USH1948H1 - High-activity catalyst for hydrogen peroxide decomposition - Google Patents
High-activity catalyst for hydrogen peroxide decomposition Download PDFInfo
- Publication number
- USH1948H1 USH1948H1 US09/045,127 US4512798A USH1948H US H1948 H1 USH1948 H1 US H1948H1 US 4512798 A US4512798 A US 4512798A US H1948 H USH1948 H US H1948H
- Authority
- US
- United States
- Prior art keywords
- catalyst
- hydrogen peroxide
- substrate
- mixture
- promoter
- 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.)
- Abandoned
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 44
- 230000000694 effects Effects 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 99
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 27
- -1 transition metal cation Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000011363 dried mixture Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 239000003380 propellant Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000001307 helium Substances 0.000 description 14
- 229910052734 helium Inorganic materials 0.000 description 14
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 14
- 150000003624 transition metals Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011067 equilibration Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000002760 rocket fuel Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- YZTQKMVBEGUONQ-UHFFFAOYSA-N manganese(4+) Chemical compound [Mn+4] YZTQKMVBEGUONQ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B01J35/56—
-
- 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
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/76—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
- B01J23/78—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 alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0211—Peroxy compounds
- C01B13/0214—Hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/04—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by auto-decomposition of single substances
-
- 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
-
- 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 high-activity hydrogen peroxide decomposition. More particularly, the present invention uses an activated catalyst for high-activity hydrogen peroxide decomposition. Most particularly, the high-activity hydrogen peroxide decomposition is sufficiently rapid enough to provide thrust within rocket and/or other power systems.
- Catalysts are used in the decomposition of hydrogen peroxide (H 2 O 2 ) for monopropellant thrusters, liquid rocket engines, hybrid rocket systems and the like. Hydrogen peroxide decomposes into water vapor and oxygen. The oxygen product can react with conventional rocket fuel or grains to provide thrust.
- hydrogen peroxide has been successfully used as an oxidizer for U.S. Navy torpedo systems, U.S.A.F. attitude control thruster“s on the X-15, and for reaction control thrusters on the NASA Scout launch vehicles and Mercury spacecraft.
- Catalyst are formed into packs by using layers of nitric acid or samarium salt activated silver plated screens.
- hydrogen peroxide decomposition activity is relatively low.
- increasing the number of screens also increases the activity, but also increases the pressure drop.
- Contaminants within the hydrogen peroxide may also plate out onto the silver screens. This reduces the active surface area, which in turn reduces the effective decomposition of the hydrogen peroxide. Additionally, the cost of the materials and fabrication are high.
- the present invention provides a high-activity hydrogen peroxide decomposition catalyst comprising an impregnated and calcined substrate with a catalyst mixture, the catalyst mixture comprising a hydrogen peroxide catalytically active compound containing a transition metal cation mixed with an alkaline promoter, wherein the substrate further comprises a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof.
- the invention further provides a process for forming a high-activity hydrogen peroxide decomposition catalyst comprising the steps of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof; mixing, in an aqueous solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter; applying the mixture over the substrate, wherein the mixture soaks the substrate surface area, thereby impregnating the substrate; drying the applied soaked mixture sufficiently causing the removal of the solvent; and calcining the dried mixture sufficiently to form an activated catalyst.
- the invention provides a product of high-activity hydrogen peroxide decomposition made by the process of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof; mixing, in a solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter; applying the mixture over the substrate, wherein the mixture soaks the substrate surface area, thereby impregnating the substrate; drying the applied soaked mixture sufficiently causing the removal of the solvent; calcining the dried mixture, wherein an activated catalyst is formed; housing the formed activated catalyst into a hydrogen peroxide reaction chamber having a hydrogen peroxide inlet port; and, flowing a compound of hydrogen peroxide through the inlet port wherein the hydrogen peroxide comes in contact with the calcined, impregnated substrate with mixture, wherein the hydrogen peroxide decomposes in a high-
- FIG. 1 is a side cross-sectional view of a singular cellular matrix activated catalyst substrate of the present invention in housing;
- FIG. 2 is a side view of the polar substrate surface bonded with manganese and potassium ions with are further bonded to oxygen;
- FIG. 3 is a schematic side view of a propulsion system of the present invention using a hydrogen peroxide mono-propellant
- FIG. 4 is a schematic side view of a rocket propulsion system of the present invention using a hydrogen peroxide mono-propellant
- FIG. 5 is a schematic side view of a rocket propulsion system of the present invention using a hydrogen peroxide bi-propellant
- FIG. 6 is a schematic side view of a rocket propulsion system of the present invention using hydrogen peroxide in a hybrid rocket propulsion system.
- the present invention is a hydrogen peroxide decomposition catalyst and process for high activity hydrogen peroxide decomposition, and the product of high-activity hydrogen peroxide decomposition.
- the present invention comprises a combination catalyst and promoter on a polar substrate to provide sufficiently rapid decomposition of hydrogen peroxide for use as a propellant in rocket thrusters and/or other motor systems.
- the decomposed hydrogen peroxide provides an environmentally clean product of water vapor and oxygen, which may also be used for additional systems.
- Decomposition of hydrogen peroxide provides chemical energy to perform work, such as powering rocket, turbine, electric, other propulsion and auxiliary equipment and the like.
- the hydrogen peroxide based propellant reduces toxic emissions, increases reliability and efficiency, reduces sound, and obscures carrier signature relative to conventional fuels.
- the present invention comprises an activated catalyst substrate 102 which may be placed in a rocket or similar housing 46 and held in place by end screens 14 within the housing 46 .
- the activated substrate 102 includes a high-activity hydrogen peroxide decomposition catalyst which has been included therein.
- the activated substrate 102 comprises a porous support material, such as alumina, silica, aluminosilicate, polar ceramics and combinations thereof.
- the activated substrates 102 have a porous surface, which maximizes the amount of catalyst impregnated and calcined thereon. Additionally, the activated substrates 102 are polar which allows a catalyst to properly arrange along the surface of the activated substrate 102 , thereby providing an activated catalyst.
- the activated substrates 102 are high temperature and non-oxidizing to withstand the temperature occasioned by the decomposition of the hydrogen peroxide.
- the temperature of decomposing hydrogen peroxide is proportional to the percentage of hydrogen peroxide available in a given propellant. For example, 100% by mass hydrogen peroxide yields a reaction product with an adiabatic decomposition temperature of 1824° F., 95% by mass hydrogen peroxide yields 1593° F., 90% by mass hydrogen peroxide yields 1364° F., 80% by mass hydrogen peroxide yields 908° F., 50% by mass hydrogen peroxide yields 212° F., and 35% by mass hydrogen peroxide yields 212° F. Any oxidizable activated catalyst substrate 102 becomes inefficient with the decomposition of the hydrogen peroxide, providing limited use.
- the activated substrate 102 may comprise a singular structured polar substrate, as shown in FIG. 1, or multiple polar substrates.
- the activated substrate 102 comprises a singular structure. More preferably, the singularly structured activated substrate 102 comprises a matrix. Most preferably, the matrix comprises a cellular matrix.
- Activated substrates 102 may include, but is not limited to, pellets, spheres, grids, and the like.
- the activated substrate 102 may be loaded within the housing 46 by placing the activated substrate 102 in line between an H 2 O 2 pressurized storage tank and an expansion chamber.
- the storage tank and expansion chamber may be any configuration which promotes the efficiency of the system, such as being cylindrical, the configuration of which is detenninable by those skilled in the art.
- the activated substrate 102 is held in place by end capture or metallic end screens 14 or other similar fixed systems, as shown in FIG. 1 .
- the activated substrate 102 is formed by impregnating and calcining a polar substrate with a catalyst mixture.
- the catalyst mixture comprises a hydrogen peroxide catalytically active compound containing a transition metal cation mixed with an alkaline promoter.
- the transition metal may be any of the elements from Groups VB, VIB, VIIB, VIII and IB of the Periodic Table of Elements, specifically listed as vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb), molybdenum (Mo), technetium (Te), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Au), tantalum (Ta), wolfram (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt) and gold (Ag).
- V vanadium
- the catalyst mixture comprises a transition metal cation selected from the group consisting of Mn, Ag, Ru, V, Fe, Cr, Co and mixtures thereof.
- transition metal cation selected from the group consisting of Mn, Ag, Ru, V, Fe, Cr, Co and mixtures thereof.
- valence states of certain transition metal cations used in the present invention include Mn +4 , Ru +4 , V +5 , CU +4 , Cr +4 , Cr +3 , Co +2 , Co + , and the like, within valence-corresponding salts thereof.
- the catalyst mixture comprises a cation selected from the group consisting of tetravalent manganese and tetravalent copper.
- the catalyst mixture comprises tetravalent manganese.
- the alkaline promoter may be any compound which provides a basic solution containing elements from Groups IA and IIA of the Periodic Table of Elements.
- the alkaline promoter contains an ion such as lithium (Li + ), potassium (K + ), sodium (Na + ), and ammonium (NH 4 + ). More preferably, the alkaline promoter contains K + ions, Na + ions, and/or combinations thereof.
- the alkaline promoter provides high stability when used in conjunction with the transition metal and polar substrate.
- the promoter and transition metal are mixed in defined molar proportions.
- the promoter and transition metal are mixed at a molar ratio of from about 0.5 to about 4.0, more preferably at a molar ratio of from about 1.0 to about 3.0, and most preferably at a molar ratio of from about 1.0 to about 2.0.
- the weight of the polar substrate is measured in relation to the weight of the calcined metals of both the transition metal and promoter of the catalyst mixture.
- the polar substrate comprises from about 0.01 weight percent to about 85.0 weight percent of the transition metal and promoter. More preferably, the polar substrate comprises from about 0.5 weight percent to about 10.0 weight percent of the transition metal and promoter. Most preferably, the polar substrate comprises from about 1.0 weight percent to about 20.0 weight percent of the transition metal and promoter.
- manganese (+4) and potassium may have a 1% weight/weight (w/w) loading on the polar substrate.
- the process for forming the high-activity hydrogen peroxide decomposition catalyst comprises the steps of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof; mixing, in a solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter; applying the mixture over the polar substrate, wherein the mixture soaks the polar substrate surface area, thereby impregnating the polar substrate; drying the applied soaked mixture sufficiently causing the removal of the solvent; and calcining the dried mixture sufficient to form an activated catalyst.
- Soluble salts of the transition metal cation and alkaline promoter are mixed into a solvent to form a catalyst mixture.
- Examples of such salts include, but are not limited to, KMnO 4 , RuCl 3 , NH 4 VO 3 , (NH 4 ) 2 Cr 2 O 7 , and/or Co(NO 3 ) 2 .
- the solvent includes aqueous and non-aqueous solutions which are suited to dissolving the transition metal cation salt and the alkaline promoter, the type of the solution being detenninable by those skilled in the art.
- the solvent comprises water. More preferably, the water solvent is distilled or deionized water.
- the solvent solution containing the mixture of transition metal cation and alkaline promoter is applied over the polar substrate.
- the application may include pouring the solution onto the polar substrate, submerging the polar substrate into the solution, and other like applications of the solution against the polar substrate which is sufficient to wet the polar substrate in bulk.
- the application of the catalyst mixture lasts for a suitable equilibration time, which allows the catalyst mixture to soak into and around the polar substrate surface area.
- the equilibration time is determinable by those skilled in the art, and preferably ranges from about 10 minutes to about 60 minutes.
- the catalyst mixture soaked polar substrate is dried in an oven sufficiently to evaporate or remove the solution, which deposits or impregnates the transition metal and promoter from the catalyst mixture on the polar substrate.
- the deposited catalyst is activated by calcination of the mixture covered polar substrate forming the activated substrate 102 . Calcining the mixture occurs by heating the impregnated polar substrate in an open atmosphere. For example, KMnO 4 transforms to a mixture of MnO 2 and K 2 O after calcination.
- the calcined mixture forms conditional metal oxides of the catalysts doped or impregnated thereon, which cause hydrogen peroxide to more readily decompose by lowering the activation energy (E a ) for decomposition.
- Heating temperatures and times vary with the selection of promoter, transition metal, amount of solvent, type of polar substrate, and the like, with the temperature and heat time being determinable by those skilled in the art.
- the impregnated mixture is preferably calcined at from about 150° C. to about 950° C. for a time period of from about 30 minutes to about 24 hours.
- FIG. 2 shows the conditional metal oxides formed on the activated substrate 102 that vary from site to site, but maintain proper stoichiometry.
- oxides of the transition metal and promoter generally form traditional bonds, such as MnO 2 , Ag 2 O, RuO 2 , V 2 O 5 , CrO 2 , Co 2 O 3 , and the like.
- the calcined combination of the polar substrate surface with the transition metal and promoter create a surface area possessing other oxide forms, such as K 2 O, and similar oxide configurations containing Li, Na, and NH 4 .
- these elements possess the general oxide structure, which varies from site to site, on the activated substrate 102 in a stable condition.
- bonds form to create such chemical forms of MnO 2 •K 2 O, which may be schematically represented as shown in FIG. 2 .
- the compounds Mn and K are attached to the polar substrate and further bond to oxygen molecules.
- the decomposition of hydrogen peroxide along the surface of the metal oxide covered activated substrate 102 does not dissipate or otherwise significantly degrade the activated substrate 102 . Significant degradation would exist when hydrogen peroxide decomposition diminishes such that the hydrogen peroxide does not function as a propellant.
- the activated substrate 102 of the present invention containing a highly porous polar substrate impregnated with a calcined transition metal and promoter, facilitates the decomposition of H 2 O 2 to a degree permitting such use of the H 2 O 2 as a rocket propellant when H 2 O 2 is flowed through an activated catalyst chamber containing the activated catalyst substrate 102 .
- a low pressure drop occurs with the highly catalytic contact of the H 2 O 2 on the activated substrate 102 .
- the decomposition of the H 2 O 2 occurs according to the following reaction:
- FIGS. 3, 4 , 5 and 6 illustrate a product of high-activity hydrogen peroxide decomposition 106 .
- the high-activity hydrogen peroxide decomposition 106 is made by the process of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof mixing, in a solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter, applying the mixture over the polar substrate, wherein the mixture soaks the polar substrate surface area, thereby impregnating the polar substrate, drying the applied soaked mixture sufficiently causing the removal of the solvent, calcining the dried mixture, wherein an activated catalyst, or activated substrate 102 is formed, housing the formed activated catalyst into a hydrogen peroxide reaction chamber 32 having a hydrogen peroxide inlet port or valve 34 , and, flowing a compound of hydrogen peroxide 36 through the
- the hydrogen peroxide 36 propellant may comprise from about 85% by mass or greater hydrogen peroxide, preferably from about 90% by mass hydrogen peroxide or greater, more preferably from about 95% by mass hydrogen peroxide or greater, and most preferably from about 98% by mass hydrogen peroxide or greater.
- the higher mass percentage of hydrogen peroxide 36 provides the greatest versatility in energy conversion, and the level of hydrogen peroxide 36 would be determinable by those skilled in the art applicable for a particular use.
- the present invention may comprise a mono-propellant, bi-propellant or multi-propellant hydrogen peroxide device.
- the present invention comprises a mono-propellant of hydrogen peroxide. More preferably, the hydrogen peroxide monopropellant consists essentially of hydrogen peroxide.
- the energy released from the high-activity hydrogen peroxide decomposition 106 is measured as adiabatic decomposition temperature. For example, at one atmosphere, 100% by mass hydrogen peroxide yields a reaction product with an adiabatic decomposition temperature of 1824° F., 95% by mass hydrogen peroxide yields 1593° F., 90% by mass hydrogen peroxide yields 1364° F., 80% by mass hydrogen peroxide yields 908° F., and from about 64.7% or less by mass hydrogen peroxide yields 212° F.
- the high-activity hydrogen peroxide decomposition 106 may propel any object capable of housing the hydrogen peroxide decomposition, preferably a rocket motor or steam engine.
- FIG. 3 illustrates the activated substrate 102 housed within a propulsion system 68 , such as a rocket, steam turbine or gas-generator, and other like movable or stationary systems, using hydrogen peroxide 36 as a mono-propellant.
- the activated substrate 102 is housed or packed into a motor or other decomposition-type chamber 32 to provide energy for movement, such as a steam turbine.
- a pressurized tank of helium (He) 42 flows helium through an open valve 44 and into a pressurized H 2 O 2 tank 45 .
- the helium pressurizes against the H 2 O 2 36 in the pressurized H 2 O 2 tank 45 , causing the H 2 O 2 36 to flow through an open valve 34 in flowline 50 , and through the activated substrate 102 .
- the contact of the H 2 O 2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H 2 O 2 36 , forming high temperature steam and oxygen within the expansion chamber 32 .
- the decomposed H 2 O 2 36 further flows into a steam turbine 48 and impinge on rotary blades, which propels the stream turbine 48 .
- the superheated steam is preferably heated to from about 1000° F. to about 1800° F., more preferably from about 1100° F.
- the temperature range for the superheated steam varies by use, and may be determined by those skilled in the art. Propulsion may be obtained using the decomposed H 2 O 2 36 from the activated substrate 102 without combustion of other reactants.
- FIG. 4 illustrates the propulsion system 68 shown in FIG. 3 as a rocket mono-propellant of hydrogen peroxide.
- the pressurized tank of helium (He) 42 flows helium through the open valve 44 and into the pressurized H 2 O 2 tank 45 .
- the helium pressurizes against the H 2 O 2 36 in the pressurized H 2 O 2 tank 45 , causing the H 2 O 2 36 to flow through the open valve 34 in flowline 50 , and through the activated substrate 102 .
- the contact of the H 2 O 2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H 2 O 2 36 , forming high temperature steam and oxygen within the expansion chamber 32 .
- Propulsion occurs when the high temperature steam and oxygen within the expansion chamber 32 flow out of a rear nozzle 52 into a jet stream 54 . Propulsion may be obtained using the decomposed H 2 O 2 36 from the activated substrate 102 without combustion of other reactants.
- FIG. 5 illustrates the rocket of the propulsion system 68 , shown in FIG. 4, as a bi-propellant of hydrogen peroxide used with a compatible second propellant.
- the pressurized tank of helium (He) 42 flows helium through the open valve 44 and into the pressurized H 2 O 2 tank 45 .
- the helium pressurizes against the H 2 O 2 36 in the pressurized H 2 O 2 tank 45 , causing the H 2 O 2 36 to flow through the open valve 34 in flowline 50 , and through the activated substrate 102 .
- the contact of the H 2 O 2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H 2 O 2 36 , forming high temperature steam and oxygen within an expansion chamber 32 .
- Propulsion occurs when the high temperature steam and oxygen within the expansion chamber 32 flow out of the rear nozzle 52 into a jet stream 54 .
- the helium travels through an open valve 60 in flowline 82 to a rocket liquid fuel tank 58 .
- the helium forces fuel from the rocket liquid fuel tank 58 through an open valve 62 in flowline 84 , through fuel injectors 64 , and into the expansion chamber 32 .
- the liquid rocket fuel in the expansion chamber 32 unites with the decomposing H 2 O 2 36 to form a powerful combustion, which emits a jet stream 54 out of the combustion chamber 32 through rear nozzle 52 .
- FIG. 6 illustrates the motor of FIG. 3 as a hybrid rocket propulsion system 68 .
- the pressurized tank of helium (He) 42 flows helium through the open valve 44 and into the pressurized H 2 O 2 tank 45 .
- the helium pressurizes against the H 2 O 2 36 in the pressurized H 2 O 2 tank 45 , causing the H 2 O 2 36 to flow through the open valve 34 in fowline 50 , and through the activated substrate 102 .
- the contact of the H 2 O 2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H 2 O 2 36 , forming high temperature steam and oxygen within an expansion chamber 32 .
- the high temperature steam and oxygen flow down the interior of a fuel grain tube 70 , combusting with fuel grain 72 , thereby consuming and eroding the interior of the fuel grain tube 70 .
- the jet stream 54 of the rocket may be shut off by closing the valve 34 and later restarted by opening the valve 34 .
- the high-activity decomposition 106 of the H 2 O 2 36 results in a significant increase in volume and temperature over a short time period. This permits the present invention to be used in high-flow applications.
- the volume increase is from about 10,000 to about 1 increase, more preferably from about 5000 to about 1 increase, and most preferably from about 1000 to about 1 increase.
- the temperature preferably increases to about 1000° F. or higher, more preferably from about 1100° F. or higher, and most preferably from about 1500° F. to about 1800° F.
- the time of decomposition preferably is from about 10 seconds or less, more preferably from about 5 seconds or less, and most preferably from about 3 seconds to 1 second.
- the present invention provides significantly higher hydrogen peroxide decomposition 106 activity and lower pressure drop.
- the activated substrate 102 is disposable or recyclable with relatively low costs of fabrication and cleaning, respectively. Furthennore, the present invention maintains a high poisoning threshold or blockage, and low weight.
- the activated substrate 102 of the present invention is suitable for use with a liquid oxidizer injection system for a bi-propellant rocket, with an oxidizer system in a hybrid rocket motor, as a gas generator, as a starter cartridge, and/or as a hydrogen peroxide mono-propellant thruster. Examples include such systems as those used in attitude control thrusters, and the Mercury and Scout rocket programs, and the like.
- 1 molar solution of sodium pennanganate was prepared by dissolving 141.93 grams of NaMnO 4 in 1 liter of deionized water. After dissolution, one mole of sodium hydroxide (40.00 grams) was added to the solution and allowed to dissolve to form the impregnation solution.
- the substrates were allowed to soak in the impregnation solution for one hour, were drained, blotted and then dried and calcined at 325° C. overnight.
- the impregnation and calcination processes were repeated twice to form the finished catalyst which contained the sodium alkaline promoter in an amount to the active manganese in a molar ratio of two to one.
- 1 molar solution of cobalt acetate tetrahydrate was made by dissolving 249.08 grams of Co(C 2 H 3 O 2 ) 2 •4H 2 O in 1 liter of distilled water. After dissolution, one mole of potassium hydroxide (56.11 grams) was added and dissolved to form the impregnation solution. Cored sections of alumina foam, used as the catalytic substrate, were dried overnight at 200° C. The impregnation solution was poured over the substrates, and the entire mass was allowed to soak for one hour at ambient conditions. The substrates were drained, blotted, and then calcined at 250° C. for two hours. The process was repeated once to form the finished catalyst which contained an equimolar ratio of cobalt and potassium, the alkaline promoter.
- 0.25 molar solution of potassium permanganate was made by dissolving 39.51 grams of KMnO 4 in 1 liter of demineralized water, forming the impregnation solution.
- Cylindrical structures of cordierite monoliths of varying pore densities were formed by diamond core drilling, having a nominal diameter of one inch and a nominal length of three inches. After machining, the cylindrical structures were washed and dried overnight at 200° C. The dried billets were soaked in the impregnation solution for two hours, drained, blotted, and then calcined for one hour at 350° C. The impregnation and calcination steps were repeated three times to yield an active catalyst containing an equimolar ratio of manganese and potassium, the alkaline promoter.
Abstract
A high-activity hydrogen peroxide decomposition catalyst comprising an impregnated and calcined substrate with a catalyst mixture. The catalyst mixture comprises a hydrogen peroxide catalytically active compound containing a transition metal cation mixed with an alkaline promoter. A process for forming a high-activity hydrogen peroxide decomposition catalyst and a product of high-activity hydrogen peroxide decomposition are disclosed.
Description
Not applicable.
The invention described herein may be manufactured and used by or for the government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.
Not applicable
1. Field of the Invention
The present invention relates to high-activity hydrogen peroxide decomposition. More particularly, the present invention uses an activated catalyst for high-activity hydrogen peroxide decomposition. Most particularly, the high-activity hydrogen peroxide decomposition is sufficiently rapid enough to provide thrust within rocket and/or other power systems.
2. Brief Description of the Related Art
Catalysts are used in the decomposition of hydrogen peroxide (H2O2) for monopropellant thrusters, liquid rocket engines, hybrid rocket systems and the like. Hydrogen peroxide decomposes into water vapor and oxygen. The oxygen product can react with conventional rocket fuel or grains to provide thrust. Within propulsion systems, hydrogen peroxide has been successfully used as an oxidizer for U.S. Navy torpedo systems, U.S.A.F. attitude control thruster“s on the X-15, and for reaction control thrusters on the NASA Scout launch vehicles and Mercury spacecraft.
Catalyst are formed into packs by using layers of nitric acid or samarium salt activated silver plated screens. Within this system, hydrogen peroxide decomposition activity is relatively low. However, increasing the number of screens also increases the activity, but also increases the pressure drop. Contaminants within the hydrogen peroxide may also plate out onto the silver screens. This reduces the active surface area, which in turn reduces the effective decomposition of the hydrogen peroxide. Additionally, the cost of the materials and fabrication are high.
Catalyst pack screens have been disclosed in U.S. Pat. Nos. 5,077,257 (Baldi), 4,927,798 (Baldi), and 4,292,208 (Baldi et al.). However, these patents do not address a low cost hydrogen peroxide catalyst applicable for use as an efficient propulsion system, providing low pressure drop and low weight.
The present invention provides a high-activity hydrogen peroxide decomposition catalyst comprising an impregnated and calcined substrate with a catalyst mixture, the catalyst mixture comprising a hydrogen peroxide catalytically active compound containing a transition metal cation mixed with an alkaline promoter, wherein the substrate further comprises a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof.
The invention further provides a process for forming a high-activity hydrogen peroxide decomposition catalyst comprising the steps of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof; mixing, in an aqueous solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter; applying the mixture over the substrate, wherein the mixture soaks the substrate surface area, thereby impregnating the substrate; drying the applied soaked mixture sufficiently causing the removal of the solvent; and calcining the dried mixture sufficiently to form an activated catalyst.
Additionally, the invention provides a product of high-activity hydrogen peroxide decomposition made by the process of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof; mixing, in a solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter; applying the mixture over the substrate, wherein the mixture soaks the substrate surface area, thereby impregnating the substrate; drying the applied soaked mixture sufficiently causing the removal of the solvent; calcining the dried mixture, wherein an activated catalyst is formed; housing the formed activated catalyst into a hydrogen peroxide reaction chamber having a hydrogen peroxide inlet port; and, flowing a compound of hydrogen peroxide through the inlet port wherein the hydrogen peroxide comes in contact with the calcined, impregnated substrate with mixture, wherein the hydrogen peroxide decomposes in a high-activity reaction thereby releasing water, oxygen and energy.
FIG. 1 is a side cross-sectional view of a singular cellular matrix activated catalyst substrate of the present invention in housing;
FIG. 2 is a side view of the polar substrate surface bonded with manganese and potassium ions with are further bonded to oxygen;
FIG. 3 is a schematic side view of a propulsion system of the present invention using a hydrogen peroxide mono-propellant;
FIG. 4 is a schematic side view of a rocket propulsion system of the present invention using a hydrogen peroxide mono-propellant;
FIG. 5 is a schematic side view of a rocket propulsion system of the present invention using a hydrogen peroxide bi-propellant; and,
FIG. 6 is a schematic side view of a rocket propulsion system of the present invention using hydrogen peroxide in a hybrid rocket propulsion system.
The present invention is a hydrogen peroxide decomposition catalyst and process for high activity hydrogen peroxide decomposition, and the product of high-activity hydrogen peroxide decomposition. The present invention comprises a combination catalyst and promoter on a polar substrate to provide sufficiently rapid decomposition of hydrogen peroxide for use as a propellant in rocket thrusters and/or other motor systems. The decomposed hydrogen peroxide provides an environmentally clean product of water vapor and oxygen, which may also be used for additional systems.
Decomposition of hydrogen peroxide provides chemical energy to perform work, such as powering rocket, turbine, electric, other propulsion and auxiliary equipment and the like. The hydrogen peroxide based propellant reduces toxic emissions, increases reliability and efficiency, reduces sound, and obscures carrier signature relative to conventional fuels.
As seen in FIG. 1, the present invention comprises an activated catalyst substrate 102 which may be placed in a rocket or similar housing 46 and held in place by end screens 14 within the housing 46. The activated substrate 102 includes a high-activity hydrogen peroxide decomposition catalyst which has been included therein. The activated substrate 102 comprises a porous support material, such as alumina, silica, aluminosilicate, polar ceramics and combinations thereof. The activated substrates 102 have a porous surface, which maximizes the amount of catalyst impregnated and calcined thereon. Additionally, the activated substrates 102 are polar which allows a catalyst to properly arrange along the surface of the activated substrate 102, thereby providing an activated catalyst. The activated substrates 102 are high temperature and non-oxidizing to withstand the temperature occasioned by the decomposition of the hydrogen peroxide. The temperature of decomposing hydrogen peroxide is proportional to the percentage of hydrogen peroxide available in a given propellant. For example, 100% by mass hydrogen peroxide yields a reaction product with an adiabatic decomposition temperature of 1824° F., 95% by mass hydrogen peroxide yields 1593° F., 90% by mass hydrogen peroxide yields 1364° F., 80% by mass hydrogen peroxide yields 908° F., 50% by mass hydrogen peroxide yields 212° F., and 35% by mass hydrogen peroxide yields 212° F. Any oxidizable activated catalyst substrate 102 becomes inefficient with the decomposition of the hydrogen peroxide, providing limited use.
The activated substrate 102 may comprise a singular structured polar substrate, as shown in FIG. 1, or multiple polar substrates. Preferably, the activated substrate 102 comprises a singular structure. More preferably, the singularly structured activated substrate 102 comprises a matrix. Most preferably, the matrix comprises a cellular matrix. Activated substrates 102 may include, but is not limited to, pellets, spheres, grids, and the like. The activated substrate 102 may be loaded within the housing 46 by placing the activated substrate 102 in line between an H2O2 pressurized storage tank and an expansion chamber. The storage tank and expansion chamber may be any configuration which promotes the efficiency of the system, such as being cylindrical, the configuration of which is detenninable by those skilled in the art. Typically, the activated substrate 102 is held in place by end capture or metallic end screens 14 or other similar fixed systems, as shown in FIG. 1.
The activated substrate 102 is formed by impregnating and calcining a polar substrate with a catalyst mixture. The catalyst mixture comprises a hydrogen peroxide catalytically active compound containing a transition metal cation mixed with an alkaline promoter. The transition metal may be any of the elements from Groups VB, VIB, VIIB, VIII and IB of the Periodic Table of Elements, specifically listed as vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb), molybdenum (Mo), technetium (Te), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Au), tantalum (Ta), wolfram (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt) and gold (Ag). Preferably the catalyst mixture comprises a transition metal cation selected from the group consisting of Mn, Ag, Ru, V, Fe, Cr, Co and mixtures thereof. Examples of valence states of certain transition metal cations used in the present invention include Mn+4, Ru+4, V+5, CU+4, Cr+4, Cr+3, Co+2, Co+, and the like, within valence-corresponding salts thereof. More preferably, the catalyst mixture comprises a cation selected from the group consisting of tetravalent manganese and tetravalent copper. Most preferably the catalyst mixture comprises tetravalent manganese.
The alkaline promoter may be any compound which provides a basic solution containing elements from Groups IA and IIA of the Periodic Table of Elements. Preferably, the alkaline promoter contains an ion such as lithium (Li+), potassium (K+), sodium (Na+), and ammonium (NH4 +). More preferably, the alkaline promoter contains K+ ions, Na+ ions, and/or combinations thereof. The alkaline promoter provides high stability when used in conjunction with the transition metal and polar substrate.
The promoter and transition metal are mixed in defined molar proportions. Preferably, the promoter and transition metal are mixed at a molar ratio of from about 0.5 to about 4.0, more preferably at a molar ratio of from about 1.0 to about 3.0, and most preferably at a molar ratio of from about 1.0 to about 2.0.
The weight of the polar substrate is measured in relation to the weight of the calcined metals of both the transition metal and promoter of the catalyst mixture. Preferably the polar substrate comprises from about 0.01 weight percent to about 85.0 weight percent of the transition metal and promoter. More preferably, the polar substrate comprises from about 0.5 weight percent to about 10.0 weight percent of the transition metal and promoter. Most preferably, the polar substrate comprises from about 1.0 weight percent to about 20.0 weight percent of the transition metal and promoter. For example, manganese (+4) and potassium may have a 1% weight/weight (w/w) loading on the polar substrate.
The process for forming the high-activity hydrogen peroxide decomposition catalyst comprises the steps of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof; mixing, in a solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter; applying the mixture over the polar substrate, wherein the mixture soaks the polar substrate surface area, thereby impregnating the polar substrate; drying the applied soaked mixture sufficiently causing the removal of the solvent; and calcining the dried mixture sufficient to form an activated catalyst.
Soluble salts of the transition metal cation and alkaline promoter are mixed into a solvent to form a catalyst mixture. Examples of such salts include, but are not limited to, KMnO4, RuCl3, NH4VO3, (NH4)2Cr2O7, and/or Co(NO3)2. The solvent includes aqueous and non-aqueous solutions which are suited to dissolving the transition metal cation salt and the alkaline promoter, the type of the solution being detenninable by those skilled in the art. Preferably, the solvent comprises water. More preferably, the water solvent is distilled or deionized water.
The solvent solution containing the mixture of transition metal cation and alkaline promoter is applied over the polar substrate. The application may include pouring the solution onto the polar substrate, submerging the polar substrate into the solution, and other like applications of the solution against the polar substrate which is sufficient to wet the polar substrate in bulk. The application of the catalyst mixture lasts for a suitable equilibration time, which allows the catalyst mixture to soak into and around the polar substrate surface area. The equilibration time is determinable by those skilled in the art, and preferably ranges from about 10 minutes to about 60 minutes. After a suitable equilibration time, the catalyst mixture soaked polar substrate is dried in an oven sufficiently to evaporate or remove the solution, which deposits or impregnates the transition metal and promoter from the catalyst mixture on the polar substrate. The deposited catalyst is activated by calcination of the mixture covered polar substrate forming the activated substrate 102. Calcining the mixture occurs by heating the impregnated polar substrate in an open atmosphere. For example, KMnO4 transforms to a mixture of MnO2 and K2O after calcination. The calcined mixture forms conditional metal oxides of the catalysts doped or impregnated thereon, which cause hydrogen peroxide to more readily decompose by lowering the activation energy (Ea) for decomposition. Heating temperatures and times vary with the selection of promoter, transition metal, amount of solvent, type of polar substrate, and the like, with the temperature and heat time being determinable by those skilled in the art. Generally, the impregnated mixture is preferably calcined at from about 150° C. to about 950° C. for a time period of from about 30 minutes to about 24 hours.
FIG. 2 shows the conditional metal oxides formed on the activated substrate 102 that vary from site to site, but maintain proper stoichiometry. Accordingly, oxides of the transition metal and promoter generally form traditional bonds, such as MnO2, Ag2O, RuO2, V2O5, CrO2, Co2O3, and the like. However, it is believed that the calcined combination of the polar substrate surface with the transition metal and promoter create a surface area possessing other oxide forms, such as K2O, and similar oxide configurations containing Li, Na, and NH4. Although normally unstable, these elements possess the general oxide structure, which varies from site to site, on the activated substrate 102 in a stable condition. For example, bonds form to create such chemical forms of MnO2•K2O, which may be schematically represented as shown in FIG. 2. In FIG. 2, the compounds Mn and K are attached to the polar substrate and further bond to oxygen molecules. The decomposition of hydrogen peroxide along the surface of the metal oxide covered activated substrate 102 does not dissipate or otherwise significantly degrade the activated substrate 102. Significant degradation would exist when hydrogen peroxide decomposition diminishes such that the hydrogen peroxide does not function as a propellant.
The activated substrate 102 of the present invention, containing a highly porous polar substrate impregnated with a calcined transition metal and promoter, facilitates the decomposition of H2O2 to a degree permitting such use of the H2O2 as a rocket propellant when H2O2 is flowed through an activated catalyst chamber containing the activated catalyst substrate 102. A low pressure drop occurs with the highly catalytic contact of the H2O2 on the activated substrate 102. The decomposition of the H2O2 occurs according to the following reaction:
Flowing 100 cc of 90 mole % H2O2 through an activated catalyst chamber causes a violent reaction to occur at temperatures of 1200° F. with stream emissions of water, oxygen and energy.
FIGS. 3, 4, 5 and 6 illustrate a product of high-activity hydrogen peroxide decomposition 106. The high-activity hydrogen peroxide decomposition 106 is made by the process of providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof mixing, in a solvent, a soluble salt containing a hydrogen peroxide catalytically active compound containing a transition metal cation with an alkaline promoter, applying the mixture over the polar substrate, wherein the mixture soaks the polar substrate surface area, thereby impregnating the polar substrate, drying the applied soaked mixture sufficiently causing the removal of the solvent, calcining the dried mixture, wherein an activated catalyst, or activated substrate 102 is formed, housing the formed activated catalyst into a hydrogen peroxide reaction chamber 32 having a hydrogen peroxide inlet port or valve 34, and, flowing a compound of hydrogen peroxide 36 through the inlet port 34 wherein the hydrogen peroxide comes in contact with the calcined, impregnated mixture, wherein the hydrogen peroxide 36 decomposes in a high-activity reaction thereby releasing water, oxygen and energy. The hydrogen peroxide 36 propellant may comprise from about 85% by mass or greater hydrogen peroxide, preferably from about 90% by mass hydrogen peroxide or greater, more preferably from about 95% by mass hydrogen peroxide or greater, and most preferably from about 98% by mass hydrogen peroxide or greater. The higher mass percentage of hydrogen peroxide 36 provides the greatest versatility in energy conversion, and the level of hydrogen peroxide 36 would be determinable by those skilled in the art applicable for a particular use.
The present invention may comprise a mono-propellant, bi-propellant or multi-propellant hydrogen peroxide device. Preferably, the present invention comprises a mono-propellant of hydrogen peroxide. More preferably, the hydrogen peroxide monopropellant consists essentially of hydrogen peroxide.
The energy released from the high-activity hydrogen peroxide decomposition 106 is measured as adiabatic decomposition temperature. For example, at one atmosphere, 100% by mass hydrogen peroxide yields a reaction product with an adiabatic decomposition temperature of 1824° F., 95% by mass hydrogen peroxide yields 1593° F., 90% by mass hydrogen peroxide yields 1364° F., 80% by mass hydrogen peroxide yields 908° F., and from about 64.7% or less by mass hydrogen peroxide yields 212° F. The high-activity hydrogen peroxide decomposition 106 may propel any object capable of housing the hydrogen peroxide decomposition, preferably a rocket motor or steam engine.
FIG. 3 illustrates the activated substrate 102 housed within a propulsion system 68, such as a rocket, steam turbine or gas-generator, and other like movable or stationary systems, using hydrogen peroxide 36 as a mono-propellant. The activated substrate 102 is housed or packed into a motor or other decomposition-type chamber 32 to provide energy for movement, such as a steam turbine. A pressurized tank of helium (He) 42 flows helium through an open valve 44 and into a pressurized H2O2 tank 45. The helium pressurizes against the H2O2 36 in the pressurized H2O2 tank 45, causing the H2O2 36 to flow through an open valve 34 in flowline 50, and through the activated substrate 102. The contact of the H2O2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H2O2 36, forming high temperature steam and oxygen within the expansion chamber 32. The decomposed H2O2 36 further flows into a steam turbine 48 and impinge on rotary blades, which propels the stream turbine 48. For steam turbine 48 use, the superheated steam is preferably heated to from about 1000° F. to about 1800° F., more preferably from about 1100° F. to about 1500° F., and most preferably from about 1100° F. to about 1200° F. The temperature range for the superheated steam varies by use, and may be determined by those skilled in the art. Propulsion may be obtained using the decomposed H2O2 36 from the activated substrate 102 without combustion of other reactants.
FIG. 4 illustrates the propulsion system 68 shown in FIG. 3 as a rocket mono-propellant of hydrogen peroxide. The pressurized tank of helium (He) 42 flows helium through the open valve 44 and into the pressurized H2O2 tank 45. The helium pressurizes against the H2O2 36 in the pressurized H2O2 tank 45, causing the H2O2 36 to flow through the open valve 34 in flowline 50, and through the activated substrate 102. The contact of the H2O2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H2O2 36, forming high temperature steam and oxygen within the expansion chamber 32. Propulsion occurs when the high temperature steam and oxygen within the expansion chamber 32 flow out of a rear nozzle 52 into a jet stream 54. Propulsion may be obtained using the decomposed H2O2 36 from the activated substrate 102 without combustion of other reactants.
FIG. 5 illustrates the rocket of the propulsion system 68, shown in FIG. 4, as a bi-propellant of hydrogen peroxide used with a compatible second propellant. The pressurized tank of helium (He) 42 flows helium through the open valve 44 and into the pressurized H2O2 tank 45. The helium pressurizes against the H2O2 36 in the pressurized H2O2 tank 45, causing the H2O2 36 to flow through the open valve 34 in flowline 50, and through the activated substrate 102. The contact of the H2O2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H2O2 36, forming high temperature steam and oxygen within an expansion chamber 32. Propulsion occurs when the high temperature steam and oxygen within the expansion chamber 32 flow out of the rear nozzle 52 into a jet stream 54. Additionally, the helium travels through an open valve 60 in flowline 82 to a rocket liquid fuel tank 58. The helium forces fuel from the rocket liquid fuel tank 58 through an open valve 62 in flowline 84, through fuel injectors 64, and into the expansion chamber 32. The liquid rocket fuel in the expansion chamber 32 unites with the decomposing H2O2 36 to form a powerful combustion, which emits a jet stream 54 out of the combustion chamber 32 through rear nozzle 52.
Combustion involving other reactants is shown in FIG. 6. FIG. 6 illustrates the motor of FIG. 3 as a hybrid rocket propulsion system 68. As shown in FIG. 6, the pressurized tank of helium (He) 42 flows helium through the open valve 44 and into the pressurized H2O2 tank 45. The helium pressurizes against the H2O2 36 in the pressurized H2O2 tank 45, causing the H2O2 36 to flow through the open valve 34 in fowline 50, and through the activated substrate 102. The contact of the H2O2 36 over the activated substrate 102 causes a rapid decomposition 106 of the H2O2 36, forming high temperature steam and oxygen within an expansion chamber 32. The high temperature steam and oxygen flow down the interior of a fuel grain tube 70, combusting with fuel grain 72, thereby consuming and eroding the interior of the fuel grain tube 70. This forms a hybrid jet stream 54 which flows through rear nozzle 52 as a jet stream 54 which propels the rocket. The jet stream 54 of the rocket may be shut off by closing the valve 34 and later restarted by opening the valve 34.
The high-activity decomposition 106 of the H2O2 36 results in a significant increase in volume and temperature over a short time period. This permits the present invention to be used in high-flow applications. Preferably the volume increase is from about 10,000 to about 1 increase, more preferably from about 5000 to about 1 increase, and most preferably from about 1000 to about 1 increase. The temperature preferably increases to about 1000° F. or higher, more preferably from about 1100° F. or higher, and most preferably from about 1500° F. to about 1800° F. The time of decomposition preferably is from about 10 seconds or less, more preferably from about 5 seconds or less, and most preferably from about 3 seconds to 1 second.
The present invention provides significantly higher hydrogen peroxide decomposition 106 activity and lower pressure drop. The activated substrate 102 is disposable or recyclable with relatively low costs of fabrication and cleaning, respectively. Furthennore, the present invention maintains a high poisoning threshold or blockage, and low weight. The activated substrate 102 of the present invention is suitable for use with a liquid oxidizer injection system for a bi-propellant rocket, with an oxidizer system in a hybrid rocket motor, as a gas generator, as a starter cartridge, and/or as a hydrogen peroxide mono-propellant thruster. Examples include such systems as those used in attitude control thrusters, and the Mercury and Scout rocket programs, and the like.
1 molar solution of sodium pennanganate was prepared by dissolving 141.93 grams of NaMnO4 in 1 liter of deionized water. After dissolution, one mole of sodium hydroxide (40.00 grams) was added to the solution and allowed to dissolve to form the impregnation solution. 400, 600, 900, and 1100 pore per in2 monolithic catalyst substrates, comprised of synthetic cordierite, manufactured by Corning Incorporated of Corning N.Y., were sliced to proper thickness of one-half inch and cored to proper diameter of one inch. These substrates were dried overnight at 200° C. The substrates were allowed to soak in the impregnation solution for one hour, were drained, blotted and then dried and calcined at 325° C. overnight. The impregnation and calcination processes were repeated twice to form the finished catalyst which contained the sodium alkaline promoter in an amount to the active manganese in a molar ratio of two to one.
1 molar solution of cobalt acetate tetrahydrate was made by dissolving 249.08 grams of Co(C2H3O2)2•4H2O in 1 liter of distilled water. After dissolution, one mole of potassium hydroxide (56.11 grams) was added and dissolved to form the impregnation solution. Cored sections of alumina foam, used as the catalytic substrate, were dried overnight at 200° C. The impregnation solution was poured over the substrates, and the entire mass was allowed to soak for one hour at ambient conditions. The substrates were drained, blotted, and then calcined at 250° C. for two hours. The process was repeated once to form the finished catalyst which contained an equimolar ratio of cobalt and potassium, the alkaline promoter.
0.25 molar solution of potassium permanganate was made by dissolving 39.51 grams of KMnO4 in 1 liter of demineralized water, forming the impregnation solution. Cylindrical structures of cordierite monoliths of varying pore densities were formed by diamond core drilling, having a nominal diameter of one inch and a nominal length of three inches. After machining, the cylindrical structures were washed and dried overnight at 200° C. The dried billets were soaked in the impregnation solution for two hours, drained, blotted, and then calcined for one hour at 350° C. The impregnation and calcination steps were repeated three times to yield an active catalyst containing an equimolar ratio of manganese and potassium, the alkaline promoter.
The foregoing summary, description, examples and drawings of the invention are not intended to be limiting, but are only exemplary of the inventive features which are defined in the claims.
Claims (13)
1. A high-activity hydrogen peroxide decomposition catalyst comprising:
an impregnated and calcined substrate with a catalyst mixture, the catalyst mixture comprising a transition metal cation mixed with an alkaline promoter, wherein the substrate comprises a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof.
2. The catalyst of claim 1, wherein the catalyst comprises a cation selected from the group consisting of Mn, Ag, Ru, V, Fe, Cr, Co and mixtures thereof.
3. The catalyst of claim 2, wherein the catalyst comprises a cation selected from the group consisting of tetravalent manganese and tetravalent copper.
4. The catalyst of claim 3, wherein the catalyst comprises tetravalent manganese.
5. The catalyst of claim 1, wherein the alkaline promoter contains an ion selected from the group consisting of Li+, K+, Na+, and NH4 +.
6. The catalyst of claim 5, wherein the alkaline promoter contains an ion selected from the group consisting of K+ and Na+.
7. The catalyst of claim I, wherein the promoter and catalyst are mixed at a molar ratio of from about 0.5 to about 4.0.
8. The catalyst of claim 7, wherein the promoter and catalyst are mixed at a molar ratio of from about 1.0 to about 2.0.
9. The catalyst of claim 1, wherein the substrate comprises from about 0.01 weight percent to about 20.0 weight percent of metals.
10. The catalyst of claim 1, wherein the substrate comprises a singular structure.
11. The catalyst of claim 10, wherein the singular structure comprises a matrix.
12. The catalyst of claim 11, wherein the matrix comprises cellular matrix.
13. A process for forming a high-activity hydrogen peroxide decomposition catalyst comprising the steps of:
providing a polar substrate comprising a porous support material selected from the group consisting of alumina, silica, aluminosilicate, polar ceramics and combinations thereof;
mixing, in a solvent, a soluble salt containing a transition metal cation with an alkaline promoter;
applying the mixture over the substrate, wherein the mixture soaks the substrate surface area, thereby impregnating the substrate;
drying the applied soaked mixture sufficiently causing the removal of the solvent; and,
calcining the dried mixture sufficient to form an activated catalyst.
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US09/045,127 USH1948H1 (en) | 1998-03-20 | 1998-03-20 | High-activity catalyst for hydrogen peroxide decomposition |
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US09/045,127 USH1948H1 (en) | 1998-03-20 | 1998-03-20 | High-activity catalyst for hydrogen peroxide decomposition |
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US09/045,127 Abandoned USH1948H1 (en) | 1998-03-20 | 1998-03-20 | High-activity catalyst for hydrogen peroxide decomposition |
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US6446909B1 (en) * | 1997-04-18 | 2002-09-10 | Robert C. Michelson | Reciprocating chemical muscle(RCM) and method for using same |
US20030017428A1 (en) * | 2001-07-02 | 2003-01-23 | Rafael Armament Development Authority Ltd. | Method and apparatus for generating superheated steam |
US6532741B2 (en) | 2001-06-29 | 2003-03-18 | United Technologies Corporation | Gas generator for producing adjustable flow |
US6652248B2 (en) | 2001-06-29 | 2003-11-25 | United Technologies Corporation | Catalyst bed |
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