TWI483774B - 新穎選擇性氫化觸媒及其用途 - Google Patents
新穎選擇性氫化觸媒及其用途 Download PDFInfo
- Publication number
- TWI483774B TWI483774B TW098128029A TW98128029A TWI483774B TW I483774 B TWI483774 B TW I483774B TW 098128029 A TW098128029 A TW 098128029A TW 98128029 A TW98128029 A TW 98128029A TW I483774 B TWI483774 B TW I483774B
- Authority
- TW
- Taiwan
- Prior art keywords
- range
- carrier
- per gram
- catalyst
- microns
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 150000001345 alkine derivatives Chemical class 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- RLOISEUPMPOJMI-UHFFFAOYSA-N 2-methylbut-1-en-1-ol Chemical group CCC(C)=CO RLOISEUPMPOJMI-UHFFFAOYSA-N 0.000 claims description 3
- QDLPJHIEFRSZJK-UHFFFAOYSA-N 2-methylbut-3-yn-1-ol Chemical group OCC(C)C#C QDLPJHIEFRSZJK-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- NONBYKDOGYGPFB-UHFFFAOYSA-N 2-[1-(2-hydroxyethylsulfanyl)ethylsulfanyl]ethanol Chemical compound OCCSC(C)SCCO NONBYKDOGYGPFB-UHFFFAOYSA-N 0.000 claims description 2
- KEVYVLWNCKMXJX-UHFFFAOYSA-N 3,7,11,15-tetramethylhexadec-1-en-3-ol Chemical group CC(C)CCCC(C)CCCC(C)CCCC(C)(O)C=C KEVYVLWNCKMXJX-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- -1 Hydroxyl hydroxyl group Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000075 oxide glass Substances 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000035484 reaction time Effects 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 2
- IUDWWFNDSJRYRV-UHFFFAOYSA-N 3,7-dimethyloct-1-en-3-ol Chemical compound CC(C)CCCC(C)(O)C=C IUDWWFNDSJRYRV-UHFFFAOYSA-N 0.000 description 2
- VZPBTNPWFOMXPI-UHFFFAOYSA-N 3,7-dimethyloct-1-yn-3-ol Chemical compound CC(C)CCCC(C)(O)C#C VZPBTNPWFOMXPI-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- WPWWHXPRJFDTTJ-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzamide Chemical compound NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F WPWWHXPRJFDTTJ-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本發明係有關一種新穎選擇性氫化觸媒及其用途。
本發明係有關一種觸媒，其包括在作為載體之多孔二氧化矽玻璃上的鈀；和關於使用此觸媒來選擇性將炔類氫化成烯類的用途。
本發明之觸媒包括在多孔二氧化矽玻璃上的鈀。
本發明之觸媒為在多孔二氧化矽玻璃上的鈀較佳。
該多孔二氧化矽玻璃顯示出下列特徵較佳：
a)顆粒直徑在範圍20至500微米內，在範圍50至400微米內較佳，在範圍80至300微米內更佳，在範圍100至200微米內最佳；及/或
b)孔洞尺寸在範圍10至400奈米內，在範圍30至250奈米內較佳，在範圍40至150奈米內更佳，在範圍50至60奈米內最佳；及/或
c)孔洞體積在範圍100至5000立方毫米/克內；在範圍250至2500立方毫米/克內較佳，在範圍500至2000立方毫米/克內更佳，在範圍1000至1500立方毫米/克內最佳；及/或
d)比表面在範圍5至500平方公尺/克內；在範圍25至300平方公尺/克內較佳，在範圍40至250平方公尺/克內更佳，在範圍50至200平方公尺/克內最佳。
該多孔二氧化矽玻璃顯示出全部的特徵a)至d)較佳，藉此本發明包括較佳/更佳/最佳特徵之任何可能的組合。此多孔二氧化矽玻璃可商業購得。由德國沃森(Wertheim)的史酷勒有限公司(Schuller GmbH)以商標崔梭迫(Trisoperl)出售者特別佳。崔梭迫為具有平均顆粒尺寸在範圍100至200微米內、平均孔洞尺寸54.47奈米、比表面93.72平方公尺/克及平均孔洞體積1255.5立方毫米/克之多孔二氧化矽玻璃。
根據本發明之觸媒可於下列官能基存在下使用來選擇性將終端C≡C三鍵氫化成終端C=C雙鍵：
◇烷基：線性C1-50
烷基、分枝C3-50
烷基、C3-20
環烷基、和具有1至50個C原子的烷基環烷基及環烷基烷基；C1-20
烷基較佳，可其為線性(C1-20
)、分枝(C3-20
)或環狀(C3-20
)或烷基環烷基(C4-20
)或環烷基烷基(C4-20
)；
◇烯基：線性C2-50
烯基、分枝C3-50
烯基；C2-20
烯基較佳，其可為線性(C2-20
)或分枝(C3-20
)；
◇雜烷基：即，非芳香族碳氫部分，包含一或多個雜原子氮及/或氧之具有3至50個C原子(3至30個C原子較佳)的飽和碳氫部分較佳，諸如醚類，例如四氫呋喃及四氫哌喃；
◇烷基芳基及芳基，諸如苯基、甲苯基、茬基、《基、萘基等等，具有6-17個C原子較佳；
◇雜芳基，具有5-17個C原子較佳，藉此該雜原子為氧或氮；該雜芳基亦可包含數個雜原子(雜原子數目≧1)，以便雜芳基亦包括包含O原子和N原子二者；實施例有吡啶基、吲哚基、呋喃基；
◇羥基(-OH)；
◇硝基氧基(-NO2
)；
◇胺基(-NH2
)；
◇-SiR1
R2
R3
，其中R1
、R2
及R3
彼此各自獨立地為烷基(線性或分枝的C1
-C6
)或芳基或烷基芳基；R1
=R2
=R3
較佳。
此意謂著炔類RC≡CH氫化成烯類RHC=CH2
，藉此R為選擇性承載雜原子O及/或N或其數種及/或如上述定義之下列官能基的碳氫部分：-OH、-NO2
、-NH2
及-SiR3
。R選自於由下列所組成之群較佳：如上述定義的烷基、烯基、芳基、烷基芳基、雜芳基，其全部可進一步承載一或多個雜原子O及/或N，或進一步官能基(諸如-OH、-NO2
、-NH2
及-SiR3
)。該炔類為異戊二烯構建嵌段的前驅物較佳。
因此，本發明亦針對此用途；和針對包括於如上述定義的觸媒存在下氫化炔類來製造烯類之步驟的方法。
通常來說，該氫化可在溫度範圍0℃至150℃內及/或在壓力範圍1巴至150巴內進行。
此炔類及對應的烯類之較佳實施例提供在下列表中：
在本發明的較佳具體實例中，炔3,7,11,15-四甲基-1-十六碳炔-3-醇(去氫異葉綠醇)氫化成烯3,7,11,15-四甲基-1-十六碳烯-3-醇(異葉綠醇)。
通常來說，此氫化可在溫度範圍0℃至150℃內進行，在溫度範圍10℃至100℃內較佳，在溫度範圍15℃至95℃內更佳，在溫度最高75℃下最佳。
氫壓力可在範圍1至50巴內變化，在範圍1.1至10巴內較佳，在範圍1.2至8巴內更佳，約6巴最佳。
此氫化在缺乏溶劑下進行較佳。
在本發明的另一個較佳具體實例中，炔2-甲基丁炔醇氫化成烯2-甲基丁烯醇。
通常來說，此氫化可在溫度範圍0℃至150℃內進行，在溫度範圍15℃至80℃內較佳，在溫度範圍20℃至75℃內更佳，在溫度約60℃下最佳。
氫壓力可在範圍1至50巴內變化，在範圍1.2至15巴內較佳，在範圍1.5至10巴內更佳，約6巴最佳。
使用讓該觸媒中毒從而減低其活性之化合物有利。此化合物通常為含硫或磷的有機化合物。較佳的觸媒毒物選自於由下列所組成之群：膦類(特別是三烷基膦類)、硫醚類、硫醇類及二硫醚類。下列特別佳：硫醚類，諸如二丙基硫醚、乙基-2-羥乙基硫醚、四氫噻吩、噻吩及2,2’-(伸乙基二硫基)-二乙醇；硫醇類，諸如2,2’-(伸乙基二氧基)-二乙硫醇；及二硫醚類，諸如丙基二硫醚及異丙基二硫醚。2,2’-(伸乙基二硫基)-二乙醇最佳。該觸媒毒物亦可使用在如上所述之去氫異葉綠醇氫化成異葉綠醇中。
在本發明的進一步較佳具體實例中，炔去氫沉香醇氫化成烯沉香醇。
通常來說，此氫化可在溫度範圍0℃至120℃內進行，在溫度範圍10℃至100℃內較佳，在溫度範圍20℃至90℃內更佳。
氫壓力可在範圍1巴至50巴內變化，在範圍1.2至15巴內較佳，在範圍1.5至10巴內更佳，約3巴最佳。
在本發明的另一個較佳具體實例中，炔3,7-二甲基-1-辛炔-3-醇氫化成烯3,7-二甲基-1-辛烯-3-醇。理想的反應條件可由熟知此技藝者在上述對其它較佳具體實例所提供的資訊之基礎上容易地找到。
現在，將在下列非為限制的實施例中闡明本發明。
在實施例中所使用的載體為由德國沃森的史酷勒有限公司出售之崔梭迫。崔梭迫為具有平均顆粒尺寸在範圍100至200微米內、平均孔洞尺寸54.47奈米、比表面93.72平方公尺/克及平均孔洞體積1255.5立方毫米/克之多孔二氧化矽玻璃。
將21毫克的Pd(OAc)2
(0.09毫莫耳)懸浮在50毫升之二氯甲烷中。加入1克的崔梭迫及移除溶劑(槽溫度：40℃/壓力：950毫巴)。在300℃的烘箱(以1000瓦預先加熱該烘箱至300℃ 20分鐘)中，燒結已摻雜Pd(OAc)2
的載體2小時。然後，負載在載體上的觸媒為約1重量%的Pd，即，10毫克Pd在1克載體上。
於200毫克根據實施例1所製備之觸媒存在下，在攪拌(2000rpm)下，在60℃及2.8巴下，氫化3.2莫耳的MBI 280分鐘。轉換為98%及產率為94%。
於100毫克根據實施例1所製備之觸媒存在下氫化3.75毫莫耳的DIP。在下表中提供進行氫化之溫度及壓力。在反應時間3小時後採取樣品，及使用氣相層析法來測量產率及選擇性。
b)反應時間：3小時
在500毫升的壓力鍋中，於106毫克根據實施例1所製備之觸媒及23毫克的2,2’-(伸乙基二硫基)-二-乙醇存在下，在80℃及2巴下，氫化265克(0.9莫耳)的DIP。以2000rpm攪拌該反應混合物4小時。轉換為99%及產率為89.6%，以DIP為準。
將3.75毫莫耳的DIP溶解在0.5毫升之醋酸乙酯中，及於100毫克根據實施例1所製備之觸媒存在下，在50℃及21巴下氫化。在反應時間1小時後採取樣品，及使用氣相層析法來測量產率及選擇性。轉換為93%(以DIP為準)及選擇性為91%(以IP為準)。
第1圖為炔類使用根據本發明之觸媒氫化成其對應的烯類之較佳實施例。
Claims (22)
- 一種觸媒之用途，其係使用該觸媒來選擇性將C≡C三鍵氫化成C=C雙鍵，且該觸媒包括在作為載體的多孔二氧化矽玻璃上之鈀。
- 如申請專利範圍第1項的用途，其中該載體具有顆粒直徑在20至500微米之範圍內。
- 如申請專利範圍第1項的用途，其中該載體具有顆粒直徑在50至400微米之範圍內。
- 如申請專利範圍第1項的用途，其中該載體具有顆粒直徑在80至300微米之範圍內。
- 如申請專利範圍第1項的用途，其中該載體具有顆粒直徑在100至200微米之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞尺寸在10至400奈米之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞尺寸在30至250奈米之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞尺寸在40至150奈米之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞尺寸在50至60奈米之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞體積在100至5000立方毫米/克之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞體積在250至2500立方毫米/克之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞體積在500至2000立方毫米/克之範圍內。
- 如申請專利範圍第1項之用途，其中該載體具有孔洞體積在1000至1500立方毫米/克之範圍內。
- 如申請專利範圍第1至13項中任一項之用途，其中該載體具有比表面在5至500平方公尺/克之範圍內。
- 如申請專利範圍第1至13項中任一項之用途，其中該載體具有比表面在25至300平方公尺/克之範圍內。
- 如申請專利範圍第1至13項中任一項之用途，其中該載體具有比表面在40至250平方公尺/克之範圍內。
- 如申請專利範圍第1至13項中任一項之用途，其中該載體具有比表面在50至200平方公尺/克之範圍內。
- 一種用來製造烯類的方法，其包括下述步驟：於一觸媒存在下氫化炔類，該觸媒包括在作為載體的多孔二氧化矽玻璃上之鈀。
- 如申請專利範圍第18項之方法，其中該炔為3,7,11,15-四甲基-1-十六碳炔-3-醇(去氫異葉綠醇)及該烯為3,7,11,15-四甲基-1-十六碳烯-3-醇(異葉綠醇)。
- 如申請專利範圍第18項之方法，其中該炔為2-甲基丁炔醇及該烯為2-甲基丁烯醇。
- 如申請專利範圍第19或20項之方法，其中該氫化於含硫化合物存在下進行。
- 如申請專利範圍第21項之方法，其中該含硫化合物為2,2’-(伸乙基二硫基)-二乙醇。
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP08162689 | 2008-08-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201016317A TW201016317A (en) | 2010-05-01 |
| TWI483774B true TWI483774B (zh) | 2015-05-11 |
Family
ID=41055027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW098128029A TWI483774B (zh) | 2008-08-20 | 2009-08-20 | 新穎選擇性氫化觸媒及其用途 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US8530707B2 (zh) |
| EP (1) | EP2328679A1 (zh) |
| JP (1) | JP5584906B2 (zh) |
| KR (1) | KR101620651B1 (zh) |
| CN (1) | CN102131578B (zh) |
| TW (1) | TWI483774B (zh) |
| WO (1) | WO2010020671A1 (zh) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8592636B2 (en) * | 2010-01-28 | 2013-11-26 | Dsm Ip Assets B.V. | Hydrogenation process |
| EP2588233B1 (en) * | 2010-07-01 | 2019-03-13 | DSM IP Assets B.V. | Novel structured catalyst |
| WO2012121156A1 (ja) * | 2011-03-09 | 2012-09-13 | 和光純薬工業株式会社 | アルキン誘導体の部分水素化反応 |
| CN102503772A (zh) * | 2011-10-11 | 2012-06-20 | 上海博鹤企业发展有限公司 | 一种生产2-甲基-3-丁烯-2-醇的方法 |
| ES2689754T3 (es) | 2012-08-20 | 2018-11-15 | Evonik Degussa Gmbh | Procedimiento para la preparación fermentativa de L-aminoácidos utilizando cepas mejoradas de la familia Enterobacteriaceae |
| EP3052459A1 (en) * | 2013-09-30 | 2016-08-10 | DSM IP Assets B.V. | Pd on ceria catalytic system for selective hydrogenations of triple bonds |
| WO2015091816A2 (en) * | 2013-12-20 | 2015-06-25 | Dsm Ip Assets B. V. | New catalytic system |
| CN110612159A (zh) * | 2017-05-01 | 2019-12-24 | 帝斯曼知识产权资产管理有限公司 | 沉积pd纳米粒子的改进方法 |
| CN107876107B (zh) * | 2017-09-29 | 2020-08-14 | 海南汉地阳光石油化工有限公司 | 一种石油加氢催化剂及其制备方法 |
| CN113891870A (zh) * | 2019-05-27 | 2022-01-04 | 帝斯曼知识产权资产管理有限公司 | 在磷化合物存在下将炔醇选择性氢化成烯醇 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182067A (zh) * | 1996-11-11 | 1998-05-20 | 弗·哈夫曼-拉罗切有限公司 | 催化氢化 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH462809A (de) | 1964-06-03 | 1968-09-30 | Hoffmann La Roche | Verwendung von schwefelorganischen Verbindungen zur Erhöhung der Selektivität von Hydrierungskatalysatoren |
| TW200836831A (en) * | 2006-11-11 | 2008-09-16 | Uop Llc | Selective hydrogenation processes using functional surface catalyst composition |
| TW200843848A (en) * | 2006-11-11 | 2008-11-16 | Uop Llc | Hydrogenation processes using functional surface catalyst composition |
-
2009
- 2009-08-20 US US13/059,477 patent/US8530707B2/en not_active Expired - Fee Related
- 2009-08-20 EP EP09782023A patent/EP2328679A1/en not_active Withdrawn
- 2009-08-20 KR KR1020117006364A patent/KR101620651B1/ko active IP Right Grant
- 2009-08-20 TW TW098128029A patent/TWI483774B/zh not_active IP Right Cessation
- 2009-08-20 JP JP2011523423A patent/JP5584906B2/ja not_active Expired - Fee Related
- 2009-08-20 CN CN200980132708.XA patent/CN102131578B/zh not_active Expired - Fee Related
- 2009-08-20 WO PCT/EP2009/060764 patent/WO2010020671A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182067A (zh) * | 1996-11-11 | 1998-05-20 | 弗·哈夫曼-拉罗切有限公司 | 催化氢化 |
Non-Patent Citations (1)
| Title |
|---|
| Janine Freitag, Monika Hermann, Matthias Nüchter, Bernd Ondruschka, Franziska Schneider, Achim Stolle，Microwave assisted synthesis using catalysts on controlled pore glass carriers，OPTICA APPLICATA，2005，35，745-752 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2328679A1 (en) | 2011-06-08 |
| CN102131578A (zh) | 2011-07-20 |
| KR101620651B1 (ko) | 2016-05-12 |
| CN102131578B (zh) | 2014-02-19 |
| TW201016317A (en) | 2010-05-01 |
| JP2012500112A (ja) | 2012-01-05 |
| US20110237841A1 (en) | 2011-09-29 |
| US8530707B2 (en) | 2013-09-10 |
| WO2010020671A1 (en) | 2010-02-25 |
| JP5584906B2 (ja) | 2014-09-10 |
| KR20110051252A (ko) | 2011-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI483774B (zh) | 新穎選擇性氫化觸媒及其用途 | |
| KR102311346B1 (ko) | 수소화반응용 촉매 및 이의 제조방법 | |
| TW201235102A (en) | Selective non-precious metal-catalyzed mono-hydrosilylation of polyunsaturated compounds | |
| CN102458659A (zh) | 不对称氢化催化剂 | |
| CN101730588A (zh) | 用于炔烃选择性加氢的催化剂及其制备方法 | |
| CN101992090A (zh) | 制备用于多不饱和烃类的选择氢化的Ni/Sn担载催化剂的方法 | |
| CN101992102A (zh) | 制备用于多不饱和烃类的选择氢化的以镍和ib族金属为基础的担载催化剂的方法 | |
| CN101007277A (zh) | 一种合成吲哚的催化剂及其制备方法 | |
| Lomelí‐Rosales et al. | A General One‐Pot Methodology for the Preparation of Mono‐and Bimetallic Nanoparticles Supported on Carbon Nanotubes: Application in the Semi‐hydrogenation of Alkynes and Acetylene | |
| JP2020533168A (ja) | アセチレン水素化触媒を強化するためのリンイリドの使用 | |
| Widenhoefer et al. | Cyclization/hydrosilylation of functionalized dienes catalyzed by a cationic palladium phenanthroline complex | |
| EP3075450B1 (en) | Method for storing activated fischer-tropsch synthesis catalyst | |
| CN102089266A (zh) | 酯类和内酯类的实用的还原方法 | |
| JP2022533821A (ja) | リン化合物の存在下でのアルキノールからアルケノールへの選択的水素化 | |
| Mori et al. | Pd (0)–polyethyleneimine complex as a partial hydrogenation catalyst of alkynes to alkenes | |
| JP2012504596A (ja) | ホスフィノオキシドベースのルテニウム錯体を有するエステル基又はカルボニル基の水素化 | |
| JP5786621B2 (ja) | 選択的水素化用触媒、その製造方法及びそれを用いる選択的水素化法。 | |
| 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 | |
| CN1042128C (zh) | 醇类的制备方法 | |
| CN103008000A (zh) | 一种含非沸石分子筛的费托合成催化剂及其制备和应用 | |
| ITMI971510A1 (it) | Procedimento per la preparazione di un catalizzatore a base di cobalto e scandio | |
| JP2009022862A (ja) | 固体触媒 | |
| JP2018118925A (ja) | 鉄錯体触媒を用いたカルボニル化合物のヒドロシリル化反応によるアルコキシシランの製造方法 | |
| RU2361666C1 (ru) | Катализатор для получения алифатических углеводородов из со и h2 | |
| KR100915095B1 (ko) | 알파, 베타-알킨 에스터 화합물의 β-보론화 방법 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |