WO2005073157A2 - Katalytisch aktive zusammensetzung und ihre verwendung in dehydrierverfahren - Google Patents
Katalytisch aktive zusammensetzung und ihre verwendung in dehydrierverfahren Download PDFInfo
- Publication number
- WO2005073157A2 WO2005073157A2 PCT/EP2005/000867 EP2005000867W WO2005073157A2 WO 2005073157 A2 WO2005073157 A2 WO 2005073157A2 EP 2005000867 W EP2005000867 W EP 2005000867W WO 2005073157 A2 WO2005073157 A2 WO 2005073157A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalytically active
- active composition
- composition according
- dehydrogenation
- oxygen
- Prior art date
Links
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- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 33
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 30
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- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
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- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 118
- 229910052760 oxygen Inorganic materials 0.000 claims description 63
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 60
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 53
- 239000001301 oxygen Substances 0.000 claims description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 47
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- 238000001035 drying Methods 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 17
- -1 silicon nitrides Chemical class 0.000 claims description 13
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- 238000004519 manufacturing process Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
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- 229910052737 gold Inorganic materials 0.000 claims description 4
- 125000002015 acyclic group Chemical group 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 79
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- 239000003054 catalyst Substances 0.000 description 51
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
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- 229910002904 Bi-Co Inorganic materials 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
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- 241000640882 Condea Species 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- 238000000605 extraction Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
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- ACWQBUSCFPJUPN-HWKANZROSA-N trans-2-methyl-2-butenal Chemical compound C\C=C(/C)C=O ACWQBUSCFPJUPN-HWKANZROSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- 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
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/681—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with arsenic, antimony or bismuth
-
- 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
- B01J23/8973—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 arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6445—Antimony
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
Definitions
- the present invention relates to a catalytically active composition, which has as active component Pd and Bi or Pd, Rh and Bi and at least one element selected from group (a) or from group (a ') and optionally applied to at least one carrier material is.
- the invention further relates to a process for the preparation of the catalytically active compositions in question and the use thereof for the dehydrogenation of hydrocarbons.
- catalyst systems based on multimetal mixed oxides are generally used.
- active compositions consisting of vanadium-based oxides, such as. B. V / MgO catalysts, VPO materials, V-Sb mixed oxides described.
- Another class known in the literature is represented by catalytically active compounds based on iron phosphate.
- iron phosphates come in addition to the common ODH (oxidehydrogenation) and DH (dehydrogenation) Reactions are also used in reactions such as the conversion of isobutyraldehyde to methacrolein or from isobutyric acid to methacrylic acid.
- crotonaldehyde is currently usually produced in the liquid phase by aldol condensation of acetaldehyde via acetaldol as an intermediate stage.
- crotonaldehyde can be used as an economically important starting product, for example in vitamin E synthesis, for the preparation of the preservative sorbic acid and for the synthesis of the lubricant 3-methoxybutanol, there is great interest in developing a suitable catalyst by which the synthesis can be carried out of crotonaldehyde can be made more economical.
- GB 1, 340.612 describes the conversion of saturated ketones to the corresponding alpha, beta-unsaturated ketones in solution over homogeneous noble metal catalysts. Homogeneous catalytic processes, however, have the disadvantage, compared to heterogeneous catalytic processes, that the catalyst is laboriously separated from the reaction mixture.
- JP 49127909 describes the conversion of butanone to butenone in the presence of water vapor on catalysts containing iron oxide in the gas phase. At 500 ° C the conversion is 5.5% and the selectivity 83%.
- No. 6,433,229 describes the dehydrogenation of cyclic ketones such as cyclopentanone in the gas phase in the absence of oxygen on various dehydrogenation catalysts.
- the catalyst activity decreases relatively quickly and the catalyst often has to be regenerated by burning off residues.
- the process must also be carried out at temperatures above 400 ° C.
- Liquid-phase dehydrogenations for the production of ⁇ , ⁇ -unsaturated ketones are also known. Salts and complex compounds of Pd, Rh and Pt are used as catalysts.
- J. Org. Chem. 36, 752 (1972) describes the Liquid phase dehydrogenation of cyclohexanone to 2-cyclohexenone on a PdCI 2 or CuCI 2 catalyst with a yield of 90%.
- the object of the present invention is to provide suitable catalytically active compositions for the gas-phase dehydrogenation of hydrocarbons, in particular oxofunctionalized hydrocarbons such as acyclic and cyclic aldehydes and ketones.
- catalytically active compositions characterized in that these are active components Pd and Bi and at least one element selected from group (a) consisting of Rh, Au, Sb, V, Cr, W, Mn, Fe, Co , Ni, Na, Cs and Ba.
- catalytically active compositions characterized in that these are active components Pd, Rh and Bi and at least one element selected from group (a 1 ) consisting of Au, Sb, V, Cr, W, Mn, Fe , Co, Ni, Pt, Cu, Ag, Na, Cs, Mg, Ca and Ba.
- a catalytically active composition has proven to be advantageous, which is characterized in that it has an active component with the following formula:
- X Rh and / or Au
- Y Au, Rh, Pt, Ag, Cr, Co, Cu, W, V, Fe or Mn
- Z Au, Rh, Pt, Ag, Cr, Co, Cu, W, V, Fe or Mn
- index a is in the range of 0.1 ⁇ a ⁇ 3
- index b is in the range of 0 ⁇ b ⁇ 3
- index c is in the range of 0.1 ⁇ c ⁇ 3
- index d is in the range of 0 ⁇ d ⁇ 3
- index e is in the range of 0 ⁇ e ⁇ 3.
- the active component of the catalytically active composition is applied to a suitable support material. Accordingly, the present invention also relates to catalytically active compositions as described above, characterized in that the active component is applied to at least one carrier material.
- any carrier material known to the person skilled in the art can be used in the context of the present invention.
- the carriers can also have all the geometries known to the person skilled in the art, for example in the form of strands, rings, extrudates, granules, granules, powders, tablets, etc.
- the present invention also relates to a catalytically active composition, as described above, which is characterized in that the at least one carrier material is selected from a group consisting of silicon carbides, silicon nitrides, carbonitrides, oxonitrides, oxocarbides, bismuth oxide, titanium oxide, zirconium oxide, boron nitride, Aluminum oxide, silicates, aluminosilicates, zeolitic and zeolite-analog materials, steatite, activated carbon, metal meshes, stainless steel meshes, steel meshes and mixtures of two or more of the aforementioned carrier materials.
- the at least one carrier material is selected from a group consisting of silicon carbides, silicon nitrides, carbonitrides, oxonitrides, oxocarbides, bismuth oxide, titanium oxide, zirconium oxide, boron nitride, Aluminum oxide, silicates, aluminosilicates
- steatite or silicon carbide are particularly preferably used as carrier material.
- the ceramic supports mentioned can be in the form of materials with a high surface area, for example greater than 100 m 2 / g.
- carriers with small surfaces (less than 100 m 2 / g) are preferably used in the context of the present invention, particularly preferably carriers with very small surfaces (less than 20 m 2 / g).
- carrier materials can also be used which contain basic components, for example magnesium oxide (MgO), calcium oxide (CaO), barium oxide (BaO) or other alkali or alkaline earth metal components.
- carrier materials with low intrinsic porosity (specific surface area ⁇ 20 m 2 / g) or without intrinsic porosity are particularly preferably used.
- the total loading of the at least one support material with at least one active component of the catalytically active composition of the type mentioned above is in the range from 0.1 to 20% by weight, preferably in the range from 8 to 15% by weight and further preferably in the range from 0.1 to 7% by weight and particularly preferably in the range from 0.5 to 4% by weight.
- the present invention also relates to a catalytically active composition of the type in question, characterized in that the total loading of the at least one support material with an active component is less than 20% by weight.
- steatite is used as carrier material in the context of the present invention, it is preferred to work with a total active component loading of 2-4% by weight, in particular 3% by weight.
- the index a is in a range of 0.1 ⁇ a 3 3, preferably 0.5 a a 2 2 and particularly preferably 0.75 a a 1,5 1.5.
- Index b is in the range from 0 b b 3 3, preferably 0.5 b b 2 2 and particularly preferably 0.75 b b 1,5 1.5.
- Index c is in the range of 0.1 c c 3 3, preferably 0.5 c c 2 2, particularly preferably 0.75 c c ⁇ 1.5.
- the indices additionally give the% by weight of the respective elements, based on the respective carrier material , on.
- the analog index values converted to the respectively selected total loading apply.
- index d lies in a range from 0 d d 1 1, preferably 0.0001 d d 0,5 0.5 and particularly preferably 0.01 d d 0,1 0.1.
- Index e is generally in a range from 0 e e 1 1, preferably 0.0001 e e 0,5 0.5 and particularly preferably 0.01 e e 0,1 0.1, the indices being the mass ratios of the respective Specify elements one below the other or in% by weight of the respective elements, based on the mass of the carrier.
- indices indicate the mass ratios of the individual elements to one another.
- Compositions of the formulas above, for which a + b + c 3 also applies, are particularly preferred.
- catalytically active compositions which have proven to be particularly advantageous have an active component of the following formula: Pdo, 75Rh ⁇ , 25Bi ⁇ Pto.o ⁇ ; Pd ⁇ , 325Rh 2 , 25Bio, 375C ⁇ o, 05; - Pdo, 85Rh ⁇ , 85Bil, 25Cro, ⁇ 5 ⁇ Pdl, 4 Rho, 375Bil, 125Pt ⁇ , lC ⁇ 0l 05; Pdl, 4 Rho, 375Bil, l25Pt ⁇ , 1 Pdo, 8 h ⁇ ⁇ 3Bio, 85Ago, 05Cao, o5, - Pd 1 ⁇ 5 Bi ⁇ ⁇ 5 C ⁇ o, o ⁇ or Pdo, 6 ⁇ , 33 Bi ⁇
- catalytically active compositions which have an active component of the following formula have proven to be particularly advantageous
- the indices indicating the proportions by weight (% by weight), based on the respective carrier material.
- These are particularly present on steatite as a carrier.
- Catalytically active compositions of the formulas have proven particularly suitable for the dehydrogenation of isovaleraldehyde to prenal
- the active components listed above are applied to steatite, silicon carbide or a mixture of both as a carrier material.
- the present invention also relates to a method for producing a catalytically active composition comprising an active component of the type mentioned above as an unsupported catalyst.
- the preferred method of preparation is the chemical method of precipitation.
- One, two or more elements from the group of active components are mixed as aqueous salt solutions and then precipitated together in the form of their hydroxides or carbonates.
- An amorphous or crystalline precipitate or a gel is formed. If necessary, the resulting precipitate can be washed salt-free.
- the product obtained is dried in a next process step. If necessary, the dried
- Solid be ground to improve homogenization of the product.
- the solid can optionally be shaped, wherein in
- the present product can optionally be plasticized by kneading and extruded into strands, or can also be pressed into tablets after admixture of auxiliary substances. The dried product is then calcined.
- the calcined product can optionally be activated and, if necessary, tested for its catalytic properties such as selectivity and activity as well as stability. Testing can be carried out by all methods known to the person skilled in the art, such as, for example, the trial use of a catalyst in selected reactions and the analysis of its catalytic properties.
- the present invention also relates to a method for producing a catalytically active composition of the type mentioned above, comprising at least one active component, characterized in that the method comprises at least the following steps:
- step (i) precipitation of the at least one active component from a solution containing its salts; (ii) drying the product produced in step (i); (iii) calcining the product dried in step (ii); (iv) optionally testing the product calcined in step (iii).
- the present invention also relates to a method for producing a supported catalytically active composition comprising an active component applied to at least one support material.
- the impregnation of the support body below the water absorption of the support or the adsorption from supernatant solution or the application of thin layers to ceramic support materials are particularly preferably used as possible synthetic routes for the preparation of supported catalysts.
- the elements of the active component are used as thermally unstable salts, for example nitrates, acetates, carbonates or hydroxides, in the context of all the processes mentioned.
- the carrier is immersed in the solution which has the elements of the respective active component in the form of their anions and is treated under precisely defined conditions with regard to concentration, mixing, temperature and time.
- the air in the carrier pores can be removed by evacuation or the carrier can be gassed before impregnation.
- the impregnation step is usually followed by a drying and calcining step.
- the respective precursor solutions can be applied to the supports individually or, preferably, as a mixture together.
- the thermally unstable anions of the respective elements which the active component has as described above, are preferably used.
- the application can be carried out by simple delivery from a pipette, but also by spraying, spray freeze-drying and all other techniques known to the person skilled in the art in this connection.
- a drying step usually follows after the application of the precursor solution. During this drying step, the materials are dried between 30 minutes and 24 hours at temperatures between 40 ° C and 150 ° C. The materials are preferably dried at 80 ° C. for 3 hours. Freeze-drying of the materials in vacuo or under reduced pressure is also preferred.
- the drying step is usually followed by a calcination step.
- Calcination is generally understood to mean heat treatment in an oxidizing atmosphere at temperatures generally above the later operating temperatures of the catalytically active composition.
- the materials are heated between 1 and 100 hours at a heating rate in the range from 0.25 ° C./min to 10 ° C./min to a final temperature between 200 ° C. and 1200 ° C. and at the selected temperature leave between 30 min and 150 hours.
- a ramp of 3 ° C./min, a final temperature of 550 ° C. and a holding time of 3 hours are preferred.
- Air, N 2 , forming gas (H 2 in N 2 , for example 5% H 2 in N 2 ), vacuum or reactive gases (Cl 2 , NH 3 and others) or in a vacuum or under reduced pressure are suitable as the calcining atmosphere.
- the calcination is preferably carried out in air or N 2 .
- the invention also relates to a method for producing a catalytically active composition comprising at least one active component, applied to at least one carrier material, characterized in that it has at least the following steps:
- step ( ⁇ ) applying a solution comprising at least one active component to at least one carrier material; (ß) drying the product produced in step (oc); ( ⁇ ) calcining the product dried in step (ß); ( ⁇ ) optionally testing the product calcined in step ( ⁇ ).
- the catalytically active compositions can be tested for their catalytic properties.
- the testing of the catalytically active compositions produced within the scope of the invention can be carried out by all methods known to the person skilled in the art Catalysts are tested for their catalytic properties such as selectivity, activity and stability.
- the catalytically active compositions produced in the context of this invention are tested by incorporating, for example, at least 1 ml of the material to be tested in a stainless steel reactor known to the person skilled in the art. Testing is preferably carried out under inert reaction conditions. After the catalytic conversion within the reactor, the subsequent product gas analysis can be carried out using all analysis methods known to the person skilled in the art, but preferably using a GC / MS with an HP-5-MS column, for the separation and determination of the products and starting materials.
- the testing for catalytic properties of the catalytically active compositions produced can be carried out on the basis of the catalytic reaction of hydrocarbons which appear suitable for this purpose to the person skilled in the art. There are no restrictions with regard to the implementation of the educts mentioned for test purposes.
- the catalytically active compositions described in the context of the present invention can be used for nucleophilic and electrophilic substitutions, addition and elimination reactions, for double bond and skeletal isomerizations, for rearrangements and redox reactions, for alkylations, disproportionations, acylations, cyclizations, hydrations, dehydrations, aminations, hydrogenations , Dehydrogenation, oxidative dehydrogenation, dehydrocyclization, hydroxylation, oxidation, partial oxidation, ammoxidation, epoxidation and combinations of these reactions and for the targeted implementation of organic molecules.
- the present invention also relates to the use of the catalytically active compositions for the dehydrogenation of hydrocarbons.
- the hydrocarbons to be dehydrogenated there are no restrictions with regard to the hydrocarbons to be dehydrogenated within the scope of the present invention.
- the catalytically active compositions according to the invention described above can in principle be used for the dehydrogenation of all hydrocarbons which appear suitable for the person skilled in the art.
- the dehydrogenation of oxofunctionalized C 4 hydrocarbons such as butanol, butyric acid, isobutanol, isobutyric acid and butyraldehyde
- oxofunctionalized C 4 hydrocarbons such as butanol, butyric acid, isobutanol, isobutyric acid and butyraldehyde
- the dehydrogenation of cyclic and acyclic carbonyl compounds particularly preferably of cyclic and acyclic aldehydes and ketones, to give the corresponding alpha, beta-unsaturated carbonyl compounds is also preferred.
- Very particularly preferred examples are the dehydrogenation of cyclopentanone to 2-cyclopentenone, from butanone to butenone, from butyraldehyde to crotonaldehyde, from cyclohexanone to 2-cyclohexenone and from isovaleraldehyde to prenal (2-methylbut-2-enal).
- the present invention thus also relates to a process for the dehydrogenation of hydrocarbons, preferably cyclic and acyclic carbonyl compounds, particularly preferably cyclic and acyclic aldehydes and ketones, to give the corresponding alpha, beta-unsaturated carbonyl compounds by contacting the hydrocarbon to be dehydrogenated with the one described above catalytically active compositions containing Pd and Bi or Pd, Rh and Bi and optionally one or more further elements from group (a) or (a ') as the active component.
- hydrocarbons preferably cyclic and acyclic carbonyl compounds, particularly preferably cyclic and acyclic aldehydes and ketones
- the dehydrogenation is particularly preferably carried out at least in the presence of oxygen.
- the present invention also relates to the use of a catalytically active composition of the above type for the dehydrogenation of hydrocarbons in the presence of oxygen, and to a corresponding process.
- the dehydrogenation of hydrocarbons is carried out using a catalytically active composition, as described above, in the presence of at least oxygen and water.
- the present invention also relates to the use of the catalytically active compositions described above for the dehydrogenation of hydrocarbons, characterized in that the dehydrogenation takes place at least in the presence of oxygen and water, and to a corresponding process.
- the oxygen content in the dehydrogenations which are carried out at least in the presence of oxygen or oxygen and water, is in the range of present invention in relation to the total volume of the starting materials supplied in the range of 1 vol.% to 50 vol.%, preferably in the range of 1 vol.% to 30 vol.% and particularly preferably in the range of 1 vol.% up to 10% by volume or from 20 to 30% by volume.
- the water content in the case of dehydrogenations which are carried out at least in the presence of oxygen and hydrogen is in the range from 1% by volume to 50% by volume, preferably in the range from 5% by volume to 35, in relation to the total volume of the starting materials supplied % By volume, particularly preferably in the range from 5% by volume to 25% by volume. If necessary, nitrogen can be added as a balance gas in the prescribed dehydrations.
- the hydrocarbon content in dehydrogenations which are carried out as described above is based on the total volume of the starting materials fed in the range from 0 to 90% by volume, preferably in the range from 0.01 to 25% by volume, particularly preferably in the range from 0.1 to 4% by volume or from 15 to 25% by volume.
- the present invention also relates to the use of a catalytically active composition, as described above, for the dehydrogenation of hydrocarbons, the hydrocarbon to oxygen ratio in the context of the present invention in a range from 3: 1 to 1:20, preferably in a range from 1: 1 to 1: 7, particularly preferably in a range from 1: 2 to 1: 5, and a corresponding method.
- the present invention also relates to the use of a catalytically active composition, as described above, for the dehydrogenation of hydrocarbons, the hydrocarbon-to-water ratio in the process according to the invention being in a range from 3: 1 to 1:50, preferably in a range from 1: 5 to 1:40, particularly preferably in a range from 1:10 to 1:30, and a corresponding method.
- the process conditions of the dehydrogenation to be carried out by means of a catalytically active composition in the context of the present invention.
- the catalytic compositions according to the invention are distinguished by the fact that they enable dehydrogenation even at relatively low temperatures of well below 400 ° C.
- the catalyst activity remains practically unchanged over a long period of time that reactivation is rarely required.
- Gaseous by-products which are easy to separate are also predominantly formed as by-products.
- reaction temperatures in the context of the dehydrogenations listed are in a range between generally 150 ° C. and 450 ° C., preferably between 200 and 450 ° C., particularly preferably between 250 ° C. and 400 ° C. and in particular between 250 and 360 ° C.
- the respective gas load (GHSV) is in a range between 100 h “1 and 100000 h “ ⁇ preferably between 500 h “1 and 30000 h “ 1 and particularly preferably between 3000 h “1 and 15000 h “ 1 .
- the following reaction conditions have proven to be favorable, inter alia, for the dehydrogenation of cyclohexanone to 2-cyclohexenone: the reaction takes place at a temperature between 360 and 450 ° C., preferably between 410 and 425 ° C.
- the load (GHSV) is between 2000 and 9000 h "1 , preferably between 3000 and 6000 h " 1 .
- the cyclohexanone content in the feed gas stream (feed) is between 1% by volume and 5% by volume, preferably between 3% by volume and 4% by volume.
- the cyclohexanone: oxygen molar ratio in the feed gas stream is around 1: 2 for maximum cyclohexanone conversion (maximum yield of 2-cyclohexenone) and is around 1: 1 for maximum selectivity of the 2-cyclohexenone formation.
- the feed gas stream can contain 5 to 15% by volume of water, preferably about 10% by volume of water.
- the following reaction conditions have proven to be favorable, inter alia, for the dehydrogenation of cyclopentanone to 2-cyclopentenone: the reaction takes place at a temperature between 370 and 410 ° C.
- the load (GHSV) is in particular between 5000 and 7000 h "1.
- the cyclopentanone content in the feed gas stream (feed) is between 3 vol.% And 5 vol.%.
- the cyclopentanone: oxygen - molar ratio in the feed gas stream is around 1: 2 for maximum cyclopentanone conversion (maximum yield of 2-cyclopentenone) and is 1: 1 for maximum selectivity of 2-cyclopentenone formation
- the feed gas stream can contain 5 to 15% by volume of water.
- the following reaction conditions have proven to be favorable for the dehydrogenation of isovaleraldehyde to prenal: the reaction takes place at a temperature between 270 ° C. and 370 ° C., preferably between 290 ° C. and 330 ° C.
- the load (GHSV) is between 1000 h "1 and 9000 h " ⁇ preferably between 3000 h "1 and 6000 h " 1 .
- the isovaleraldehyde content in the feed gas stream is between 1 and 5% by volume, preferably 2 to 3% by volume.
- Molar ratio in the feed gas stream is between 1: 1 to 1:15, preferably in the range from 1: 3 to 1: 8.
- the feed gas stream can have between 0 and 30 vol .-% water, preferably it contains 10 to 20 vol .-% water.
- the dehydrogenation catalyst can be fixed in the reactor or e.g. be used in the form of a fluidized bed and have a corresponding shape. Suitable are e.g. Forms such as grit, tablets, monoliths, spheres or extrudates (strands, wagon wheels, stars, rings).
- a suitable form of reactor is a fixed bed or Rohrbündelr 'eaktor.
- the catalyst is located as a fixed bed in a reaction tube or in a bundle of reaction tubes.
- the reaction tubes are usually heated indirectly in that a gas, for example a hydrocarbon such as methane, is burned in the space surrounding the reaction tubes or a heat transfer medium (salt bath, rolling gas, etc.) is used.
- the reaction tubes can also be heated electrically with heating jackets.
- a typical dehydrogenation tube bundle reactor comprises approximately 10 to 32,000 reaction tubes.
- the regeneration is carried out by burning off the coke deposited on the catalyst surface in the presence of oxygen.
- air or oxygen which can be diluted with inert gases, is added to the feed gas stream which contains the compound to be dehydrogenated, the content of which in the gas stream can be reduced to 0% by volume during the regeneration.
- the regeneration is carried out at a temperature of generally 200 to 400 ° C.
- the catalytically active composition according to the invention are first at temperatures from 200 to 400 ° C, preferably from 250 to 350 ° C in a period of 1 min to 100 h, preferably 10 min to 24 h, particularly preferably burned off for 30 minutes to 1.5 hours, so that the coke deposited on the catalyst surface burns to form carbon dioxide.
- the combustion is preferably carried out at a temperature around 350 ° C. in an atmosphere of about 1% oxygen in nitrogen, preferably 5% oxygen in nitrogen, particularly preferably about 10% oxygen in nitrogen.
- the atmosphere surrounding the catalytically active composition is flushed with oxygen-free nitrogen.
- the third step in the regeneration is a hydrogen treatment of the catalytically active composition. This is preferably carried out at temperatures in the range from 220 to 280 ° C., particularly preferably from 250 to 270 ° C. in the presence of forming gas. Forming gas with a composition of about 3% hydrogen in nitrogen is particularly preferably used.
- the hydrogen treatment takes place in a period of 1 min to 100 h, preferably 10 min to 24 h, particularly preferably 30 min to 1.5 h.
- the atmosphere surrounding the catalytically active composition is then flushed free of hydrogen.
- working up the liquid water-containing reaction product preferably comprises extraction with an organic solvent, for example dichloromethane, chloroform, methyl tert-butyl ether or ethyl acetate, or an azeotropic distillation with one which is more volatile than the starting material and product organic solvents to remove the water content.
- organic solvent for example dichloromethane, chloroform, methyl tert-butyl ether or ethyl acetate
- an azeotropic distillation with one which is more volatile than the starting material and product organic solvents to remove the water content.
- the distillation of higher-boiling organic compounds for example a mixture of cyclopentanone and 2-cyclopentenone, can be carried out under reduced pressure.
- a bottom liquefier, for example propylene carbonate is preferably added to reduce the thermal load on the higher-boiling components to be distilled.
- the examples show the production of various catalytically active compounds and their testing for catalytic properties. Unless otherwise stated in the individual examples, 1 ml of the respective catalytically active composition is used for the test.
- Example 1 Pd-Rh-Bi-Co on steatite (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 2 Pd-Rh-Bi-Ag on steatite (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 3 Pd-Rh-Bi-Pt on steatite (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates. After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 5 Pd-Bi-Au on steatite (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 6 Pd-Bi-Rh on steatite (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 7 Pd-Bi-Rh on steatite (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 h.
- the calcination is then carried out for 3 h at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 8 Pd-Bi on steatite (total loading: 2% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 h.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 9 Pd-Bi-Rh-Sb on steatite (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- butyraldehyde At 350 ° C and a GHSV of 3000 h _1 (1% butyraldehyde, 4% oxygen, 20% water in nitrogen), 54.0% butyraldehyde was converted with a selectivity to crotonaldehyde of 33.7%. This corresponds to a yield of crotonaldehyde of 18.2%.
- Example 10 Pd-Bi-Rh-Pt on silicon carbide (total loading: 3% by weight)
- the corresponding amount of the solutions is applied by pipette at 4 different locations on the ceramic support.
- the material is then dried in a drying cabinet at 80 ° C. for 16 hours.
- the calcination is then carried out for 3 hours at 550 ° C. in a nitrogen atmosphere (6 Nl / min N 2 ).
- 1 ml of the material is introduced into a stainless steel tube reactor (inert under the reaction conditions, no activity with regard to the target reaction) and heated from the outside to the reaction temperature.
- the product gas analysis is carried out via GC / MS with an HP-5-MS column for the separation and determination of the oxygenates.
- the active mass After conditioning under feed conditions (see below), the active mass achieves its optimal catalytic performance after 3-7 days.
- Example 1 The material from Example 1 (installation of 1 ml of catalyst volume in the test reactor) became representative of the entire claimed material class at 300 ° C and the feed conditions: 1% butyraldehyde, 4% O 2 , 25% H 2 O and the rest N 2 at various Gas pollution tested. The results are shown in Figure 1.
- the maximum yield (conversion approx. 60%, selectivity approx. 60%) at gas loads between 6000 h "1 and 7000 h " 1 can be clearly seen.
- the maximum selectivity of approx. 68% with approx. 45% conversion is 10,000 h "1 .
- Example 2 The material from Example 1 (installation of 1 ml of catalyst volume in the test reactor) was representative of the entire claimed material class at 300 ° C. and the feed conditions 1% butyraldehyde, 22% H 2 O, GHSV 7000 h "1 and rest N 2 at different oxygen partial pressures The results are shown in Figure 2. The maximum yield at oxygen partial pressures between 3% and 5% can be seen clearly, the maximum selectivity of about 45% at about 35% conversion is 1% O 2 and the maximum of Yield at 5% O 2 (conversion 60%, selectivity 40%, yield 24%).
- Example 2 The material from Example 2 (installation of 1 ml of catalyst volume in the test reactor) became representative of the entire claimed material class at various temperatures and feed conditions: 1% butyraldehyde, 4% O 2 , 15% H 2 O, rest N 2 and GHSV 10000 h "1 tested. The results are shown in Figure 3. The yield maximum at 310 ° C (conversion about 55%, selectivity about 75%, yield about 40%) can be clearly seen. The maximum selectivity is 290 ° C (conversion approx. 30%, selectivity approx. 83%).
- Example 1 The material from Example 1 (installation of 1 ml of catalyst volume in the test reactor) was representative of the entire material class claimed for various Water content at 300 ° C and the feed conditions: 1% butyraldehyde, 4% O 2 , rest N 2 and GHSV 5000 h '1 tested. The results are shown in Figure 4. The maximum yield at 25% H 2 O (conversion approx. 70%, selectivity approx. 45%, yield approx. 30%) can be clearly seen. The maximum selectivity is 10% water content (conversion approx. 60%, selectivity approx. 50%).
- Example 15 Various catalytically active compositions comprising an active component on steatite (total loading 3% by weight)
- the materials 11 to 19 were produced analogously to example 1.
- a catalyst was obtained which had the composition Pdo , 6% Bi ⁇ , o % Rh ⁇ , 33% Ago , o 8 o / J steatite, indices the mass of the respective element, based on the weight of the support, in% by weight specify.
- the catalyst was prepared as described in Example 16. A catalyst of the composition Pd 1> 5% Bi 1 , 5 o / o Co 0 , o % steatite was obtained.
- Figures 1 to 4 show the conversion ( ⁇ [%]), selectivity of CRA formation ( ⁇ [%]) and CRA yield (A [%]) of the catalytic conversion of butyraldehyde to crotonaldehyde (CRA), which according to examples 11 were obtained to 14, depending on the (each au f ⁇ he ⁇ _Achse applied) GHSV [h “1] ( Figure 1), the oxygen partial pressure [%] ( Figure 2), the reaction temperature [° C] ( Figure 3) and the water content [%] ( Figure 4) again.
- Example 21 Pd-Rh-Bi on steatite (total loading 3% by weight)
- the solution (total 1,400 ⁇ L, corresponding to the previously determined water absorption of the steatite carrier) is applied to the steatite using a pipette.
- the impregnated material is then dried in a drying cabinet at 80 ° C. for 16 hours. It is then calcined in a muffle furnace at 550 ° C. in a nitrogen atmosphere for 3 h.
- Catalysts of different compositions were prepared analogously to Example 21 and tested analogously to Example 22 for their catalytic activity in the dehydrogenation of cyclohexanone to 2-cyclohexenone.
- the catalyst composition, feed composition and conversion, selectivity and yield of the dehydrogenation of cyclohexanone to 2-cyclohexenone carried out on these catalysts are summarized in Table 14 below.
- Catalysts of different compositions were prepared analogously to Example 21 and tested for their catalytic activity in the dehydrogenation of isovaleraldehyde to prenal analogously to Example 22.
- the catalyst composition, feed composition and conversion, selectivity and yield of the dehydrogenation of isovaleraldehyde to prenal carried out on these catalysts are summarized in Table 15 below.
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Abstract
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EP05701242A EP1711452A2 (de) | 2004-01-30 | 2005-01-28 | Katalytisch aktive zusammensetzung und ihre verwendung in dehydrierverfahren |
US10/587,191 US7495132B2 (en) | 2004-01-30 | 2005-01-28 | Catalytically active composition and the use thereof in dehydration methods |
JP2006550119A JP2007519517A (ja) | 2004-01-30 | 2005-01-28 | 触媒活性組成物及びその脱水素法における使用 |
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DE102004004801.0 | 2004-01-30 | ||
DE200410004801 DE102004004801A1 (de) | 2004-01-30 | 2004-01-30 | Katalytisch aktive Zusammensetzung und ihre Verwendung in Dehydrierverfahren |
DE200410043495 DE102004043495A1 (de) | 2004-09-08 | 2004-09-08 | Katalytisch aktive Zusammensetzung und ihre Verwendung in Dehydrierverfahren |
DE102004043495.6 | 2004-09-08 |
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US (1) | US7495132B2 (de) |
EP (1) | EP1711452A2 (de) |
JP (1) | JP2007519517A (de) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008006792A1 (de) | 2006-07-11 | 2008-01-17 | Basf Se | Verfahren zur dehydrierung von alkoholen |
EP3257831A3 (de) * | 2016-06-16 | 2018-03-21 | International Flavors & Fragrances Inc. | Kreislaufwirtschaftsverfahren zur herstellung von ungesättigten verbindungen |
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GB2478981B (en) * | 2010-03-26 | 2012-02-15 | Univ Southampton | Fuel cell, catalyst and methods |
JP6094428B2 (ja) * | 2013-08-22 | 2017-03-15 | 宇部興産株式会社 | シクロヘキサノンの製造方法及びその装置 |
EP3475256B1 (de) * | 2016-06-27 | 2024-01-24 | Firmenich SA | Dehydrierungsreaktion |
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- 2005-01-28 WO PCT/EP2005/000867 patent/WO2005073157A2/de not_active Application Discontinuation
- 2005-01-28 JP JP2006550119A patent/JP2007519517A/ja active Pending
- 2005-01-28 US US10/587,191 patent/US7495132B2/en not_active Expired - Fee Related
- 2005-01-28 EP EP05701242A patent/EP1711452A2/de not_active Withdrawn
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008006792A1 (de) | 2006-07-11 | 2008-01-17 | Basf Se | Verfahren zur dehydrierung von alkoholen |
JP2009542772A (ja) * | 2006-07-11 | 2009-12-03 | ビーエーエスエフ ソシエタス・ヨーロピア | アルコールの脱水素法 |
US7847129B2 (en) | 2006-07-11 | 2010-12-07 | Basf Aktiengesellschaft | Method for dehydrogenating alcohols |
CN101489967B (zh) * | 2006-07-11 | 2012-06-20 | 巴斯夫欧洲公司 | 醇的脱氢方法 |
EP3257831A3 (de) * | 2016-06-16 | 2018-03-21 | International Flavors & Fragrances Inc. | Kreislaufwirtschaftsverfahren zur herstellung von ungesättigten verbindungen |
US10435345B2 (en) | 2016-06-16 | 2019-10-08 | International Flavors & Fragrances Inc. | Circular economy methods of preparing unsaturated compounds |
EP3628653A1 (de) * | 2016-06-16 | 2020-04-01 | International Flavors & Fragrances Inc. | Kreislaufwirtschaftsverfahren zur herstellung von ungesättigten verbindungen |
US11753360B2 (en) | 2016-06-16 | 2023-09-12 | International Flavors & Fragrances Inc. | Circular economy methods of preparing unsaturated compounds |
Also Published As
Publication number | Publication date |
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EP1711452A2 (de) | 2006-10-18 |
TW200530171A (en) | 2005-09-16 |
US20070167318A1 (en) | 2007-07-19 |
US7495132B2 (en) | 2009-02-24 |
WO2005073157A3 (de) | 2006-04-27 |
JP2007519517A (ja) | 2007-07-19 |
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