EP2231329A2 - Katalysatorpulver - Google Patents
KatalysatorpulverInfo
- Publication number
- EP2231329A2 EP2231329A2 EP08870192A EP08870192A EP2231329A2 EP 2231329 A2 EP2231329 A2 EP 2231329A2 EP 08870192 A EP08870192 A EP 08870192A EP 08870192 A EP08870192 A EP 08870192A EP 2231329 A2 EP2231329 A2 EP 2231329A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- particles
- catalyst
- precipitation
- catalyst powder
- catalytically active
- 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.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 53
- 150000002739 metals Chemical class 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- 150000004679 hydroxides Chemical class 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011164 primary particle Substances 0.000 claims description 10
- 239000012876 carrier material Substances 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 150000001722 carbon compounds Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910003174 MnOOH Inorganic materials 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—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
- 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
- B01J23/72—Copper
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
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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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Definitions
- carbon nanotubes carbon nanotubes
- CCVD process catalytic carbon vapor deposition
- the contacting of catalytically active Metals with the gaseous carbon compound, in particular low molecular weight hydrocarbons takes place in a fixed bed (powder bed), in a moving fixed bed or in a fluidized bed.
- the catalyst is used in a calcined form in the reactor, wherein the beginning of the reaction, the active centers of the catalyst are reduced from oxide to metal.
- the diameter of the carbon nanotubes and fibers is determined essentially by the dimension of the catalytically active metal particles.
- the metal particles whose dimensions must be in the nanometer range, and to ensure the handling of the catalysts, they are applied to catalytically inert support materials, usually oxide ceramics, which are not reduced by hydrogen in the catalytically reaction, so that they are superficial domains of catalytically active Form metals whose dimensions determine the diameter of the fibers.
- a disadvantage of the CCVD process is that the catalyst becomes inactive in the reaction by increasing the access of the gaseous carbon compound to the catalytically active domains by the fibers formed is hampered.
- the yield of CNT per g of catalyst is dependent on the starting carbon compounds, the type of catalyst, its structure and the process conditions such as temperature, pressure, concentration, etc.
- EP 1401763 B1 is based on finely divided aluminum hydroxide
- Support material which is recovered from a gel by drying and milling, which is mixed with a solution of cobalt acetate and iron nitrate in a mortar and then dried.
- Other support materials such as oxides, hydroxides and carbonates of calcium, magnesium, cerium, titanium and lanthanum and their combinations and catalytically active metals Ni, Cu, V, Mo and Sn and mixtures thereof are also described.
- the weight ratio of carrier material to catalytically active metals is about 30: 1. It is achieved a yield of up to 200% carbon nanotubes or fibers based on the weight of the catalyst. The catalyst must therefore be removed from the carbon nanotubes or fibers consuming.
- such a multi-stage production process for the catalyst is complicated and leads only to a small proportion of catalytically active metals, correspondingly low yields of CNT based on the catalyst.
- WO 2006/050903 a single-stage precipitation process for the catalyst is also already disclosed in which support material and active metals are precipitated together from aqueous solutions of the respective nitrates.
- the teaching of the WO document is concerned in particular with the optimization of the composition of the catalytically active metals to obtain a high yield of CNT based on the catalyst used, with active metal compositions Mn-Co, which may optionally further contain Mo, with MgO as a carrier material, with 60 mol.% of active metal and 40 mol.% of support metal yields of 5 to 350 times CNT based on the weight of the catalyst.
- Catalyst is therefore not required in most applications.
- the co-precipitation of catalytically active metals and support material is, however, in relation to the desired properties for the preparation of CNT (reproducible catalytic activity and uniformity of dimensions of the catalytically active domains) difficult to control.
- the processing of the nitrate-containing mother liquor from the precipitation which is already necessary for reasons of environmental protection, is complicated.
- the catalyst particles consisting of support materials and domains of catalytically active metals have sufficient fluidity with regard to handling, ie have at least an average particle size in the range of a few ⁇ m, and, on the other hand, decay during the catalytic process, so that the catalytically active domains or primary particles remain well accessible or accessible even with growing CNT for the gaseous starting carbon compound. Due to the co-precipitation of support materials and catalytically active metals as hydroxides and subsequent thermal conversion into oxides, it comes to a strong, the disintegration of
- the object of the invention is to provide a simple process for the preparation of catalysts, which overcomes the disadvantages of the prior art.
- the precipitation of catalytically active metals and support materials from corresponding salt solutions takes place locally without any intermediate work-up prior to the combination of locally separate precipitation suspensions.
- This makes it possible, in particular to control the precipitation of the catalytically active metals in the sense of a uniform particle size to produce uniform diameter of the CNT and to produce clearly separated primary particles of support materials and catalytically active metals.
- the novel process is preferably based on a sulfate system, ie the starting compounds for the catalytically active metals and the support materials are used as aqueous sulfate solutions.
- chlorides also leads to good products and is unproblematic in terms of wastewater.
- the precipitation is preferably carried out by means of alkali hydroxide, in particular ammonia and / or sodium hydroxide solution, so that after removal of the precipitated solid, a mother liquor containing readily worked-up ammonium sulfate and / or sodium sulfate is formed.
- alkali hydroxide in particular ammonia and / or sodium hydroxide solution
- the precipitation preferably takes place in a common container with two regions for mixing the salt solution containing the catalytically active metals with the base solution on the one hand and the carrier material salt solution with the mother liquor or further base solution on the other hand. This allows the separate control of the precipitation conditions such as pH, concentration and temperature for the precipitation of catalytically active metals on the one hand and
- the two mixing ranges are expediently equipped with one stirrer each.
- the mixture may also be characterized by e.g. tangential or countercurrent injection of the respective reaction solutions in the respective mixing area.
- the mixing range for precipitating the catalytically active metals is preferably less than 1/100, more preferably less than 1/500, and more than 1/3000 of the container volume, with a correspondingly short residence time in the mixing range of less than one minute.
- Suitable catalytically active metals are unstable carbide-forming metals, in particular Fe, Ni, Co, Cu, Mn, Sn and Zn and mixtures thereof. They are present after the precipitation as hydroxides or oxyhydroxides. Particularly preferred are mixtures of Co and Mn in the ratio of 1: 3 to 3: 1 molar, optionally further modified by Mo in an amount up to 10% molar.
- the metal salt solutions of the catalytically active metals are introduced into the region of a first stirrer, wherein a high supersaturation of the mother liquor in the region of the first stirrer is produced, preferably by simultaneous excess introduction of alkali into the region of this first stirrer.
- the pH in the area of the first stirrer becomes lower
- oxygen or oxygen-containing gas such as air can be injected into the region of the first stirrer in order to produce a simultaneous one
- the carrier metal salt solutions are introduced into the second stirrer zone and mixed here with the alkaline mother liquor, wherein the hydroxides of the carrier metal are precipitated.
- a basic solution preferably ammonia solution and / or sodium hydroxide solution
- a pH of 8 to 11 is generally sufficient here.
- the precipitation of the support materials takes place at a pH of 9 to 10.5.
- Preferred support metals are Mg, Al, Ca, Si, Ti, Y, Zr and mixtures thereof, which can be modified by contents of V, Mo and / or W. Preference is given to Mg or Al, in particular Mg, more preferably up to 10 mol% Mo.
- the precipitation conditions for the carrier metal hydroxides are adjusted to produce hydroxide particles having an average diameter of 2 to 10 times the diameter of the hydroxide particles of the catalytically active metals.
- the salts of the catalytically active metals and the salts of the carrier metals are introduced into the reactor in a molar ratio of between 0.2 and 2, preferably between 0.7 and 1.3, calculated as oxides.
- the suspension obtained is stirred for a period of time, so that an agglomeration of the hydroxide particles is effected. This period may extend over 0.5 to 10 hours, preferably 1 to 3 hours.
- different hydroxide particles are initially deposited on each other, so that in the agglomerates predominantly carrier material primary particles are superficially agglomerated with superficial particles of active material.
- Spheroidal agglomerate particles are predominantly obtained which have a mean agglomerate diameter of up to 80 ⁇ m, preferably 2 to 50 ⁇ m, particularly preferably less than 20 ⁇ m.
- the spherical ones Agglomerate particles have a porosity of> 5% by volume, preferably> 10% by volume and more preferably of> 20% by volume.
- the resulting, consisting of carrier primary particles and catalytically active primary particles agglomerates are separated from the mother liquor, washed neutral and dried and calcined in air at 350 to 500 0 C.
- the calcination subsequent to drying may also be carried out immediately before the catalytic process is carried out before or during the activation phase.
- FIG. 1 shows schematically a reactor 1 suitable for the preferably continuous performance of the process according to the invention.
- the reactor has a reactor vessel 2 with two agitators 3 and 4, with corresponding mixing areas in which the agitators develop shearing action on the vessel liquid.
- the stirrer area for the precipitation of the catalytically active metals is shielded by a cylindrical shield plate 5 which is open in the vertical direction. In the volume small
- Stirrer area in the agitator 3 is fed via line 6 in the preferred case, aqueous active metal sulfate solution and via line 7 sodium hydroxide solution and / or aqueous ammonia solution.
- the carrier metal sulfates are fed via line 8 and optionally sodium hydroxide solution and / or ammonia solution via line 9.
- dilution water can be fed via line 10 to control the maturation and agglomeration process of the hydroxides precipitated in the stirrer zones.
- precipitation suspension is withdrawn via line 11.
- a reactor is shown schematically, the third stirrer 12 and a shield 13 for more separate precipitation of the carrier metals having.
- the same reference numerals as in Figure 1 denote the same elements.
- the separation of particles from the mother liquor can be carried out by methods known per se, for example by sedimentation, in cyclones, rotary separators or by filtration.
- the catalyst powders according to the invention can be used for the production of carbon nanotubes and / or carbon fibers.
- a reactor according to FIG. 1 is used.
- the laboratory reactor has a liquid volume of 10 I.
- the stirrer area 3 has a volume of 20 ml.
- the streams 6 to 10 corresponding to the reference numbers in FIG. 1 are supplied at room temperature in the amount and concentration shown in Table 1.
- the material flows are regulated gravimetrically. In each case after setting stationary conditions, the solid is filtered off from the mother liquor over 3 hours, washed neutral on the filter and dried at 150 ° C. and calcined at 420 ° C. in air.
- the average catalyst particle size becomes optically 35 to 40 ⁇ m
- the particles consist of spherically agglomerated carrier particles which are superficially coated with a large number of smaller oxide particles of the catalytically active metals.
- the activity of the catalyst powders is tested as follows: 0.5 g of each
- Catalyst powder are filled in a thin layer in a quartz boat, which is inserted into a quartz glass tube.
- the quartz glass tube is placed in a tube furnace and connected to gas pipes on both sides.
- the Quartz glass tube is rinsed with a mixture of 60 vol .-% hydrogen and 40 vol.% Argon and heated slowly under flowing purge gas to 630 0 C, wherein the oxide particles of the catalytically active metals are reduced to the metal. Due to the consequent decrease in volume of the catalytically active primary particles, there are stresses in the agglomerates which lead to the disintegration of the agglomerates. After 60 minutes then 50% of the purge gas is replaced by ethene (ethylene).
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102008004135.1A DE102008004135B4 (de) | 2008-01-11 | 2008-01-11 | Katalysatorpulver |
PCT/EP2008/067877 WO2009087040A2 (de) | 2008-01-11 | 2008-12-18 | Katalysatorpulver |
Publications (1)
Publication Number | Publication Date |
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EP2231329A2 true EP2231329A2 (de) | 2010-09-29 |
Family
ID=40718845
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP08870192A Withdrawn EP2231329A2 (de) | 2008-01-11 | 2008-12-18 | Katalysatorpulver |
Country Status (4)
Country | Link |
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EP (1) | EP2231329A2 (de) |
DE (1) | DE102008004135B4 (de) |
TW (1) | TWI433728B (de) |
WO (1) | WO2009087040A2 (de) |
Families Citing this family (3)
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DE102013214229A1 (de) * | 2013-07-19 | 2015-01-22 | Bayer Materialscience Ag | Verfahren zur Herstellung eines effizienten Katalysators für die Produktion mehrwandiger Kohlenstoffnanoröhrchen, mehrwandiges Kohlenstoffnanoröhrchen und Kohlenstoffnanoröhrchenpulver |
EP2835177A1 (de) * | 2013-08-06 | 2015-02-11 | Bayer Technology Services GmbH | Herstellung von Co-Mn Katalysatoren auf einem Kohlenstoffträger und Verwendung zur Herstellung von Kohlenstoffnanoröhren |
DE102015108749A1 (de) | 2015-06-02 | 2016-12-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur großmaßstäblichen, nasschemischen Herstellung von ZnO Nanopartikeln mit Hilfe von Luftblasen |
Family Cites Families (13)
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AT36124B (de) | 1905-04-17 | 1909-02-10 | Albert Hellwig | Apparat zur Beschleunigung des Filtrierens und Auslaugens extrakthaltiger Substanzen. |
NL190750C (nl) * | 1984-06-21 | 1994-08-01 | Unilever Nv | Nikkelaluminaat katalysator, de bereiding daarvan en het hydrogeneren van onverzadigde organische verbindingen daarmee. |
EP0200315A3 (de) * | 1985-03-25 | 1988-05-25 | Imperial Chemical Industries Plc | Katalysatoren |
CA1321863C (en) * | 1986-06-06 | 1993-09-07 | Howard G. Tennent | Carbon fibrils, method for producing the same, and compositions containing same |
IT1248656B (it) * | 1990-05-29 | 1995-01-26 | Mini Ricerca Scient Tecnolog | Processo per la produzione del precursore di un catalizzatore precipitato per la sintesi dell`ammoniaca. |
JP3858625B2 (ja) * | 2000-07-27 | 2006-12-20 | 株式会社豊田中央研究所 | 複合酸化物とその製造方法及び排ガス浄化用触媒とその製造方法 |
FR2826596B1 (fr) * | 2001-06-28 | 2004-08-13 | Toulouse Inst Nat Polytech | Compositon catalytique pour la fabrication selective de nanotubes de carbone ordonne en lit fluidise, et son procede de fabrication |
US7572427B2 (en) | 2001-07-03 | 2009-08-11 | Facultes Universitaires Notre-Dame De La Paix | Catalyst supports and carbon nanotubes produced thereon |
JP3797313B2 (ja) * | 2002-10-28 | 2006-07-19 | トヨタ自動車株式会社 | 金属酸化物粒子の製造法及び排ガス浄化用触媒 |
WO2005115612A1 (en) * | 2004-05-28 | 2005-12-08 | Mintek | Catalyst containing gold on support containing zinc oxide and production and use thereof |
DE102004054959A1 (de) * | 2004-11-13 | 2006-05-18 | Bayer Technology Services Gmbh | Katalysator zur Herstellung von Kohlenstoffnanoröhrchen durch Zersetzung von gas-förmigen Kohlenverbindungen an einem heterogenen Katalysator |
DE102005032071A1 (de) * | 2005-07-08 | 2007-01-11 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung e.V. | Nanoporöse Katalysatorteilchen, deren Herstellung und deren Verwendung |
DE102006007147A1 (de) * | 2006-02-16 | 2007-08-23 | Bayer Technology Services Gmbh | Verfahren zur kontinuierlichen Herstellung von Katalysatoren |
-
2008
- 2008-01-11 DE DE102008004135.1A patent/DE102008004135B4/de not_active Expired - Fee Related
- 2008-12-18 WO PCT/EP2008/067877 patent/WO2009087040A2/de active Application Filing
- 2008-12-18 EP EP08870192A patent/EP2231329A2/de not_active Withdrawn
-
2009
- 2009-01-09 TW TW098100550A patent/TWI433728B/zh active
Non-Patent Citations (1)
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See references of WO2009087040A2 * |
Also Published As
Publication number | Publication date |
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WO2009087040A2 (de) | 2009-07-16 |
TWI433728B (zh) | 2014-04-11 |
TW200948478A (en) | 2009-12-01 |
DE102008004135B4 (de) | 2014-03-06 |
DE102008004135A1 (de) | 2009-07-23 |
WO2009087040A3 (de) | 2012-03-29 |
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