EP2858749A2 - Verwendung von thermisch behandelten geträgerten kobaltkatalysatoren mit polyzyklischer aromatischer struktur aus stickstoffliganden zur hydrierung von nitroaromaten - Google Patents
Verwendung von thermisch behandelten geträgerten kobaltkatalysatoren mit polyzyklischer aromatischer struktur aus stickstoffliganden zur hydrierung von nitroaromatenInfo
- Publication number
- EP2858749A2 EP2858749A2 EP13729648.9A EP13729648A EP2858749A2 EP 2858749 A2 EP2858749 A2 EP 2858749A2 EP 13729648 A EP13729648 A EP 13729648A EP 2858749 A2 EP2858749 A2 EP 2858749A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- phenanthroline
- cobalt
- hydrogenation
- dimethyl
- use according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003446 ligand Substances 0.000 title claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 21
- 239000010941 cobalt Substances 0.000 title claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 16
- -1 aromatic nitro compounds Chemical class 0.000 title claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 15
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- ZPGVCQYKXIQWTP-UHFFFAOYSA-N 4,7-dimethoxy-1,10-phenanthroline Chemical compound C1=CC2=C(OC)C=CN=C2C2=C1C(OC)=CC=N2 ZPGVCQYKXIQWTP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 claims description 4
- 150000005041 phenanthrolines Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 claims description 3
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- ZYGNPGHWZACAER-UHFFFAOYSA-N cobalt;1,10-phenanthroline Chemical compound [Co].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 ZYGNPGHWZACAER-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007669 thermal treatment Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001299 aldehydes Chemical group 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JBKICBDXAZNSKA-UHFFFAOYSA-N tcmdc-123507 Chemical compound C1=CC=C2NC(C=3C=CC=C(N=3)C=3NC4=CC=CC=C4N=3)=NC2=C1 JBKICBDXAZNSKA-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 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
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
- B01J23/75—Cobalt
-
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/38—Nitrogen atoms
- C07D215/40—Nitrogen atoms attached in position 8
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Definitions
- the invention relates to the use of thermally treated supported supported cobalt catalysts for the selective hydrogenation of nitroaromatics to the corresponding aromatic amines.
- the invention also relates to novel thermally treated supported cobalt catalysts and their preparation.
- Non-volatile organometallic complexes of iron and cobalt have been described as precursors for heterogeneous catalysts in WO 2010/051619 A1 for the reduction of oxygen in fuel cells.
- nitroaromatics are substituted and unsubstituted nitrobenzenes and substituted and unsubstituted heterocyclic nitroaromatics.
- the nitroaromatics contain one or more functional groups having unsaturated carbon-carbon, carbon-nitrogen and / or carbon-oxygen bonds to substituents of aromatic nuclei and halogens (F, Cl, Br, I) and halogen-carbon compounds.
- the catalyst systems used according to the invention are prepared in situ from cobalt precursor catalysts, immobilized on an inorganic support and then subjected to a thermal treatment (pyrolysis).
- cobalt precursor catalysts are cobalt-amine complexes wherein cobalt is bound to aromatic or heterocyclic nitrogen ligands. They are eg obtained by reaction of cobalt salts with aromatic or heterocyclic nitrogen ligands (L) and thus form the non-volatile organo-cobalt complexes (Co-L). The nitrogen atoms associated with the cobalt remain associated with it and thus form the precursor complex. The interactions between Co and ligand L provide the opportunity to modify the shape, electronic, and chemical properties of cobalt-amine complexes.
- Aromatic nitrogen ligands (L) are known to the person skilled in the art. For the purposes of the invention are suitable as nitrogen ligands all aromatic nitrogen compounds which undergo a poly-aromatic structure with the cobalt atom.
- they are ligands from the group of phenanthrolines having the general formula:
- R to R 8 is identical or different hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkyl, amino, carboxy, halogen, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, preferably selected from the group comprising Me, et, OMe, NH 2, COOH, phenyl, F, Cl, Br, .... Etc. or
- Pyridines such as terpyridine, 2,6-ß / 's-benzimidazol-pyridine, 1, 1-bipyridine, pyridine.
- nitrogen ligands which are selected from the group consisting of: L1: 1, 10-phenanthroline (C 12 H 10 N 2) L2: terpyridine (C ⁇ HnNs) L3: 2,6-b / s-benzimidazol-pyridine ( C 19 H 13 N-bipyridine (C 10 H 8 N 2 ) L 5 : pyridine (C 5 H 5 N),
- L4 1, 1'-bipyridine L5 pyridine and the 1, 10-phenantholine derivatives L1b: 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline, L1c: 4,7-dimethoxy-1, 10 phenanthroline and L1d: 2,9-dimethyl-1,10-phenanthroline.
- the preparation of the cobalt precursor catalysts is carried out according to methods known per se, e.g. by reacting a cobalt salt such as cobalt (II) acetate tetrahydrate in a solvent with the respective nitrogen ligand.
- a cobalt salt such as cobalt (II) acetate tetrahydrate
- oxides such as TiO 2 or Al 2 O 3 can be used as inorganic supports.
- a preferred carrier used eg Vulcan XC72R, commercially available from Cabot Corporation US
- Vulcan XC72R is a synthetically produced soot with high surface area (20-300m 2 / g) and electrical conductivity.
- a solution of the previously preformed and unisolated cobalt-ligand complex is absorbed onto the support material and the solvent removed.
- This is followed by the pyrolysis step, preferably under inert gas conditions.
- the thermal treatment can be carried out at 600-1100 ° C, with pyrolyses between 750 and 850 ° C generate catalysts with particularly good catalytic activity and stability. Higher temperatures lead to a loss of catalytic activity, lower temperatures mean lower stabilities.
- cobalt-containing particles are formed on the carbon-nitrogen surface.
- the inventive optimization of the catalyst treatment by pyrolysis has a significant influence on the activity and selectivity of the catalyst, so that the catalytic material according to the invention can be used surprisingly for the hydrogenation of many nitroaromatics.
- the hydrogenation of nitroaromatic compounds is carried out at temperatures of 60 to 200 ° C, preferably at about 90 to 120 ° C.
- the catalysts supported on carbon with the formula Co-L / C are particularly preferably used according to the invention for the hydrogenation of nitroaromatics, where L has the abovementioned meaning for L1 to L5.
- L has the abovementioned meaning for L1 to L5.
- the essential portion of the aromatic amines obtained after the hydrogenation still contains all the multiple bonds to substituents of aromatic nuclei that were present before the hydrogenation.
- the catalyst systems of the invention are tolerant to all functional groups. Furthermore, they are inexpensive and environmentally friendly. They are thus extremely suitable for the industry for the selective hydrogenation of nitroaromatics and lead to corresponding aniline derivatives as well as using heteronitroaromatics to corresponding heteroaromatic amines, which are also valuable building blocks for the production of a variety of agrochemicals and pharmaceuticals.
- the catalysts can be reused several times without loss of activity. They can easily be washed after each reaction and dried overnight.
- the catalyst system Co-Ll / C in the reaction of nitrobenzene to aniline in the 11th cycle after 8 hours still an almost complete conversion> 99% and a yield of 98%.
- the invention also relates to novel supported cobalt-nitrogen ligand complexes, wherein the carrier is a carbon carrier (C) having the formula Co-L / C, which is thermally at 750 - 850 0 C was treated.
- the ligand L is selected from the group comprising:
- L4 1, 1'-bipyridine L5 pyridine and the 1, 10-phenantholine derivatives
- L1 b 2,9-dimethyl-, 7-diphenyl-1, 10-phenanthroline
- L1c 4,7-dimethoxy-1, 10 phenanthroline
- L1d 2,9-dimethyl-1,10-phenanthroline.
- Cobalt (II) acetate tetrahydrate (125 mg, 0.5 mmol) and 1, 10-phenanthroline (180 mg, 1.0 mmol) (Co: phenanthroline 1: 2 molar ratio) are dissolved in ethanol (50 ml) for stirred for about 30 minutes at room temperature.
- carbon black 700 mg
- the reaction mixture is refluxed at 60 ° C for 4 h. Thereafter, the reaction mixture is cooled to room temperature and ethanol is removed under vacuum. The resulting solid is dried at 60 ° C for 12 h and then crushed to a fine powder. Subsequently, the thermal treatment (pyrolysis) of the powder is carried out at 800 ° C for 2 h under argon.
- the measured internal temperature in the autoclave is 104-106 ° C.
- the autoclave is placed in a water bath and cooled to room temperature. Finally, the remaining hydrogen gas is drained and the samples are removed from the autoclave, washed with ethylene chloride and analyzed by GC and GC-MS.
- the reactions are carried out on a larger scale (5 mmol nitroaromatic).
- An autoclave (100 ml) is charged with the cobalt catalyst (100 mg), THF (20 ml), hexadecane as internal standard (1 ml) and nitrobenzene (630 ⁇ l). Hydrogen is introduced twice into the autoclave and hydrogenated at 60 bar. After each reaction, the catalyst is washed thoroughly with ethyl acetate and dried under mild vacuum overnight.
- the catalyst system Co-LI / C according to the invention proves to be particularly reactive and selective. As seen from the above Table 1, in the presence of a homogeneous catalyst complex consisting of cobalt and phenanthroline (Table 1, No. 11), even when 10 times the amount is used, no aniline is formed. Likewise, an iron catalyst analogous to the system of the invention did not lead to aniline formation (Table 1, entry 10).
- Table 2 shows the hydrogenation of substituted nitroaromatics to industrially relevant anilines.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Thermal Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102012209634A DE102012209634A1 (de) | 2012-06-08 | 2012-06-08 | Verwendung von thermisch behandelten geträgerten Kobaltkatalysatoren zur Hydrierung von Nitroaromaten |
PCT/EP2013/061757 WO2013182665A2 (de) | 2012-06-08 | 2013-06-07 | Verwendung von thermisch behandelten geträgerten kobaltkatalysatoren zur hydrierung von nitroaromaten |
Publications (1)
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EP2858749A2 true EP2858749A2 (de) | 2015-04-15 |
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ID=48652012
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EP13729648.9A Withdrawn EP2858749A2 (de) | 2012-06-08 | 2013-06-07 | Verwendung von thermisch behandelten geträgerten kobaltkatalysatoren mit polyzyklischer aromatischer struktur aus stickstoffliganden zur hydrierung von nitroaromaten |
Country Status (4)
Country | Link |
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US (1) | US20150307538A1 (nl) |
EP (1) | EP2858749A2 (nl) |
DE (1) | DE102012209634A1 (nl) |
WO (1) | WO2013182665A2 (nl) |
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CN105418439A (zh) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | 一种生产3-氯-4-氟苯胺的方法及装置 |
EP3554689A1 (en) * | 2016-12-19 | 2019-10-23 | H. Hoffnabb-La Roche Ag | Nitrogen-containing biopolymer-based catalysts, their preparation and uses in hydrogenation processes, reductive dehalogenation and oxidation |
CN114345413A (zh) * | 2021-04-19 | 2022-04-15 | 杭州师范大学 | 一种芳香酸配位铁钴固氮催化剂及其制备方法和应用 |
CN114618495B (zh) * | 2022-03-09 | 2023-10-20 | 中南大学 | 一种多级孔碳负载的氮硫共配位的钴单原子催化剂及其制备方法和应用 |
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EP0820808B1 (de) * | 1996-07-23 | 2002-09-04 | Degussa AG | Multimetallischer Katalysator und Verfahren zur Herstellung substituierter aromatischer Amine |
AU2002222642A1 (en) * | 2000-12-14 | 2002-06-24 | Nissan Chemical Industries Ltd. | Method for producing indole derivative |
MX261990B (es) * | 2002-02-14 | 2008-11-07 | Monsanto Technology Llc | Catalizador de oxidacion y procedimiento para su preparacion y procedimiento para oxidacion mediante el uso del mismo. |
DK1831440T3 (da) * | 2004-11-16 | 2010-11-08 | Hyperion Catalysis Int | Fremgangsmåder til fremstilling af katalysatorer understøttet på carbonnanorørnetværk |
US7678728B2 (en) * | 2006-10-16 | 2010-03-16 | Stc.Unm | Self supporting structurally engineered non-platinum electrocatalyst for oxygen reduction in fuel cells |
DE102008028070A1 (de) * | 2008-06-12 | 2009-12-17 | Bayer Technology Services Gmbh | Katalysator und Verfahren zur Hydrierung von organischen Verbindungen |
US8580704B2 (en) * | 2008-11-10 | 2013-11-12 | Institut National De La Recherche Scientifique | Catalyst precursors, catalysts and methods of producing same |
US8835343B2 (en) * | 2010-09-27 | 2014-09-16 | Uchicago Argonne, Llc | Non-platinum group metal electrocatalysts using metal organic framework materials and method of preparation |
-
2012
- 2012-06-08 DE DE102012209634A patent/DE102012209634A1/de not_active Withdrawn
-
2013
- 2013-06-07 US US14/405,963 patent/US20150307538A1/en not_active Abandoned
- 2013-06-07 EP EP13729648.9A patent/EP2858749A2/de not_active Withdrawn
- 2013-06-07 WO PCT/EP2013/061757 patent/WO2013182665A2/de active Application Filing
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US20150307538A1 (en) | 2015-10-29 |
DE102012209634A1 (de) | 2013-12-12 |
WO2013182665A3 (de) | 2014-02-13 |
WO2013182665A2 (de) | 2013-12-12 |
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