JP4002884B2 - ソルビトールの製造 - Google Patents
ソルビトールの製造 Download PDFInfo
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- JP4002884B2 JP4002884B2 JP2003503351A JP2003503351A JP4002884B2 JP 4002884 B2 JP4002884 B2 JP 4002884B2 JP 2003503351 A JP2003503351 A JP 2003503351A JP 2003503351 A JP2003503351 A JP 2003503351A JP 4002884 B2 JP4002884 B2 JP 4002884B2
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- Prior art keywords
- catalyst
- ruthenium
- hydrogenation
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 title claims abstract description 28
- 239000000600 sorbitol Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 16
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 8
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 150000003304 ruthenium compounds Chemical class 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 56
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 55
- 239000002245 particle Substances 0.000 claims description 23
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 7
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 24
- 229960002920 sorbitol Drugs 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000012876 carrier material Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- 229960001031 glucose Drugs 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VAAILMLOAHTPQK-UHFFFAOYSA-N nitroxyl anion;ruthenium(4+);trinitrate Chemical compound [Ru+3]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VAAILMLOAHTPQK-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 description 4
- 229960004903 invert sugar Drugs 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- 229930091371 Fructose Natural products 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- 229930195725 Mannitol Natural products 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000594 mannitol Substances 0.000 description 3
- 235000010355 mannitol Nutrition 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000005846 sugar alcohols Chemical class 0.000 description 3
- -1 titanium halide Chemical class 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 150000002016 disaccharides Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 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 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006345 epimerization reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 229960002737 fructose Drugs 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 230000037361 pathway Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- RADGOBKLTHEUQO-UHFFFAOYSA-N ruthenium(4+) Chemical compound [Ru+4] RADGOBKLTHEUQO-UHFFFAOYSA-N 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000010956 selective crystallization Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B01J35/615—
-
- B01J35/617—
Description
i)非晶質二酸化ケイ素をベースとする担体材料を低分子量ルテニウム化合物のハロゲン非含有水溶液で1回または複数回処理し、次に200℃以下、好ましくは≦180℃、特には≦150℃で前記処理済み担体材料を乾燥し、
ii)i)で得られた固体を100〜350℃、好ましくは150〜350℃、特には200〜320℃で水素によって還元し、
工程ii)を工程i)の直後に実施することにより得られるルテニウム触媒を用いることで達成されることを見出した。
1.手法A:非焼成粉末状ハロゲン非含有触媒
所定量の個々の担体材料に、個々の担体材料が吸収することができる最大量の硝酸ニトロシルルテニウム(III)水溶液を含浸させた。個々の担体材料によって吸収することができる最大量は、基準サンプルに基づいて予め求めておいたものである。各場合で、担体材料においてルテニウムの所望濃度が得られるような溶液濃度とした。
乾燥後に得られた固体を空気流下に400℃で4時間加熱してから、水素化を行った以外は、手法Aと同様にして触媒を製造した。
硝酸ニトロシルルテニウム(III)に代えて塩化ルテニウム(III)を用いた以外、手法Aと同様にして触媒を製造した。
所定量の円柱形担体材料ストランド(直径:4mm、長さ:3〜10mm)に、個々の担体材料が吸収できる最大量の硝酸ニトロシルルテニウム(III)溶液を含浸させた。個々の担体材料が吸収する最大量は、基準サンプルに基づいて予め求めておいたものである。各場合で、担体材料においてルテニウムの所望濃度が得られるような溶液濃度とした。
硝酸ニトロシルルテニウム(III)に代えて塩化ルテニウム(III)を用いた以外、手法Dと同様にして触媒を製造した。
1)下記の特性を有するシリカゲル粉末
SiO2含有量:>99.95重量%、
比BET表面積:523m2/g、
水分吸収:1.4mL/g、
細孔容積:0.75mL/g(DIN66134記載の窒素ポロメトリーによって測定)、
所定孔径:60Å、
粒径:63〜200μm。
SiO2含有量:>99.95重量%、
比BET表面積:317m2/g、
水分吸収:1.4mL/g、
粒径:<63μm。
SiO2含有量:>99.95重量%、
比BET表面積:270m2/g、
水分吸収:1.5mL/g、
粒径:<63μm。
SiO2含有量:>99.95重量%、
比BET表面積:68m2/g、
水分吸収:1.04mL/g、
粒径:<63μm。
TiO2含有量:>99.9重量%、
比BET表面積:325m2/g、
水分吸収:0.84mL/g、
粒径:<63μm。
ZrO2含有量:>99.5重量%、
比BET表面積:138m2/g、
水分吸収:0.7mL/g、
粒径:<63μm。
Al2O3含有量:>99.5重量%、
比BET表面積:226m2/g、
水分吸収:1.1mL/g、
細孔容積:0.54mL/g、
粒径:<63μm。
比BET表面積:1306m2/g、
水分吸収:1.7mL/g。
MgO含有量:>99重量%、
比BET表面積:81m2/g、
水分吸収:3.2mL/g、
粒径:<63μm。
Al2O3/SiO2比:30/70、
比BET表面積:482m2/g、
細孔容積:0.33mL/g、
水分吸収:0.57mL/g、
粒径:<63μm。
Al2O3含有量:>99.95重量%、
比BET表面積:80m2/g、
水分吸収:1.05mL/g、
細孔容積:0.67mL/g(DIN66134)、
粒径:<100μm。
SiO2含有量:>99.5重量%(0.3重量%Na2O)、
比BET表面積:169m2/g、
水分吸収:0.95mL/g、
細孔容積:0.7mL/g(DIN66134)。
一般的水素化手法
濃度30重量%のD(+)グルコース水溶液1200mLと個々の触媒3gとを、撹拌機、サンプリングおよび水素加圧用の装置を備えた2.5リットルのオートクレーブに入れた。窒素によって触媒を不活性化した。次に、水素圧を50バールとし、オートクレーブを加熱して120℃とした。反応中、撹拌を1000rpmで行った。反応中の変換率を測定するため、20分ごとにサンプル採取を行い、HPLCによってソルビトールおよびマンニトールの含有量を測定した。遅くとも20時間後に反応を停止した。表2には、最大収率を得るのに必要な時間を示している。さらに、ソルビトール形成に関する選択性および副生成物としてのマンニトールの形成も報告してある。
IIで記載の一般的水素化手法と同様にして、個々の触媒0.9g存在下に、300mlオートクレーブ中、100バールの水素下にて90℃で、30重量%のD-グルコース水溶液180mLを水素化した。変換率および選択性を、IIで記載のようにHPLCによって測定した。表3に、最大収率を得るのに必要な時間を示している。さらにソルビトール形成に関する選択性も報告してある。
使用したリアクタは、触媒を充填した加熱可能ステンレス製反応管であった。反応配置には、原料用給液ポンプ、循環ポンプ、サンプリング用装置ならびに液面制御および排気ガス制御を有する分離装置を設けた。濃度30重量%の個々の単糖類または二糖類溶液240mLをこの反応配置で、100oCおよび水素圧50バールにて速度50mL/(g(触媒)×h)で循環させ、その間にIIで記載の分析によって、原料の減少、生成物の増加および副生成物の形成を測定した。変換率99.4%が得られた時点で反応を停止した。最大収率を得るのに必要な接触時間を、選択性とともに表4に示してある。
Claims (10)
- ルテニウム触媒存在下での水素化によってソルビトールを形成する単糖類の水溶液の接触水素化によってソルビトールを製造する方法であって、前記ルテニウム触媒が、
i)非晶質二酸化ケイ素をベースとする担体材料を低分子量ルテニウム化合物のハロゲン非含有水溶液で1回または複数回処理し、次に200℃以下で前記処理済み担体材料を乾燥し、
ii)i)で得られた固体を100〜350℃で水素によって還元し、
工程ii)を工程i)の直後に実施することによって得られるルテニウム触媒である、前記方法。 - 前記非晶質二酸化ケイ素をベースとする担体が50〜700m2/gの範囲のBET表面積を有する請求項1に記載の方法。
- 前記ルテニウム触媒が、担体重量基準で0.2〜10重量%の量でルテニウムを含む請求項1または2に記載の方法。
- 前記ルテニウム触媒が該触媒の総重量基準で0.05重量%未満のハロゲンを含み、
−非晶質二酸化ケイ素をベースとする担体材料ならびに
−前記担体上に原子レベルでの分散形態および/またはルテニウム粒子の形態で存在するルテニウム元素
からなり、前記触媒が10nmを超える粒径を有するルテニウム粒子および/または凝集塊を実質的に含まない、請求項1に記載の方法。 - 前記単糖類を4〜10の範囲のpHを有する水溶液として用いる請求項1〜4のいずれかに記載の方法。
- 前記単糖類がグルコースである請求項1〜5のいずれかに記載の方法。
- 前記水素化を10〜500バールの範囲の水素分圧で行う請求項1〜6のいずれかに記載の方法。
- 前記水素化を40〜250℃で行う請求項1〜7のいずれかに記載の方法。
- 前記水素化を固定床触媒上で行う請求項1〜8のいずれかに記載の方法。
- 水素化を懸濁液の形態で触媒を含む液相中で行う請求項1〜9のいずれかに記載の方法。
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DE10128203A DE10128203A1 (de) | 2001-06-11 | 2001-06-11 | Verfahren zur Herstellung von Sorbit |
PCT/EP2002/006349 WO2002100539A2 (de) | 2001-06-11 | 2002-06-10 | Verfahren zur herstellung von sorbit durch hydrierung geeigneter mono- und disaccharide an einem ru/si02-katalysator |
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DE (2) | DE10128203A1 (ja) |
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JP2006509833A (ja) * | 2002-12-11 | 2006-03-23 | ビーエーエスエフ アクチェンゲゼルシャフト | 糖アルコールの連続的製造方法 |
MY148259A (en) * | 2005-12-21 | 2013-03-29 | Virent Inc | Catalysts and methods for reforming oxygenated compounds |
RU2427422C2 (ru) * | 2006-03-01 | 2011-08-27 | Нэшнл Юниверсити Корпорейшн Хоккайдо Юниверсити | Катализатор гидролиза целлюлозы и/или восстановления продуктов гидролиза целлюлозы и способ получения из целлюлозы сахарных спиртов |
BRPI0719504A2 (pt) * | 2006-12-20 | 2017-10-24 | Virent Energy Systems Inc | "reator de fluxo descendente concorrente concorrente para converter um material de partida líquido em um produto gasoso não condensável mediante a utilização de um catalisador heterogêneo, sistema de geração de energia e método para a manufatura de gás não condensável" |
US8017818B2 (en) | 2007-03-08 | 2011-09-13 | Virent Energy Systems, Inc. | Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons |
PT2164975E (pt) | 2007-07-06 | 2012-03-08 | Basf Se | Processo para a produção de uma solução aquosa de glicose |
BRPI0815978A2 (pt) | 2007-08-29 | 2015-02-18 | Basf Se | Processo para preparar aminas, e, usos de um efluente de reação, e de uma monoamina |
AU2009285699B2 (en) * | 2008-08-27 | 2014-04-10 | Virent, Inc. | Synthesis of liquid fuels from biomass |
US8697924B2 (en) | 2008-09-05 | 2014-04-15 | Shell Oil Company | Liquid fuel compositions |
BRPI1010126A2 (pt) * | 2009-06-30 | 2016-03-15 | Virent Inc | método de regeneração de um catalizador de hidrogenação e método para a hidrogenação de uma açucar e a regeneração em linha de um catalizador de hidrogenação que contém depósitos carbonáceos |
US9303226B2 (en) | 2009-12-31 | 2016-04-05 | Shell Oil Company | Direct aqueous phase reforming of bio-based feedstocks |
US9447347B2 (en) | 2009-12-31 | 2016-09-20 | Shell Oil Company | Biofuels via hydrogenolysis-condensation |
EP2569264A1 (en) | 2010-05-12 | 2013-03-20 | Shell Oil Company | Process including hydrogenolysis of biomass followed by dehydrogenation and aldol condensation for producing alkanes |
AU2011253083B2 (en) | 2010-05-12 | 2014-08-21 | Shell Internationale Research Maatschappij B.V. | Process including hydrogenolysis of biomass followed by dehydrogenation and aldol condensation to produce alkanes |
JP5823756B2 (ja) * | 2010-07-21 | 2015-11-25 | 国立大学法人北海道大学 | 糖アルコールの製造方法 |
US20120289747A1 (en) * | 2011-05-11 | 2012-11-15 | Carl-Bosch-Strasse 38 | Catalysts for the hydrogenation of aromatic amines |
EP3416740B1 (en) | 2016-02-19 | 2021-01-06 | Intercontinental Great Brands LLC | Processes to create multiple value streams from biomass sources |
CN115043705B (zh) * | 2022-06-28 | 2023-06-23 | 南京工业大学 | 一种催化剂催化制备山梨醇的方法 |
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US2868847A (en) * | 1956-10-05 | 1959-01-13 | Engelhard Ind Inc | Hydrogenation of mono-and disaccharides to polyols |
US3963788A (en) | 1974-08-20 | 1976-06-15 | Kruse Walter M | Polyhydric alcohol production using ruthenium zeolite catalyst |
US4072628A (en) * | 1974-11-05 | 1978-02-07 | Ici Americas Inc. | Regeneration of supported ruthenium catalyst |
US3963789A (en) | 1974-12-12 | 1976-06-15 | Kruse Walter M | Polyhydric alcohol production using RU on clay supports |
US4487980A (en) | 1982-01-19 | 1984-12-11 | Uop Inc. | Method for hydrogenating aqueous solutions of carbohydrates |
FR2526782A1 (fr) * | 1982-05-14 | 1983-11-18 | Metaux Precieux Cie | Procede de preparation de chlorure de ruthenium et catalyseur obtenu a partir de ce chlorure |
US4380680A (en) | 1982-05-21 | 1983-04-19 | Uop Inc. | Method for hydrogenating aqueous solutions of carbohydrates |
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EP1412083A2 (de) | 2004-04-28 |
DE50212905D1 (de) | 2008-11-27 |
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BR0210334A (pt) | 2004-09-21 |
JP2004532275A (ja) | 2004-10-21 |
DE10128203A1 (de) | 2002-12-12 |
CN1524015A (zh) | 2004-08-25 |
ES2312591T3 (es) | 2009-03-01 |
DK1412083T3 (da) | 2009-02-23 |
AU2002317792A1 (en) | 2002-12-23 |
EP1412083B1 (de) | 2008-10-15 |
WO2002100539A8 (de) | 2003-12-24 |
ATE411105T1 (de) | 2008-10-15 |
CA2449522A1 (en) | 2002-12-19 |
US7022824B2 (en) | 2006-04-04 |
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