CN101411975A - Use of carbon-supported transitional metal carbides catalyst in hydrazine decomposition reaction - Google Patents
Use of carbon-supported transitional metal carbides catalyst in hydrazine decomposition reaction Download PDFInfo
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- CN101411975A CN101411975A CNA2007101575627A CN200710157562A CN101411975A CN 101411975 A CN101411975 A CN 101411975A CN A2007101575627 A CNA2007101575627 A CN A2007101575627A CN 200710157562 A CN200710157562 A CN 200710157562A CN 101411975 A CN101411975 A CN 101411975A
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- catalyst
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- hydrazine
- decomposition reaction
- hydrazine decomposition
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Abstract
The invention relates to a catalyst for hydrazine decomposition reaction, in particular to a hydrazine decomposition catalyst loaded by a charcoal carrier. The active composition is carbide of W, Mo, Ni, Co, Cr, Fe, V, Nb, Ti, Zr and other transition metals. The catalyst has similar hydrazine decomposition performance with traditional Ir/Al2O3 and has good application prospect in various power systems taking liquid hydrazine as fuel and gas generating systems.
Description
Technical field
The present invention relates to be used for the catalyst of hydrazine decomposition reaction, a kind of specifically is carrier with the raw material of wood-charcoal material, is the application of catalyst in hydrazine decomposition reaction of active component with single constituent element or bi-component transition metal carbide.
Background technology
Hydrazine is a kind of stable liquid at normal temperatures, about 250 ℃ pyrolysis can take place.Under the effect of catalyst decomposition reaction can take place at a lower temperature, generate nitrogen, hydrogen and the ammonia gas mixture body of HTHP.For a long time, hydrazine is widely used in the attitude control system of aerospace craft as liquid fuel, the emergency power system of aircraft, and the buoyant device of sounding balloon, shipwreck or submarine etc.
Present most popular hydrazine decomposing catalyst is the 20-40%Ir/ γ-Al of U.S. Shell company development
2O
3Catalyst [U.S.Pat.4,124,538].But activity of such catalysts component iridium is rare noble metal, is a kind of senior strategic materials, costs an arm and a leg; And the carrier of catalyst is the aluminium oxide through special processing, so the cost of this catalyst is very high.Therefore development of new, hydrazine decomposing catalyst becomes the research emphasis of various countries' researcher cheaply.
[PCT Int.Appl.WO 9,633,803] have reported that the transition metal carbide of pure phase is used for the result of hydrazine decomposition reaction, show that this type of catalyst has and the similar hydrazine degrading activity of precious metal iridium catalyst.CHEN XIAOWEIs etc. [CN 01101118.1] have been reported with γ-Al
2O
3Support type Mo for carrier
2The hydrazine degrading activity of C catalyst.The experimental result of engine shows that this catalyst has good catalytic activity in hydrazine decomposition reaction.
Various raw material of wood-charcoal material are widely used in all kinds of liquid phase reactors and the hydrogen-involved reaction as carrier, but the application in hydrazine decomposition reaction does not also have patent and bibliographical information as carrier with it.
Summary of the invention
The object of the present invention is to provide a kind of low cost, high performance support type hydrazine decomposing catalyst, its carrier is the raw material of wood-charcoal material, and active component is single constituent element or multicomponent transition metal carbide.
For achieving the above object, technical scheme of the present invention is:
The application of a kind of carbon-supported transitional metal carbides catalyst in hydrazine decomposition reaction, described catalyst can be used formula A
xB
yC/Z represents that it is a loaded catalyst, and A is W or Mo, and B is Ni, Co, Cr, Fe, V, Nb, Ti or Zr, and C is a carbon, and Z is the charcoal carrier, wherein 0≤x≤4,0≤y≤4.
The charcoal carrier of described catalyst is various raw material of wood-charcoal material such as active carbon, carbon black, CNT, activated carbon fiber, carbon nano-fiber/carbon felt composite material or mesopore raw material of wood-charcoal material.Active component is A
xB
ySingle constituent element of C or bi-component transition metal carbide, its loading is 10-60wt%.
This catalyst preparation process is as follows:
With transition metal A or/and in the mixed solution of the water-soluble and ethanol of the soluble-salt of B (mass content of ethanol is 0-100%), adopt the method for dipping to support on the charcoal carrier, flooded 1-24 hour, 100-150 ℃ of oven dry 6-24 hour, in 350-500 ℃ of inert atmosphere roasting 2-6 hour, make presoma.
Presoma is pressed document [Journal of Solid State Chemistry 59 (1985) 348] and [CN116921C] reported method, carry out the temperature programming reaction respectively in methane and hydrogen mixed gas or in the pure hydrogen, heating rate is 0.5-20 ℃/minute, reaction velocity is 500-20000/ hour, final reaction temperature is 600-1000 ℃, reaction time is 0.5-5 hour, can prepare different carbon-supported transitional metal carbides catalysts.
Catalyst of the present invention can be used for all kinds of hydrazine decomposition reactions, thereby the hydrazine that can be further used for the buoyant device of the emergency power system of attitude control system, aircraft of aerospace craft and sounding balloon, shipwreck or submarine decomposes in the engine.
Advantage of the present invention is:
1. this catalyst preparation process is simple, can produce in batches.Because activity of such catalysts component and carrier are respectively cheap transition metal carbon compounds is and cheap raw material of wood-charcoal material therefore to greatly reduce preparation cost.
2. because the charcoal carrier has that specific area is big, intensity is high, is easy to advantage such as moulding, the charcoal that helps preparing carries the practical application of carbon compound catalyst in hydrazine decomposition reaction.
3. with traditional Ir/ γ-Al
2O
3Catalyst is compared, and this catalyst has suitable hydrazine and decomposes initial activity and higher hydrazine decomposition efficiency, therefore can partially or completely substitute Ir/ γ-Al in hydrazine decomposition reaction
2O
3Catalyst.
The specific embodiment
Embodiment 1
WC
x/ AC-c Preparation of catalysts
Take by weighing 0.31g, 1.38g, the 2.44g ammonium metatungstate is dissolved in respectively in the 3.0ml deionized water, the settled solution that obtains is distinguished incipient impregnation to 2.0g active carbon (AC) carrier, drying is 12 hours under the room temperature, in 120 ℃ of baking ovens dry 12 hours then, roasting is 4 hours under 500 ℃ of nitrogen atmospheres, makes WO
3/ AC presoma.With WO
3/ AC presoma, program temperature reaction in methane and hydrogen mixed gas (methane content is 25%) is raised to 450 ℃ with the speed of 10 ℃/min from room temperature, speed with 1 ℃/min is raised to 850 ℃ again, after keeping 2 hours under this temperature, be cooled to room temperature, this catalyst is labeled as WC
x/ AC-c makes activity of such catalysts constituent mass loading and is respectively: 10wt%, 33.3wt%, 55wt%.
Embodiment 2
W
2The C/AC-h Preparation of catalysts
Method for preparing catalyst is with embodiment 1, and difference from Example 1 is, the mixed air of methane in the temperature programming course of reaction and hydrogen changed make pure hydrogen.This catalyst is labeled as W
2C/AC-h, active component quality loading is 10wt%, 33.3wt%, 55wt%.
Embodiment 3
WNiC
x/ AC-h Preparation of catalysts
Taking by weighing 1.04g ammonium metatungstate and 1.19g nickel nitrate is dissolved in and is made into mixed solution (mol ratio of tungsten and nickel is 1:1) in the 3.0ml deionized water, with the settled solution incipient impregnation that obtains to 2.0g active carbon (AC) carrier, drying is 12 hours under the room temperature, in 120 ℃ of baking ovens dry 12 hours then, roasting is 4 hours under 500 ℃ of nitrogen atmospheres, makes WNiO
4/ AC presoma.With WNiO
4/ AC presoma, program temperature reaction in hydrogen is raised to 450 ℃ with the speed of 10 ℃/min from room temperature, and the speed with 1 ℃/min is raised to 850 ℃ again, after keeping 2 hours under this temperature, is cooled to room temperature.This catalyst is labeled as WNiC
x/ AC-h (active component 33.3wt%).
Embodiment 4
WCoC
x/ AC-h Preparation of catalysts
Method for preparing catalyst is with embodiment 3, and difference from Example 3 is, the mixed solution of 1.04g ammonium metatungstate and 1.19g nickel nitrate is changed into the mixed solution of 1.04g ammonium metatungstate and 1.19g cobalt nitrate.The catalyst that makes is labeled as WCoC
x/ AC-h (active component 33.3wt%).
Embodiment 5
Ir/ γ-Al
2O
3Preparation of catalysts
2.56g Chloroiridic Acid solution (mass concentration of Ir is 24.2%) is impregnated into 10g γ-Al
2O
3On the carrier, put into 100 ℃ of baking ovens oven dry 6 hours, reductase 12 hour under 300 ℃ of hydrogen makes Ir/ γ-Al
2O
3(24.8wt%) catalyst.
Embodiment 6
Preparation of catalysts
The Ir/AC method for preparing catalyst is with embodiment 3, and difference is with it, with γ-Al
2O
3Carrier changes absorbent charcoal carrier into, makes Ir/AC (33.3wt%) catalyst.
Embodiment 7
The evaluation of catalyst
Evaluating catalyst of the present invention carries out on the 1N engine.Experiment is adopted gas to squeeze to push away mode and is supplied hydrazine fuel, beds is preheated to experimental temperature after, by solenoid control hydrazine decomposition reaction process.P is pressed in combustion
cWith reaction bed temperature T
cThe use respective sensor is measured.
(1) different catalysts hydrazine degrading activity compares, and hydrazine degrading activity evaluation result sees Table 1.
As can be seen from Table 1, be the metal iridium catalyst of preparing carriers, single constituent element or bi-component transition metal carbide catalyst with the active carbon, bed temperature that produces in catalysis hydrazine decomposable process and combustion are pressed and all are higher than Ir/ γ-Al
2O
3Catalyst illustrates with the active carbon to be that the catalyst of carrier has higher hydrazine decomposition efficiency.t
90Be an important indicator that embodies the engine overall performance, in general, t
90Less than 1000ms, just reach requirement of actual application substantially.The result shows in the table 1, Ir/ γ-Al
2O
3The t of catalyst
90Be 410ms, the t of single constituent element or bi-component transition metal carbide catalyst
90Between 400ms and 600ms, with Ir/ γ-Al
2O
3Catalyst is suitable, illustrates that it has good application prospects.WNiC
x/ AC-h and WCoC
xThe t of/AC-h catalyst
90Be respectively 405ms and 415ms, all less than W
2The t of C/AC-h catalyst
90, illustrate that the adding of second component has improved the startup acceleration of catalyst.
Table 1 different catalysts hydrazine degrading activity relatively
Annotate: case is pressed 0.8MPa, 180 ℃ of start-up temperature, 30 seconds stable states
(2) will use the minimum start-up temperature of two kinds of loaded tungsten carbide catalysts of active carbon of distinct methods preparation to compare, comparative result sees Table 2.As can be seen from Table 2,33.3wt%W
2The minimum start-up temperature of C/AC-h catalyst is starkly lower than 33.3wt%WC
xCatalyst illustrates the W that adopts the preparation of hydrogen temperature programming reaction method
2The C/AC-h catalyst has better hydrazine and decomposes the startup activity.
The minimum start-up temperature of table 2 catalyst relatively
(3) with 33.3wt%W
2The hydrazine stability of factorization of C/AC-h catalyst and 33.3wt% Ir/AC catalyst compares, and comparative result sees Table 3.
The stability of table 3 catalyst relatively
As can be seen from Table 3,33.3wt% W
2After the C/AC-h catalyst has experienced stable state experiment in 10 times 30 seconds, the catalyst quality loss seldom, and after 33.3wt% Ir/AC catalyst only experiences the experiment of 2 times 30 seconds stable states, the catalyst quality loss reaches more than 60%, illustrates that the tungsten carbide catalyst that active carbon supports has better hydrazine stability of factorization.
Claims (4)
1. the application of carbon-supported transitional metal carbides catalyst in hydrazine decomposition reaction, it is characterized in that: described catalyst can be used formula A
xB
yC/Z represents that it is a loaded catalyst, and A is W or Mo, and B is Ni, Co, Cr, Fe, V, Nb, Ti or Zr, and C is a carbon, and Z is the charcoal carrier, wherein 0≤x≤4,0≤y≤4; Wherein, active component is A
xB
ySingle constituent element of C or bi-component transition metal carbide, its loading is 10-60wt%.
2. according to the described application of claim 1, it is characterized in that: described charcoal carrier is active carbon, carbon black, CNT, activated carbon fiber, carbon nano-fiber/carbon felt composite material or mesopore raw material of wood-charcoal material.
3. according to the described application of claim 1, it is characterized in that: described catalyst can be used formula A
xC/Z represents that wherein A is W or Mo, 1＜x＜2.
4. according to the described application of claim 1, it is characterized in that: described catalyst can be used formula A
2C/Z represents that wherein A is W or Mo.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011050691A1 (en) * | 2009-10-27 | 2011-05-05 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst supported on mesoporous carbon, preparation and application thereof |
| CN102161003A (en) * | 2011-02-14 | 2011-08-24 | 东南大学 | Preparation and application method of hydrazine-degrading catalyst |
| US20120065052A1 (en) * | 2010-09-14 | 2012-03-15 | Basf Se | Process for producing a carbon-comprising support |
| WO2012035501A1 (en) * | 2010-09-14 | 2012-03-22 | Basf Se | Process for producing carbon-comprising support |
| CN102631932A (en) * | 2011-02-14 | 2012-08-15 | 中国科学院大连化学物理研究所 | Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof |
| US20150083585A1 (en) * | 2012-04-20 | 2015-03-26 | Brookhaven Science Associates, Llc | Molybdenum and Tungsten Nanostructures and Methods for Making and Using Same |
| US9352304B2 (en) | 2010-03-17 | 2016-05-31 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Methods for preparing ethylene glycol from polyhydroxy compounds |
| CN111646870A (en) * | 2020-05-06 | 2020-09-11 | 北京航天试验技术研究所 | Catalyst applied to low-temperature starting monopropellant and preparation method thereof |
-
2007
- 2007-10-19 CN CNA2007101575627A patent/CN101411975A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013508148A (en) * | 2009-10-27 | 2013-03-07 | 中国科学院大▲連▼化学物理研究所 | Tungsten carbide catalyst supported on mesoporous carbon, its preparation and application |
| US8889585B2 (en) | 2009-10-27 | 2014-11-18 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Mesoporous carbon supported tungsten carbide catalysts, preparation and applications thereof |
| RU2528389C2 (en) * | 2009-10-27 | 2014-09-20 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайенсез | Mesoporous carbon supported tunsten-carbide catalysts, production and use thereof |
| US20120178974A1 (en) * | 2009-10-27 | 2012-07-12 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Mesoporous carbon supported tungsten carbide catalysts, preparation and applications thereof |
| WO2011050691A1 (en) * | 2009-10-27 | 2011-05-05 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst supported on mesoporous carbon, preparation and application thereof |
| US9352304B2 (en) | 2010-03-17 | 2016-05-31 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Methods for preparing ethylene glycol from polyhydroxy compounds |
| CN103118779A (en) * | 2010-09-14 | 2013-05-22 | 巴斯夫欧洲公司 | Process for producing carbon-comprising support |
| US8709964B2 (en) | 2010-09-14 | 2014-04-29 | Basf Se | Process for producing a carbon-comprising support |
| WO2012035501A1 (en) * | 2010-09-14 | 2012-03-22 | Basf Se | Process for producing carbon-comprising support |
| US20120065052A1 (en) * | 2010-09-14 | 2012-03-15 | Basf Se | Process for producing a carbon-comprising support |
| CN102161003B (en) * | 2011-02-14 | 2012-09-19 | 东南大学 | Preparation and application method of hydrazine-degrading catalyst |
| CN102631932A (en) * | 2011-02-14 | 2012-08-15 | 中国科学院大连化学物理研究所 | Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof |
| CN102631932B (en) * | 2011-02-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | Nickel-base metal catalyst for preparing hydrogen by hydrazine decomposition at room temperature, as well as preparation and application thereof |
| CN102161003A (en) * | 2011-02-14 | 2011-08-24 | 东南大学 | Preparation and application method of hydrazine-degrading catalyst |
| US20150083585A1 (en) * | 2012-04-20 | 2015-03-26 | Brookhaven Science Associates, Llc | Molybdenum and Tungsten Nanostructures and Methods for Making and Using Same |
| CN111646870A (en) * | 2020-05-06 | 2020-09-11 | 北京航天试验技术研究所 | Catalyst applied to low-temperature starting monopropellant and preparation method thereof |
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Open date: 20090422 |