TWI764937B - 用於製備1,4-丁二醇之方法及催化劑 - Google Patents
用於製備1,4-丁二醇之方法及催化劑 Download PDFInfo
- Publication number
- TWI764937B TWI764937B TW106133095A TW106133095A TWI764937B TW I764937 B TWI764937 B TW I764937B TW 106133095 A TW106133095 A TW 106133095A TW 106133095 A TW106133095 A TW 106133095A TW I764937 B TWI764937 B TW I764937B
- Authority
- TW
- Taiwan
- Prior art keywords
- catalyst
- hydrogenation
- range
- carried out
- nickel
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims description 51
- 230000008569 process Effects 0.000 title claims description 20
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims abstract description 34
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 107
- 238000005984 hydrogenation reaction Methods 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000006260 foam Substances 0.000 abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 229910052759 nickel Inorganic materials 0.000 description 32
- 239000000243 solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000004411 aluminium Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000002386 leaching Methods 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013590 bulk material Substances 0.000 description 5
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical compound OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002318 adhesion promoter Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- -1 hydroxy aldehydes Chemical class 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OZCRKDNRAAKDAN-HNQUOIGGSA-N (e)-but-1-ene-1,4-diol Chemical compound OCC\C=C\O OZCRKDNRAAKDAN-HNQUOIGGSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
- C07C29/136—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 of >C=O containing groups, e.g. —COOH
- C07C29/14—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 of >C=O containing groups, e.g. —COOH of a —CHO 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
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/20—Dihydroxylic alcohols
- C07C31/207—1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Nanotechnology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本發明係關於一種藉由在具有多孔性泡體結構及至高0.8 kg/L的容積密度之雷氏型(Raney type)催化劑存在下氫化2-丁炔-1,4-二醇(BYD)或4-羥基丁醛(4-HBA)之用於製備1,4-丁二醇(BDO)的方法,其中該巨觀的孔具有在100至5000 μm範圍之尺寸。
Description
1,4-丁二醇本身尤其是用在紡織、皮革、食品和醫藥工業中。彼作為中間物主要是用於製備熱塑性聚酯。此外,BDO是在一些重要化學中間物和溶劑諸如四氫呋喃(THF)、γ-丁內酯或吡咯啶之製造中的合成先質。
最頻繁地用於製造BDO之工業方法是基於藉由經改質鎳催化劑所催化之2-丁炔-1,4-二醇(BYD)的連續氫化。此方法之單一階段變化型一般係在固定床反應器中於80-160℃和約300巴之壓力下進行。也已知一種BYD之二階段氫化,其中主要製造2-丁烯-1,4-二醇(BED)的第一階段係在約40巴之較低壓力下進行。在第二階段中,在300巴下將BED轉化以產生BDO。此外,其他用於製造BDO之方法已知是基於乙炔作為主原料。例如,烯丙醇藉由以合成氣(CO+H2
)氫甲醯化可轉化成4-羥基丁醛(4-HBA)且進一步氫化以產生BDO,其中二步驟也可同時進行。關於BDO的進一步資料被描述於例如烏爾曼工業化學百科全書 (Ullmann’s Encyclopedia of Industrial Chemistry)之“丁二醇類、丁烯二醇和丁炔二醇”章中,該章係在線上 15.06.2000, DOI:10.1002/14356007.a04_455公布。 頻繁用於該氫化之該“雷氏型”鎳催化劑通常係藉由形成一種至少二元金屬合金,其經常包含鋁(Al)和鎳(Ni),及隨後瀝濾出鋁而製備。此類方法的描述被揭示於例如US 1628190 A、US 1915473 A、US 2139602、US 2977327公開本中。 US 2967893 A揭示銅改質之粉狀鎳催化劑之漿液,其作為用於將BYD氫化成BDO的促進劑。 該催化劑先質的活化能在用於製造BDO之氫化反應器之外進行或在該反應器中原位進行,例如如EP 0340970 A2及DE 2004611 A1所述。 DE 2004611 A揭示一種藉由氫化BYD之水溶液之用於製造BDO的連續方法。使用具有開口之顆粒狀鎳鋁催化劑的固定床,其已藉由從由主要約35至60重量%鎳和約40至65重量%鋁構成之鎳鋁合金移除約5至30%的鋁而被活化。形成該固定床之催化劑粒子具有在約2 cm至1.4 mm之範圍之粒度,較佳約1 cm至2 mm。 EP 0807464 A1揭示一種利用經改質雷氏鎳催化劑之催化性氫化羥基醛類和環狀羥基醚類的方法,該催化劑包含40-98重量%之Ni、1-50重量%之Al、0.05-15重量%之Fe及隨意之0.05-10重量%之選自由Cr、Mo、W、Co、Mn和Ti組成之群組中至少一種金屬。若該反應係在漿液床反應器中進行,則此催化劑可為粉末型。若該反應係在固定床反應器中(諸如在DE 2004611 A中)進行,則在EP 0807464 A1中揭示之此催化劑也可為顆粒型。 EP 1833778 B1揭示一種用於氫化4-羥基丁醛(HBA)成為1,4-丁二醇(BDO)及/或用於氫化2-甲基-3-羥基丙醛(HMPA)成為2-甲基-1,3-丙二醇的方法,其中HBA及/或HMPA之水溶液藉由與氫化催化劑(其為經鉬活化之鎳催化劑)之固定床接觸而在絕熱氫化區中與氫接觸。
迄今已知在工業應用中用於製造BDO之方法的缺點是對鎳的極高需求,該鎳在這些方法中作為雷氏型氫化催化劑使用。如上述,顆粒型鎳催化劑一般用在連續方法中,該鎳催化劑係呈非經活化先質被導入該反應器中且藉由瀝濾出鋁而在原位被活化。這些催化劑一般具有大於1.5 kg/L之容積密度,使得在以催化劑填充5至50 m3
之反應器時,如在這些催化劑獲得足夠的產物產率的慣常活性的情況下所需者,使用在8與100噸之間的鎳。 因在地殼中有約0.01%之質量分率,鎳是該更稀有之金屬之一者。經濟可行之量的可得性被限制。此外,對用於工業應用(例如在電子和材料部門中)之鎳的全球需求持續增加。 本發明之目的因此是要提供一種用於催化性製備1,4-丁二醇之經濟,及特別關於鎳需求而言,最節約資源的方法。進一步的目的是要提供催化劑,藉由催化劑之手段,可在工業相關之製程條件下,以充分產率和選擇率進行適當化學反應以產生BDO。 這些目的係藉由一種藉由氫化2-丁炔-1,4-二醇或4-羥基丁醛之用於製備1,4-丁二醇之方法達成,其中將包含2-丁炔-1,4-二醇或4-羥基丁醛之水溶液與氫和具有多孔性泡體結構及不大於0.8 kg/L的容積密度之經活化鎳催化劑接觸,其中巨觀的孔具有在100至5000 μm範圍內之尺寸。 根據本發明之方法係在水之存在下進行。較佳地,使用1至70重量%之BYD或4-HBA的水溶液作為反應物。取決於該反應器之概念和程序而定,與該經活化鎳催化劑接觸之反應物溶液可包含至高60重量%的BDO目標產物。若內部進行根據本發明之方法的氫化反應器是迴路反應器,則此特別適用。 根據本發明之方法較佳是在10至350巴範圍之氫壓力下進行。在此,4-HBA之氫化較佳是在10至110巴(特佳40至100巴)下進行。較佳在50至350巴(特佳75至320且尤其佳100至300巴)範圍之氫壓力下將BYD氫化成BDO。 根據本發明之方法可在50℃至250℃之溫度下進行。較佳在50至200℃,特佳在50至150℃且尤其佳在50至100℃之溫度範圍將4-HBA氫化成BDO。較佳在50至150℃之溫度範圍,特佳在70至140℃且尤其佳在80至135℃之溫度範圍將BYD氫化成BDO。根據本發明之用於氫化BYD或4-HBA之方法可批次地或連續地進行。在攪拌槽反應器中批次地操作(成組操作)的情況下,所用之催化劑可呈鬆散形式在反應混合物中攪拌。在完成反應後,該催化劑可例如藉由過濾、引流出/抽送出該上澄反應溶液或以此技藝之技術人員已知之其他方式從該反應混合物分離出。 較佳使用固持裝置於所用之催化劑。若根據本發明之方法係在攪拌槽反應器中批次地進行,則該催化劑較佳係配置在接近該攪拌軸之固持裝置中,使得通過該插置在該固持裝置中之催化劑床之反應混合物的流動藉由該攪拌器產生。此具體例與該催化劑之鬆散(亦即非固定)使用相比之優點是不需在另外製程步驟中從該催化劑後續分離出該產物混合物。 根據本發明之方法較佳在固定床反應器中(例如在滴流床反應器或液體填充反應器中)、在氣泡塔中或在此技藝中已知類型之其他反應器中連續進行。所有這些反應器類型可以“單程(once through)”模式操作,其中將該等反應物(進料)導入該反應器中且在反應後移除產物混合物。或者,可使來自該反應器之該產物混合物之一部分返回到反應區中(循環流)。在此一循環規劃(循環模式)中,進料對循環流之重量比率是0.025至0.25,較佳是0.05至0.15,特佳是0.05至0.1。 BYD可在單一階段或二階段中轉化成BDO。BYD氫化成BDO之單一階段反應規劃較佳連續地進行,其中該催化劑呈固定床存在於絕熱操作的反應器中。 在該反應器入口之溫度則較佳在80至100℃之範圍,在該反應器出口之溫度係在110-150℃之間。在此情況下,在進行氫化成BDO之反應的反應區中的溫度是在110與135℃之間的範圍。 在批次式模式操作之攪拌槽反應器中,根據本發明氫化BYD成BDO的具體例的情況下,較佳選擇二階段溫度規劃。為此目的,在開始反應時於該攪拌槽中的溫度維持在90至105℃之範圍,以致丁炔-1,4-二醇至少部分地與氫反應以產生丁烯-1,4-二醇。為極大化完成BYD轉化成丁烯-1,4-二醇,理想滯留時間可藉由偵測在此期間取用的氫量來決定。在均等於BYD用量之化學計量的氫被用掉後,結束第一反應階段。接著在此攪拌槽中之溫度增至130至135℃且維持直至完成氫化以產生1,4-丁二醇。 用於根據本發明之方法之優化反應規劃,該氫化係在pH4.0至9.0下進行。 經活化鎳催化劑基本上對此技藝之技術人員也已知是該雷氏型催化劑或基本上是“雷氏鎳催化劑”。彼等通常係藉由形成至少二元金屬合金,其經常包含鋁(Al)和鎳(Ni),且隨後瀝濾出鋁而製備。 在根據本發明之方法中使用之該經活化鎳催化劑具有不大於0.8 kg/L,較佳為0.1至0.7 kg/L,特佳為0.2至0.6 kg/L之容積密度。 容積密度dSch
(有時稱為固體之經傾注密度(poured density))是顆粒狀固體與充滿該等粒子間之空穴的空氣的混合物的質量對體積的比率。此技藝之技術人員常用之此參數可藉由測量用圓筒之手段而藉由測定固體之限定床體積(VF
)的質量(MF
)而測定:。 該容積密度可藉由緩慢添加限定量之滴濕(drop-wet)催化劑至充滿水之1L標準測量用圓筒中而測定。在完成該催化劑之沉降後,從刻度讀出該催化劑床之體積。根據以下等式計算該容積密度dSch
:, 其中MF
是以乾質量計催化劑的用量且VF
是在使用水下觀察之該床體積。該經活化催化劑之乾質量可藉由充滿水和催化劑之具有限定體積的容器與僅充滿水之具有相同體積之容器的重量比較而決定。該乾催化劑之質量藉由該二重量之差乘以密度係數k而得知,該密度係數k是得自該乾催化劑之密度除以該乾催化劑與水之密度差的商。密度係數可直接從技術文獻及/或該雷氏型催化劑之製造商和經銷商之處置指導取得且一般是約1.2。該催化劑床之體積對此技藝之技術人員是可藉由讀出所用之測量用圓筒的刻度而直接取得的。該方法與該雷氏型催化劑之粒度無關,亦即與彼是顆粒或泡體材料之床或彼是水下的粉末催化劑無關。 在根據本發明之方法中使用之經活化鎳催化劑包含65至98重量%,較佳地70至95重量%,特佳地80至90重量%之鎳和0至15重量%,較佳地0至13重量%,特佳地4至13重量%,尤其佳地7至13重量%之鋁。另外,在根據本發明之方法的較佳具體例中,使用經活化鎳催化劑,其具有至高10重量%,較佳地0.05至5重量%,特佳地0.1至2重量%之鉬(Mo)及/或0至10重量%,較佳地0.05至5重量%,特佳地1.5至3.5重量%之選自由鐵和鉻組成之群組中的一或多種元素。 在根據本發明之方法中使用之經活化鎳催化劑較佳具有至高70 mm之平均粒度。原則上,最佳粒度是可控制的且與所用反應器中盛行之條件相區配合。該經活化鎳催化劑較佳呈鬆散材料被使用,其具有至高50 mm之粒度,特佳具有至高30 mm之粒度,特佳具有不大於10 mm之粒度。對於具有在5 μm至125 mm之粒度的粒子的平均粒度可藉由根據DIN 66165之篩分析來測定。或者,平均粒度可藉由顯微鏡之手段而光學測定,其中應測定至少100個個別值的數目平均。 在根據本發明之方法中使用之經活化鎳催化劑具有1至200 m2
/g,較佳地10至120 m2
/g,特佳地70至100 m2
/g之BET表面積。比表面積(為簡化之故也稱為BET表面積)係依照DIN 9277藉由根據如在J.Am.Chem.Soc.1938.Vol.60, pp.309-319中描述之布厄特法(Brunauer-Emmett-Teller method)的氮吸附被測定。 在根據本發明之方法中使用之經活化鎳催化劑較佳具有巨觀的泡體結構。包含很多空穴之多孔性金屬泡體結構可以例如藉由氣體對液化金屬的作用及後續的冷卻而形成。對獲得此種結構之另一選項是使用有機泡體結構作為用於施加金屬之模板且隨後藉由焚化移除該有機模板。 根據本發明之方法使用之經活化鎳催化劑較佳具有多孔性泡體結構,其中該巨觀的孔具有在200至2500 μm(特佳400至1200 μm)範圍之尺寸。該巨觀之孔的尺寸可使用例如在“The Guide 2000 of Technical Foams”第四冊第四部份之33-41頁中描述之方法測定。該巨觀之孔的尺寸可藉由光學測量經選擇之孔的孔直徑而測定。對至少100個不同的孔重複此測量,接著該孔直徑之平均值由此測量計算以作為分析結果。 本發明進一步提供一種具有多孔性泡體結構及不大於0.8 kg/L的容積密度之經活化鎳催化劑,其中該巨觀之孔具有在100至5000 μm範圍之尺寸。尤其,可使用此經活化鎳催化劑於一種藉由氫化2-丁炔-1,4-二醇或4-羥基丁醛之用於製備1,4-丁二醇的方法中,其中使包含2-丁炔-1,4-二醇或4-羥基丁醛之水溶液與氫和經活化鎳催化劑接觸。 與在根據本發明之方法中使用之催化劑相關之所有以上定義和與該等分析方法相關之說明對應地適用於下述之根據本發明的經活化鎳催化劑。 根據本發明之經活化鎳催化劑具有不大於0.8 kg/L,較佳地0.1至0.7 kg/L,特佳地0.2至0.6 kg/L之容積密度。根據本發明之經活化鎳催化劑包含65至98重量%,較佳地70至95重量%,特佳地80至90重量%之鎳和0至15重量%,較佳地0至13重量%,特佳地4至13重量%,尤其佳地7至13重量%之鋁。另外,根據本發明之經活化鎳催化劑的較佳具體例包含至高10重量%,較佳地0.05至5重量%,特佳地0.1至2重量%之鉬(Mo)及/或0至10重量%,較佳地0.05至5重量%,特佳地1.5至3.5重量%之選自由鐵和鉻組成之群組中的一或多種元素。 根據本發明之經活化鎳催化劑較佳具有至高70 mm之平均粒度。原則上,最佳粒度是可控制的且與所用反應器中盛行之條件區配。根據本發明之該經活化鎳催化劑較佳呈鬆散材料被使用,其具有至高50 mm之粒度,特佳具有至高30 mm之粒度,特佳具有不大於10 mm之粒度。 根據本發明之經活化鎳催化劑具有1至200 m2
/g,較佳地10至120 m2
/g,特佳地70至100 m2
/g之BET表面積。 根據本發明之經活化鎳催化劑較佳具有多孔性泡體結構,其中該巨觀之孔具有在200至2500 μm(特佳400至1200 μm)範圍之尺寸。 為製備根據本發明之經活化鎳催化劑,鎳金屬泡體以黏合促進劑噴灑,以鋁粉末塗布且由此所得材料受到熱處理。接著,進行在該熱處理後所得之Ni/Al材料的還原、分離及/或成形。根據本發明之經活化鎳催化劑係藉由瀝濾出其中所含之鋁的至少一部分而從彼獲得。 待用以製備根據本發明之催化劑的鎳金屬泡體較佳以具有邊長至多500 mm且厚度不大於5 mm之片形式被使用。為改良鋁粉末對該鎳泡體之黏合性,此泡體起初以黏合促進劑處理。可以利用任何改良金屬與有機材料間之黏合性的黏合促進劑。例如聚乙亞胺溶液是合適的。 在施加該鋁粉末至該鎳金屬泡體之後,該材料歷經到在500至1000℃(較佳是600至800℃)之溫度範圍的熱處理,其中來自前述塗布方法之水分和有機殘餘物首先被移除且隨後鋁至少部分被液化且被合金化於該鎳泡體結構中。該熱處理係在不含氧之惰性氣體氣氛中實施以防止破壞性氧化層形成。 所得材料(以鋁改質之鎳金屬泡體)接著隨意地被粉碎、分離及/或歷經合適的成形。可例如藉由雷射切割或雷射光束切割來實施粉碎且分離以鋁改質之該鎳金屬泡體。所得材料碎片(粒子)較佳為最大邊長不大於50 mm之立方體或平行六面體形且其整體形成蓬鬆材料。 在下一步驟中,根據本發明之催化劑係藉由活化該以鋁改質之鎳泡體而獲得。為此目的,該鋁之至少一部分從該材料化學地瀝濾出。為此目的,使用鹼性水溶液,較佳是選自由氫氧化鈉、氫氧化鉀或氫氧化鋰組成之群組中之鹼金屬氫氧化物溶液,特佳是氫氧化鈉水溶液。在該催化劑製備中所利用之鹼金屬氫氧化物水溶液的濃度通常可以在0.1與60重量%之間。較佳以5至50重量%(特佳5至35重量%)之氫氧化鈉水溶液在20℃至100℃(較佳在40℃至85℃,特佳在50℃至80℃)之溫度下實施瀝濾出鋁。除了上述之其他反應條件之外,在此使用之瀝濾時間(亦即該氫氧化鈉水溶液與該以鋁改質之鎳金屬泡體之反應時間)係與待設定在成品中之鋁含量有關,且可以在2與240分鐘之間。 在所生成之根據本發明之該經活化鎳催化劑中,維持原初使用之鎳泡體的巨觀泡體結構。在接近表面之區中實施至少部分地瀝濾出該鋁,在該區中生成高孔隙度之催化活性鎳結構。根據本發明之催化劑的BET表面積較佳大於所用鎳金屬泡體的BET表面積。 為改良根據本發明之該經活化鎳催化劑之活性、選擇率及/或使用壽命,可以添加各種摻雜劑及/或促進劑。這可以藉由合金化摻雜劑金屬於該催化劑製備所用鎳金屬泡體中及/或藉由濕化學後處理根據本發明之該經活化鎳催化劑而實施。例如,該摻雜劑金屬可藉由較佳從合適先質之水溶液中沉澱或還原分解而施加。較佳施加選自由下列組成之群組中一或多種摻雜劑元素:鉑(Pt)、鈀(Pd)、銠(Rh)、釕(Ru)、鋨(Os)、銥(Ir)、鐵(Fe)、鈷(Co)、鉻(Cr)、鉬(Mo)、鎢(Wo)、錳(Mn)、錸(Re)、銅(Cu)、銀(Ag)和金(Au)。特佳是Fe、Co、Cr及/或Mo。 本發明係在下文中參考一些實例和圖來特別闡明。
實例1 市售成卷中且具有厚1.9 mm、寬300 mm及平均孔度580 μm之鎳泡體係以市售之黏合促進劑溶液噴灑,以鋁粉末塗布且在700℃下熱處理。在冷卻後,如是所得材料以雷射切割成邊長4 mm × 4 mm及厚1.9 mm之正方片。 所得之鬆散材料被配置在用於催化性活化之固定床中且隨後藉由抽送通過5M NaOH溶液(氫氧化鈉水溶液)而濕式化學處理。使該鬆散材料之一部分A在70℃下歷經此濕式化學後處理5分鐘之時間。該鬆散材料之一部分B在60℃下利用氫氧化鈉水溶液後處理15分鐘之時間。二部分後續都以水清洗直至抽送通過該固定床後之清洗溶液已達到pH<10。 如是所得之二催化活性鬆散材料部分的組成藉由ICP-OES分析。結果編輯在下表中。在上表中指明之容積密度係藉由緩慢添加限定量之滴濕催化劑至充滿水之1L標準測量用圓筒中而測定。在完成該催化劑之沉降後,從刻度讀出該催化劑床之體積。該容積密度dSch
係根據以下等式計算:其中MF
是以乾質量計所用催化劑的量且VF
是在使用水下觀察之該床體積。該經活化催化劑之乾質量係藉由充滿水和催化劑之具有限定體積的容器與僅充滿水之具有相同體積之容器的重量比較而決定。該乾催化劑之質量藉由該二重量之差乘以密度係數k而給定,該密度係數k是得自該乾催化劑之密度除以該乾催化劑與水之密度差的商。密度係數可直接從技術文獻及/或該雷氏型催化劑之製造商和經銷商之處置說明取得且一般是約1.2。該催化劑床之體積對此技藝之技術人員可藉由讀出所用之測量用圓筒的刻度而直接取得。該方法與該雷氏型催化劑之粒度無關,亦即與彼是顆粒或泡體材料之床或彼是水下的粉末催化劑無關。 催化劑A被導入具有500 ml總體積之攪拌槽反應器中以調查在丁炔-1,4-二醇(BYD)氫化成1,4-丁二醇(BDO)中的催化效率。起初將300 mL的水饋入該反應器中,將5 mL催化劑A導入接近該攪拌軸之定位在水平面下方的籃中。在關閉該反應器,氣氛改變且以氫填充該反應器高至80巴壓力之後,86.6克之50%的BYD水溶液抽送入在攪拌下之該反應器中且將該反應器加熱至100℃。在100分鐘之反應時間後,在該反應器中之溫度增至135℃且進一步維持260分鐘。在冷卻至室溫後,將該反應混合物樣品移除且藉由氣相層析法分析。從該反應混合物之各成分的經測量濃度,測定該丁炔二醇轉化率、給出BDO之產率和BDO選擇率以及基於該催化劑之空間時間產率STYBDO,V
。結果編輯在下表中。經陳述之量係計算如下: • BYD轉化率係定義為基於所用BYD的莫耳量計之所消耗BYD的莫耳量:其中 n0
(BYD)=所用BYD的莫耳量且 n(BYD)=在該反應結束時BYD的莫耳量 • BDO產率係定義為基於所用BYD的莫耳量計之所得BDO的莫耳量:• BDO選擇率係定義為所形成之所欲產物BDO的量對所轉化之反應物BYD的量的比率:• 基於催化劑體積之空間時間產率係定義為基於催化劑體積(公升)計之製造輸出量,其中製造輸出量應了解意思是基於該反應時間t(小時)計之每次反應運作所生成之所欲BDO產物的質量(kg):實例2: 如實例1中描述地製備催化劑,其中該濕化學後處理係以10重量%氫氧化鈉水溶液在60℃下進行60分鐘之時間。藉由ICP-OES之分析給出所得之具有89重量%之鎳和11重量%之鋁之催化活性蓬鬆材料(催化劑C)的組成。該材料具有dSch
=0.3kg/L之容積密度。該容積密度在根據實例1中描述之程序測定。 也針對催化劑C在攪拌槽反應器中對丁炔-1,4-二醇(BYD)氫化成1,4-丁二醇(BDO)的催化效能調查催化劑C。如實例1中描述地進行實驗設置、程序和評估。 結果編輯在下表中。從催化劑C之容積密度和基於該催化劑體積之空間時間產率,能計算基於該催化劑質量計之空間時間產率STYBDO,m
如下:其為STYBDO,m
=4.55 kg/(kg cat*h)。 實例3: 如實例1中描述地製備催化劑,其中該濕化學後處理係以10重量%氫氧化鈉水溶液在80℃下進行90分鐘之時間。在完成以氫氧化鈉水溶液濕化學處理後,鉬從鉬酸鹽水溶液中沉澱在該催化劑上。藉由ICP-OES之分析給出所得之具有91重量%之鎳、8.7重量之%鋁和0.3重量%之鉬之催化活性蓬鬆材料(催化劑D)的組成。該材料具有容積密度dSch
=0.32 kg/L。該容積密度根據實例1中描述之程序測定。 將催化劑D用在先導固定床反應器中以在60℃之溫度和100巴之氫壓力下氫化4-羥基丁醛(HBA)成BDO且顯示實際定量之HBA轉化率與極良好之BDO產率和BDO選擇率。 比較用實例: 顆粒型經活化鎳催化劑係如先前技術(例如DE 2004611A)得知者被製備且用在用於製備BDO的常見工業工廠中。就此而論,藉由熔化鎳和鋁,由42重量%鎳和58重量%鋁組成之合金被製造,歷經機械粉碎且過篩以獲得具有1.8至4 mm之粒度的顆粒部分。此合金丸粒部分在鬆散填充之固定床中藉由抽送10重量%氫氧化鈉水溶液通過該固定床而在60℃下催化性活化60分鐘之時間且隨後以水清洗直至所得清洗溶液之pH達到<10。所得催化劑具有容積密度dSch
=1.7 kg/L。該容積密度根據實例1中描述之程序測定。該鋁含量是約37重量%鋁。 也針對在攪拌槽反應器中之根據該先前技術之此催化劑對丁炔-1,4-二醇(BYD)氫化成1,4-丁二醇(BDO)的催化效能調查該此催化劑。如實例1中描述地進行實驗設置、程序和評估。 結果編輯在下表中。從根據該先前技術之催化劑之容積密度和基於該催化劑體積之空間時間產率,能計算基於該催化劑質量計之空間時間產率STYBDO,m
。其為0.75 kg/(kg cat*h)。 在對該催化劑A(來自實例1)和C(來自實例2)之該攪拌槽實驗中所得結果與使用根據該先前技術之催化劑(比較用實例)所得之特徵比較:在固定轉化率下,在BDO產率和BDO選擇率方面,催化劑A顯示些微改良,催化劑C顯示明顯改良。 並且,比較使用根據該先前技術之顆粒型催化劑(比較用實例)和本發明之催化劑C所獲得之基於該催化劑質量的空間時間產率。可清楚確認本發明之催化劑C比該先前技術在該值方面增加六倍。 用於工業之固定床反應器之所得的鎳節約量在以下以作為包含20 m3
之催化劑床的一般BDO反應器的實例計算。在夜以繼日之連續操作模式中,此一工廠係以每年平均至少8000操作小時來高效操作。對根據該先前技術之顆粒型鎳催化劑(比較用實例),在1.29 kg/(L cat*h)=1.29 t/(m3
cat*h)之基於催化劑體積的空間時間產率下,每年由該工廠所製造之BDO的量是1.29 × 20 × 8000 t = 206400 t之BDO。使用根據該先前技術之催化劑(其在60-65重量%之鎳含量下具有1.7 kg/L = 1.7 t/m3
的容積密度),需要至少20 × 1.7 × 0.6 t =20.4 t之鎳。 為於實例2之催化劑C(其具有1.37 kg/(L cat*h)= 1.37 t/(m3
cat*h)之基於催化劑體積之空間時間產率)上製造相同量之BDO,需要206400/(1.37*8000)m3
=18.83 m3
之催化劑。這對應於節省1.17 m3
之催化劑體積或5.85%。在0.3 kg/L=0.3 t/m3
之本發明催化劑C的容積密度下所需之催化劑C之量是18.83 × 0.3 t=5.649t的催化劑C。這在89重量%之鎳含量下對應於5 t之鎳需求,與之相比,使用根據該先前技術之顆粒型催化劑有至少20.4 t之鎳需求。 因此,鎳之需求量藉由根據本發明之方法可降至現行量的1/4,這意味著提供一種極有效率之用於製備1,4-丁二醇的方法。
Claims (14)
- 一種具有多孔性泡體結構及不大於0.8kg/L的容積密度之經活化鎳催化劑,其中該多孔性泡體結構為經鋁改質之鎳金屬泡體,其隨意地被粉碎、分離及/或歷經合適的成形,其中巨觀的孔具有在100至5000μm範圍之尺寸。
- 如申請專利範圍第1項之經活化鎳催化劑,其中該催化劑具有至多70mm之平均粒度。
- 如申請專利範圍第1或2項之經活化鎳催化劑,其中該催化劑呈邊長不大於50mm之立方形粒子之鬆散材料存在。
- 如申請專利範圍第1或2項之經活化鎳催化劑,其中該催化劑具有不大於15重量%之鋁含量。
- 如申請專利範圍第1或2項之經活化鎳催化劑,其中該巨觀的孔具有在200至2500μm範圍之尺寸。
- 如申請專利範圍第1或2項之經活化鎳催化劑,其中該催化劑包含0.05至10重量%之至少一種選自由鉬、鐵和鉻所組成群組的元素。
- 一種用於製備1,4-丁二醇的方法,其係藉由氫化2-丁炔-1,4-二醇或4-羥基丁醛,其特徵在於,將包含2-丁炔-1,4-二醇或4-羥基丁醛之水溶液與氫和如申請專利範圍第1至6項中任一項之經活化鎳催化劑接觸。
- 如申請專利範圍第7項之方法,其中該4-羥基丁醛之氫化係在10至110巴範圍之氫壓力下進行。
- 如申請專利範圍第8項之方法,其中該氫化係在50至200℃之溫度範圍下進行。
- 如申請專利範圍第7項之方法,其中該2-丁炔-1,4-二醇之氫化係在50至350巴範圍之氫壓力下進行。
- 如申請專利範圍第10項之方法,其中該氫化係在50至150℃之溫度範圍下進行。
- 如申請專利範圍第10或11項之方法,其中該氫化連續地進行,其中該催化劑呈固定床存在於絕熱操作之反應器中且反應器入口之溫度是在80至100℃之範圍且反應器出口之溫度是在110至150℃之範圍。
- 如申請專利範圍第10或11項之方法,其中該氫化係在攪拌槽反應器中批次地進行,其中該催化劑被配置在接近 該攪拌器之軸的固持裝置中,而使得通過催化劑床之反應混合物的流動藉由該攪伴器產生。
- 如申請專利範圍第13項之方法,其中在開始反應時於該攪拌槽中之溫度被維持在90至105℃之範圍,而使得該2-丁炔-1,4-二醇至少部分地與氫反應以產生2-丁烯-1,4-二醇,且該溫度接著提高到130至135℃且被維持直到該氫化完成以產生1,4-丁二醇。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16191735.6A EP3300799A1 (de) | 2016-09-30 | 2016-09-30 | Verfahren und katalysator zur herstellung von 1,4-butandiol |
??16191735.6 | 2016-09-30 | ||
EP16191735.6 | 2016-09-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201829361A TW201829361A (zh) | 2018-08-16 |
TWI764937B true TWI764937B (zh) | 2022-05-21 |
Family
ID=57042820
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW106133095A TWI764937B (zh) | 2016-09-30 | 2017-09-27 | 用於製備1,4-丁二醇之方法及催化劑 |
Country Status (8)
Country | Link |
---|---|
US (1) | US11260375B2 (zh) |
EP (2) | EP3300799A1 (zh) |
JP (1) | JP7069134B2 (zh) |
KR (1) | KR102629663B1 (zh) |
CN (1) | CN109789391A (zh) |
AR (1) | AR109612A1 (zh) |
TW (1) | TWI764937B (zh) |
WO (1) | WO2018060269A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3300798A1 (de) | 2016-09-30 | 2018-04-04 | Evonik Degussa GmbH | Katalysatorfestbett enthaltend metallschaumkörper |
US11401224B2 (en) | 2018-02-14 | 2022-08-02 | Evonik Operations Gmbh | Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes |
CN112469502A (zh) * | 2018-08-08 | 2021-03-09 | 格雷斯公司 | 催化剂、其制备方法和选择性氢化方法 |
KR20210038540A (ko) | 2019-09-25 | 2021-04-07 | 에보닉 오퍼레이션스 게엠베하 | 촉매 반응기 |
CN110790634B (zh) * | 2019-10-14 | 2022-07-12 | 万华化学集团股份有限公司 | 一种1,3-丁二醇的制备方法 |
CN114377685B (zh) * | 2020-10-22 | 2024-02-27 | 上海迅凯新材料科技有限公司 | 镍基催化剂、制备方法及其在加氢合成1,3-丁二醇中的应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1486291A (zh) * | 2001-01-16 | 2004-03-31 | �������¹ɷ�����˾ | 制备饱和有机化合物的方法 |
US7612241B1 (en) * | 2009-03-23 | 2009-11-03 | Lyondell Chemical Technology, L.P. | Hydroformylation process |
CN103966473A (zh) * | 2013-02-06 | 2014-08-06 | 艾蓝腾欧洲有限公司 | 表面改性的金属泡沫体、其制备方法及其用途 |
Family Cites Families (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1628190A (en) | 1926-05-14 | 1927-05-10 | Raney Murray | Method of producing finely-divided nickel |
US1915473A (en) | 1930-12-31 | 1933-06-27 | Raney Murray | Method of preparing catalytic material |
US2139602A (en) | 1935-06-17 | 1938-12-06 | Raney Murray | Method of reclaiming catalytic material from spent catalytic material |
US2895819A (en) * | 1957-09-03 | 1959-07-21 | Bjorksten Res Lab Inc | Method for preparing a catalytic metal foam and use thereof |
US2977327A (en) | 1958-09-26 | 1961-03-28 | Raney Catalyst Company Inc | Process of producing nickel catalysts |
US2967893A (en) | 1958-12-30 | 1961-01-10 | Gen Aniline & Film Corp | Hydrogenation of 2-butyne-1, 4-diol to 1, 4-butanediol |
CA922738A (en) | 1969-01-31 | 1973-03-13 | G. Low Frederick | Hydrogenation of aqueous butynediol over a nickel-aluminum catalyst |
US3839011A (en) * | 1973-07-31 | 1974-10-01 | Int Nickel Co | Nickel-aluminum particle with improved grindability |
US4049580A (en) | 1976-07-23 | 1977-09-20 | The United States Of America As Represented By The Secretary Of The Interior | Method for producing supported Raney nickel catalyst |
US4879420A (en) | 1988-05-06 | 1989-11-07 | E.I. Du Pont De Nemours And Company | Preparation of mixtures of butanediols |
US5399793A (en) | 1993-11-29 | 1995-03-21 | Exxon Chemical Patents Inc. | Hydrogenation catalyst for oxo alcohol process |
US5888923A (en) | 1996-04-15 | 1999-03-30 | Dairen Chemical Corporation | Modified Raney nickel catalyst and a process for preparing diols by using the same |
DE19641707A1 (de) * | 1996-10-10 | 1998-04-16 | Basf Ag | Verfahren zur Herstellung von 1,4-Butandiol durch katalytische Hydrierung von 1,4-Butindiol |
DE19933450A1 (de) * | 1999-07-16 | 2001-01-18 | Degussa | Metallkatalysatoren |
US6399793B1 (en) | 2000-08-16 | 2002-06-04 | Bristol-Myers Squibb Company | Process for the preparation of α' chloroketones |
CN1342633A (zh) * | 2000-09-12 | 2002-04-03 | 上海石油化工股份有限公司 | 由3-羟基丙醛加氢制备1,3-丙二醇的方法 |
DE10101647A1 (de) * | 2001-01-16 | 2002-07-18 | Degussa | Verfahren zur Herstellung von substituierten Aminen durch Hydrierung von substituierten organischen Nitroverbindungen |
US20030047505A1 (en) | 2001-09-13 | 2003-03-13 | Grimes Craig A. | Tubular filter with branched nanoporous membrane integrated with a support and method of producing same |
DE10245510A1 (de) | 2002-09-27 | 2004-04-08 | Scholz, Paul-Friedrich, Dr.-Ing. | Abgasfilter für Verbrennungsmotoren und Verfahren zu seiner Herstellung |
US7375053B2 (en) | 2003-04-07 | 2008-05-20 | W. R. Grace & Co.- Conn. | Nickel and cobalt plated sponge catalysts |
AU2003276141A1 (en) | 2003-10-22 | 2005-05-19 | Degussa Ag | The use of activated granulates of base metals for organic transformations |
CN100376323C (zh) * | 2004-12-03 | 2008-03-26 | 中国石油化工股份有限公司 | 一种泡沫金属加氢催化剂及其制备方法和应用 |
US6969780B1 (en) | 2004-12-20 | 2005-11-29 | Lyondell Chemical Technology, L.P. | Production of butanediol |
DE102005042184A1 (de) * | 2005-09-06 | 2007-03-08 | Basf Ag | Verfahren zur Abtrennung von polymeren Nebenprodukten aus 1,4-Butindiol |
DE102005042185A1 (de) * | 2005-09-06 | 2007-03-08 | Basf Ag | Verfahren zur Abtrennung von polymeren Nebenprodukten aus 1,4-Butindiol |
EP1922146A1 (en) | 2005-09-08 | 2008-05-21 | Evonik Degussa GmbH | The production and use of supported activated base metal catalysts for organic transformation |
DE102007027837A1 (de) | 2007-06-13 | 2008-12-18 | Eads Deutschland Gmbh | Verfahren zur Herstellung einer metallischen Mikrostruktur für einen Mikroreaktor |
US20110011772A1 (en) | 2009-07-15 | 2011-01-20 | Stephen Raymond Schmidt | Nickel and Cobalt Plated Sponge Catalysts |
US20120154983A1 (en) * | 2010-10-08 | 2012-06-21 | The Regents Of The University Of California | Method of Fabrication of Carbon Nanofibers on Nickel Foam |
WO2012101550A1 (de) * | 2011-01-24 | 2012-08-02 | Basf Se | Hydrierkatalysator aus nickel auf kohlenstoff |
US8574340B2 (en) * | 2011-02-27 | 2013-11-05 | Board Of Trustees Of The University Of Alabama | Methods for preparing and using metal and/or metal oxide porous materials |
CN102949981B (zh) * | 2011-08-17 | 2015-09-30 | 香港城市大学 | 多孔基底与一维纳米材料的复合材料及其制备方法、其表面改性的复合材料及制备方法 |
CN102744083B (zh) * | 2012-06-26 | 2015-11-18 | 华烁科技股份有限公司 | 1,4-丁炔二醇加氢制1,4-丁二醇专用雷尼镍-铝-x催化剂的制备及活化方法 |
EP2799465A1 (de) | 2013-04-29 | 2014-11-05 | Evonik Industries AG | Verfahren zur Aufreinigung von Poly(arylenethern) |
CN104888808B (zh) | 2014-03-07 | 2018-08-17 | 中国石油化工股份有限公司 | 一种复合型催化剂及其制备方法 |
CN104945225B (zh) * | 2014-03-27 | 2017-02-15 | 中国石油化工股份有限公司 | 一种癸烯醛加氢制备醇的方法 |
PT3037400T (pt) | 2014-12-23 | 2018-10-23 | Evonik Degussa Gmbh | Hidrogenação livre de cromo de misturas de hidroformilação |
US9943818B2 (en) * | 2016-06-20 | 2018-04-17 | Air Products And Chemicals, Inc. | Steam-hydrocarbon reforming reactor |
WO2018054740A1 (de) | 2016-09-23 | 2018-03-29 | Basf Se | Verfahren zur bereitstellung eines katalysatorfestbetts, das dotierte strukturierte katalysatorformkörper enthält |
KR20190052674A (ko) | 2016-09-23 | 2019-05-16 | 바스프 에스이 | Co 및 일체형 촉매 성형체를 함유하는 고정 촉매 층의 존재 하에서 유기 화합물을 수소화시키는 방법 |
SG11201901571RA (en) | 2016-09-23 | 2019-04-29 | Basf Se | Process for providing a catalytically active fixed bed for the hydrogenation of organic compounds |
US20200016579A1 (en) | 2016-09-23 | 2020-01-16 | Basf Se | Method for activating a fixed catalyst bed which contains monolithic shaped catalyst bodies or consists of monolithic shaped catalyst bodies |
EP3300798A1 (de) | 2016-09-30 | 2018-04-04 | Evonik Degussa GmbH | Katalysatorfestbett enthaltend metallschaumkörper |
DE102017202404A1 (de) | 2017-02-15 | 2018-08-16 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Isophoronaminoalkohol (IPAA) |
US11401224B2 (en) | 2018-02-14 | 2022-08-02 | Evonik Operations Gmbh | Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes |
KR20210038540A (ko) | 2019-09-25 | 2021-04-07 | 에보닉 오퍼레이션스 게엠베하 | 촉매 반응기 |
KR20220068220A (ko) | 2019-09-25 | 2022-05-25 | 에보닉 오퍼레이션스 게엠베하 | 금속 발포체 및 이의 제조 방법 및 이의 촉매로서의 사용 |
KR20220069941A (ko) | 2019-09-25 | 2022-05-27 | 에보닉 오퍼레이션스 게엠베하 | 코발트를 함유하는 금속 발포체 엘리먼트 및 이의 제조 방법 |
JP2022549862A (ja) | 2019-09-25 | 2022-11-29 | エボニック オペレーションズ ゲーエムベーハー | 金属物体およびその製造方法 |
EP3797901B1 (de) | 2019-09-25 | 2021-09-08 | Evonik Operations GmbH | Metallschaumkörper und verfahren zu seiner herstellung |
-
2016
- 2016-09-30 EP EP16191735.6A patent/EP3300799A1/de not_active Withdrawn
-
2017
- 2017-09-27 WO PCT/EP2017/074528 patent/WO2018060269A1/en unknown
- 2017-09-27 EP EP17772724.5A patent/EP3519091A1/en active Pending
- 2017-09-27 US US16/338,015 patent/US11260375B2/en active Active
- 2017-09-27 CN CN201780060484.0A patent/CN109789391A/zh active Pending
- 2017-09-27 TW TW106133095A patent/TWI764937B/zh active
- 2017-09-27 KR KR1020197012273A patent/KR102629663B1/ko active IP Right Grant
- 2017-09-27 JP JP2019517288A patent/JP7069134B2/ja active Active
- 2017-09-29 AR ARP170102718A patent/AR109612A1/es active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1486291A (zh) * | 2001-01-16 | 2004-03-31 | �������¹ɷ�����˾ | 制备饱和有机化合物的方法 |
US7612241B1 (en) * | 2009-03-23 | 2009-11-03 | Lyondell Chemical Technology, L.P. | Hydroformylation process |
CN103966473A (zh) * | 2013-02-06 | 2014-08-06 | 艾蓝腾欧洲有限公司 | 表面改性的金属泡沫体、其制备方法及其用途 |
Also Published As
Publication number | Publication date |
---|---|
EP3519091A1 (en) | 2019-08-07 |
US11260375B2 (en) | 2022-03-01 |
TW201829361A (zh) | 2018-08-16 |
JP2019534874A (ja) | 2019-12-05 |
WO2018060269A1 (en) | 2018-04-05 |
US20190232256A1 (en) | 2019-08-01 |
AR109612A1 (es) | 2018-12-26 |
EP3300799A1 (de) | 2018-04-04 |
CN109789391A (zh) | 2019-05-21 |
KR102629663B1 (ko) | 2024-01-25 |
KR20190055833A (ko) | 2019-05-23 |
JP7069134B2 (ja) | 2022-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI764937B (zh) | 用於製備1,4-丁二醇之方法及催化劑 | |
JP3802056B2 (ja) | アルコールの製造法 | |
EP1440046B1 (en) | Hydrogenolysis of sugars, sugar alcohols and glycerol | |
CN105732308B (zh) | 加氢甲酰化混合物的无铬氢化 | |
EP1935487A1 (en) | Composition comprising sugars or sugar alcohols | |
EP3752477B1 (en) | Method for the preparation of c3-c12-alcohols by catalytic hydrogenation of the corresponding aldehydes | |
CA2968981C (en) | Process for production of hexanetriol from 5-hydroxymethylfurfural | |
CN107778138B (zh) | 一种1,4-丁炔二醇两段加氢制备1,4-丁二醇的方法 | |
WO2006116193A1 (en) | Hydrogenation catalyst and hydrogenation method | |
CN104011002A (zh) | 制备1,6-己二醇的方法 | |
KR20010041595A (ko) | 카르보닐 화합물의 수소화 방법 | |
EP3408250B1 (en) | Single-step conversion of n-butyraldehyde to 2-ethylhexanal | |
CN108025292A (zh) | 改进的含铜的多金属催化剂及使用其制备生物基1,2-丙二醇的方法 | |
JPS5827642A (ja) | 新規なルテニウム/炭素−水素化用触媒 | |
JP2018131442A (ja) | イソホロンアミノアルコール(ipaa)を製造する方法 | |
WO2010099078A1 (en) | Process for making 1, 2-propane diol from hydrogenation of glycerol | |
JPH01168345A (ja) | 水素化触媒、その製造方法及び該触媒を用いる水素化方法 | |
CN114149301B (zh) | 一种氢化柠檬醛制备香茅醇的方法 | |
CN114522738B (zh) | 一种由3-乙酰氧基丙醛一步加氢制备1,3-丙二醇的方法 | |
JP3016727B2 (ja) | 改質ラニーニッケル触媒とその触媒によるジオール化合物の製造方法 | |
CN1122568C (zh) | 一种用于3-羟基丙醛加氢制备1,3-丙二醇的催化剂 | |
CN107353180B (zh) | 3-羟基丙醛水溶液加氢制备1,3-丙二醇联产1,2-丙二醇的方法 | |
CN114292173B (zh) | 一种羟基香茅醛的制备方法及所采用的催化剂 |