CN102958607A - 新的结构化催化剂 - Google Patents
新的结构化催化剂 Download PDFInfo
- Publication number
- CN102958607A CN102958607A CN2011800325741A CN201180032574A CN102958607A CN 102958607 A CN102958607 A CN 102958607A CN 2011800325741 A CN2011800325741 A CN 2011800325741A CN 201180032574 A CN201180032574 A CN 201180032574A CN 102958607 A CN102958607 A CN 102958607A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- linearity
- branching
- described catalyst
- nano particle
- 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 78
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000004615 ingredient Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000007530 organic bases Chemical class 0.000 claims abstract description 6
- 239000011782 vitamin Substances 0.000 claims abstract description 4
- 229940088594 vitamin Drugs 0.000 claims abstract description 4
- 229930003231 vitamin Natural products 0.000 claims abstract description 4
- 235000013343 vitamin Nutrition 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 44
- 229910045601 alloy Inorganic materials 0.000 claims description 23
- 239000000956 alloy Substances 0.000 claims description 23
- 239000012634 fragment Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 229920000914 Metallic fiber Polymers 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 235000021466 carotenoid Nutrition 0.000 claims description 3
- 150000001747 carotenoids Chemical class 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-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
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007725 thermal activation Methods 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 239000007858 starting material Substances 0.000 claims 2
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 239000000835 fiber Substances 0.000 abstract description 5
- -1 carotinoids Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 39
- 238000005984 hydrogenation reaction Methods 0.000 description 19
- 229910052763 palladium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011981 lindlar catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- JRRAOUJVHVWGEP-UHFFFAOYSA-N [S].C(C)O.C(C)O Chemical compound [S].C(C)O.C(C)O JRRAOUJVHVWGEP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 229960002238 methylpentynol Drugs 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000009941 weaving Methods 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- 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
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Crystallography & Structural Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种新颖的结构化催化剂,其基于包覆具有Pd纳米颗粒的碱性氧化物层的经烧结的金属纤维(SMF),涉及在所述催化剂和有机碱的存在下使有机化合物与氢的反应,并且涉及通过使用该反应所制备的维生素、类胡萝卜素、香料成分和/或食品或饲料成分。
Description
本发明涉及一种新颖的结构化催化剂,其基于包覆具有Pd纳米颗粒的碱性氧化物层的经烧结的金属纤维(SMF),涉及在所述催化剂和有机碱的存在下使有机化合物与氢的反应,并且涉及通过使用该反应所制备的维生素、类胡萝卜素、香料成分和/或食品或饲料成分。
炔醇到烯醇的选择性催化氢化是精细化工中的重要工艺。已知基于Pd的催化剂能提供最高的选择性和产率。优先形成烯烃醇归因于较之半氢化产物对乙炔醇的更强吸附。已知钯的催化性能受到其分散体系、担载物性质以及促进剂和添加剂的使用的强烈影响。考虑到这些因素来设计催化剂,可令目标产物产率增加以及催化剂得以被再利用。
通常,以1-2nm的小颗粒存在的低配位数的Pd原子提供过强的炔醇吸附,这导致周转频率和选择性降低。该现象已知为几何效应或“集团(ensemble)”效应。与高度分散的Pd相比,7-10nm大小的颗粒在对2-丁炔-1,4-二醇和2-甲基-3-丁炔-2-醇(MBY)的氢化中展示出更好的催化性能。
工业中,上述氢化通常用Lindlar催化剂(通过乙酸铅改良的5%Pd/CaCO3)并通常加入喹啉,在搅拌槽式反应器中进行。作为精细粉末的Lindlar催化剂难以操作,并且在反应后需要进行过滤。就这方面来说,结构化催化剂对于工艺紧凑和安全来说是有好处的。整体料(monolith)、膜、金属栅网、二维玻璃和碳纤维在液相氢化中被用作为催化剂担载物。在3-甲基-1-戊炔-3-醇和2-丁炔-1,4-二醇的氢化中,整体料催化剂显示出与浆料催化剂相似的选择性,但是相对于每Pd负载的活性要低得多。在2-甲基-3-丁炔-2-醇氢化中使用高选择性的双金属Pd-Ru(9∶1)H2-可透过膜会受到高含量的贵金属和每克Pd的低生产效率的限制。金属栅网具有约100cm2/g的低几何表面积的缺点。2-丁炔-1,4-二醇氢化中使用的活性碳纤维织物具有低机械强度。
从现有技术中可知,规整型金属基催化剂的生产需要相对较为苛刻的条件。用于该催化体系的合金通常含有金,必须加热至超过1000℃数小时。此外,使用无水有机溶剂和稳定剂(例如乙偶姻和/或单乙醇胺)来涂布合金表面。
本发明的目标是寻找一种结构化催化剂,其具有比得上现有技术中已知结构化催化剂的催化性能,但是其易于处理并且易于从反应混合物中分离,用于最终的回收利用,并且其可以通过使用较低的温度并且避免使用溶剂(使用溶剂是环境不友好的)来制备。
业已令人惊讶地发现,一种结构化催化剂克服了上述缺点,该结构化催化剂是基于包覆有经Pd-纳米颗粒浸渍的碱性氧化物层(优选包含ZnO或包含ZnO和Al2O3)的经烧结的金属纤维(SMF),并且其中的合金不含有Al。
因此,本发明涉及一种结构化催化剂,其基于包覆有经Pd-纳米颗粒浸渍的碱性氧化物层的经烧结的金属纤维(SMF),其特征在于,所述SMF含有合金,其中所述合金不含Al。
优选地,所述碱性氧化物层包含ZnO或包含ZnO和Al2O3。
由金属微纤维构成的三维经烧结金属纤维(SMF)被选用为结构化催化剂的担载物。SMF具有高热导率(这在放热的氢化中是个巨大的优势)、高孔隙率和高渗透性。金属纤维矩阵还充当微米级的静态混合器,以消除沟流(channeling)。此外,开发旨在增强催化氢化的催化剂时,高机械强度、化学稳定性和热稳定性、易于成型使得SMF成为合适的担载物材料。
短语“不含铝”表示该合金可以包含痕量的铝(Al)。Al不是有意添加到合金中的。Al的含量小于0.1重量%(wt.-%)(wt.-%是基于合金的总重量)。
ZnO薄层包覆的SMF已知是2-甲基-3-丁炔-2-醇氢化的高效担载物。Pd纳米颗粒由预先制备的溶胶沉积,在氢气氛围中对材料进行加热,以生成PdyZnx相。ZnO层既充当碱性担载物又充当Pd促进剂。针对机械稳定性对Pd/ZnO/SMF材料进行测试,在MBY氢化中对其催化行为进行研究。
还可以用ZnO和Al2O3(以及与任选的一种或更多种其他金属氧化物)的混合物来包覆SMF。所述其他金属氧化物可以例如为MgO、MnO、Cr2O3、CuO和Fe2O3。
术语“结构化催化剂”在本文中被用于表示这样的催化剂,其中,催化剂的空间组织受到控制。结构化催化剂是本领域已知的,例如,参见Chimia 56(4),2002,159-163。结构化催化剂的例子是陶瓷载体构造(蜂窝)和纤维结构,尤其是丝状(纺织或无纺的)材料。优选地,不含Al的金属纤维材料被用于本发明的催化剂。优选地,这些材料的单根纤维优选具有约2μm至约100μm的直径,尤其是不超过约20μm的直径。可对这些材料进行化学处理,以改变比表面积和/或使得它们具有包覆层,例如金属(例如Al、Ti、Mg、Zn等)氧化物的包覆层。
在本发明一个优选的实施方式中,SMF由不锈钢(其任选可以预氧化)组成。
在本发明的上下文,术语“不锈钢”是根据EN 10088:2005中定义的标准形式。不锈钢包含至少10.5wt.-%的铬(Cr)。铬的含量可以高达26wt.-%。某些类型的不锈钢还包含Ni、Mn、C、Mo、Ti和/或Nb。
在本发明另一个实施方式中,Pd-纳米颗粒为pd0-纳米颗粒。
本发明的另一个实施方式涉及一种结构化催化剂,其中一部分Pd-纳米颗粒在PdyMx相内,其中M为Zn或Zn和Al以及任选的Cr、Mn、Co和/或Mg,并且其中PdyMx优选地在氢气氛中通过热活化形成。
通常,Pd-纳米颗粒的尺寸介于0.5-100nm之间,优选介于2-20nm之间,更优选介于2-15nm之间,特别优选介于5-12nm之间,最优选介于7-10nm之间。ZnO层也可以是颗粒结构化的ZnO层。
基于所述催化剂的重量,所述催化剂通常包含0.001-5wt.-%的Pd纳米颗粒,优选0.01-2wt.-%,更优选0.05-1wt.-%,最优选0.1-0.3wt.-%。
本发明进一步涉及一种如上面所定义的结构化催化剂,其中基于所述催化剂的重量,所述催化剂包含0.01-20wt.-%的ZnO和/或MgO(或氧化物的混合物,例如Al2O3、MnO2、Cr2O3、CuO和Fe2O3),优选0.1-10wt-%,更优选1.5-10wt-%,最优选2-8wt-%。
结构化催化剂的制备通常包括下列步骤:
1)预处理(清洁和煅烧)合金担载物;
2)用金属氧化物包覆所述合金担载物;
3)在经包覆的合金担载物上合成并沉积Pd纳米颗粒;
4)后处理该催化剂。
通常,进行步骤1)以除去合金表面的所有污染。可以使用符合该目的的任何适当方法。一种适当的方法是用沸腾的甲苯处理该合金至少30分钟。然后干燥所述合金。随后,本发明所用的合金在小于600℃的温度下在空气中氧化。通常该步骤在约450℃的温度下进行(现有技术的合金通常需要在大于1000℃的温度下进行!)。
因此,本发明的另一个实施方式是一种用于制备如上面所定义的结构化催化剂的方法,其中在所述预处理步骤中,反应(处理)温度小于600℃,优选为约450℃。
随后,在水中进行步骤2)。将包覆层的前驱体溶于水。通常将合金浸入该溶液,随后进行干燥步骤和至少一个煅烧步骤。因此,本发明的另一个实施方式是一种用于制备如上面所定义的结构化催化剂的方法,其中在所述包覆步骤中,水被用作溶剂。
根据一些众所周知的方法来进行步骤3)。通常,将适当的Pd盐(例如PdCl2)与稳定剂(例如Na2MoO4.H2O)一起溶解,并通过H2还原以得到稳定的Pd溶胶。用水稀释所得到的Pd溶胶,来自步骤1)和步骤2)的经处理的合金被放入该溶液中一定的时间。随后将如此处理的合金干燥。根据一些众所周知的方法进行步骤4)。通常,用含有氢气的气流在300℃下处理步骤3)所得到的材料。
根据本发明的结构化催化剂被用于有机材料的氢化方法中。因此,本发明还涉及一种在如上面所定义的催化剂的存在下使有机原料与氢反应的方法。
优选地,这些反应中的有机原料包含碳-碳三键。更优选地,所述有机原料为炔醇。特别优选的有机原料是式(I)的化合物。
其中
R1为H、线性或支化的C5-C35烷基片段或线性或支化的C5-C35烯基片段,其中C链可以是取代的,并且
R2为线性或支化的C1-C4烷基片段,其中C链可以是取代的。
优选的式(I)化合物是这样的化合物,其中
R1为H、线性或支化的C5-C30烷基片段或线性或支化的C5-C30烯基片段,其中C链可以是取代的,并且
R2为线性或支化的C1-C4烷基片段,其中C链可以是取代的。
更优选的式(I)化合物是这样的化合物,其中
R1为H、线性或支化的C6-C16烷基片段或线性或支化的C6-C16烯基片段,其中C链可以是取代的,并且
R2为C1-C2烷基片段,其中C链可以是取代的。
最优选的式(I)化合物是这样的化合物,其中
R1为线性或支化的C6-、C11-或C16-烷基片段或线性或支化的C6-、C11-或C16-烯基片段,并且
R2为线性或支化的C1-C2烷基片段。
用于如上面所公开的方法的特别优选的化合物的实例为2-甲基-3-丁炔-2-醇(MBY)和去氢异植醇(DIP)。
根据本发明的氢化可以在传统用于氢化的条件下进行。
根据本发明的方法(其中使用如上面所定义的结构化催化剂)通常在1.1-30bar、优选1.1-15bar、更优选1.5-10bar、最优选2-8bar的压力下进行。
根据本发明的方法(其中使用如上面所定义的结构化催化剂)通常在250K-420K、优选273K-380K、更优选274K-350K、最优选295K-330K的温度下进行。
根据本发明的方法(其中使用如上面所定义的结构化催化剂)可以进一步包含向反应中添加至少一种有机碱的步骤,所述至少一种有机碱优选为3,6-二硫杂-1,8-辛二醇、噻吩、二丙基硫醚、四氢噻吩、喹啉、吡啶和二乙氨基乙醇。在使用所述碱的情况下,碱与Pd的比例介于1∶1和500∶1之间,优选介于2∶1和150∶1之间,更优选介于5∶1和50∶1之间,最优选介于10∶1和30∶1之间。
根据本发明的方法(其中使用如上面所定义的结构化催化剂,其中有机原料与氢反应)在如上面所定义的所述催化剂的存在下以及任选地在溶剂的存在下进行,其中所述溶剂优选为水。
根据本发明的方法(其中使用如上面所定义的结构化催化剂)通常进一步包括在反应之后分离催化剂并将用过的催化剂暴露于超声辐射,优选地在含有醇(例如乙醇)的容器中进行。
通过根据本发明的方法(其中使用如上面所定义的结构化催化剂)得到的反应产物优选地作为维生素、类胡萝卜素、香料成分和/或食品成分的中间体。
下述实施例将进一步阐述本发明,而不对其加以限制。除非另外指出,所有给出的百分比和份都是相对于重量,温度以K或℃给出。
实施例
材料
经烧结的金属纤维(SMFSS)、不锈钢316L、40FP3(得自SouthwestScreens & Filters SA(现为Bekaert SA Belgium))。
实施例1:0.19% Pd/5%(Al2O3+ZnO)/SMFSS
步骤1):预处理
为去除污染,在煮沸的甲苯中处理SMFSS板(10×10cm,m=6-7g)0.5小时,并进行空气干燥。在空气中于450℃下对SMFSS进行3小时氧化。冷却至室温之后,将经处理的SMFSS储存在干燥的气氛中。
步骤2):用混合的氧化物包覆担载物
用ZnO+Al2O3(Zn∶Al的比例=1∶1)层来浸涂按步骤1)所述来清洁的SMFSS板。按下列方法制备ZnO+Al2O3前驱体溶液:将200gAl(NO3)3·9H2O溶于700ml蒸馏水中。将该溶液加热至95℃。将43.4gZnO加入该溶液。保持加热和搅拌直到ZnO完全溶解。然后将溶液冷却到室温。按下列方法进行ZnO+Al2O3(Zn∶Al的比例=1∶1)层的沉积:将SMFSS板浸入ZnO+Al2O3前驱体溶液中,随后在室温下在空气中干燥(1小时),在450℃下煅烧(1小时,温度斜率为2℃/min)。浸渍-干燥-煅烧循环重复2次,以沉积约5wt.-%的ZnO+Al2O3(Zn∶Al的比例=1∶1)。将所制备的5%(ZnO+Al2O3)/SMFSS储存在干燥气氛中。
步骤3):Pd纳米颗粒的合成和Pd纳米颗粒的沉积
按下列方法制备Pd纳米颗粒溶液:加热(90-95℃)和搅拌(磁力棒)下将0.121g Na2MoO4·H2O和0.088g PdCl2溶于20ml去离子水中。继续加热和搅拌直到水完全蒸发,从而使PdCl2完全溶解。蒸发-溶解循环重复2次。最后,加入50ml去离子水以溶解残留物。通过在室温下在经过滤的Pd前驱体溶液中鼓泡氢化(250ml/min)1小时形成Pd溶胶。这样做之后,溶液颜色从棕色变成黑色。
在烧杯中用去离子水稀释50ml所得Pd溶胶至4L。所得到的溶液是黑色且不透明的。将步骤1)和2)中所制备的经包覆的SMFSS板完全浸入溶胶中,并在搅拌(磁力棒)下保持2小时。为了提供均匀的Pd纳米颗粒沉积,板每隔15分钟翻转180度。在该过程中,溶液变得几乎透明且无色。SMF板的颜色变成深灰色。Pd沉积之后,用水冲洗催化剂并在环境温度下干燥1小时。发现所产生的Pd含量为0.19wt.-%。将所制备的材料储存在干燥的气氛中。
步骤4):后处理
使所制备的催化剂在H2-Ar气氛(比例为1∶9,总流量为450ml/min)经历高温还原处理(300℃;温度斜率为10℃/min)2小时。在H2-Ar流中冷却之后,将催化剂储存在干燥的气氛中。
实施例2:0.2% Pd/5%(ZnO+MgO+Al2O3)/SMFSS
与实施例1类似地进行所有步骤,除了步骤2)。
使用不同的包覆层体系来进行担载物的包覆。用ZnO+MgO+Al2O3(Zn∶Mg∶Al摩尔比为1∶1∶2)层来包覆SMFSS。按下列方法来制备ZnO+MgO+Al2O3前驱体溶液:将200g Al(NO3)3·9H2O溶于700ml蒸馏水中。将该溶液加热至95℃。将11.0g MgO和21.7g ZnO加入该溶液。保持加热和搅拌直到MgO和ZnO完全溶解。然后将溶液冷却到室温。
按下列方法进行ZnO+MgO+Al2O3(Zn∶Mg∶Al摩尔比为1∶1∶2)层的沉积:将SMFSS板浸入ZnO+MgO+Al2O3前驱体溶液中,随后在室温下在空气中干燥(1小时),在450℃下煅烧(1小时,温度斜率为2℃/min)。浸渍-干燥-煅烧循环重复2次,以沉积约5wt.-%的ZnO+MgO+Al2O3(Zn∶Mg∶Al摩尔比为1∶1∶2)。将所制备的5%(ZnO+MgO+Al2O3)/SMFSS储存在干燥气氛中。
实施例3:0.2% Pd/5%(ZnO)/SMFSS
与实施例1类似地进行所有步骤,除了步骤2)。使用不同的包覆层体系来进行担载物的包覆。用ZnO层来浸涂SMFSS。
实施例4:0.2% Pd/5%(Cr2O3+Al2O3+ZnO)/SMFSS
重复根据实施例1的步骤,不同之处在于,在包覆步骤中加入一定量的Cr(NO3)3从而使10wt.-%的氧化层为Cr2O3。
实施例5:0.2% Pd/5%(MnO+Al2O3+ZnO)/SMFSS
重复根据实施例1的步骤,不同之处在于,在包覆步骤中加入一定量的Mn(NO3)2从而使10wt.-%的氧化层为MnO。
实施例6:0.2% Pd/5%(CunO+Al2O3+ZnO)/SMFSS
重复根据实施例1的步骤,不同之处在于,在包覆步骤中加入一定量的Cu(NO3)2从而使10wt.-%的氧化层为CuO。
实施例7:选择性DIP氢化
一般说明
在装有加热夹套和氢气供应系统的不锈钢间歇式反应器(150或250ml的高压釜,Buchi AG,Uster,Switzerland)中进行氢化。将结构化催化剂(0.8-1.6g)置于安装在自出气的中空轴搅拌器上的两个金属网(2×4-8.5cm)之间。将隔板置于反应器内部以消除涡旋的形成。用底物和催化剂填充反应器,用N2吹洗。在工作温度下,用氢气吹洗反应器并加压。在反应过程中,反应器的压力保持恒定。实验在65-80℃和4-8bar H2压力、以及1800-2000rpm的强力搅拌下进行。分别借助于Pt-100温度传感器和压力传感器来控制温度和压力。借助于计算机监测并记录整个反应期间的氢气消耗、反应温度、反应压力和搅拌速度。通过取样管定期从反应器中取出反应混合物的样品并通过GC分析。
产品产量定义为Y=mol底物(转化为产品)/mol底物(引入的)·100%,转化率为X=mol底物(发生反应的)/mol底物(引入的)·100%,对产品的选择性为S=Y/X·100%。
在装有加热夹套和氢气供应系统的半间歇式不锈钢反应器(150ml,Büchi AG)中进行无溶剂的选择性DIP氢化反应。将SMF催化剂置于安装在自出气的中空轴搅拌器上的两个栅网之间。实验在80℃和0.4bar H2压力、以及1800-2000rpm的搅拌下进行。在一些实验中,向反应混合物中添加改性剂2,2′-亚乙基二硫二乙醇(cmod=5.9·10-4-1.2·10-2wt.-%)。
实施例8:0.2% Pd/5% ZnO/SMFSS
重复实施例3,但使用Pd(CH3COO)2来代替PdCl2。
表2.在选择性DIP氢化中使用用Pd(CH3COO)2制备的结构化催化剂
实施例9:MBY的氢化
在250ml的反应器中、在65℃和H2压力(4bar)下使用200ml的2-甲基-3-丁炔-2-醇(MBY)和按实施例3所述制备的催化剂(1.0-1.6g)来进行2-甲基-3-丁炔-2-醇(MBY)向2-甲基-3-丁烯-2-醇(MBE)的无溶剂选择性氢化。
实施例10:2-丁炔-1,4-二醇的氢化
在150ml的反应器中、在80℃和H2压力(15bar)下使用100ml的熔融B3D和按实施例1所述制备的催化剂(0.6-1.0g)来进行2-丁炔-1,4-二醇(B3D)向2-丁烯-1,4-二醇(B2D)的无溶剂选择性氢化。
表3.结构化催化剂的性能
No. | m催化剂(g) | Rini(mol/molPd.s) | 选择性(%) |
9 | 1.53 | 4.55 | 97.3(X=97%) |
10 | 0.65 | 2.41 | 98.8(X=99%) |
Claims (26)
1.一种结构化催化剂,其基于包覆有经Pd-纳米颗粒浸渍的碱性氧化物层的经烧结的金属纤维(SMF),其特征在于,所述SMF含有合金,其中所述合金不含Al。
2.如权利要求2所述的催化剂,其中所述碱性氧化物层包含ZnO或包含ZnO和Al2O3。
3.如权利要求1或2所述的催化剂,其中所述合金是不锈钢。
4.如权利要求1、2或3所述的催化剂,其中所述碱性氧化物层的部分为至少一种其他金属氧化物,所述其他金属优选为Cr、Mn、Cu或Mg。
5.如前面任何一个权利要求所述的催化剂,其中所述合金是预氧化的。
6.如权利要求1至5中任意一项所述的催化剂,其中所述Pd-纳米颗粒是pd0-纳米颗粒。
7.如权利要求1至6中任意一项所述的催化剂,其中所述Pd-纳米颗粒的一部份处于PdyMx相中,其中M为Zn或Zn和Al以及任选的Cr、Mn、Co和/或Mg,并且其中所述PdyMx相在氢气氛中通过热活化形成。
8.如权利要求1至7中任意一项所述的催化剂,其中所述Pd-纳米颗粒的尺寸在0.5-100nm之间,优选地在2-20nm之间,更优选地在5-12nm之间,最优选地在7-10nm之间。
9.如权利要求1至8中任意一项所述的催化剂,其中基于所述催化剂的重量,所述催化剂含有0.001-5wt.-%的Pd纳米颗粒,优选地,0.01-2wt.-%,更优选地,0.05-1wt.-%,最优选地,0.1-0.3wt.-%。
10.如权利要求1至9中任意一项所述的催化剂,其中基于所述催化剂的重量,所述催化剂包含0.01-20wt.-%的ZnO和/或MgO以及任选的Cr、Mn、Cu和/或Al,优选0.1-10wt-%,更优选1.5-10wt-%,最优选2-8wt-%。
11.一种在权利要求1至10中任意一项所述催化剂的存在下使有机原料与氢反应的方法。
12.如权利要求11所述的方法,其中所述有机原料包含碳-碳三键。
13.如权利要求11所述的方法,其中所述起始物料是炔醇。
15.如权利要求14所述的方法,其中
R1为H、线性或支化的C5-C30烷基片段或线性或支化的C5-C30烯基片段,其中所述C链可以是取代的,并且
R2为线性或支化的C1-C4烷基片段,其中所述C链可以是取代的。
16.如权利要求14所述的方法,其中
R1为H、线性或支化的C6-C16烷基片段或线性或支化的C6-C16烯基片段,其中所述C链可以取代的,并且
R2为C1-C2烷基片段,其中所述C链可以是取代的。
17.如权利要求14所述的方法,其中
R1为线性或支化的C6-、C11-或C16-烷基片段或线性或支化的C6-、C11-或C16-烯基片段,并且
R2为C1-C2烷基片段。
18.如权利要求14所述的方法,其中所述有机原料选自由2-甲基-3-丁炔-2-醇(MBY)和去氢异植醇(DIP)组成的组。
19.如权利要求11至18中任意一项所述的方法,其中压力介于1.1和30bar之间,优选介于1.1和15bar之间,更优选介于1.5和10bar之间,最优选介于2和8bar之间。
20.如权利要求11至19中任意一项所述的方法,其中反应温度介于250K和420K之间,优选介于273K和380K之间,更优选介于274K和350K之间,最优选介于295K和335K之间。
21.如权利要求11至20中任意一项所述的方法,其中所述方法还包括向所述方法添加至少一种有机碱,所述有机碱优选为3,6-二硫杂-1,8-辛二醇、噻吩、二丙基硫醚、四氢噻吩、喹啉、吡啶和二乙氨基乙醇。
22.如权利要求21所述的方法,其中所述喹啉和所述Pd的比例介于1∶1至500∶1之间,优选介于2∶1至150∶1之间,更优选介于5∶1至50∶1之间,最优选介于10∶1至30∶1之间。
23.一种在权利要求1所述的催化剂和任选溶剂的存在下使有机原料与氢反应的方法。
24.如权利要求23所述的方法,其中所述溶剂是水。
25.如权利要求11所述的方法,所述方法还包括在所述反应后分离所述催化剂以及将用过的催化剂暴露于超声辐射,优选在含有醇的容器中进行。
26.如权利要求11所述的方法,其中所述反应产物是维生素、类胡萝卜素、香料成分和/或食物成分的中间体。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710445744.8A CN107262112A (zh) | 2010-07-01 | 2011-07-01 | 新的结构化催化剂 |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH10792010 | 2010-07-01 | ||
CH1079/10 | 2010-07-01 | ||
PCT/EP2011/061159 WO2012001166A1 (en) | 2010-07-01 | 2011-07-01 | Novel structured catalyst |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710445744.8A Division CN107262112A (zh) | 2010-07-01 | 2011-07-01 | 新的结构化催化剂 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102958607A true CN102958607A (zh) | 2013-03-06 |
Family
ID=44629995
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2011800325741A Pending CN102958607A (zh) | 2010-07-01 | 2011-07-01 | 新的结构化催化剂 |
CN201710445744.8A Pending CN107262112A (zh) | 2010-07-01 | 2011-07-01 | 新的结构化催化剂 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710445744.8A Pending CN107262112A (zh) | 2010-07-01 | 2011-07-01 | 新的结构化催化剂 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9101917B2 (zh) |
EP (1) | EP2588233B1 (zh) |
CN (2) | CN102958607A (zh) |
ES (1) | ES2725203T3 (zh) |
WO (1) | WO2012001166A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106345508A (zh) * | 2016-08-22 | 2017-01-25 | 浙江新和成股份有限公司 | 一种用于炔醇选择性加氢的催化剂及其制备方法和应用 |
CN116475416A (zh) * | 2023-06-20 | 2023-07-25 | 紫金矿业集团黄金珠宝有限公司 | 一种具备储存香味功能的贵金属饰品制造工艺 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112014020919B1 (pt) * | 2012-02-24 | 2020-10-27 | Dsm Ip Assets B.V | sistema catalítico em pó para processos de hidrogenação |
KR102103038B1 (ko) * | 2012-02-24 | 2020-04-22 | 디에스엠 아이피 어셋츠 비.브이. | Fe-합금을 포함하는 금속 분말형 촉매 |
EP2817095B1 (en) * | 2012-02-24 | 2022-09-14 | DSM IP Assets B.V. | Use of a metal powderdous catalyst comprising a cocrmo-alloy |
KR102061377B1 (ko) | 2012-04-18 | 2020-02-17 | 디에스엠 아이피 어셋츠 비.브이. | 수소화 반응에 유용한 장치(ii) |
JP6238211B2 (ja) * | 2012-04-18 | 2017-11-29 | ディーエスエム アイピー アセッツ ビー.ブイ. | 水素化反応に有用な装置(iii) |
US9381489B2 (en) | 2012-04-18 | 2016-07-05 | Dsm Ip Assets B.V. | Device useful for hydrogenation reactions (I) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5063194A (en) * | 1989-08-11 | 1991-11-05 | Basf Aktiengesellschaft | Palladium catalyst |
CN1311179A (zh) * | 1999-12-23 | 2001-09-05 | Basf公司 | 通过固定床负载的钯催化剂部分氢化炔烃制c10-c30烯烃 |
CN101616733A (zh) * | 2007-02-19 | 2009-12-30 | 帝斯曼知识产权资产管理有限公司 | 基于包覆有经钯纳米颗粒浸渍的氧化锌层的经烧结金属纤维的用于炔醇氢化的催化剂 |
CN102131578A (zh) * | 2008-08-20 | 2011-07-20 | 帝斯曼知识产权资产管理有限公司 | 包含在多孔硅玻璃上的钯的新颖选择性氢化催化剂及其用途 |
-
2011
- 2011-07-01 EP EP11741538.0A patent/EP2588233B1/en active Active
- 2011-07-01 ES ES11741538T patent/ES2725203T3/es active Active
- 2011-07-01 US US13/807,972 patent/US9101917B2/en active Active
- 2011-07-01 WO PCT/EP2011/061159 patent/WO2012001166A1/en active Application Filing
- 2011-07-01 CN CN2011800325741A patent/CN102958607A/zh active Pending
- 2011-07-01 CN CN201710445744.8A patent/CN107262112A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5063194A (en) * | 1989-08-11 | 1991-11-05 | Basf Aktiengesellschaft | Palladium catalyst |
CN1311179A (zh) * | 1999-12-23 | 2001-09-05 | Basf公司 | 通过固定床负载的钯催化剂部分氢化炔烃制c10-c30烯烃 |
CN101616733A (zh) * | 2007-02-19 | 2009-12-30 | 帝斯曼知识产权资产管理有限公司 | 基于包覆有经钯纳米颗粒浸渍的氧化锌层的经烧结金属纤维的用于炔醇氢化的催化剂 |
CN102131578A (zh) * | 2008-08-20 | 2011-07-20 | 帝斯曼知识产权资产管理有限公司 | 包含在多孔硅玻璃上的钯的新颖选择性氢化催化剂及其用途 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106345508A (zh) * | 2016-08-22 | 2017-01-25 | 浙江新和成股份有限公司 | 一种用于炔醇选择性加氢的催化剂及其制备方法和应用 |
CN106345508B (zh) * | 2016-08-22 | 2019-06-18 | 浙江新和成股份有限公司 | 一种用于炔醇选择性加氢的催化剂及其制备方法和应用 |
CN116475416A (zh) * | 2023-06-20 | 2023-07-25 | 紫金矿业集团黄金珠宝有限公司 | 一种具备储存香味功能的贵金属饰品制造工艺 |
CN116475416B (zh) * | 2023-06-20 | 2023-09-19 | 紫金矿业集团黄金珠宝有限公司 | 一种具备储存香味功能的贵金属饰品制造工艺 |
Also Published As
Publication number | Publication date |
---|---|
US9101917B2 (en) | 2015-08-11 |
EP2588233A1 (en) | 2013-05-08 |
EP2588233B1 (en) | 2019-03-13 |
WO2012001166A1 (en) | 2012-01-05 |
CN107262112A (zh) | 2017-10-20 |
ES2725203T3 (es) | 2019-09-20 |
US20130217923A1 (en) | 2013-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102958607A (zh) | 新的结构化催化剂 | |
CN101616733B (zh) | 基于包覆有经钯纳米颗粒浸渍的氧化锌层的经烧结金属纤维的用于炔醇氢化的催化剂 | |
CN102741206B (zh) | 氢化方法 | |
JP5415425B2 (ja) | 水素化および脱水素化反応において使用する焼結耐性触媒ならびにその製造方法 | |
CN111437852B (zh) | 一种用于乙炔选择加氢的铜基催化剂及其制备方法 | |
CN101850273B (zh) | 由co气相偶联合成草酸酯的规整催化剂及其制备方法 | |
JP2021526458A (ja) | 貴金属担持触媒及びその製造方法、並びに応用 | |
CN113145144B (zh) | 一种Ni3P/SiO2催化剂及其制备方法和应用 | |
JP6447940B2 (ja) | 新規な触媒システム | |
JP2016175079A (ja) | 気相酸化による塩素製造のための触媒および方法 | |
CN101455962A (zh) | 由环己酮二聚物脱氢制备邻苯基苯酚的催化剂及其制备方法 | |
WO2020094921A1 (en) | Catalyst for dehydrogenation, method for preparing the catalyst and use | |
JP2020518433A (ja) | 水素化プロセスのための金属粉末状触媒 | |
CN115155577A (zh) | 一种甘油选择性氧化制备1,3-二羟基丙酮的催化剂及制备方法 | |
CN116273055A (zh) | 一种镍基双金属催化剂及其制备方法和应用 | |
CN116196929A (zh) | 一种铜镍基催化剂的制备方法及其在乙醇转化制乙腈中的应用 | |
CN118356975A (zh) | 一种Cu-M双组分单原子催化剂及其制备方法和应用 | |
CN117753435A (zh) | 单原子合金催化剂及其制备方法和在选择性加氢转化技术中应用 | |
WO2014057075A1 (en) | Stepwise hydrogenation of specific isoprenoids |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130306 |