quantify the product. The results are shown in Table 1. In the table, PDO represents propanediol, nP represents n-propanol, DMI represents 1,3-dimethylimidazolidinone, NMP represents N-methylpyrrolidinone, and H 2 WO 4 represents tungstic acid.
比較例１
酸を下記表２に示すものに代え、溶媒量を０．５ｍＬとしたこと以外は実施例１と同様にしてグリセリンの水素化反応を行い生成物の定量を行った。結果を表２に示す。表中、Sc(Tf)3はスカンジウムトリフレートを示し、その他は表１と同様である。また、BF3はメタノールコンプレックスを用いた。
Comparative Example 1
The acid was replaced with the one shown in Table 2 below, and the amount of the solvent was changed to 0.5 mL, and the hydrogenation reaction of glycerin was performed in the same manner as in Example 1 to quantify the product. The results are shown in Table 2. In the table, Sc (Tf) 3 represents scandium triflate, and the others are the same as in Table 1. Further, BF 3 was used methanol complex.
表１及び表２の比較より、酸はプロトン供与能の高い固体酸が好ましいことが理解される。 From the comparison of Table 1 and Table 2, it is understood that the acid is preferably a solid acid having a high proton donating ability.
本発明は、プロパンジオールを製造する分野において有用である。 The present invention is useful in the field of producing propanediol.
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Cited By (9)
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| WO2009093486A1 (en) * | 2008-01-21 | 2009-07-30 | Kao Corporation | Method for producing hydrogenolysis product of polyhydric alcohol |
| KR101205897B1 (en) | 2010-04-19 | 2012-11-29 | 한국과학기술연구원 | The noble metal based catalyst supported on complex metal oxide and the method for the producing of 1,2-propanediol |
| JP2013067598A (en) * | 2011-09-26 | 2013-04-18 | Ube Industries Ltd | Process for production of 1,3-diol compound |
| JP2013166096A (en) * | 2012-02-14 | 2013-08-29 | Osaka Univ | Glycerol hydrogenating decomposition catalyst, and method for manufacturing 1, 3-propane diol using the same |
| JP2013216623A (en) * | 2012-04-10 | 2013-10-24 | Daicel Corp | Method for producing propanediol |
| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| CN111774089A (en) * | 2020-07-28 | 2020-10-16 | 中国科学院上海高等研究院 | Glycerol hydrodeoxygenation catalyst and preparation method and application thereof |
| CN113030353A (en) * | 2019-12-25 | 2021-06-25 | 上海奥博生物医药技术有限公司 | Method for measuring content of (S) -1, 2-propylene glycol chiral isomer |
| CN115594565A (en) * | 2022-12-15 | 2023-01-13 | 南京舒宜汇科学仪器有限公司（Cn） | Process for preparing 1, 3-propylene glycol by glycerol hydrogenation |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009093486A1 (en) * | 2008-01-21 | 2009-07-30 | Kao Corporation | Method for producing hydrogenolysis product of polyhydric alcohol |
| JP2009173550A (en) * | 2008-01-21 | 2009-08-06 | Kao Corp | Method for producing hydrogenolysis product of polyhydric alcohol |
| US8158834B2 (en) | 2008-01-21 | 2012-04-17 | Kao Corporation | Method for producing hydrogenolysis product of polyhydric alcohol |
| KR101205897B1 (en) | 2010-04-19 | 2012-11-29 | 한국과학기술연구원 | The noble metal based catalyst supported on complex metal oxide and the method for the producing of 1,2-propanediol |
| JP2013067598A (en) * | 2011-09-26 | 2013-04-18 | Ube Industries Ltd | Process for production of 1,3-diol compound |
| JP2013166096A (en) * | 2012-02-14 | 2013-08-29 | Osaka Univ | Glycerol hydrogenating decomposition catalyst, and method for manufacturing 1, 3-propane diol using the same |
| JP2013216623A (en) * | 2012-04-10 | 2013-10-24 | Daicel Corp | Method for producing propanediol |
| US9447011B2 (en) | 2012-11-21 | 2016-09-20 | University Of Tennessee Research Foundation | Methods, systems and devices for simultaneous production of lactic acid and propylene glycol from glycerol |
| CN113030353A (en) * | 2019-12-25 | 2021-06-25 | 上海奥博生物医药技术有限公司 | Method for measuring content of (S) -1, 2-propylene glycol chiral isomer |
| CN111774089A (en) * | 2020-07-28 | 2020-10-16 | 中国科学院上海高等研究院 | Glycerol hydrodeoxygenation catalyst and preparation method and application thereof |
| CN115594565A (en) * | 2022-12-15 | 2023-01-13 | 南京舒宜汇科学仪器有限公司（Cn） | Process for preparing 1, 3-propylene glycol by glycerol hydrogenation |
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