EP4313407A1 - Nouveau catalyseur au nickel supporté sur de la silice - Google Patents
Nouveau catalyseur au nickel supporté sur de la siliceInfo
- Publication number
- EP4313407A1 EP4313407A1 EP22717158.4A EP22717158A EP4313407A1 EP 4313407 A1 EP4313407 A1 EP 4313407A1 EP 22717158 A EP22717158 A EP 22717158A EP 4313407 A1 EP4313407 A1 EP 4313407A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- hydrogenation
- nickel
- present
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 146
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 31
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 15
- -1 aromatic alkynes Chemical class 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 238000000034 method Methods 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
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 6
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000000197 pyrolysis Methods 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 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
- 239000000843 powder Substances 0.000 description 9
- 229920000877 Melamine resin Polymers 0.000 description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- 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
- 238000005119 centrifugation Methods 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 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
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 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
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 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
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 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
- 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
- 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
- 239000007810 chemical reaction solvent Substances 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
- 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
- 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
- 239000000919 ceramic Substances 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
- 229940035564 duration Drugs 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material 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
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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 nickel (Ni) 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 nickel nanoparticles 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 nickel 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 nickel 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 nickel 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 nickel nano particles and a nitrogen 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 nickel ligand complex)
- At least one nickel salt is used.
- Ni(ll) salt(s) and/or Ni(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) the at least one Ni salt is at least one Ni(ll) salt and/or at least one Ni(0) salt.
- Preferred nickel salts are for example Ni(OAc)2, Ni(acac)2, N1CO3, NiBr2, NiCp2, (TMEDA)Ni(CH 3 )2, Ni(acac) 2 (TMEDA) and Ni(COD) 2 .
- the present invention relates to a catalyst (C2), which is catalyst (C) or (C1), wherein step 1) the at least one nickel salt is chosen from the group consisting of Ni(OAc) 2 , Ni(acac) 2 , NiCOs, NiCI 2 , NiBr 2, NiCp 2 , (TMEDA)Ni(CH 3 ) 2 and Ni(COD) 2 .
- the present invention relates to a catalyst (C2’), which is catalyst (C) or (C1), wherein step 1) the at least one nickel salt is chosen from the group consisting of Ni(OAc) 2 , Ni(acac) 2 , NiCOs, NiCp 2 , (TMEDA)Ni(CH 3 ) 2 , Ni(acac) 2 (TMEDA) and Ni(COD) 2 .
- the ligand used in step 1) to form the nickel 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-bipyridine, guanidinium chloride, terpyridine, starch, saccharose and urea).
- the ligand is monodentate and/or polydentate (such as melamine, chitin, phenanthroline, 4,4-bipyridine, 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) the 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 nickel 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 nickel 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 nickel 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 nickel salts to the ligand is from 1 :1 to 1 :10.
- 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 nickel salts to the ligand is 1 :1.
- the formation of the nickel ligand complex is usually done in at least one solvent.
- the nickel 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 nickel ligand complex is carried out in at least one solvent.
- the present invention relates to a catalyst (C7’), which is catalyst (C7), wherein the 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 the at least one solvent chosen from the group consisting of water, methanol, ethanol, propanol, acetone, ethylene carbonate and toluene.
- the Ni 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), (CT) or (C7”), wherein step 1) the formation of the nickel 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), (CT) or (C7”), wherein step 1) the formation of the nickel 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), (CT) or (C7”), wherein step 1) the formation of the nickel ligand complex is carried out a temperature range of from 20 to 30 °C.
- Step 2) depositing of the nickel ligand complex
- nickel ligand complex is not isolated from the reaction mixture of step 1).
- silica S1O2
- S1O2 is added directly into the reaction mixture of step 1) after the nickel 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 Ni.
- a usual amount of S1O2 added to the reaction mixture is such that the in the reaction mixture the molar ratio of Ni to S1O2 is 1 : 150 to 1 : 100, preferably 1 : 120 to 1 :80.
- 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 Ni.
- the present invention relates to a catalyst (C10’), which is catalyst (C10), wherein the molar ratio of Ni 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 Ni 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.
- the deposited reaction product nickel ligand complex absorbed into pores and on the surface of the porous silica
- Step 3) drying and pyrolyzing the reaction product of step 2)
- 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 the obtained solid form from step 3a) is pyrolyzed.
- 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), (C ), (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), (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”) 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 nickel 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 nickel 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 : 0.05 to 2 wt-%, based on the total weight of the powderous catalyst, and Ni : 1.5 to 6 wt-%, based on the total weight of the powderous catalyst.
- the rest of the 100 % is the silica.
- the so produced powderous Ni 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), (C ), (C3), (C4), (C5), (C6), (C6’), (C6”), (C6’”), (C7), (C7’), (C7”), (C8), (C8’), (C8”), (C9), (C10), (C10’), (C10”), (C11), (C1 f), (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- 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, 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.
- R- -R (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)
- 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, 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, 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 - C20 alkylene, 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.
- 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. Therefore, the present invention relates to a hydrogenation (H3’”), which is hydro genation (H3), wherein the compound of formula (la)
- the present invention relates to a hydrogenation (H3””), which is hydro genation (H3), wherein the compound of formula (lb)
- the present invention relates to a hydrogenation (H3’””), which is hydro- genation (H3), wherein the compound of formula (lc)
- H3 hydro- genation
- 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), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””) or(H3””’), wherein hydrogenation is carried out in at least one solvent.
- H4 hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””) or(H3””’
- the present invention relates to a hydrogenation (H4’), which is hydrogena tion (H4), wherein the at least one solvent is chosen from the group consisting of acetonitrile, ethanol and propanol.
- the present invention relates to a hydrogenation (H5), which is hydrogena tion (H), (H1), (H2), (H3), (H3’), (H3”), (H3’”), (H3””) or(H3””’), wherein hydrogenation is carried out without any solvent.
- the hydrogenation according to the present invention is usually carried out at elevated 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. Therefore, the present invention relates to a hydrogenation (H7), which is hydrogena tion (H), (H 1 ), (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).
- H2 gas pure or as a mixture
- the hydrogenation according to the present invention is carried out at elevated pres sure.
- the absolute pressure used is between 1 and 50 bar, preferably between 1 and 40 bar.
- 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). Prefer ably 0.5 - 4 mol-%.
- 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 0.1 - 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).
- H9 hydrogenation
- the hydrogenation can be carried out batch-wise or continuously.
- the present invention relates to a hydrogenation (H10), which is hydro genation (H), (H1), (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), (H1), (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.
- Example 1 Catalyst Synthesis In a 250 mL round bottomed flask Ni(0Ac) 2 .4H 2 0 (0.27 g, 1.10 mmol), melamine (0.14 g, 1.10 mmol), EtOH (45 mL) and distilled water (1.5 mL) were stirred at room temperature for 15 mins. A pale green solution with some suspended melamine formed. The flask was placed in an oil bath pre-heated to 60 °C and stirred for 1 h. Some melamine remained undissolved. S1O2 (Aerosil 0X50, 1.61 g) was added so that the Ni was ca. 4 wt. % relative to S1O2.
- the suspension was stirred at RT over night (22 h). Solvent was removed via rotary evaporation (45 °C, 80 mbar) to leave a pale green powder which was dried overnight (19 h) at RT under high vacuum.
- the dry solid was ground to a fine powder and 0.534 g was placed in a ceramic 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, purging with argon the entire time.
- 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 (0.25 mmol), nickel cat alyst (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 autoclave.
- the au toclave was sealed and flushed twice with H2 (10 bar below the required pressure, or 5 bar for reactions performed with 5 bar H2) and then charged with the required H2 pressure.
- the autoclave was placed in an aluminium block pre-heated to the reaction temperature and maintained at this temperature for the desired time, 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 centrifugation (5000 RPM, 2 minutes).
- 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 The activity and selectivity of the Ni catalysts (of Table 1) at elevated H2 pressure (30 bar) for 2 h.
- Table 3 The activity and selectivity of the Ni catalysts (of Table 1) at low H2 pressure (5 bar) for 15 h.
- Table 5 The activity and selectivity of the Ni catalysts (of Table 1) when heptane is the reaction solvent.
- 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
- nickel catalyst (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 (10 bar below the required pressure, or 5 bar for reactions performed with 5 bar H2) and then charged with the required H2 pressure.
- the autoclave is placed in an aluminium block pre-heated to the reaction temperature and maintained at this temperature for the desired time, 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 reaction mixture diluted with chloroform (1 mL). The catalyst and reaction mixture are separated via centrifugation (5000 RPM, 2 minutes). The recovered catalyst is washed with ethyl acetate (3 x 4 mL), separating via centrifuga tion 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.
- 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), nickel catalyst (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 (10 bar below the required pressure, or 5 bar for reactions performed with 5 bar H2) and then charged with the required H2 pressure.
- the autoclave is placed in an aluminium block pre-heated to the reaction temperature and maintained at this tem perature for the desired time, 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 reaction mixture diluted with chloroform (1 ml_). The catalyst and reaction mixture are separated via centrifugation (5000 RPM, 2 minutes). 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 re action mixture is filtered through a celite plug and the product composition analysed via GC.
- Linalool is obtained in good yields.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21164783 | 2021-03-25 | ||
PCT/EP2022/057602 WO2022200410A1 (fr) | 2021-03-25 | 2022-03-23 | Nouveau catalyseur au nickel supporté sur de la silice |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4313407A1 true EP4313407A1 (fr) | 2024-02-07 |
Family
ID=75277790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP22717158.4A Pending EP4313407A1 (fr) | 2021-03-25 | 2022-03-23 | Nouveau catalyseur au nickel supporté sur de la silice |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP4313407A1 (fr) |
CN (1) | CN117042875A (fr) |
WO (1) | WO2022200410A1 (fr) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20220012915A (ko) * | 2019-05-27 | 2022-02-04 | 디에스엠 아이피 어셋츠 비.브이. | 인 화합물의 존재 하에서의 알키놀의 알케놀로의 선택적 수소화 |
-
2022
- 2022-03-23 WO PCT/EP2022/057602 patent/WO2022200410A1/fr active Application Filing
- 2022-03-23 CN CN202280022960.0A patent/CN117042875A/zh active Pending
- 2022-03-23 EP EP22717158.4A patent/EP4313407A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
WO2022200410A1 (fr) | 2022-09-29 |
CN117042875A (zh) | 2023-11-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111111785B (zh) | 一种cof材料负载过渡金属催化剂及其制备方法和应用 | |
Mehnert | Palladium-grafted mesoporous MCM-41 material as heterogeneous catalyst for Heck reactions | |
Huang et al. | Highly active and recyclable heterogeneous iridium pincer catalysts for transfer dehydrogenation of alkanes | |
Nikoorazm et al. | Synthesis and characterization of Ni (II)–Vanillin–Schiff base–MCM-41 composite as an efficient and reusable nanocatalyst for multicomponent reactions | |
US10213777B2 (en) | Metal complex and supported metal complex having disiloxane as ligand, method for production therefor, and supported metal catalyst prepared by using the same | |
CN107824209B (zh) | 用于喹啉类化合物选择性加氢的催化剂及其制备方法 | |
CN111085232A (zh) | 一种氮掺杂多孔碳包覆非贵金属催化剂催化糠醛制备糠醇的方法 | |
CN115999629B (zh) | 一种用于α-烯烃氢甲酰化制备醛的多相催化剂及其制备方法和用途 | |
Ganesamoorthy et al. | Highly efficient homogeneous and heterogenized ruthenium catalysts for transfer hydrogenation of carbonyl compounds | |
WO2022200411A1 (fr) | Nouveau catalyseur au cobalt supporté sur de la silice | |
Uysal et al. | New heterogeneous B (OEt) 3-MCM-41 catalyst for preparation of α, β-unsaturated alcohols | |
EP4313407A1 (fr) | Nouveau catalyseur au nickel supporté sur de la silice | |
CN104588057B (zh) | 用于烯烃氢甲酰化合成醛和醇的多相催化剂及其制备方法 | |
Li et al. | Gold Promotion of MCM-41 supported ruthenium catalysts for selective hydrogenation of α, β-unsaturated aldehydes and ketones | |
CA1306597C (fr) | Procede pour preparer des alanates d'halogenures de magnesium, et leur utilisation | |
CN113372303B (zh) | 一种制备四氢呋喃二甲醇二烷基醚的方法 | |
EP2726202B1 (fr) | Procédé de préparation d'un dimère de bromure de tri-tert-butylphosphine-palladium(i) | |
JP3773293B2 (ja) | アンモニア合成触媒の製造法 | |
Shylesh et al. | Catalytic Meerwein-Ponndorf-Verley reductions over mesoporous silica supports: Rational design of hydrophobic mesoporous silica for enhanced stability of aluminum doped mesoporous catalysts | |
KR20100098363A (ko) | 불균일 구리 나노 촉매 및 그 제조방법 | |
KR102048140B1 (ko) | 메탄올 카르보닐화 불균일 촉매 및 이를 이용한 아세트산과 메틸 아세테이트의 제조 방법 | |
JP4694712B2 (ja) | チタン含有固体触媒及びこれを用いたエポキシ化合物の製造法 | |
CN107285994B (zh) | 一种肉桂醛选择性加氢合成肉桂醇的方法 | |
CN114602475B (zh) | 一种疏水性镍碳催化剂及其制备方法与应用 | |
KR101076628B1 (ko) | 불균일 구리 나노 촉매 및 그 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20230822 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DSM IP ASSETS B.V. |