EP4313406A1 - New cobalt catalyst supported on silica - Google Patents
New cobalt catalyst supported on silicaInfo
- Publication number
- EP4313406A1 EP4313406A1 EP22717159.2A EP22717159A EP4313406A1 EP 4313406 A1 EP4313406 A1 EP 4313406A1 EP 22717159 A EP22717159 A EP 22717159A EP 4313406 A1 EP4313406 A1 EP 4313406A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- cobalt
- present
- hydrogenation
- relates
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 149
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 34
- 239000010941 cobalt Substances 0.000 title claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 85
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 33
- 239000011541 reaction mixture Substances 0.000 claims description 17
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- -1 aromatic alkynes Chemical class 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 150000004700 cobalt complex Chemical class 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229920000136 polysorbate Polymers 0.000 description 5
- 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 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920002101 Chitin Polymers 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 4
- 239000011981 lindlar catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000001371 (5E)-3,5-dimethylocta-1,5,7-trien-3-ol Substances 0.000 description 3
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 description 3
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 3
- ZJIQIJIQBTVTDY-SREVYHEPSA-N dehydrolinalool Chemical compound CC(=C)\C=C/CC(C)(O)C=C ZJIQIJIQBTVTDY-SREVYHEPSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000003880 polar aprotic solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 2
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 2
- MULUCORRSAVKOA-UHFFFAOYSA-N 3,7,11,15-tetramethylhexadec-1-yn-3-ol Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)C#C MULUCORRSAVKOA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910019131 CoBr2 Inorganic materials 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000286904 Leptothecata Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 235000013681 dietary sucrose Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229930007744 linalool Natural products 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- 206010037544 Purging Diseases 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
-
- 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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
Definitions
- the present invention relates to a new cobalt (Co) catalyst for selective hydrogena tions.
- a Lindlar catalyst is a heterogeneous catalyst that consists of palladium deposited on calcium carbonate and treated with lead. The catalyst is used for the hydrogenation of alkynes to alkenes (i.e. without further reduction into alkanes). Thus if a compound contains a double bond as well as a triple bond, the triple bond is reduced to a double bond with high selectivity.
- This invention relates to the replacement of the "Lindlar catalyst” for the synthesis of vitamin and nutritional product precursors via hydrogenation of both terminal and in ternal alkynes.
- a new specific catalyst consisting of cobalt nanoparti cles and nitrogen doped carbon supported on silica has the same properties in regard to hydrogenation performance but which is free palladium-free as well as lead-free.
- the present invention relates to a catalyst comprising cobalt nanoparticles and nitrogen doped carbon layer, which is supported on silica and which is palladium-free as well as lead-free.
- palladium-free and lead-free in the context of the present invention it is meant that no palladium and lead is added to the catalyst system intentionally. It might be possible that such metals are present in very low traces.
- the catalyst according to the present invention is produced usually (and preferably) in the following way
- Step 1) a cobalt ligand complex is formed which is then Step 2) deposited within the pores and onto the surface of porous silica (usually by a wet impregnation procedure), and Step 3) the reaction product of step 2) is dried and afterwards pyrolyzed (at high temperature of at least 600 °C).
- the present invention relates to a catalyst (C) obtainable by (comprising)
- step 2) depositing the cobalt ligand complex of step 1) on the porous silica support (usually by a wet impregnation procedure) to form an absorbed reaction prod uct, and
- step 3 drying and pyrolyzing (at high temperature at least 600 °C) the absorbed prod uct of step 2) to obtain the catalyst.
- a very reactive catalyst consisting of cobalt na noparticles and a cobalt doped carbon layer, which is supported on silica and which is palladium-free and lead-free.
- This so obtained catalyst has excellent properties in the hydrogenation of alkynes as will be shown below.
- Step 1) (forming the cobalt ligand complex)
- At least one cobalt salt is used.
- Co(ll) salt(s), Co(l) salt(s) and/or Co(0) salt(s) are used.
- the anion can be any anion. This is not crucial for the properties of the obtained catalyst.
- the present invention relates to a catalyst (C1), which is catalyst (C), wherein step 1) at least one Co salt is at least one Co(ll) salt and/or at least one Co(l) salt and/or at least one Co(0) salt.
- Preferred cobalt salts are for example Co(OAc) 2 , Co(acac) 2 , C0CO 3 , C0CP 2 , (TMEDA)CO(CH 3 ) 2 , Co(acac) 2 (TMEDA) and Co(COD) 2 .
- the present invention relates to a catalyst (C2), which is catalyst (C) or (C1), wherein step 1) at least one cobalt salt is chosen from the group consisting of CO(OAC) 2 , Co(acac) 2 , C0CO3, C0CI2, CoBr 2, C0CP2, (TMEDA)Co(CH 3 )2 and CO(COD) 2 .
- the present invention relates to a catalyst (C2’), which is catalyst (C) or (C1), wherein step 1) at least one cobalt salt is chosen from the group consisting of CO(OAC)2, Co(acac)2, C0CO3, C0CP2, (TMEDA)Co(CH3)2, Co(acac)2(TMEDA) and CO(COD) 2 .
- the ligand used in step 1) to form the cobalt ligand complex can be any commonly known and used ligand.
- the ligand can be monodentate and/or polydentate (such as melamine, chitin, phenanthroline, 4,4-bipyridine, guanidinium chloride, terpyridine, starch, saccharose and urea). This means also a mixture of different ligands can be used.
- Preferred ligands are chosen from the group consisting of melamine, chitin, phenan- throline, 4,4-bipyridine, guanidinium chloride, terpyridine and urea.
- the present invention relates to a catalyst (C3), which is catalyst (C), (C1) (C2) or (C2’), wherein step 1) the ligand is monodentate and/or polydentate (such as melamine, chitin, phenanthroline, 4,4-biperidine, guanidinium chloride, terpyridine, starch, saccharose and urea).
- the ligand is monodentate and/or polydentate (such as melamine, chitin, phenanthroline, 4,4-biperidine, guanidinium chloride, terpyridine, starch, saccharose and urea).
- the present invention relates to a catalyst (C4), which is catalyst (C), (C1), (C2), (C2’) or (C3), wherein step 1) at least one ligand comprises at least one N atom.
- the present invention relates to a catalyst (C5), which is catalyst (C), (C1), (C2), (C2’), (C3) or (C4), wherein step 1) the ligand is chosen from the group consist ing of melamine, chitin, phenanthroline, 4,4-bipyridine, guanidinium chloride, terpyri dine and urea.
- the molar ratio of the cobalt salts to the ligand can vary. Usually it goes from 1 : 1 to 1 :15.
- the present invention relates to a catalyst (C6), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is from 1 :1 to 1 :15.
- 1 :1 to 1 :12 Preferably 1 :1 to 1 :12, more preferably 1 :1 to 1 :10 most preferred is a 1 :1 molar ratio
- the present invention relates to a catalyst (C6’), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is from 1 :1 to 1 :12.
- the present invention relates to a catalyst (C6”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is from 1 :1 to 1 :10. Therefore, the present invention relates to a catalyst (C6’”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is 1 :1.
- the formation of the cobalt ligand complex is usually done in at least one solvent.
- the cobalt ligand complex should be soluble (at least partially in the solvent, which is used).
- the solvents are usually polar protic or polar aprotic solvent. Suitable solvents are for example water, polar protic solvents such as alcohols, polar aprotic solvents like ke tones and esters.
- Preferred solvents are chosen from the group consisting of water, methanol, ethanol, propanol, acetone, ethylene carbonate, toluene, and mixtures thereof.
- the present invention relates to a catalyst (C7), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”) or (C6’”), wherein step 1) the formation of the cobalt ligand complex is carried out in at least one solvent.
- the present invention relates to a catalyst (C7’), which is catalyst (C7), wherein at least one solvent is a polar protic or polar aprotic solvent.
- the present invention relates to a catalyst (C7”), which is catalyst (C7), wherein at least one solvent chosen from the group consisting of water, methanol, ethanol, propanol, acetone, ethylene carbonate and toluene.
- the Co ligand complex formation can be done at a temperature range of from 5 to 50 °C. Preferably 15 to 40 °C, more preferred is a range from 20 to 30 °C.
- the present invention relates to a catalyst (C8), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’) or (C7”), wherein step 1 ) the formation of the cobalt ligand complex is carried out a temperature range of from 5 to 50 °C.
- the present invention relates to a catalyst (C8’), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’) or (C7”), wherein step 1 ) the formation of the cobalt ligand complex is carried out a temperature range of from 15 to 40 °C.
- the present invention relates to a catalyst (C8”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’) or (C7”), wherein step 1 ) the formation of the cobalt ligand complex is carried out a temperature range of from 20 to 30 °C.
- Step 2) depositing of the cobalt ligand complex
- cobalt ligand complex is not isolated from the reaction mixture of step 1).
- silica S1O2 is added directly into the reaction mixture of step 1) after the cobalt ligand complex is formed.
- Fumed silica is an amorphous silica fused into branched, chainlike, three-dimensional secondary particles which then agglomerate into tertiary particles, a white powder with extremely low bulk density and thus high surface area.
- Such fumed silicas are available commercially from a variety of suppliers, such as Evonik, GRACE, Palmer Holland Inc, Applied Material Solutions, AGSCO Corporation and many more.
- the present invention relates to a catalyst (C9), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’) or (C8”), wherein step 2) the silica used is fumed silica.
- the silica is added to the reaction mixture usually in a molar excess to the Co.
- a usual amount of S1O2 added to the reaction mixture is such that the in the reaction mixture the molar ratio of Co to S1O2 is 1 : 150 to 1 :100, preferably 1 : 120 to 1 :80. Therefore, the present invention relates to a catalyst (C10), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”) or (C9), wherein step 2) the silica is added to the reaction mixture in a molar excess to the Co.
- the present invention relates to a catalyst (C10’), which is catalyst (C10), wherein the molar ratio of Co to S1O2 is 1 : 150 to 1 :100.
- the present invention relates to a catalyst (C10”), which is catalyst (C10), wherein the molar ratio of Co to S1O2 is 1 : 120 to 1 :80.
- the absorption step is carried out at a temperature range of from 5 to 50 °C. Prefer ably 15 to 40 °C, more preferably 20 to 30 °C.
- the present invention relates to a catalyst (C11 ), which is catalyst (C), (C1 ), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’) or (C10”), wherein step 2) the absorption step is carried out at a temperature range of from 5 to 50 °C.
- the present invention relates to a catalyst (C1 T), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’) or (C10”), wherein step 2) the absorption step is car ried out at a temperature range of from 15 to 40 °C.
- the present invention relates to a catalyst (C11 ”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’) or (C10”), wherein step 2) the absorption step is car ried out at a temperature range of from 20 to 30 °C.
- step 3a the solvent (or mixture of sol vents) is removed (the majority of the solvent should be removed, at least 70 wt-% of the solvent, based on the total amount of the solvent used).
- this is done by evaporation (usually under vacuum) of the sol vent. This is done at elevated temperature (30 - 60 °C) and under milder vacuum (30 to 200 mbar).
- the present invention relates to a catalyst (C12), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’) or (C11”), wherein step 3a) the sol vent (or mixture of solvents) is removed (the majority of the solvent should be re moved, at least 70 wt-% of the solvent, based on the total amount of the solvent used).
- the present invention relates to a catalyst (C12’), which is catalyst (C12), wherein step 3a) the removal of the solvent is done by evaporation (preferably at elevated temperature (30 - 60 °C) an under milder vacuum (30 to 200 mbar)).
- reaction solid product (a powder) is usually and preferably dried under high vacuum and elevated temperature.
- the present invention relates to a catalyst (C13), which is catalyst (C), (C1 ), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12) or (C12’), wherein the reaction product of step 3a) is dried (and preferably under high vacuum and elevated temperature).
- step 3b In a second step of step 3), which can be called step 3b), the obtained solid form from step 3a) is pyrolyzed.
- step 3 a) Usually the powder obtained from step 3 a) is comminuted (i.e. by grinding) to a fine powder before the pyrolysis. This fine powder is then pyrolysed usually in an oven (under inert atmosphere) at a temperature of at least 600 °C.
- the present invention relates to a catalyst (C14), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’) or (C13), wherein the reaction product of step 3a) is comminuted (i.e. by grinding) to a fine powder before the pyrolysis.
- the reaction product of step 3a) is comminuted (i.e. by grinding) to a fine powder before the pyrolysis.
- the present invention relates to a catalyst (C15), which is catalyst (C), (C1 ), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13) or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature of at least 600 °C.
- the present invention relates to a catalyst (C15’), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13) or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature be tween 600 - 1200 °C.
- the present invention relates to a catalyst (C15”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13) or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature be tween 650 - 1100 °C.
- the present invention relates to a catalyst (C15’”), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13) or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature be tween 700 - 1100 °C.
- the duration of the pyrolysis is usually between 1 and 10 hours.
- the present invention relates to a catalyst (C16), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13), (C14), (C15), (C15’), (C15”) or (C15’”), wherein step 3b) the duration of the pyrolysis is be tween 1 and 10 hours.
- the catalyst is obtained as a powder (powderous catalyst).
- the present invention relates to a catalyst made by the process steps as defined and disclosed above.
- the carbon content, the hydrogen content, the nitrogen content and the cobalt content of the powderous catalysts obtained by the process as described above can be de termined by elemental analysis.
- the present invention relates to a catalyst comprising cobalt nanoparticles and nitrogen doped carbon layer, which is supported on silica and which is free from palladium as well as free from lead and comprising C : 0.5 to 5 wt-%, based on the total weight of the powderous catalyst, and H : 0.01 to 2 wt-%, based on the total weight of the powderous catalyst, and N : 0.02 to 2 wt-%, based on the total weight of the powderous catalyst, and Co : 2 to 7 wt-%, based on the total weight of the powderous catalyst.
- the rest of the 100 % is the silica.
- the so produced powderous Co catalyst is used as a catalyst in hydrogenation reac tions, especially in selective hydrogenations.
- the catalyst is used for the hydrogena tion of alkynes to alkenes (i.e. without further reduction into alkanes).
- the present invention relates to a hydrogenation (H), wherein at least one catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13), (C14), (C15), (C15’), (C15”) and/or (C15’”) is used.
- the present invention relates to a hydrogenation (H1), which is hydrogena tion (H), wherein the hydrogenation is a selective hydrogenation.
- the present invention relates to a hydrogenation (H2), which is hydrogena tion (H) or (H1), wherein the hydrogenation of alkynes to alkenes.
- R is H; linear or branched, or cyclic Ci - C20 alkyl, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes; or linear or branched, or cyclic C2- C20 alkylene, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes, and Ri is linear or branched, or cyclic C 3 - C 45 alkyl, which can be substituted by OH, NH, NH 2 , C(O), aromatic alkynes; linear or branched or cyclic C 3 - C 45 alkylene, which can be substituted by OH, NH, NH 2 , C(O), aromatic alkynes.
- the use of the catalyst of the present invention allows hydrogenation of the com pounds of formula (I) to the corresponding alkene compound of formula (G) wherein R and R1 have the same meanings are defined for the compound of formula (I).
- the present invention relates to a hydrogenation (H3), which is hydrogen ated to (H), (H1) or (H2), wherein compounds of formula (I) (I) wherein
- R is H; linear or branched, or cyclic Ci - C 20 alkyl, which can be substituted by OH, NH, NH 2 , C(O) and/or aromatic alkynes; or linear or branched, or cyclic C 2 - C 20 alkylene, which can be substituted by OH, NH, NH 2 , C(O) and/or aromatic alkynes, and
- Ri is linear or branched, or cyclic C 3 - C 45 alkyl, which can be substituted by OH, NH, NH2, C(O), aromatic alkynes; linear or branched or cyclic C3 - C45 alkylene, which can be substituted by OH, NH, NH 2 , C(O), aromatic alkynes, are hydrogenated selectively.
- Preferred compounds are those of formula (I), wherein R is H, and
- Ri is linear or branched, or cyclic C 3 - C 45 alkyl, which can be substituted by OH; linear or branched C 3 - C 45 alkylene, which can be substituted by OH. More preferred compounds are those of formula (I), wherein R is H, and
- Ri is linear or branched, or cyclic C3 - C20 alkyl, which can be substituted by OH; linear or branched C3 - C2oalkylene, which can be substituted by OH.
- the present invention relates to a hydrogenation (H3’), which is hydrogena tion (H3), wherein R is H, and R1 is linear or branched, or cyclic C 3 - C 45 alkyl, which can be substituted by OH; linear or branched C 3 - C 45 alkylene, which can be substituted by OH.
- H3 hydrogenation
- R1 is linear or branched, or cyclic C 3 - C 45 alkyl, which can be substituted by OH
- linear or branched C 3 - C 45 alkylene which can be substituted by OH.
- the present invention relates to a hydrogenation (H3”), which is hydro genation (H3), wherein R is H, and
- Ri is linear or branched, or cyclic C 3 - C 20 alkyl, which can be substituted by OH; linear or branched C 3 - C 20 alkylene, which can be substituted by OH.
- the present invention relates to a hydrogenation (H3’”), which is hydro- genation (H3), wherein the compound of formula (la) ) is hydrogenated.
- the present invention relates to a hydrogenation (H3””), which is hydro- genation (H3), wherein the compound of formula (lb) is hydrogenated. Therefore, the present invention relates to a hydrogenation (H3’””), which is hydro genation (H3), wherein the compound of formula (lc) ) is hydrogenated.
- the hydrogenation using the catalyst according to the present invention is usually carried out in at least one solvent.
- suitable solvents are acetonitrile, ethanol and propanol.
- the present invention relates to a hydrogenation (H4), which is hydrogena tion (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””) or (H3’””), wherein hydrogena tion is carried out in at least one solvent. Therefore, the present invention relates to a hydrogenation (H4’), which is hydrogena tion (H4), wherein at least one solvent is chosen from the group consisting of acetoni trile, ethanol and propanol.
- the present invention relates to a hydrogenation (H5), which is hydrogena tion (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””) or (H3’””), wherein hydrogena tion is carried out without any solvent.
- the hydrogenation according to the present invention is usually carried out at ele vated temperatures.
- the present invention relates to a hydrogenation (H6), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’) or (H5), wherein hydrogenation is carried out at elevated temperatures.
- the present invention relates to a hydrogenation (H6’), which is hydrogena tion (H6), wherein hydrogenation is carried out at a temperature between 15 - 150 °C.
- the present invention relates to a hydrogenation (H6”), which is hydro genation (H6), wherein hydrogenation is carried out at a temperature between 20 to 140 °C.
- the hydrogenation according to the present invention is carried by using H2 gas (pure or as a mixture).
- H2 gas pure or as a mixture
- Preferably pure H2 gas is used.
- the present invention relates to a hydrogenation (H7), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’) or (H6”), wherein H2 gas (pure or as a mixture) is used (preferably pure H2 gas).
- H7 hydrogena hydrogenation
- H1 hydrogena tion
- H2 pure or as a mixture
- H2 gas pure or as a mixture
- H2 gas pure or as a mixture
- the present invention relates to a hydrogenation (H8), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”) or (H7), wherein the hydrogenation is carried out at elevated pressure.
- the present invention relates to a hydrogenation (H8’), which is hydrogena tion (H8), wherein the hydrogenation is carried out at an absolute pressure between 1 and 50 bar.
- the present invention relates to a hydrogenation (H8”), which is hydro genation (H8), wherein the hydrogenation is carried out at an absolute pressure be tween 1 and 40 bar.
- the amount of the catalyst used in the hydrogenation according to the present inven tion is between 0.1 - 5 mol-% (in view of the compound to the hydrogenated). Pref erably 0.5 - 4 mol-%.
- the present invention relates to a hydrogenation (H9), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’) or (H8”), wherein the catalyst is used in an amount between 0.1 - 5 mol-% (in view of the compound to the hydrogenated).
- the present invention relates to a hydrogenation (H9’), which is hydrogena tion (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’) or (H8”), wherein the catalyst is used in an amount between 0.5 - 4 mol-% (in view of the compound to the hydrogenated).
- a further advantage of the catalyst according to the present invention is that it can be recycled and reused, and the activity of the catalyst stays on a similar level.
- the hydrogenation can be carried out batch-wise or continuously. Therefore, the present invention relates to a hydrogenation (H10), which is hydro genation (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’), (H8”), (H9) or (H9’), wherein the hydrogenation is carried out batch-wise.
- the present invention relates to a hydrogenation (H11), which is hydro genation (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’), (H8”), (H9) or (H9’), wherein the hydrogenation is carried out continuously.
- the oven was held at the final temperature for 2 h, purg ing with argon the entire time. The oven was allowed to cool to room temperature, the crucible removed, and the catalyst (0.228 g, 87 % yield) transferred to a sample vial for storage.
- the catalyst synthesis has also been demonstrated with a molar ratio of metal pre cursor to melamine of 1 :5, 1 :10. All catalysts ratios were pyrolyzed at 800 °C and 1000 °C.
- Table 1 shows the elemental analysis of the catalysts of the examples.
- Table 1 Elemental analysis of the prepared catalysts (pyrolysis temp 800 °C).
- the catalytic activity tests were performed in a 300 ml autoclave advanced with an internal aluminium plate to include eight uniform reaction glass vials (4 ml) with cap, septum, and needle. 3,7,11 ,15-tetramethylhexadec-1-yn-3-ol (72.4 mg, 0.25 mmol), cobalt catalyst (3.2 mg, 1 mol %) and MeCN (2 mL) were placed in a 4 ml_ vial. A cap with a septum punctured by a needle, to allow entry of H2, was fitted. The vial was placed in an aluminium plate which was inserted into a 300 mL stainless steel auto clave.
- Table 3 The effect of solvent on the reactivity of the catalyst 1 of Table 1 .
- Table 4 The effect of an 8 h reaction time on the catalytic performance of the cata lysts of table 1
- Table 6 The effect of a 100 °C reaction temperature on the catalytic performance of the catalysts of table 1 rate 750 RPM, 30 bar H 2 , 15 h).
- the cobalt catalyst could be recovered from the reaction mixture via centrifugation and washed with ethyl acetate. After drying, the catalyst could then be used with similar activity (Table 7: ).
- the catalytic activity tests are performed in a 300 ml autoclave advanced with an internal aluminium plate to include eight uniform reaction glass vials (4 ml) with cap, septum, and needle.
- MBY (0.25 mmol
- cobalt catalyst 3.2 mg, 1 mol %)
- MeCN 2 mL
- the vial is placed in an aluminium plate which is inserted into a 300 mL stainless steel autoclave.
- the autoclave is sealed and flushed twice with H2 (20 bar) and then charged with H2 (30 bar).
- the autoclave is placed in an aluminium block pre-heated to 120 °C and maintained at this temperature for 15 h with a stir rate of 750 ppm. Following the reaction, the autoclave is cooled in an ice-water bath and the pressure released. Dodecane (40 pL) is added as internal standard and the reac tion mixture diluted with chloroform (1 mL). The catalyst and reaction mixture are sep arated via centrifugation (5000 RPM, 1 minute). The recovered catalyst is washed with ethyl acetate (3 x 4 mL), separating via centrifugation as before, and then dried under high vacuum for ca. 22 h. The reaction mixture is filtered through a celite plug and the product composition analysed via GC.
- the catalytic activity tests are performed in a 300 ml autoclave advanced with an internal aluminium plate to include eight uniform reaction glass vials (4 ml) with cap, septum, and needle.
- Dehydrolinalool (0.25 mmol), cobalt catalyst (3.2 mg, 1 mol %) and MeCN (2 mL) are placed in a 4 ml_ vial.
- the vial is placed in an aluminium plate which is inserted into a 300 mL stainless steel autoclave.
- the autoclave is sealed and flushed twice with H2 (20 bar) and then charged with H2 (30 bar).
- the autoclave is placed in an aluminium block pre-heated to 120 °C and maintained at this temperature for 15 h with a stir rate of 750 ppm. Following the reaction, the autoclave is cooled in an ice- water bath and the pressure released. Dodecane (40 pL) is added as internal stand ard and the reaction mixture diluted with chloroform (1 mL). The catalyst and reaction mixture are separated via centrifugation (5000 RPM, 1 minute). The recovered cata- lyst is washed with ethyl acetate (3 x 4 mL), separating via centrifugation as before, and then dried under high vacuum forca. 22 h. The reaction mixture is filtered through a celite plug and the product composition analysed via GC.
- Linalool is obtained in good yields.
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Abstract
The present invention relates to a new cobalt (Co) catalyst for selective hydrogenations of alkynes to alkenes. The catalyst is prepared by impregnating fumed silica with a cobalt complex comprising, for instance, melamine, drying the impregnated material and pyrolysing it to obtain cobalt nanoparticles and nitrogen-doped carbon supported on silica.
Description
NEW COBALT CATALYST SUPPORTED ON SILICA
The present invention relates to a new cobalt (Co) catalyst for selective hydrogena tions.
There are known many catalysts for hydrogenation. An important kind for these reac tions are the Lindlar catalysts
Lindlar catalysts are very important and well known catalysts. A Lindlar catalyst is a heterogeneous catalyst that consists of palladium deposited on calcium carbonate and treated with lead. The catalyst is used for the hydrogenation of alkynes to alkenes (i.e. without further reduction into alkanes). Thus if a compound contains a double bond as well as a triple bond, the triple bond is reduced to a double bond with high selectivity.
Lindlar catalysts are very useful and powerful catalyst, but nevertheless the replace ment of the Lindlar catalyst is desirable due to the toxicity of lead and the high cost of palladium therein.
This invention relates to the replacement of the "Lindlar catalyst” for the synthesis of vitamin and nutritional product precursors via hydrogenation of both terminal and in ternal alkynes.
The goal was to find a catalyst, which has the same properties as a classic Lindlar catalyst, but which is free of palladium and lead. Furthermore, the catalyst should be recyclable and re-usable.
Surprisingly, it was found that a new specific catalyst consisting of cobalt nanoparti cles and nitrogen doped carbon supported on silica has the same properties in regard to hydrogenation performance but which is free palladium-free as well as lead-free.
Therefore the present invention relates to a catalyst comprising cobalt nanoparticles and nitrogen doped carbon layer, which is supported on silica
and which is palladium-free as well as lead-free.
By the terms “palladium-free” and “lead-free” in the context of the present invention it is meant that no palladium and lead is added to the catalyst system intentionally. It might be possible that such metals are present in very low traces.
The catalyst according to the present invention is produced usually (and preferably) in the following way
Step 1) a cobalt ligand complex is formed which is then Step 2) deposited within the pores and onto the surface of porous silica (usually by a wet impregnation procedure), and Step 3) the reaction product of step 2) is dried and afterwards pyrolyzed (at high temperature of at least 600 °C).
Therefore, the present invention relates to a catalyst (C) obtainable by (comprising)
1) forming a cobalt ligand complex;
2) depositing the cobalt ligand complex of step 1) on the porous silica support (usually by a wet impregnation procedure) to form an absorbed reaction prod uct, and
3) drying and pyrolyzing (at high temperature at least 600 °C) the absorbed prod uct of step 2) to obtain the catalyst.
As a result of the process a very reactive catalyst is formed consisting of cobalt na noparticles and a cobalt doped carbon layer, which is supported on silica and which is palladium-free and lead-free.
This so obtained catalyst has excellent properties in the hydrogenation of alkynes as will be shown below.
In the following, the process steps of producing the catalyst are discussed in more detail.
Step 1) (forming the cobalt ligand complex)
For the formation of the cobalt ligand complex at least one cobalt salt is used.
Usually Co(ll) salt(s), Co(l) salt(s) and/or Co(0) salt(s) are used. The anion can be any anion. This is not crucial for the properties of the obtained catalyst.
Therefore, the present invention relates to a catalyst (C1), which is catalyst (C), wherein step 1) at least one Co salt is at least one Co(ll) salt and/or at least one Co(l) salt and/or at least one Co(0) salt.
Suitable cobalt salts are for example Co(OAc)2 (Ac = acetyl), Co(acac)2 (acac = acet- ylacetonate), C0CO3, C0CI2, CoBr2, C0CP2 (Cp = cyclopentadienyl), (TMEDA)CO(CH3)2 (TMEDA = Tetramethylethylenediamine), Co(acac)2(TMEDA) and CO(COD)2 (COD = Cyclooctadiene).
Preferred cobalt salts are for example Co(OAc)2, Co(acac)2, C0CO3, C0CP2, (TMEDA)CO(CH3)2, Co(acac)2(TMEDA) and Co(COD)2.
Therefore, the present invention relates to a catalyst (C2), which is catalyst (C) or (C1), wherein step 1) at least one cobalt salt is chosen from the group consisting of CO(OAC)2, Co(acac)2, C0CO3, C0CI2, CoBr2, C0CP2, (TMEDA)Co(CH3)2 and CO(COD)2.
Therefore, the present invention relates to a catalyst (C2’), which is catalyst (C) or (C1), wherein step 1) at least one cobalt salt is chosen from the group consisting of CO(OAC)2, Co(acac)2, C0CO3, C0CP2, (TMEDA)Co(CH3)2, Co(acac)2(TMEDA) and CO(COD)2.
The ligand used in step 1) to form the cobalt ligand complex can be any commonly known and used ligand. The ligand can be monodentate and/or polydentate (such as melamine, chitin, phenanthroline, 4,4-bipyridine, guanidinium chloride, terpyridine, starch, saccharose and urea). This means also a mixture of different ligands can be used. Preferred are ligands comprising at least one N atom.
Preferred ligands are chosen from the group consisting of melamine, chitin, phenan- throline, 4,4-bipyridine, guanidinium chloride, terpyridine and urea.
Therefore, the present invention relates to a catalyst (C3), which is catalyst (C), (C1) (C2) or (C2’), wherein step 1) the ligand is monodentate and/or polydentate (such as melamine, chitin, phenanthroline, 4,4-biperidine, guanidinium chloride, terpyridine, starch, saccharose and urea).
Therefore, the present invention relates to a catalyst (C4), which is catalyst (C), (C1), (C2), (C2’) or (C3), wherein step 1) at least one ligand comprises at least one N atom.
Therefore, the present invention relates to a catalyst (C5), which is catalyst (C), (C1), (C2), (C2’), (C3) or (C4), wherein step 1) the ligand is chosen from the group consist ing of melamine, chitin, phenanthroline, 4,4-bipyridine, guanidinium chloride, terpyri dine and urea.
The molar ratio of the cobalt salts to the ligand can vary. Usually it goes from 1 : 1 to 1 :15.
Preferably 1 :1 to 1 : 12, more preferably 1 :1 to 1 :10, most preferred is a 1 :1 molar ratio.
Therefore, the present invention relates to a catalyst (C6), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is from 1 :1 to 1 :15.
Preferably 1 :1 to 1 :12, more preferably 1 :1 to 1 :10 most preferred is a 1 :1 molar ratio
Therefore, the present invention relates to a catalyst (C6’), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is from 1 :1 to 1 :12.
Therefore, the present invention relates to a catalyst (C6”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is from 1 :1 to 1 :10.
Therefore, the present invention relates to a catalyst (C6’”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4) or (C5), wherein step 1) the molar ratio of the cobalt salts to the ligand is 1 :1.
The formation of the cobalt ligand complex is usually done in at least one solvent. The cobalt ligand complex should be soluble (at least partially in the solvent, which is used).
The solvents are usually polar protic or polar aprotic solvent. Suitable solvents are for example water, polar protic solvents such as alcohols, polar aprotic solvents like ke tones and esters.
Preferred solvents are chosen from the group consisting of water, methanol, ethanol, propanol, acetone, ethylene carbonate, toluene, and mixtures thereof.
Therefore, the present invention relates to a catalyst (C7), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”) or (C6’”), wherein step 1) the formation of the cobalt ligand complex is carried out in at least one solvent.
Therefore, the present invention relates to a catalyst (C7’), which is catalyst (C7), wherein at least one solvent is a polar protic or polar aprotic solvent.
Therefore, the present invention relates to a catalyst (C7”), which is catalyst (C7), wherein at least one solvent chosen from the group consisting of water, methanol, ethanol, propanol, acetone, ethylene carbonate and toluene.
The Co ligand complex formation can be done at a temperature range of from 5 to 50 °C. Preferably 15 to 40 °C, more preferred is a range from 20 to 30 °C.
Therefore, the present invention relates to a catalyst (C8), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’) or (C7”), wherein step 1 ) the formation of the cobalt ligand complex is carried out a temperature range of from 5 to 50 °C.
Therefore, the present invention relates to a catalyst (C8’), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’) or (C7”), wherein step 1 ) the formation of the cobalt ligand complex is carried out a temperature range of from 15 to 40 °C.
Therefore, the present invention relates to a catalyst (C8”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’) or (C7”), wherein step 1 ) the formation of the cobalt ligand complex is carried out a temperature range of from 20 to 30 °C.
At the end the Co ligand complex is formed.
Step 2) depositing of the cobalt ligand complex
Usually the cobalt ligand complex is not isolated from the reaction mixture of step 1). Usually the silica (S1O2) is added directly into the reaction mixture of step 1) after the cobalt ligand complex is formed.
Preferably fumed silica is used. Fumed silica is an amorphous silica fused into branched, chainlike, three-dimensional secondary particles which then agglomerate into tertiary particles, a white powder with extremely low bulk density and thus high surface area.
Such fumed silicas are available commercially from a variety of suppliers, such as Evonik, GRACE, Palmer Holland Inc, Applied Material Solutions, AGSCO Corporation and many more.
Therefore, the present invention relates to a catalyst (C9), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’) or (C8”), wherein step 2) the silica used is fumed silica.
The silica is added to the reaction mixture usually in a molar excess to the Co.
A usual amount of S1O2 added to the reaction mixture is such that the in the reaction mixture the molar ratio of Co to S1O2 is 1 : 150 to 1 :100, preferably 1 : 120 to 1 :80.
Therefore, the present invention relates to a catalyst (C10), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”) or (C9), wherein step 2) the silica is added to the reaction mixture in a molar excess to the Co.
Therefore, the present invention relates to a catalyst (C10’), which is catalyst (C10), wherein the molar ratio of Co to S1O2 is 1 : 150 to 1 :100.
Therefore, the present invention relates to a catalyst (C10”), which is catalyst (C10), wherein the molar ratio of Co to S1O2 is 1 : 120 to 1 :80.
The absorption step is carried out at a temperature range of from 5 to 50 °C. Prefer ably 15 to 40 °C, more preferably 20 to 30 °C.
Therefore, the present invention relates to a catalyst (C11 ), which is catalyst (C), (C1 ), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’) or (C10”), wherein step 2) the absorption step is carried out at a temperature range of from 5 to 50 °C.
Therefore, the present invention relates to a catalyst (C1 T), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’) or (C10”), wherein step 2) the absorption step is car ried out at a temperature range of from 15 to 40 °C.
Therefore, the present invention relates to a catalyst (C11 ”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’) or (C10”), wherein step 2) the absorption step is car ried out at a temperature range of from 20 to 30 °C.
The deposited reaction product (cobalt ligand complex absorbed into pores and on the surface of the porous silica) is obtained.
Step 3) drying and pyrolyzing the reaction product of step 2)
In a first step of step 3), which can be called step 3a), the solvent (or mixture of sol vents) is removed (the majority of the solvent should be removed, at least 70 wt-% of the solvent, based on the total amount of the solvent used).
Usually and preferably this is done by evaporation (usually under vacuum) of the sol vent. This is done at elevated temperature (30 - 60 °C) and under milder vacuum (30 to 200 mbar).
Therefore, the present invention relates to a catalyst (C12), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’) or (C11”), wherein step 3a) the sol vent (or mixture of solvents) is removed (the majority of the solvent should be re moved, at least 70 wt-% of the solvent, based on the total amount of the solvent used).
Therefore, the present invention relates to a catalyst (C12’), which is catalyst (C12), wherein step 3a) the removal of the solvent is done by evaporation (preferably at elevated temperature (30 - 60 °C) an under milder vacuum (30 to 200 mbar)).
Afterwards the so obtained reaction solid product (a powder) is usually and preferably dried under high vacuum and elevated temperature.
Therefore, the present invention relates to a catalyst (C13), which is catalyst (C), (C1 ), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12) or (C12’), wherein the reaction product of step 3a) is dried (and preferably under high vacuum and elevated temperature).
In a second step of step 3), which can be called step 3b), the obtained solid form from step 3a) is pyrolyzed.
Usually the powder obtained from step 3 a) is comminuted (i.e. by grinding) to a fine powder before the pyrolysis.
This fine powder is then pyrolysed usually in an oven (under inert atmosphere) at a temperature of at least 600 °C.
Usually at a temperature between 600 - 1200 °C (preferably at 650 to 1100 °C, more preferably 700 to 1100 °C).
Therefore, the present invention relates to a catalyst (C14), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’) or (C13), wherein the reaction product of step 3a) is comminuted (i.e. by grinding) to a fine powder before the pyrolysis.
Therefore, the present invention relates to a catalyst (C15), which is catalyst (C), (C1 ), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13) or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature of at least 600 °C.
Therefore, the present invention relates to a catalyst (C15’), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13) or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature be tween 600 - 1200 °C.
Therefore, the present invention relates to a catalyst (C15”), which is catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13) or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature be tween 650 - 1100 °C.
Therefore, the present invention relates to a catalyst (C15’”), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13)
or (C14), wherein the reaction product of step 3a) is pyrolysed at a temperature be tween 700 - 1100 °C.
The duration of the pyrolysis is usually between 1 and 10 hours.
Therefore, the present invention relates to a catalyst (C16), which is catalyst (C), (C1), (C2), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13), (C14), (C15), (C15’), (C15”) or (C15’”), wherein step 3b) the duration of the pyrolysis is be tween 1 and 10 hours.
At the end of this process the catalyst is obtained as a powder (powderous catalyst).
Furthermore, the present invention relates to a catalyst made by the process steps as defined and disclosed above.
The carbon content, the hydrogen content, the nitrogen content and the cobalt content of the powderous catalysts obtained by the process as described above can be de termined by elemental analysis.
The values of these contents vary depending on the amount of the various ingredients (such as Co salt, ligand) as well as on the pyrolysis conditions (temperature and du ration).
Typical values are for
C : 0.5 to 5 wt-%, based on the total weight of the powderous catalyst H : 0.01 to 2 wt-%, based on the total weight of the powderous catalyst N : 0.02 to 2 wt-%, based on the total weight of the powderous catalyst Co : 2 to 7 wt-%, based on the total weight of the powderous catalyst.
Therefore the present invention relates to a catalyst comprising cobalt nanoparticles and nitrogen doped carbon layer, which is supported on silica and which is free from palladium as well as free from lead and comprising C : 0.5 to 5 wt-%, based on the total weight of the powderous catalyst, and
H : 0.01 to 2 wt-%, based on the total weight of the powderous catalyst, and N : 0.02 to 2 wt-%, based on the total weight of the powderous catalyst, and Co : 2 to 7 wt-%, based on the total weight of the powderous catalyst.
The rest of the 100 % is the silica.
The so produced powderous Co catalyst is used as a catalyst in hydrogenation reac tions, especially in selective hydrogenations. The catalyst is used for the hydrogena tion of alkynes to alkenes (i.e. without further reduction into alkanes).
Therefore, the present invention relates to a hydrogenation (H), wherein at least one catalyst (C), (C1), (C2), (C2’), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C11’), (C11”), (C12), (C12’), (C13), (C14), (C15), (C15’), (C15”) and/or (C15’”) is used.
Therefore, the present invention relates to a hydrogenation (H1), which is hydrogena tion (H), wherein the hydrogenation is a selective hydrogenation.
Therefore, the present invention relates to a hydrogenation (H2), which is hydrogena tion (H) or (H1), wherein the hydrogenation of alkynes to alkenes.
Preferred compound, which are hydrogenated selectively, are those of formula (I)
wherein
R is H; linear or branched, or cyclic Ci - C20 alkyl, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes; or linear or branched, or cyclic C2- C20 alkylene, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes, and
Ri is linear or branched, or cyclic C3 - C45 alkyl, which can be substituted by OH, NH, NH2, C(O), aromatic alkynes; linear or branched or cyclic C3- C45 alkylene, which can be substituted by OH, NH, NH2, C(O), aromatic alkynes.
The use of the catalyst of the present invention allows hydrogenation of the com pounds of formula (I) to the corresponding alkene compound of formula (G)
wherein R and R1 have the same meanings are defined for the compound of formula (I).
Therefore, the present invention relates to a hydrogenation (H3), which is hydrogen ated to (H), (H1) or (H2), wherein compounds of formula (I)
(I) wherein
R is H; linear or branched, or cyclic Ci - C20 alkyl, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes; or linear or branched, or cyclic C2- C20 alkylene, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes, and
Ri is linear or branched, or cyclic C3 - C45 alkyl, which can be substituted by OH, NH, NH2, C(O), aromatic alkynes; linear or branched or cyclic C3 - C45 alkylene, which can be substituted by OH, NH, NH2, C(O), aromatic alkynes, are hydrogenated selectively.
Preferred compounds are those of formula (I), wherein R is H, and
Ri is linear or branched, or cyclic C3 - C45 alkyl, which can be substituted by OH; linear or branched C3 - C45 alkylene, which can be substituted by OH.
More preferred compounds are those of formula (I), wherein R is H, and
Ri is linear or branched, or cyclic C3 - C20 alkyl, which can be substituted by OH; linear or branched C3 - C2oalkylene, which can be substituted by OH.
Most preferred are the compounds of formula (la), (lb) and (lc)
Therefore, the present invention relates to a hydrogenation (H3’), which is hydrogena tion (H3), wherein R is H, and R1 is linear or branched, or cyclic C3 - C45 alkyl, which can be substituted by OH; linear or branched C3 - C45 alkylene, which can be substituted by OH.
Therefore, the present invention relates to a hydrogenation (H3”), which is hydro genation (H3), wherein R is H, and
Ri is linear or branched, or cyclic C3 - C20 alkyl, which can be substituted by OH; linear or branched C3 - C20 alkylene, which can be substituted by OH.
Therefore, the present invention relates to a hydrogenation (H3’”), which is hydro- genation (H3), wherein the compound of formula (la)
)
is hydrogenated.
Therefore, the present invention relates to a hydrogenation (H3””), which is hydro- genation (H3), wherein the compound of formula (lb)
is hydrogenated. Therefore, the present invention relates to a hydrogenation (H3’””), which is hydro genation (H3), wherein the compound of formula (lc) )
is hydrogenated.
The hydrogenation using the catalyst according to the present invention is usually carried out in at least one solvent.
When using solvents then suitable solvents are acetonitrile, ethanol and propanol.
It is also possible to carry out the hydrogenation without any solvents.
Therefore, the present invention relates to a hydrogenation (H4), which is hydrogena tion (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””) or (H3’””), wherein hydrogena tion is carried out in at least one solvent.
Therefore, the present invention relates to a hydrogenation (H4’), which is hydrogena tion (H4), wherein at least one solvent is chosen from the group consisting of acetoni trile, ethanol and propanol.
Therefore, the present invention relates to a hydrogenation (H5), which is hydrogena tion (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””) or (H3’””), wherein hydrogena tion is carried out without any solvent.
The hydrogenation according to the present invention is usually carried out at ele vated temperatures.
Usually it is carried out at a temperature between 15 - 150 °C. preferably 20 to 140 °C.
Therefore, the present invention relates to a hydrogenation (H6), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’) or (H5), wherein hydrogenation is carried out at elevated temperatures.
Therefore, the present invention relates to a hydrogenation (H6’), which is hydrogena tion (H6), wherein hydrogenation is carried out at a temperature between 15 - 150 °C.
Therefore, the present invention relates to a hydrogenation (H6”), which is hydro genation (H6), wherein hydrogenation is carried out at a temperature between 20 to 140 °C.
The hydrogenation according to the present invention is carried by using H2 gas (pure or as a mixture). Preferably pure H2 gas is used.
Therefore, the present invention relates to a hydrogenation (H7), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’) or (H6”), wherein H2 gas (pure or as a mixture) is used (preferably pure H2 gas).
The hydrogenation according to the present invention is carried out at elevated pres sure. Usually the absolute pressure used is between 1 and 50 bar, preferably between 1 and 40 bar.
Therefore, the present invention relates to a hydrogenation (H8), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”) or (H7), wherein the hydrogenation is carried out at elevated pressure.
Therefore, the present invention relates to a hydrogenation (H8’), which is hydrogena tion (H8), wherein the hydrogenation is carried out at an absolute pressure between 1 and 50 bar.
Therefore, the present invention relates to a hydrogenation (H8”), which is hydro genation (H8), wherein the hydrogenation is carried out at an absolute pressure be tween 1 and 40 bar.
The amount of the catalyst used in the hydrogenation according to the present inven tion is between 0.1 - 5 mol-% (in view of the compound to the hydrogenated). Pref erably 0.5 - 4 mol-%.
Therefore, the present invention relates to a hydrogenation (H9), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’) or (H8”), wherein the catalyst is used in an amount between 0.1 - 5 mol-% (in view of the compound to the hydrogenated).
Therefore, the present invention relates to a hydrogenation (H9’), which is hydrogena tion (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’) or (H8”), wherein the catalyst is used in an amount between 0.5 - 4 mol-% (in view of the compound to the hydrogenated).
A further advantage of the catalyst according to the present invention is that it can be recycled and reused, and the activity of the catalyst stays on a similar level.
The hydrogenation can be carried out batch-wise or continuously.
Therefore, the present invention relates to a hydrogenation (H10), which is hydro genation (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’), (H8”), (H9) or (H9’), wherein the hydrogenation is carried out batch-wise.
Therefore, the present invention relates to a hydrogenation (H11), which is hydro genation (H), (H 1 ), (H2), (H3), (H3’), (H3”), (H3’”), (H3””), (H3’””), (H4), (H4’), (H5), (H6), (H6’), (H6”), (H7), (H8), (H8’), (H8”), (H9) or (H9’), wherein the hydrogenation is carried out continuously.
The following examples serve to illustrate the invention. If not otherwise stated all parts given are related to the weight and the temperature is given in °C
Examples
Example 1 : Catalyst Synthesis
In a 250 mL round bottomed flask Co(OAc)24H20 (0.12 g, 0.48 mmol), melamine (0.06 g, 0.48 mmol), EtOH (30 mL) and distilled water (1 mL) were stirred at RT for 15 mins. A pink solution with some suspended melamine formed. The flask was placed in an oil bath pre-heated to 60 °C and stirred for 1 h. S1O2 (Aerosil 0X50,
0.70 g) was added so that the Co was ca. 4 wt. % relative to S1O2. The suspension was stirred at RT overnight (22 h). Solvent was removed via rotary evaporation (45 °C, 80 mbar) to leave a pink powder which was dried overnight (19 h) at RT under high vacuum. The dry solid was ground to a fine powder and 0.262 g placed in a ce ramic crucible with a lid. The crucible was placed in an oven which was evacuated to ca. 5 mbar and then flushed with argon. The oven was heated to 800 °C with a heating rate of 25 °C/min. The oven was held at the final temperature for 2 h, purg ing with argon the entire time. The oven was allowed to cool to room temperature, the crucible removed, and the catalyst (0.228 g, 87 % yield) transferred to a sample vial for storage.
The catalyst synthesis has also been demonstrated with a molar ratio of metal pre cursor to melamine of 1 :5, 1 :10. All catalysts ratios were pyrolyzed at 800 °C and 1000 °C.
The following table (Table 1) shows the elemental analysis of the catalysts of the examples.
Table 1 : Elemental analysis of the prepared catalysts (pyrolysis temp 800 °C).
Hydrogenation Examples
Reduction of 3,7,11,15-tetramethylhexadec-1-yn-3-ol to isophytol using the catalyst 1 - 3 of Table 1.
General Procedure
The catalytic activity tests were performed in a 300 ml autoclave advanced with an internal aluminium plate to include eight uniform reaction glass vials (4 ml) with cap, septum, and needle. 3,7,11 ,15-tetramethylhexadec-1-yn-3-ol (72.4 mg, 0.25 mmol), cobalt catalyst (3.2 mg, 1 mol %) and MeCN (2 mL) were placed in a 4 ml_ vial. A cap with a septum punctured by a needle, to allow entry of H2, was fitted. The vial was placed in an aluminium plate which was inserted into a 300 mL stainless steel auto clave. The autoclave was sealed and flushed twice with H2 (20 bar) and then charged with H2 (30 bar). The autoclave was placed in an aluminium block pre-heated to 120 °C and maintained at this temperature for 15 h with a stir rate of 750 ppm. Following the reaction, the autoclave was cooled in an ice-water bath and the pressure released. Dodecane (40 pL) was added as internal standard and the reaction mixture diluted with chloroform (1 mL). The catalyst and reaction mixture were separated via centrif ugation (5000 RPM, 1 minute). The recovered catalyst was washed with ethyl acetate (3 x 4 mL), separating via centrifugation as before, and then dried under high vacuum for ca. 22 h. The reaction mixture was filtered through a celite plug and the product composition analysed via GC.
Table 2: catalytic performance of the catalysts of table 1
Conditions: Substrate 0.25 mmol, Co catalyst (1 mol %), MeCN (2 mL), (120 °C, stir rate 750 RPM, 30 bar H2, 15 h).
Table 3: The effect of solvent on the reactivity of the catalyst 1 of Table 1 .
Conditions:
Co catalyst (1 mol %), Solvent (2 mL), (120 °C, stir rate 750 RPM, 30 bar H2, 15 h).
Table 4: The effect of an 8 h reaction time on the catalytic performance of the cata lysts of table 1
Conditions:
Co catalyst (1 mol %), MeCN (2 mL), (120 °C, stir rate 750 RPM, 30 bar H2, 8 h).
Table 5: The effect of a 20 bar H2 pressure on the catalytic performance of the cata lysts of table 1
rate 750 RPM, 20 bar H2, 15 h).
Table 6: The effect of a 100 °C reaction temperature on the catalytic performance of the catalysts of table 1
rate 750 RPM, 30 bar H2, 15 h).
After the reaction, the cobalt catalyst could be recovered from the reaction mixture via centrifugation and washed with ethyl acetate. After drying, the catalyst could then be used with similar activity (Table 7: ).
Table 7: Recycling demonstrated for the catalyst 1 of Table 1.
Conditions: Substrate 0.25 mmol, Co catalyst (1 mol %), MeCN (2 mL), (120 °C, stir rate 750 RPM, 30 bar H2, 15 h).
Reduction of MBY (2-methyl-3-butyn-2-ol) to MBE (2-methyl-3-buten-2-ol) using the catalyst 1 - 3 of Table 1
General Procedure
The catalytic activity tests are performed in a 300 ml autoclave advanced with an internal aluminium plate to include eight uniform reaction glass vials (4 ml) with cap, septum, and needle. MBY (0.25 mmol), cobalt catalyst (3.2 mg, 1 mol %) and MeCN (2 mL) are placed in a 4 ml_ vial. A cap with a septum punctured by a needle, to allow entry of H2, is fitted. The vial is placed in an aluminium plate which is inserted into a 300 mL stainless steel autoclave. The autoclave is sealed and flushed twice with H2 (20 bar) and then charged with H2 (30 bar). The autoclave is placed in an aluminium block pre-heated to 120 °C and maintained at this temperature for 15 h with a stir rate of 750 ppm. Following the reaction, the autoclave is cooled in an ice-water bath and the pressure released. Dodecane (40 pL) is added as internal standard and the reac tion mixture diluted with chloroform (1 mL). The catalyst and reaction mixture are sep arated via centrifugation (5000 RPM, 1 minute). The recovered catalyst is washed with ethyl acetate (3 x 4 mL), separating via centrifugation as before, and then dried under high vacuum for ca. 22 h. The reaction mixture is filtered through a celite plug and the product composition analysed via GC.
MBE is obtained in good yields.
Reduction of DLL (Dehydrolinalool) to Linalool using the catalyst 1 - 3 of Table 1
General Procedure
The catalytic activity tests are performed in a 300 ml autoclave advanced with an internal aluminium plate to include eight uniform reaction glass vials (4 ml) with cap, septum, and needle. Dehydrolinalool (0.25 mmol), cobalt catalyst (3.2 mg, 1 mol %)
and MeCN (2 mL) are placed in a 4 ml_ vial. A cap with a septum punctured by a needle, to allow entry of H2, is fitted. The vial is placed in an aluminium plate which is inserted into a 300 mL stainless steel autoclave. The autoclave is sealed and flushed twice with H2 (20 bar) and then charged with H2 (30 bar). The autoclave is placed in an aluminium block pre-heated to 120 °C and maintained at this temperature for 15 h with a stir rate of 750 ppm. Following the reaction, the autoclave is cooled in an ice- water bath and the pressure released. Dodecane (40 pL) is added as internal stand ard and the reaction mixture diluted with chloroform (1 mL). The catalyst and reaction mixture are separated via centrifugation (5000 RPM, 1 minute). The recovered cata- lyst is washed with ethyl acetate (3 x 4 mL), separating via centrifugation as before, and then dried under high vacuum forca. 22 h. The reaction mixture is filtered through a celite plug and the product composition analysed via GC.
Linalool is obtained in good yields.
Claims
1. A catalyst obtainable by
1 ) forming a cobalt ligand complex;
2) depositing the cobalt ligand complex of step 1) on the porous silica support (usually by a wet impregnation procedure) to form an absorbed reaction product, and
3) drying (step 3a) and pyrolyzing (step 3b) (at high temperature at least 600 °C) the absorbed product of step 2) to obtain the catalyst.
2. Catalyst according to claim 1 , wherein step 1) at least one Co salt is at least one Co(ll) salt and/or at least one Co(l) salt and/or at least one Co(0) salt.
3. Catalyst according to claim 1 , wherein step 1) at least one cobalt salt is chosen from the group consisting of Co(OAc)2, Co(acac)2, C0CO3, C0CP2, (TMEDA)CO(CH3)2, Co(acac)2(TMEDA) and Co(COD)2.
4. Catalyst according to any of the preceding claims, wherein step 1) the ligand is monodentate and/or polydentate.
5. Catalyst according to any of the preceding claims, wherein step 1) the ligand comprises at least one N atom.
6. Catalyst according to any of the preceding claims, wherein step 1 ) the molar ratio of the cobalt salts to the ligand is from 1 :1 to 1 :15.
7. Catalyst according to any of the preceding claims, wherein step 1) the formation of the cobalt ligand complex is carried out in at least one solvent.
8. Catalyst according to any of the preceding claims, wherein step 2) the silica is fumed silica.
9. Catalyst according to any of the preceding claims, wherein step 2) the silica is added to the reaction mixture in a molar excess to the Co.
10. Catalyst according to any of the preceding claims, wherein the reaction product of step 3a) is pyrolyzed at a temperature between 600 - 1200 °C.
11. A hydrogenation process, wherein at least one catalyst of any of claims 1 - 10 is used.
12. Hydrogenation process according to claim 11 , wherein hydrogenation is a hydro genation of alkynes to alkenes.
13. Hydrogenation process according to claim 11 or claim 12, wherein compounds of formula (I)
wherein
R is H; linear or branched, or cyclic Ci - C20 alkyl, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes; or linear or branched, or cyclic C2- C20 alkylene, which can be substituted by OH, NH, NH2, C(O) and/or aromatic alkynes, and
Ri is linear or branched, or cyclic C3 - C45 alkyl, which can be substituted by OH, NH, NH2, C(O), aromatic alkynes; linear or branched or cyclic C3 - C45 alkylene, which can be substituted by OH, NH, NH2, C(O), aromatic alkynes, are hydrogenated selectively.
14. Hydrogenation process according to any of claims 11 to 13, wherein the hydro genation is carried out in at least one solvent.
15. Hydrogenation process according to any of claims 11 to 13, wherein the hydro genation is carried out without any solvent.
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|---|---|---|---|
| EP21164785 | 2021-03-25 | ||
| PCT/EP2022/057605 WO2022200411A1 (en) | 2021-03-25 | 2022-03-23 | New cobalt catalyst supported on silica |
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