CN1348835A - Prepn and application of hydrazine decomposing catalyst - Google Patents
Prepn and application of hydrazine decomposing catalyst Download PDFInfo
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- CN1348835A CN1348835A CN00123085A CN00123085A CN1348835A CN 1348835 A CN1348835 A CN 1348835A CN 00123085 A CN00123085 A CN 00123085A CN 00123085 A CN00123085 A CN 00123085A CN 1348835 A CN1348835 A CN 1348835A
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000010436 fluorite Substances 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052737 gold Inorganic materials 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 229910052953 millerite Inorganic materials 0.000 abstract 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910003417 La0.2Sr0.8 Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 229910002714 Ba0.5Sr0.5 Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019029 PtCl4 Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000034964 establishment of cell polarity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/02—Preparation of nitrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to catalyst for decompose pure hydrazine or hydrated hydrazine into N2 and H2 under room temperature and its preparation method. Said catalyst is composed of XYC, in which X is one or several metal element including Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt, Au; Y is one of perovskite type, fluorspar type, millerite type composite oxides, C is conductive carbon which can be added or not added said catalyst. The invented catalyst can selectively decompose pure hydrazine or hydrated hydrazine to produce H2, which can be used as hydrogen source of fuel battery or as hydrogen source in metal processing.
Description
The present invention relates to a catalyst, in particular, it is a catalyst capable of decomposing hydrazine into N at normal temp2And H2The preparation of the catalyst and its use.
Hydrazine is a widely used chemical raw material containing hydrogen. Hydrazine decomposition is mainly carried out in the following ways:
from the above thermodynamic data, it can be seen that hydrazine is easily decomposed, and the product is mainly NH3，N2. Over the past 60 years, researchers have conducted extensive research on the decomposition of hydrazine on metal single crystal surfaces, metals, and metal supported catalysts, and it is believed that there are two ways of breaking the hydrazine intramolecular bonds: one is the cleavage of the N-H bond; the second is the cleavage of the N-N bond. The N-H bond energy is 84KJ-1And the N-N bond energy is 60kJ-1So that the cleavage of the N-N bond is thermodynamically easier. The adsorption dissociation studies of hydrazine on the Surface of metal single crystals showed (M.L. Wagner ed al., Surface Science 257 (1991)) 113-: hydrazine is selective in N-H and N-N bond cleavage on the surfaces of different metal single crystals, such as Fe (111), Ru (001), Rh (111), Pd (100), Os (100), Ir (111) and Pt (111). The N-N bond is easily broken on the Fe (111) crystal face. On the Pt (111) crystal face, N-H bonds are easily activated and broken. Ken-Ichi Aika et al (journal of Catalysis 19, 140-143(1970)) studied the decomposition performance of Ir, Ru, Pt, Ni, Co, Rh, Fe, W, Mo metals or hydrazine on catalysts prepared on brownmillerite or diatomaceous earth and found that the decomposition product of hydrazine is N at below 200 deg.C2And NH3H is not detected2And (4) generating. Small amounts of H detected above 200 deg.C2. In addition, in the early daysThe hydrazine is used for rocket attitude adjustment, and the catalyst used is Ir/AL2O3(T.J.Jenning et al, U.S. Pat. No. 3,3503212, 1970; Greer et al, J.Spacecraft and rocks, 1971, 8, 105-2And NH3. Thermodynamic data indicate that hydrazine decomposes to N at room temperature2And H2It is possible, but to date, that no hydrazine can be decomposed to H selectively at room temperature on a catalyst at high rates2And N2The report of (1).
It is an object of the present invention to provide a novel catalyst which can effectively solve the above problems and which can decompose hydrazine into hydrogen and nitrogen with high selectivity at room temperature.
The purpose of the invention is realized as follows: the general formula of the composition of the catalyst can be represented as follows: XYC, wherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, Y is perovskite type or fluorite type or conite type composite oxide, C is nano carbon black, X can be one or more metals, Y is one of three types of oxides, and C can be added or not added.
The catalyst can be divided into a supported type and a mixed type: the supported type has a general formula of X/Y, wherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, Y is a perovskite type or fluorite type or conite type composite oxide, X can be one or more metals, Y is one of three types of oxides, and the supporting amount of X on Y is 0.5-20%; the general formula of the composition of the mixed type is represented as (X/C)a+YbWherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, C is nano carbon black, Y is perovskite type or fluorite type or coniferous composite oxide, X can be one or more metals, Y is one of three types of oxides, and the loading amount of X on C is 0.5-40%. and a and b are the mass of two X/C and Y, and the ratio of a to b is 0.1-10.
In the invention, the preferable components of the first type of catalyst are supported in the amount of 1-10%, and the preferable components of the second type of catalyst are supported in the amount of 10-25%, 1>a: b> 0.1.
Many conventional and advanced catalyst preparation methods can be used for the above catalyst preparation, and for the X/Y type catalyst, including a metal salt solution impregnation-calcination-reduction method; dipping-reduction-drying method, metal carbonyl compound thermal decomposition chemical deposition method, grinding-roasting-reduction method. For (X/C)a+YbThe preparation method of the type catalyst can be divided into two steps: the first step is the preparation of X/C, including the dipping-roasting-reduction method of metal salt solution; dipping-reduction-drying method, metal carbonyl compound thermal decomposition chemical deposition method, grinding-roasting-reduction method. The second step is the mixing of X/C and Y, and comprises a mechanical mixing method, a grinding method and a grinding-ultrasonic oscillation method.
The preparation method of the supported catalyst comprises the following steps: firstly adopting a sol-gel method (using EDTA and citric acid as a common complexing agent, using soluble metal salt as an initial raw material, using hexanediol and glycerol as a dispersing agent, stirring the system at a constant temperature of 70-90 ℃ to form a transparent colloid, curing the colloid at 100-150 ℃, pre-roasting at 250-350 ℃ for 1-10 hours, and finally roasting at 1000-1400 ℃ for 1-100 hours) or a solid grinding method (using nitrate of metal as a raw material, mixing and fully grinding, then roasting at 1000-1400 ℃, taking out the mixture every 1-5 hours, fully grinding and roasting, repeating for 5-10 times) to prepare the perovskite or fluorite or coniferous ore type composite oxide, then adding ethanol or water, formaldehyde, KOH, and the soluble metal salt or acid solution to be loaded, stirring for 1-4 hours at 20-60 ℃, filtering or standing and pouring the upper layer solution, washing with clear water to enable the pH value to reach 7, and then drying at 80-150 ℃.
The preparation method of the mixed catalyst comprises the following steps: dispersing the nano carbon black by using ethanol, then adding formaldehyde, KOH and required metal soluble salt, stirring for 1-4 hours at the temperature of 20-60 ℃, filtering or standing and pouring the upper layer solution, washing with clear water to enable the pH value to reach 7, and drying at the temperature of 80-150 ℃ to obtain X/C. Mixing and grinding the X/C and the perovskite type or fluorite type or coniferous type composite oxide obtained in the preparation process of the supported catalyst, then immersing the mixed solid into distilled water solution for ultrasonic oscillation for 0.1-3 h, and drying at 80-150 ℃.
The catalyst of the invention can decompose pure hydrazine or hydrazine hydrate to generate gas which can be used as hydrogen source of proton exchange membrane fuel cell at normal temperature, and air breathing is adopted at normal temperature to make the voltage of single cell reach 0.8V and the current density reach 150mA/cm2。
Further, the above hydrogen gas can be used as a hydrogen source in metal processing.
Compared with the existing hydrazine decomposition catalyst material, the catalyst provided by the invention can be used for decomposing hydrazine or hydrazine hydrate at normal temperature with high selectivity to generate hydrogen, and the data listed in the table 1 reflects the hydrogen selectivity of the catalyst when the catalyst is used for hydrazine decomposition. Wherein the selectivity for hydrogen is represented by S, S ═ 2[ H []2]X100/2[H2]+3[NH3]. TABLE 1 catalyst Temp (. degree. C.) SPd/La0.2Sr0.8Co0.2Fe0.8O325 65
50 80Pt/La0.2Sr0.8Co0.2Fe0.8O325 70
50 90Ir/La0.2Sr0.8Co0.2Fe0.8O325 20
50 25W/La0.2Sr0.8Co0.2Fe0.8O325 30
50 40Rh/Ba0.2Sr0.8Co0.2Fe0.8O325 50
50 60Fe/Ba0.2Sr0.8Co0.2Fe0.8O325 10
50 20
From the above table data, it can be seen that the selectivity of hydrogen when hydrazine decomposition is carried out using the catalyst of the present invention is 92%. This indicates that this series of catalysts has high hydrogen selectivity.
The invention is described in detail below with reference to specific embodiments and the attached drawing figures:
FIG. 1 shows Ba0.5Sr0.5Co0.6Fe0.4O3-δPowder diffraction XRD pattern.
Fig. 2 is a schematic view of an application example (a fuel cell using hydrogen generated by hydrazine decomposition as a raw material) of the present invention.
Fig. 3 is a polarization curve diagram of a proton membrane fuel cell stack using hydrogen generated by hydrazine decomposition as a hydrogen source, and the cell polarization curve diagram is tested on an evaluation device.
Example 1 Supported catalyst and method for preparing the same
The general formula of the supported catalyst is (X/C)a+YbWherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, C is nano carbon black, Y is one of three types of oxides, and the loading amount of X on C is 0.5-40%. and a and b are the mass of two X/C and Y, and the ratio of a to b is 0.1-10. The catalyst composition of this example was: (10% Pt/C)1+(Ba0.5Sr0.5Co0.6Fe0.4O3-δ)1. The preparation method comprises the following steps:
perovskite type Ba prepared by complexation method0.5Sr0.5Co0.6Fe0.4O3-δAn oxide. 70g of EDTA acid is weighed, dissolved in 200ml of concentrated ammonia water under heating, and 0.1mol of Ba (NO) is added3)2Heating the crystal to dissolve, and then adding 0.1mol of Sr (NO)3)2，0.12mol Co(NO3)2，0.08molFe(NO3)3Heating 80 the mixed solutionStirring at temperature, evaporating to obtain transparent hot-soluble mauve colloid, curing at 120 deg.C for several hours,then pre-roasting for 3 hours at 300 ℃, and finally roasting for 7 hours in a muffle furnace at 950 ℃ to obtain black powder. XRD powder diffraction method determination shows that pure phase perovskite type structure is formed, as shown in figure 1. The BET specific surface area measurement shows that the specific surface area of the powder is 5-10 m 2/g. The grain size of the powder is calculated to be 15-40nm by an XRD diffraction peak half-peak width method. 1.8g of XC-72 carbon powder and 700ml of ethanol are mixed and evenly dispersed by ultrasonic waves, and then 0.54g H is added2PtCl4And 120ml of 33% formaldehyde, and placed in a constant temperature water bath of 80 ℃ and stirred for 1 hour, and then 240g of 50% KOH solution was added dropwise and stirred for 20 min. After the reaction is finished, the solution is cleared, the supernatant is poured out, and the solution is washed for a plurality of times by using secondary deionized water to wash off K in the solution+、Cl-Until the pH of the solution is about 7. The obtained product is dried in a drying oven at 80 ℃ for 3h and at 120 ℃ for 3h to obtain the Pt/C. Pt/C was mixed with the same mass of Ba0.5Sr0.5Co0.6Fe0.4O3-δMixing, grinding, tabletting under 15Mpa, and crushing into 40-60 mesh granules to obtain the final product.
Example 2 Mixed catalyst and Process for its preparation
The general formula of the mixed catalyst is: X/Y, wherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, Y is perovskite type or fluorite type or conite type composite oxide, X can be one or more metals, Y is one of three types of oxides, and the loading amount of X on Y is 0.5-20%. The catalyst composition of this example was: 10% Pt/La0.2Ba0.8Co0.3Fe0.7Oδ. The preparation method comprises the following steps:
perovskite La prepared by complexation method0.2Ba0.8Co0.3Fe0.7Oδ70g of EDTA acid is weighed and dissolved in 200ml of concentrated ammonia water under heating, and 0.04mol of La (NO) is added3)3，0.16molBa(NO3)2，0.06molCo(NO3)2，Fe(NO3)3Adding into the solution, stirring at 80 deg.C to obtain colloid with water evaporation, solidifying at 120 deg.C for several hours, pre-roasting at 300 deg.C for 2 hours, and roasting at 1050 deg.C in muffle furnace for 10 hours to obtain powder. 0.9g of La0.2Ba0.8Co0.3Fe0.7OδAdding into 350ml ethanol solvent, dispersing with ultrasonic wave, adding 0.27gH2PtCl4And 60ml of 33% formaldehyde, and placed in a constant temperature water bath of 80 ℃ and stirred for 1 hour, and then 60 g of a 50% KOH solution was dropped and stirred for 20 min. After the solution is settled, pouring out the supernatant, washing with secondary deionized water, settling, pouring out the supernatant, repeating the steps for several times to wash off K in the solution+、Cl-Until the pH of the solution is about 7. The catalyst is dried in a drying oven for 3 hours at the temperature of 80 ℃ and dried at the temperature of 120 ℃ for 3 hoursAnd (4) hours. Tabletting and crushing into 40-60 mesh granules to obtain the finished catalyst.
Examples of the applications of the invention
With La0.2Sr0.8Co0.2Fe0.8Oδ+ Pt/C is a hydrazine hydrate catalyst and hydrogen gas is produced in a reactor as in figure 2 and supplied to the fuel cell. In the figure, 1 is a fuel cell, 2 is a gas guide pipe, 3 is a catalytic reaction tank, 4 is hydrazine hydrate, and 5 is a catalyst. Reacting at room temperature, adding 0.03gLa0.2Sr0.8Co0.2Fe0.8Oδ+ Pt/C catalyst, La0.2Sr0.8Co0.2Fe0.8OδThe mass ratio of the Pt/C substance to the Pt/C substance is 1: 1. H produced by hydrazine decomposition2Entering the fuel cell, measuring the voltage of a single cell to be 0.8V and the current density to be 150mA/cm2. The performance curve of the cell is shown in figure 3. After 1 week of catalytic reaction, no significant change in cell performance was observed.
Claims (6)
1. A preparation and application of hydrazine decomposition catalyst is characterized in that the catalyst comprises the following components:
XYC, wherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, Y is perovskite type or fluorite type or conite type composite oxide, C is nano carbon black, X can be one or more metals, Y is one of three types of oxides, and C can be added or not added.
2. The catalyst of claim 1, wherein: the metal-supported composition is as follows:
X/Y, wherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, Y is perovskite type or fluorite type or conite type composite oxide, X can be one or more metals, Y is one of three types of oxides, and the loading amount of X on Y is 0.5-20%.
3. The catalyst of claim 1, wherein: the mixed type composition is as follows:
(X/C)a+Ybwherein X is Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, In, Os, Ir, Pt and Au metal elements, C is nano carbon black, Y is one of three types of oxides, and the loading amount of X on C is 0.5-40%. and a and b are the mass of two X/C and Y, and the ratio of a to b is 0.1-10.
4. A method of preparing the catalyst of claim 2, wherein: firstly adopting a sol-gel method (using EDTA and citric acid as a common complexing agent, using soluble metal salt as an initial raw material, using hexanediol and glycerol as a dispersing agent, stirring the system at a constant temperature of 70-90 ℃ to form a transparent colloid, curing the colloid at 100-150 ℃, pre-roasting at 250-350 ℃ for 1-10 hours, and finally roasting at 1000-1400 ℃ for 1-100 hours) or a solid grinding method (using nitrate of metal as a raw material, mixing and fully grinding, then roasting at 1000-1400 ℃, taking out the mixture every 1-5 hours, fully grinding and roasting, repeating for 5-10 times) to prepare the perovskite or fluorite or coniferous ore type composite oxide, then adding ethanol or water, formaldehyde, KOH, and the soluble metal salt or acid solution to be loaded, stirring for 1-4 hours at 20-60 ℃, filtering or standing and pouring the upper layer solution, washing with clear water to enable the pH value to reach 7, and then drying at 80-150 ℃.
5. A method of preparing the catalyst of claim 3, wherein: dispersing the nano carbon black by using ethanol, then adding formaldehyde, KOH and required metal soluble salt, stirring for 1-4 hours at the temperature of 20-60 ℃, filtering or standing and pouring the upper layer solution, washing with clear water to enable the pH value to reach 7, and drying at the temperature of 80-150 ℃ to obtain X/C. Mixing and grinding X/C and the perovskite type or fluorite type or coniferous ore type composite oxide prepared by the method according to claim 3, then immersing the mixed solid into distilled water solution for ultrasonic oscillation for 0.1-3 h, and drying at 80-150 ℃.
6. A catalyst as claimed in claim 1, 2 or 3, wherein: the catalyst can be used for hydrogen source generation of a proton exchange membrane fuel cell.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00123085A CN1348835A (en) | 2000-10-17 | 2000-10-17 | Prepn and application of hydrazine decomposing catalyst |
| PCT/CN2000/000409 WO2002032573A1 (en) | 2000-10-17 | 2000-10-30 | The preparation of a hydrazine decomposition catalyst and its use |
| AU2001212663A AU2001212663A1 (en) | 2000-10-17 | 2000-10-30 | The preparation of a hydrazine decomposition catalyst and its use |
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| Application Number | Priority Date | Filing Date | Title |
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| CN00123085A CN1348835A (en) | 2000-10-17 | 2000-10-17 | Prepn and application of hydrazine decomposing catalyst |
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| CN1348835A true CN1348835A (en) | 2002-05-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN00123085A Pending CN1348835A (en) | 2000-10-17 | 2000-10-17 | Prepn and application of hydrazine decomposing catalyst |
Country Status (3)
| Country | Link |
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| CN (1) | CN1348835A (en) |
| AU (1) | AU2001212663A1 (en) |
| WO (1) | WO2002032573A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161003A (en) * | 2011-02-14 | 2011-08-24 | 东南大学 | Preparation and application method of hydrazine-degrading catalyst |
| CN102558244A (en) * | 2012-01-10 | 2012-07-11 | 大连理工大学 | O-benzenedithiol and diazene bridged binuclear iron complex and preparation method and application thereof |
| CN102603808A (en) * | 2012-02-03 | 2012-07-25 | 大连理工大学 | O-benzene dithiol and ammonia/amine bridged binuclear iron complex as well as preparation method and application thereof |
| CN105561775A (en) * | 2015-12-23 | 2016-05-11 | 中国科学院兰州化学物理研究所 | Catalytic oxidation method of unsymmetrical dimethylhydrazine waste gas |
| CN105777458A (en) * | 2014-12-26 | 2016-07-20 | 比亚迪股份有限公司 | Automatic ignition powder for gas generator of air bag restraint system of automobile and preparation method of automatic ignition powder |
| CN113026051A (en) * | 2021-03-12 | 2021-06-25 | 中国科学技术大学 | Ruthenium-manganese oxide solid solution, preparation method thereof and application of ruthenium-manganese oxide solid solution as acidic oxygen precipitation reaction electrocatalyst |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230312431A1 (en) | 2020-01-22 | 2023-10-05 | Xi'an Crysten Materials Technology Corporation Limited | Compounds and preparation method therefor and use thereof as energetic materials |
| CN111871420B (en) * | 2020-08-03 | 2023-07-18 | 重庆工业职业技术学院 | Preparation method and application of titanium-based tin dioxide-supported fluorite-shaped nickel oxide electrocatalyst |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4122671A (en) * | 1962-10-26 | 1978-10-31 | Shell Oil Company | Hydrazine decomposition and other reactions |
| US4324819A (en) * | 1970-10-20 | 1982-04-13 | United Aircraft Corporation | Catalyst for hydrazine decomposition and the method of producing the catalyst |
| US4348303A (en) * | 1970-10-20 | 1982-09-07 | United Technologies Corporation | Catalyst for hydrazine decomposition |
| JPS59199022A (en) * | 1983-04-26 | 1984-11-12 | Matsushita Electric Ind Co Ltd | Method for reducing nox |
| JP3245605B2 (en) * | 1991-02-15 | 2002-01-15 | 独立行政法人産業技術総合研究所 | Method for producing catalyst for hydrazine decomposition |
-
2000
- 2000-10-17 CN CN00123085A patent/CN1348835A/en active Pending
- 2000-10-30 AU AU2001212663A patent/AU2001212663A1/en not_active Abandoned
- 2000-10-30 WO PCT/CN2000/000409 patent/WO2002032573A1/en active Application Filing
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161003A (en) * | 2011-02-14 | 2011-08-24 | 东南大学 | Preparation and application method of hydrazine-degrading catalyst |
| WO2012109846A1 (en) * | 2011-02-14 | 2012-08-23 | 东南大学 | Methods for preparation and use of catalyst for hydrazine degradation |
| CN102161003B (en) * | 2011-02-14 | 2012-09-19 | 东南大学 | Preparation and application method of hydrazine-degrading catalyst |
| CN102558244A (en) * | 2012-01-10 | 2012-07-11 | 大连理工大学 | O-benzenedithiol and diazene bridged binuclear iron complex and preparation method and application thereof |
| CN102558244B (en) * | 2012-01-10 | 2014-06-25 | 大连理工大学 | O-benzenedithiol and diazene bridged binuclear iron complex and preparation method and application thereof |
| CN102603808A (en) * | 2012-02-03 | 2012-07-25 | 大连理工大学 | O-benzene dithiol and ammonia/amine bridged binuclear iron complex as well as preparation method and application thereof |
| CN102603808B (en) * | 2012-02-03 | 2014-08-27 | 大连理工大学 | O-benzene dithiol and ammonia/amine bridged binuclear iron complex as well as preparation method and application thereof |
| CN105777458A (en) * | 2014-12-26 | 2016-07-20 | 比亚迪股份有限公司 | Automatic ignition powder for gas generator of air bag restraint system of automobile and preparation method of automatic ignition powder |
| CN105561775A (en) * | 2015-12-23 | 2016-05-11 | 中国科学院兰州化学物理研究所 | Catalytic oxidation method of unsymmetrical dimethylhydrazine waste gas |
| CN113026051A (en) * | 2021-03-12 | 2021-06-25 | 中国科学技术大学 | Ruthenium-manganese oxide solid solution, preparation method thereof and application of ruthenium-manganese oxide solid solution as acidic oxygen precipitation reaction electrocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002032573A1 (en) | 2002-04-25 |
| AU2001212663A1 (en) | 2002-04-29 |
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