TWI782921B - 含有金屬發泡體之固定式觸媒床 - Google Patents
含有金屬發泡體之固定式觸媒床 Download PDFInfo
- Publication number
- TWI782921B TWI782921B TW106133099A TW106133099A TWI782921B TW I782921 B TWI782921 B TW I782921B TW 106133099 A TW106133099 A TW 106133099A TW 106133099 A TW106133099 A TW 106133099A TW I782921 B TWI782921 B TW I782921B
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- Taiwan
- Prior art keywords
- metal foam
- catalytically active
- fixed bed
- active metal
- reaction
- Prior art date
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- 239000006262 metallic foam Substances 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004804 winding Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000005932 reductive alkylation reaction Methods 0.000 claims description 2
- 238000006268 reductive amination reaction Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 150000001720 carbohydrates Chemical class 0.000 claims 1
- 235000014633 carbohydrates Nutrition 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002318 adhesion promoter Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000003698 laser cutting Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 101150025733 pub2 gene Proteins 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical class ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical compound OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004182 chemical digestion Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 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
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- -1 metal oxide compound Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000011022 operating instruction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
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- 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
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2495—Net-type reactors
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
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- 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
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- B01J8/0278—Feeding reactive fluids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
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- 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
- C07C29/15—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 oxides of carbon exclusively
- C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
本發明係關於具有體積不超過500 mL的催化活性金屬發泡體之固定床,其係由至少95重量%的金屬所組成。該固定床係用於三相反應混合物之催化反應。
Description
本發明係關於催化活性金屬發泡體之固定床觸媒、及用於氣體和液體反應物之混合物在已配置固定觸媒床的反應器中之催化反應的方法。
非均相催化方法非常廣泛地用於工業實務中。此方法的例子包括氨、甲醇和Fischer-Tropsch合成、數種氧化反應和氫化方法及許多其他反應。此方法中的數者述於Ullmann’s Encyclopedia of Industrial Chemistry中之標題為“Heterogeneous Catalysis and Solid Catalysts,3.Industrial Applications”的章節,2011年10月15日於線上發佈,DOI:10.1002/14356007.o05_o03。
許多此方法在以不同的方式建構和操作的固定床反應器中進行,請參考例如,Ullmann’s Encyclopedia of Industrial Chemistry in the chapter entitled“Catalytic Fixed-Bed Reactors”,2012年7月15日於線上發佈,DOI:
10.1002/14356007.o05_o03。
開發打造用於特定應用領域之新穎的非均相觸媒為現代工業和學術研究之重要目標。因此,此非均相觸媒可具有各種形狀、粒子尺寸和其他材料性質,此更特別述於例如,Ullmann’s Encyclopedia of Industrial Chemistry之標題為“Heterogeneous Catalysis and Solid Catalysts,2.Development and Types of Solid Catalysts”的章節,2011年10月15日於線上發佈,DOI:10.1002/14356007.o05_o02。
金屬發泡體為此技術中習知者且通常作為功能性材料或提供結構的材料,亦參考Ullmann’s Encyclopedia of Industrial Chemistry,章節標題“Metallic Foams”,2012年7月15日發佈,DOI:10.1002/14356007.c16_c01.pub2。因此,鎳發泡體可用於例如作為電池中的電極或作為過濾元件。
以金屬發泡體為底的材料的催化應用極有限。金屬發泡體目前通常被用於均相催化的氣相反應。這些應用尤其包括來自燃燒引擎的廢氣之催化性後處理、煙道氣的催化性純化、用於自一氧化碳和水蒸氣製造氫的水-氣轉移反應、或甲烷的蒸汽重組反應。該等應用中,由於該金屬發泡體的高孔隙度,所以由該金屬發泡體在流動通過的反應介質中所累積的動態壓力相當低。
由於先前技術中已經知道的多孔金屬發泡體本身無催化活性且在用於非均相催化應用中的幾何表面積
不足,所以這些已知的應用要求額外的塗覆以便將催化活化施用於金屬發泡體上。此造成相對於流動通過的反應介質的動態壓力顯著提高,此通常造成在非均相催化應用中的效率顯著耗損。
DE 10245510 A1揭示一種用於內燃機的廢氣濾器,其包含發泡體作為深度過濾元件,其包含分佈於建構材料的基質中之氧化反應觸媒,且其可用以移除和催化後燃燒煙灰粒子。
AICHE Journal,2015,Vol.61,No.12,p.4323-4331揭示在固定床反應器中使用具16mm直徑片形式之Ni-Al2O3/Ni金屬發泡體觸媒在CO2的氣相氫化反應中以提供甲烷。此鎳發泡體作為惰性觸媒載體,其表面上已施以活性Ni/Al2O3塗層。藉此製得的觸媒包含12.6重量%的NiO和4.2重量%的Al2O3。
Catalysis Today,2016,Vol.273,p.221-233另描述金屬發泡體通常無法提供足夠大的表面積以用於催化應用。因此須施用具高表面積的活化塗層(washcoat)及接著浸以催化活性組份。
大型工業規模化學應用通常為液體,通常是有機化合物與氣相反應物之反應。經塗覆的催化金屬發泡體不適用於此應用,此因通常相對高黏度的液體反應物無法滲入金屬發泡體之被塗層窄化的孔洞中,並因此而無法與孔洞中的催化活性中心接觸之故。目前,此應用通常施用壓片或擠出的氧化型模製體,其事先例如浸以惰性金屬
溶液而經過催化性活化處理。一些模製體確實展現高BET表面積。但是,這些氧化性模製體之可供利用的幾何表面積有限,使得此模製體在基本上具有數立方米體積的反應器中的催化效率因為反應物至催化活性中心的物質轉移欠佳而受限。
ACS Catal.2016,Vol.6,p.5432-5440揭示經碳奈米纖維(CNF)塗覆的鎳發泡體及其在固定床反應器中在液相中的亞硝酸化合物之氫化反應的用途。文中所述觸媒具有相對高比例的碳比例(27重量%)。
本發明的一個目的是能夠在三相系統中在固定床觸媒床上進行有效率的催化反應,同時降低和/或克服巨觀質量轉移限制及先前技術方法所遭遇之因為固定觸媒床上的高動態壓力所造成的限制二者、及提供用於彼之適當的觸媒。
藉包含用於至少一種於液相中的反應組份和至少一種氣相組份之催化反應的催化活性金屬發泡體之固定床達成此目的,其中該催化活性金屬發泡體具有不超過500毫升的體積、由至少95重量%的金屬所組成且以鬆散物質形式配設置於填充床中。
“金屬發泡體”是指具有高孔隙度和在固態材料
的不規則結構的區域之間具有許多互聯結構的剛性金屬發泡體。此金屬發泡體亦被稱為“蜂窩狀金屬”,“金屬發泡體”一詞更被廣為使用。“金屬發泡體”一詞已明述於技術文獻中且更特別地例如闡釋於Ullmann’s Encyclopedia of Industrial Chemistry之標題為“Metallic Foams”的章節,此於2012年7月15日於線上發佈,DOI:10.1002/14356007.c16_c01.pub2。
瞭解本發明之上下文中的“催化活性金屬發泡體”是指未包含會造成金屬發泡體中的孔隙窄化之額外塗層的金屬發泡體。本發明之上下文中的催化活性金屬發泡體在無額外之具催化活性或其他情況的塗層之情況下在各目標反應中具催化活性。根據本發明之固定床也不含有額外的催化活性塗層。
根據本發明之催化活性金屬發泡體係具有可由其尺寸準確計算的體積之外部不連續結合之不均勻成形的幾何體。根據本發明之催化活性金屬發泡體較佳地為圓柱形、環形、長方體、平行六面體、或立方體。此發泡體的體積通常可藉由發泡體之可測得的底面積乘以其同樣是可測得的高度而得到。
本發明上下文中的固定或填充床是指固定排列於空間中之聚集體,即,在空間上固定於反應器中和/或反應區中之具有由個別個體、片、或粒子所組成的一或多種物質的鬆散填充物。
根據本發明之固定床亦可包含,除了催化活
性金屬發泡體以外,其他可能的催化惰性構份,例如填料或流動中斷和/或干擾元素。
根據本發明之固定床較佳地含括50重量%,更特別佳地超過80重量%,極特別佳地超過95重量%,的催化活性金屬發泡體。極特別佳地,本發明之固定床由催化活性金屬發泡體所構成。
存在於根據本發明之固定床中的催化活性金屬發泡體含括至少95重量%,較佳地至少97重量%,更特別佳地至少98重量%,極特別佳地至少99重量%的金屬。
理解“金屬”是指元素週期表第IA(除了氫以外)、IIA、IB-VIIIB(過渡金屬)、IIIA(除了硼以外)、IVA(此處:Sn和Pb)、VA(此處:Bi)和VIA(此處:Po)。
存在於根據本發明之固定床中的催化活性金屬發泡體較佳地包含一或多種選自由鎳、鈷、鐵、銀、鉑、鉻、鉬和鎢所組成的群組之金屬。特別佳地,存在於根據本發明之固定床中的催化活性金屬發泡體包含一或多種選自由鎳、鈷和所組成的群組之金屬。極特別佳地,存在於根據本發明之固定床中的催化活性金屬發泡體包含65至98重量%,較佳70至95重量%,且特別佳地80至90重量%的鎳或鈷。
存在於根據本發明之固定床中的催化活性金屬發泡體較佳地另包含至多25重量%,特別佳地2至20重量%,極特別佳地4至15重量%,的鋁。對於大部分的應用具體實施例,包含7至13重量%的鋁特別適用。
存在於根據本發明之固定床中的催化活性金屬發泡體另包含至多10重量%,較佳地0.05至5重量%,特別佳地0.1至2重量%,的鉬(Mo)和/或0至10重量%,較佳地0.05至5重量%,特別佳地1.5至3.5重量%,的一或多種選自由鐵和鉻所組成的群組之金屬。
存在於根據本發明之固定床中的催化活性金屬發泡體另包含低於5重量%的氧於金屬氧化物化合物中,此乃由於此氧化物結構的存在會顯著降低根據本發明之催化活性金屬發泡體在相關目標反應中之催化活性之故。根據本發明之催化活性金屬發泡體較佳地包含低於3重量%,極特別佳地低於1重量%,的氧化物。特別適當之催化活性金屬發泡體的氧含量較佳地低於7500ppm,特別佳地低於5000ppm且極特別佳地低於3000ppm。
根據本發明之催化活性金屬發泡體的金屬和氧含量可以先前技術中已知且嫻於此技術者習知的元素分析方法測定,例如-在進行適當的濕式化學消解程序之後-藉光學放射光譜術(ICP-OES)測定金屬含量。氧含量可適當地藉紅外光譜術例如使用LECO TCH 600分析儀測定所得的CO2而得到。在測定根據本發明之催化活性金屬發泡體的氧含量之前,該發泡體可能需要排除來自環繞的介質之氧污染物而明確地去活化。此特別適用於在空氣中會自燃的催化活性並因此而在使用之前在作為保護性介質的水下操作之具體實施例。必須於初時溫和地自此材料移除水,例如藉由小心地以無水有機溶劑清洗(例如乙醇,
其具有一些吸收在催化活性發泡體的孔隙中之殘留的水的能力)。接著清除溶劑殘餘物和殘留的水。去活化可以藉由在真空下或在保護性氣流(氮或氬)中緩慢地加熱至至多200℃的方式進行。
在根據本發明之固定床中,該催化活性金屬發泡體可以鬆散的填充材料形式存在,其中1L體積之此鬆散的填充材料的重量不超過0.8kg。1L體積之此鬆散的填充材料的重量較佳地為0.1至0.7kg,極特別佳地為0.2至0.6kg。據此,存在於根據本發明之固定床中的催化活性金屬發泡體較佳地具有不超過0.8kg/L,特別佳地由0.1至0.7kg/L,極特別佳地由0.2至0.6kg/L的整體密度。
整體密度dSch,有時亦是指固體的澆注密度(poured density),是固體(其可為顆粒)和空氣(其充填介於固體/固體主體的粒子之間的孔隙)之混合物的質量對體積的比。此嫻於此技術者常用的參數可利用量筒和天平,藉由測定固體之界定的鬆散填充體積(VF)的質量(MF)而定出。
dSch=MF/VF
藉由將指定量的滴濕觸媒緩慢添加至充滿水的1L標準量筒中可定出整體密度。在觸媒完全沉積之後,讀取觸媒床的體積刻度。根據下式計算整體密度dSch。
dSch=MF/VF
其中MF是觸媒用量(以乾質量計)和VF是觀察到之觸媒床在
水面下的體積。藉由充滿水和觸媒之具指定體積的容器與僅充滿水之相同體積的容器之比較稱重而定出經活化的觸媒的乾質量。由兩個重量的差異乘以密度因子k(其自乾觸媒的密度和介於乾觸媒和水之間的密度差之間的商得知)得到乾觸媒的質量。密度因子可直接自技術文獻和/或Raney型觸媒的製造商和經銷商的操作指示得到,且基本上約1.2。藉由讀取所用量筒的刻度,嫻於此技術者可直接取得觸媒床的體積。此方法與Raney型觸媒的粒子尺寸無關,即,與彼為顆粒或發泡材料床或是在水中的粉末觸媒無關。
存在於根據本發明之固定床中的催化活性金屬發泡體具有不超過500毫升(mL)的體積。根據本發明之催化活性金屬發泡體的幾何形狀和尺寸及其體積是可控制的,可用於因應所用反應器的主要條件以於在反應介質上最小的反壓(counterpressure)時維持物質轉移的最佳條件。在根據本發明之固定床的較佳具體實施例中,該催化活性金屬發泡體具有不超過200mL,特別佳地由0.02至100mL,且極佳地由0.02至50mL的體積。
存在於根據本發明之固定床中的催化活性金屬發泡體較佳地為圓柱形、環形、長方體、平行六面體、或立方體形式。這些較佳地製自具有至少300mm的邊緣長度和0.5至10mm,較佳1至5mm的厚度之金屬發泡片。由這些金屬發泡片,可例如藉雷射切割/雷射束切割得到較小的幾何體,較佳地具有長方體或平行六面體形狀且最大邊
緣長度不超過50mm,較佳地不超過25mm且特別佳地不超過10mm。可以相同方式製得具有0.5至10mm,較佳1至5mm的邊緣長度之立方體。亦可藉此製備模式製備環形體。其外徑較佳地於100mm,特別佳地低於50mm且極特別佳地低於20mm。選擇內徑使得形成的環寬度較佳為2至80mm。
根據本發明之固定床中的催化活性金屬發泡體可具有圓柱形,其中可藉由纏繞金屬發泡片而形成圓柱形。由具有25至500毫升體積的圓柱形催化活性金屬發泡體所構成之根據本發明之固定床特別適用於具有數立方米體積的大型工業規模的固定床反應器。圓柱形金屬發泡體亦可製自具有至少300mm的邊緣長度和0.5至10mm,較佳1至5mm的厚度之金屬發泡片。此處,金屬發泡片沿著其長邊緣纏繞直到形成具有所欲標的直徑的圓柱“捲”,及之後例如藉雷射切割/雷射束切割以得到所欲長度。為改良物質轉移和提高反應介質流經所用催化活性金屬發泡體的擾流,金屬發泡片可以在纏繞之前製成波狀-類似於波狀片金屬,使得在所得的圓筒形金屬發泡體中的層狀流徑最小化。
存在於根據本發明之固定床中的催化活性金屬發泡體具有巨觀發泡結構。包含許多孔隙之多孔的金屬發泡體結構可以例如藉氣體在液化金屬上的作用及後續的冷卻而形成。用以達成此結構的另一選項係使用有機發泡結構作為施用金屬的模板及後續藉焚化以移除有機模板。
存在於根據本發明之金屬發泡體中的巨觀孔較佳地具有在100至5000μm,特別佳地由200至2500μm,特別佳地由400至1200μm,範圍內的尺寸。巨觀孔的尺寸可以使用例如“The Guide 2000 of Technical Foams”,book 4,part 4,pages 33-41中所述的方法定出。巨觀孔的尺寸可藉對選定的孔的孔徑進行光學測定而定出。以至少100個不同的孔重複此測定並由此計算平均孔徑作為分析結果。
存在於根據本發明之固定床中的催化活性金屬發泡體較佳地具有1至200m2/g,特別佳地10至120m2/g,極特特別佳地70至100m2/g,的BET表面積。此比表面積亦簡化稱為BET表面積,係依照DIN 9277,根據J.Am.Chem.Soc.1938,Vol.60,p.309-319中描述的Brunauer-Emmett-Teller方法藉氮吸附測定。
存在於根據本發明之固定床中的催化活性金屬發泡體例如可藉至少二元金屬合金以外的至少一種金屬的化學瀝濾(chemical leaching)得到。
“Raney-型”活化的鎳或鈷觸媒,亦被稱為Raney觸媒,特別適合作為根據本發明之固定床中的催化活性金屬發泡體。因此,以下以催化活性鎳發泡體為例子描述催化活性金屬發泡體的較佳製法。所闡明的製造步驟可以在適當的變化製備參數後應用於文中未明確描述的其他金屬發泡體。
欲製造催化活性鎳發泡體,市售的鎳發泡體經黏著促進劑處理並經鋁粉塗覆。可以使用任何可改良金
屬和有機材料之間的黏著性之黏著促進劑。例如,聚伸乙亞胺溶液是適合的。
在這些程序步驟中,鎳發泡體保留其延展性,且可例如以適合製造圓柱體的方式成形。在後續的熱處理中,特定地移除黏著促進劑中的氧、初始水氣和有機化學品殘渣。之後鋁溶於鎳發泡體中以形成中間金屬相(intermetallic phase)。所得的鎳/鋁合金發泡體的空間結構包括對應於所用的鎳發泡體的孔結構(幾何形狀、孔隙度、尺寸),所用的鎳發泡體的原始特徵在此程序步驟中完全保留。據此,所得的鎳/鋁合金發泡體不包含窄化孔隙的塗層。
該熱處理較佳地在介於500℃和1000℃,特別佳地介於600℃和750℃,之間的溫度範圍內進行。該熱處理在無氧的惰性氣體環境中進行以免形成中斷的氧化物相和層。
在該熱處理之後,可藉例如雷射切割/雷射束切割來粉碎和/或分離材料,如果在熱處理之前的成形步驟中尚未進行這些程序的話。
如此得到的鎳/鋁成形體,藉由瀝濾(leaching)出至少一部分存在於其中的鋁,而製得根據本發明之催化活性鎳發泡體。此處使用的是鹼性水溶液,較佳為鹼金屬氫氧化物溶液,其中該鹼金屬氫氧化物選自由氫氧化鈉、氫氧化鉀或氫氧化鋰所組成之群組。特別佳的是氫氧化鈉水溶液。此方法步驟中使用之鹼金屬氫氧化物水溶液的濃
度通常介於0.1和60重量%之間。鋁的瀝濾較佳是以5至50重量%,特別佳地5至35重量%,之氫氧化鈉水溶液於20℃至100℃,較佳地於40℃至85℃,特別佳地於50℃至80℃,的溫度進行。此處所用瀝濾時間,即,氫氧化鈉溶液與經鋁改質的鎳金屬發泡體反應的時間,可介於2和240分鐘之間。
在存在於根據本發明之固定床中的上述催化活性金屬發泡體中,保留原始使用的金屬發泡體的巨觀發泡體結構。上述實例中,Ni/Al合金中的鋁至少部分瀝濾發生在形成高孔隙度催化活性鎳結構之接近表面的區域。藉此得到的催化活性鎳發泡體的BET表面積較佳地大於在活化之前所用金屬發泡體的BET表面積。
本發明另外提出一種用於至少一種於液相中的反應物組份和至少一種氣相組份在根據本發明之包含催化活性金屬發泡體之固定床存在下之催化反應的方法,其中該催化活性金屬發泡體具有不超過500毫升的體積,由至少95重量%的金屬所組成。
根據本發明之上述固定床用於至少一種於液相中的反應物組份和至少一種氣相組份之催化反應。此三相反應可以不連續(批次)或連續操作進行。根據本發明之方法較佳地以連續操作方式進行。可使得根據本發明之固定床在操作期間內空間固定之所有的反應器類型均可用於根據本發明之方法。因此,例如,可以使用攪拌槽反應器、固定床反應器或嫻於此技術者已知的其他設備。
根據本發明之方法在攪拌槽反應器中進行時,根據本發明之固定床較佳是在支撐裝置(retaining device)中。該裝置較佳地配置於接近攪拌器軸心處,其中該配置方式使得攪拌器產生通過被引至該支撐裝置中的固定床之反應混合物流。
根據該反應之方法較佳地以連續操作在固定床反應器中進行,例如,在滴流床反應器或充滿液體的反應器或在此技術中已知的其他固定床反應器類型中進行。所有適當的反應器類型可以“一次通過(once through)”模式操作,其中反應物(進料)引至反應器中,在根據本發明之固定床中反應之後,移除產物混合物。或者,一部分的產物混合物自反應器回送至反應區中(循環流)。在此循環方式(循環模式)中,進料對循環流的重量比是0.025至0.25,較佳為0.05至0.15,特別佳為0.05至0.1。
根據本發明之方法較佳地在總體積至少0.5m3的反應器中以連續操作方式進行,特別佳地,在總體積為1至500m3及特別佳地5至100m3的反應器中進行。
根據本發明之方法之催化反應較佳為以於液相中的反應物組份的形式存在且包含至少一種不飽和C-C鍵和/或至少一種官能基之至少一種物質的氫化反應。氫作為氣相組份。
用於氫化反應且存在於液相中之該反應物組份較佳地為選自由烯類、炔類、不飽和醇類、芳族化合物、有機硝基和亞硝基化合物、有機異氰酸酯類、有機氰
化物化合物、醛類和酮類所組成之群組的至少一種物質。根據本發明之方法中之催化反應特別可為選自由糖類所組成的群組之物質的氫化反應,其中用於氫化反應的糖之後任意地以水溶液形式施用至根據本發明之固定床。
本發明之催化活性金屬發泡體固定床另適用於醇類的脫氫反應以提供醛類和/或酮類、或用於醛類和/或酮類的還原性胺化反應。根據本發明之固定床亦可用於合成脂肪酸或用於有機化合物的還原性烷化反應。
根據本發明之固定床的其他應用領域為氣相中的非均相催化反應,如,由乙烯至環氧乙烷的氧化反應或根據Ostwald方法之原理的氨氧化反應。
以下以對照實例的方式更特別地闡釋本發明。以1,4-丁炔二醇提供丁二醇的氫化反應為例子說出根據本發明之鬆散填充的固定床之製造和使用。
實例1
成捲市售之具有1.9mm的厚度、300mm的寬度和580μm的平均孔隙尺寸的鎳發泡體經以市售的黏著促進劑溶液噴灑,以鋁粉塗覆,並在無氧下於約700℃進行熱處理。冷卻之後,所得的材料以雷射切割成具有2mm×2mm的邊緣長度和1.9mm的厚度之正方形片。為使具有催化活性,將所得鬆散的填充材料配置於鬆散填充的固定床中,並藉由於80℃至90℃抽取10重量%的氫氧化鈉水溶液使通過該鬆散填充的固定床達70分鐘以進行濕式化學後處
理,接著以水清洗直到抽取通過該鬆散填充的固定床之洗液的pH<10。
比較例
大型工業規模之由1,4-丁炔二醇(BYD)得到1,4-丁二醇的氫化反應使用粒型活化鎳觸媒,如,例如DE 2004611A中揭示者。製得此觸媒作為比較用材料。此處,藉由熔化鎳和鋁,製得由50重量%鎳和50重量%鋁所組成的合金,進行機械粉碎並過篩以得到平均粒子尺寸為2mm的粒子部分。藉由抽取10重量%氫氧化鈉水溶液於60℃使通過該觸媒達60分鐘及接著以水清洗直到所得洗液的pH<10,使此合金粒部分在鬆散填充的固定床中具有催化活性。
實例2
實例1之本發明之催化活性金屬發泡體和得自比較例的先前技術觸媒在連續固定床設備中測試其用於由丁炔-1,4-二醇(BYD)得到1,4-丁二醇的氫化反應之活性。此處,本發明之催化活性金屬發泡體和得自比較例的先前技術觸媒二者各引至具有12mm的內徑和175mm的長度及18ml的有效體積的管狀反應器中。引入的固定觸媒床的體積是10ml。該管狀反應器配置於用於加熱的GC爐中。反應器上游放置充滿玻璃球的管,其為進入反應器的入口部分,用以加熱和預混合反應物。於275bar的氫壓,反應
器被連續供以由50重量%水、20重量%丁炔-1,4-二醇和30重量%1,4-丁二醇所組成的液體進料流,其中,已藉由添加稀的氫氧化鈉溶液,建立pH 7.3至7.5的環境。操作選用液體時空速度(LHSV)為2.75h-1的模式。該反應器加熱至120℃。
反應器連續操作的期間內,提取數日之反應產物的樣品,並於固定間隔時間藉氣體層析術分析其組成。這些連續試驗的結果彙整於表1。
發現使用本發明之催化活性鎳發泡體固定床所達到的催化活性高於使用先前技術固定床所達到者。本發明之催化活性鎳發泡體固定床另展現顯著改良的運行時間,即,相較於先前技術固定床,能夠以較高活性程度連續操作顯著更長的時間。
Claims (15)
- 一種固定床,其包含用於至少一種於液相中的反應物組份與至少一種氣相組份之催化反應的催化活性金屬發泡體,其特徵在於該催化活性金屬發泡體具有不超過500毫升的體積、由至少95重量%的金屬所組成且以鬆散物質形式配置於填充床中,其中該催化活性金屬發泡體具有不超過7500ppm的氧含量,及其中該催化活性金屬發泡體具有1至200m2/g的BET表面積。
- 如請求項1之固定床,其中該催化活性金屬發泡體包含一或多種選自由鎳、鈷、鐵、銀、鉑、鉻、鉬和鎢所組成的群組之金屬。
- 如請求項2之固定床,其中該催化活性金屬發泡體另包含至多25重量%的Al。
- 如請求項1之固定床,其中該催化活性金屬發泡體以鬆散的填充材料形式存在於固定床中,其中1L體積之此鬆散的填充材料的重量不超過0.8kg。
- 如請求項1之固定床,其中該催化活性金屬發泡體為圓柱形、環形、長方 體、平行六面體、或立方體。
- 如請求項5之固定床,其中該催化活性金屬發泡體為圓柱形,其中藉由纏繞金屬發泡片而形成該圓柱形。
- 如請求項6之固定床,其中該金屬發泡片在纏繞之前被製成波狀。
- 如請求項1之固定床,其中該催化活性金屬發泡體具有尺寸在100至5000μm範圍內的巨觀孔。
- 一種用於至少一種於液相中的反應物組份和至少一種氣相組份在如請求項1至8中任一項之固定床存在下之催化反應的方法。
- 如請求項9之方法,其中該方法係在總體積至少0.5m3的反應器中以連續操作的方式進行。
- 如請求項9或10之方法,其中該催化反應係氫化反應,其中氫為該氣相組份,及於液相中的該反應物組份包含至少一種不飽和的C-C鍵和/或至少一種官能基。
- 如請求項9之方法,其中該催化反應係選自由烯類、炔類、不飽和醇類、芳族化合物、有機硝基和亞硝基化合物、有機異氰酸酯類、有機氰化物化合物、醛類和酮類所組成群組中之至少一種物質的氫化反應,且其中氫係用作為該氣相組份。
- 如請求項12之方法,其中該催化反應係選自糖類的物質之氫化反應。
- 如請求項9或10之方法,其中該催化反應係由醇類脫氫得到醛類和/或酮類的反應、或是醛類和/或酮類的還原性胺化反應。
- 如請求項9或10之方法,其中該催化反應係脂肪胺類之合成或有機化合物的還原性烷化反應。
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- 2017-09-27 JP JP2019517219A patent/JP7479149B2/ja active Active
- 2017-09-27 BR BR112019006251-3A patent/BR112019006251B1/pt active IP Right Grant
- 2017-09-27 EP EP17777243.1A patent/EP3519090A1/en active Pending
- 2017-09-27 MX MX2019003614A patent/MX2019003614A/es unknown
- 2017-09-27 TW TW106133099A patent/TWI782921B/zh active
- 2017-09-27 CN CN201780060485.5A patent/CN109789389A/zh active Pending
- 2017-09-27 WO PCT/EP2017/074491 patent/WO2018060245A1/en unknown
- 2017-09-27 KR KR1020197012065A patent/KR102444992B1/ko active IP Right Grant
- 2017-09-29 AR ARP170102726A patent/AR109768A1/es active IP Right Grant
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TW201815463A (zh) | 2018-05-01 |
WO2018060245A1 (en) | 2018-04-05 |
KR20190055831A (ko) | 2019-05-23 |
EP3300798A1 (de) | 2018-04-04 |
MX2019003614A (es) | 2019-06-17 |
US20190232257A1 (en) | 2019-08-01 |
BR112019006251A2 (pt) | 2019-06-25 |
US11090637B2 (en) | 2021-08-17 |
JP2019530572A (ja) | 2019-10-24 |
AR109768A1 (es) | 2019-01-23 |
EP3519090A1 (en) | 2019-08-07 |
KR102444992B1 (ko) | 2022-09-19 |
BR112019006251B1 (pt) | 2022-08-23 |
CN109789389A (zh) | 2019-05-21 |
JP7479149B2 (ja) | 2024-05-08 |
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