CN104028284B - A kind of application of Ni-based framework metal catalyst in hydrazine decomposing hydrogen-production - Google Patents
A kind of application of Ni-based framework metal catalyst in hydrazine decomposing hydrogen-production Download PDFInfo
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- CN104028284B CN104028284B CN201310069639.0A CN201310069639A CN104028284B CN 104028284 B CN104028284 B CN 104028284B CN 201310069639 A CN201310069639 A CN 201310069639A CN 104028284 B CN104028284 B CN 104028284B
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- 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
Abstract
The present invention relates to a kind of Ni-based framework metal catalyst prepares the application in hydrogen in hydrazine decomposition.Specifically with nickeliferous framework metal as catalyst, under the conditions of 0 100 °C of alkaline assistants, hydrazine or the hydrazine aqueous solution fast decoupled of variable concentrations is made to obtain hydrogen and nitrogen, the selectivity of hydrogen is more than 99%.Catalyst raw material of the present invention is easy to get, preparation process is simple, has that hydrogen production efficiency is high, accessory substance is few, catalyst is easily reclaimed, an advantage such as with low cost, with potential application prospect.
Description
Technical field
The present invention relates to a kind of application of Ni-based framework metal catalyst in hydrazine decomposing hydrogen-production, specifically using nickel
Base matrix type metal catalytic hydrazine or hydrazine aqueous solution decomposition prepare a kind of method of hydrogen.
Background technology
Hydrogen as a kind of clean energy resource, with cleaning, efficiently, application form variation many advantages, such as, therefore always
Since receive much concern.The safety storage of hydrogen and transport are to hinder one of technical bottleneck of Hydrogen Energy development, particularly may move and set
The storage of standby upper hydrogen is always important research topic.The research of hydrogen storage material focuses primarily upon two aspects, one at present
It is physics hydrogen storage, for example with high pressure hydrogen storage tank, novel high-capacity hydrogen storage material etc.；Its two be using chemical reaction hydrogen manufacturing,
Partial oxidation or steam reformation of such as hydro carbons, alcohols etc., the medium that compound is stored as a kind of hydrogen.Due to institute
Hydrogen content in the compound of research will be significantly larger than the hydrogen content in physics hydrogen storage material, and therefore, chemical hydrogen storage material is regarded
For most possibly meeting one of approach of hydrogen storage demand on mobile device.
The molecular formula of hydrazine is N2H4, it is a kind of energized fluid material of hydrogen-rich, the mass content of hydrogen is up to 12.5wt%.Hydrazine
Hydrate soln, such as a hydrazine hydrate (N2H4·H2O), it is liquid at room temperature, property is more stable than pure hydrazine, but still has
Up to 8.0wt% releases hydrogen amount, be above the mobile device hydrogen storage material hydrogen content that USDOE (DOE) proposes standard (>=
4.5wt%).Additionally, hydrazine will not produce CO after decomposing, it is convenient to omit the process of CO selectively removings, and the by-product for decomposing completely
Thing is only N2, it is not necessary to reclaimed and separated, enormously simplify last handling process.If it is possible to the hydrogen in hydrazine is existed
Discharge under temperate condition, can be used as a kind of preferable hydrogen storage material, be particularly suitable as movement and set
Standby hydrogen source.
Hydrazine can be decomposed by two kinds of approach：
Decompose N completely2H4→N2(g)+2H2(g) (1)；
Decomposed 3N2H4→4NH3+N2(g) (2).
In hydrazine decomposition reaction, above two approach can occur simultaneously, and include the elementary reaction of multistep.Wherein, if
N-H keys preferentially rupture, and are conducive to the carrying out for reacting (1)；If N-N keys first rupture, it is easy to the carrying out for reacting (2).From thermodynamics
Angle says that N-N bond energys are 60KJ/mol, and N-H bond energys are 84KJ/mol, and under cryogenic, the fracture of N-N keys is more easy.
But if N-N keys preferentially rupture in course of reaction, reaction is preferentially carried out according to response path (2), and then generates a large amount of NH3, shadow
Ring the efficiency of hydrogen manufacturing.It is thus desirable to from suitable catalyst, promoting N-H keys preferentially to rupture, with making reaction selectivity according to road
Footpath (1) is carried out, and then efficient-decomposition hydrazine obtains more hydrogen, the follow-up separating step of simplification.
In recent years, hydrazine is caused scientific circles and business circles as the technology that a kind of liquid hydrogen storage material is used for online hydrogen manufacturing
Extensive concern, and efficiently, the development and utilization of high selectivity catalyst for preparing hydrogen be the key for realizing this process.Wherein, non-
Noble metal catalyst is cheap and easy to get due to which, becomes the focus of research.It has been reported that non-precious metal catalyst mainly include gold
Category alloy catalyst, composite oxide catalysts and loaded catalyst.Japanese Scientists report Ni-Fe alloy nano particles
For being hydrated in hydrazine decomposition reaction, by the use of NaOH as auxiliary agent, with high hydrogen selective (S.K.Singh, et al.,
Journal of the American Chemical Society,2011,133,19638).Perovskite type metal combined oxidation
Thing, also being capable of high selectivity decomposition hydrazine hydrogen making in the presence of a large amount of KOH used as catalyst（B.Zhao,et al.,
Int.J.Hydrogen Energy,2012,37,1133）.Chinese patent（Publication number CN1348835A）Metal is reported and has answered
The combination catalyst for closing oxide realizes that hydrazine hydrate decomposes the process of hydrogen making, can provide hydrogen source or work for fuel cell
Hydrogen source in for intermetallic composite coating is used.Additionally, support type Ni based metal catalysts are shown in the reaction of hydrazine hydrate decomposing hydrogen-production
Very high activity and selectivity, but the catalyst hydrogen manufacturing selective at room temperature for 93% (L.He, et al.,
Angewandte Chemie International Edition,2012,51,6191).Although above-mentioned non-precious metal catalyst
The selectivity that upper hydrazine decomposes product hydrogen is all higher, but for nano-particle and composite oxide catalytic, its catalysis activity is generally relatively low,
Produce hydrogen speed relatively slow；And for supported Ni catalyst, a small amount of NH in product3Follow-up separating step can still be affected.
Accordingly, it would be desirable to develop a kind of catalyst for taking into account high activity and high selectivity, realize under temperate condition, decomposing hydrazine or the hydrazine aqueous solution
Hydrogen making.
Framework metal catalyst is the catalyst that a class has high activity, Large ratio surface, and its use range extensively, is especially fitted
In for liquid phase reactor.By the modulation of presoma alloy, and the change of alkali activation condition, catalyst structure and property can be realized
The modulation of matter, improves the stability and activity of skeleton catalyst, can apply in the reaction of hydrazine decomposing hydrogen-production.
Content of the invention：
The present invention is aiming at the problems referred to above, there is provided hydrazine decomposes a kind of Ni-based framework metal catalyst in a mild condition
Application in hydrogen manufacturing.
In order to realize that the above-mentioned purpose of the present invention, the present invention are adopted the following technical scheme that：
A kind of application of Ni-based framework metal catalyst in hydrazine decomposing hydrogen-production, with nickeliferous framework metal as catalyst,
Under the conditions of 0-100 °C of alkaline assistant, hydrazine raw material decomposes are made to obtain hydrogen and nitrogen.
The nickeliferous framework metal is skeleton nickel or skeleton nickel-base alloy, and wherein active metal composition formula is Ni100- xMx, 0≤x≤20, M can be one or two or more kinds in Pt, Ir, Au, Rh, Ru, Pd, Ag, Fe, Co, Cu, Zn, Mo, W, La.
Framework metal catalyst presoma alloy is added in NaOH solution in catalyst preparation process, stirring, magnetic point
From, Ni-based framework metal catalyst is obtained, the concentration of NaOH solution is 2.0-10.0mol L-1, temperature is maintained at 40-90 °C, instead
1-4h between seasonable.
Catalyst precursor is nickel-base alloy, and formula is Ni50-xAl50-yMx+y, 0≤x≤10,0≤y≤10, M can be Pt,
One or two or more kinds in Ir, Au, Rh, Ru, Pd, Ag, Fe, Co, Cu, Zn, Mo, W, La.With molar percent, described
In framework metal catalyst presoma alloy, the content of Ni is 40-50%, and the content of Al is 40-50%, and the component of residue≤20% can
For one or two or more kinds in Pt, Ir, Au, Rh, Ru, Pd, Ag, Fe, Co, Cu, Zn, Mo, W, La.
Hydrazine raw material is that pure hydrazine or concentration are 0.1-16.0mol L-1The hydrazine aqueous solution, preferable reaction temperature be 10-80 °C.
Base agent need to be added before reaction in the reaction system of hydrazine raw material, and described alkaline assistant is NaOH, KOH, Ca
(OH)2、Ba(OH)2In one or two or more kinds.Concentration of the alkaline assistant in initial reaction liquid is 0.01-5.00mol L-1.
Alkaline assistant is 0.02-10.00 with the mass ratio of raw material, and catalyst is 0.05-0.80 with the mass ratio of raw material.
The invention has the advantages that：
1. method for preparing catalyst is simple, raw material is easy to get, cheap.Catalyst has very strong magnetic, it is easy to separate,
Can repeatedly use.
2. there is hydrogen selective height in matrix type nickel based metal catalyst in hydrazine decomposing hydrogen-production, and reaction condition is gentle, secondary
The advantage such as product is few, with potential application prospect.
Specific embodiment
Embodiment 1
The preparation of Ni-based framework metal catalyst
Catalyst precursor is Ni50-xAl50-yMx+y, 0≤x≤10, the alloy of 0≤y≤10, after crushing as 20-300 mesh,
It is added to and uses 5.00mol L-1NaOH solution in, stirring, bath temperature control at 80 °C, the reaction time is 3h.Reaction terminates
Afterwards, deionized water cyclic washing catalyst, to cleaning solution in neutrality, is separated using magnet, is obtained Ni-based framework metal
Catalyst.Work as x, y is respectively 0, when alloy powder is 40 mesh, obtains Raney Ni-40.Work as x, y is respectively 0, and alloy powder is
During 300 mesh, Raney Ni-300 catalyst is obtained.Work as x=2, y=0, when M is Pt, obtain Raney Ni-Pt catalyst；Work as x=1,
When y=1, M are W, Raney Ni-W catalyst is obtained.
Embodiment 2
Application of the Ni-based framework metal catalyst catalyst in hydrazine decomposition
This reaction is carried out in closed drainage system, and experimentation is as follows：First, the deionized water of 4mL is urged with 0.1g
Agent is closed by system after adding in three-necked bottle；Then, 0.50ml hydrazine hydrate solutions are injected in above-mentioned three-necked bottle, is obtained initial
Concentration is 0.10-0.45mol L-1Hydrazine solution, start simultaneously at timing, reaction temperature is between 0-100 °C.Hydrazine catalytic decomposition is produced
Raw gas first by absorption by Hydrochloric Acid device will likely accessory substance NH3Absorb, it is ensured that remaining is only hydrogen and nitrogen.Right
The product gas are collected, and the activity for calculating reaction by the gas production for reading the unit interval, by reading cumulative gas production
Calculate the selectivity of reaction.
Embodiment 3
The catalysis activity test that different alkali concns decompose to hydrazine hydrate
Using the single active center's Raney Ni-300 catalyst prepared in embodiment 1, add respectively different amounts of
It is 0.01-5.00mol L that NaOH makes its initial concentration in reactant liquor-1, Raney Ni-300+NaOH catalyst system and catalyzings are obtained,
And in reacting for hydrazine hydrate decomposing hydrogen-production described in embodiment 2.
The active testing result of different catalysts is compared, as shown in table 1.
The hydrazine decomposing hydrogen-production test result of 1 different catalysts of table（30 °C, initial hydrazine concentration is 0.32mol L-1）
As seen from Table 1, single active center's skeletal nickel catalyst of 300 mesh has height to the room-temperature decomposition hydrogen manufacturing of hydrazine hydrate
Up to 83% selectivity, the significantly larger than catalyst of 40-60 mesh.
Used as a kind of auxiliary agent, itself decomposes to hydrazine does not have catalytic action to highly basic.And a small amount of highly basic auxiliary agent is added catalytic body
In system, then can significantly improve the hydrogen manufacturing selectivity of skeletal nickel catalyst.When the concentration of NaOH is 0.05mol L-1When, catalyst
Hydrogen manufacturing selectively bring up to 94%, and be higher than 0.50mol L-1Afterwards, the selectivity of catalyst reaches>99%, almost without NH3's
Generate.
Embodiment 4
Impact of the component of catalyst to hydrazine decomposing hydrogen-production
The single active center prepared in embodiment 1 and dynamics model catalyst are used for hydrazine hydrate described in embodiment 2
In hydrogen production reaction, test result is as shown in table 2.
Impact of 2 catalytic component of table to hydrazine decomposing hydrogen-production（30 °C, initial hydrazine concentration is 0.32mol L-1）
Can see from table 2, mix the dynamics model skeletal nickel catalyst after other components and show better than single work
The activity and selectivity of property center framework Raney nickel.
Embodiment 5
Catalyst life is tested
Multiple circulation has been carried out to adding Raney Ni-300+NaOH (0.50) catalyst system and catalyzing after NaOH in embodiment 2
Hydrazine hydrate decomposing hydrogen-production active testing, method of testing as described in Example 1, reaction temperature be 30 °C, each circulation after be catalyzed
Agent is utilized with magnet separation and recovery, and adding NaOH makes its concentration in initial reaction liquid be maintained at 0.50mol L-1, test
As a result such as table 3.
The multiple circulation active testing results contrast table of 3 embodiment of table, 1 catalyst
As seen from Table 3, the selectivity through 20 loop test rear catalysts has no and is decreased obviously, and the catalysis is described
Agent has good stability, has good prospects for use.
Claims (9)
1. application of a kind of Ni-based framework metal catalyst in hydrazine decomposing hydrogen-production, it is characterised in that：With nickeliferous framework metal
For catalyst, under the conditions of 0-100 DEG C of alkaline assistant, hydrazine raw material decomposes are made to obtain hydrogen and nitrogen；
The nickeliferous framework metal is skeleton nickel-base alloy, and wherein active metal composition formula is Ni100-xMx, 0 ＜ x≤20, M
One kind in Pt, W or two kinds.
2. application according to claim 1, it is characterised in that：By framework metal catalyst forerunner in catalyst preparation process
Body alloy is added in NaOH solution, and stirring, Magnetic Isolation obtain Ni-based framework metal catalyst；The concentration of the NaOH solution is
2.0-10.0mol·L-1, temperature is maintained at 40-90 DEG C, reaction time 1-4h.
3. application according to claim 2, it is characterised in that：Catalyst precursor is nickel-base alloy, and formula is Ni50- xAl50-yMx+y, 0≤x≤10,0≤y≤10, M one kind or two kinds in Pt, W.
4. application according to claim 3, it is characterised in that：With molar percent, described framework metal catalyst
In presoma alloy, the content of Ni is 40-50%, and the content of Al is 40-50%, remaining≤20% group is selected from Pt, W
A kind of or two kinds.
5. application according to claim 1, it is characterised in that：Hydrazine raw material is that pure hydrazine or concentration are 0.1-16.0mol L-1
The hydrazine aqueous solution.
6. application according to claim 1, it is characterised in that：Preferable reaction temperature is 10-80 DEG C.
7. application according to claim 1, it is characterised in that：Alkalescence need to be added before reaction in the reaction system of hydrazine raw material
Auxiliary agent, described alkaline assistant are NaOH, KOH, Ca (OH)2、Ba(OH)2In one or two or more kinds.
8. the application according to claim 1 or 7, it is characterised in that：Concentration of the alkaline assistant in initial reaction liquid is
0.01-5.00mol·L-1.
9. the application according to claim 1 or 7, it is characterised in that：Alkaline assistant is 0.02- with the mass ratio of raw material
10.00, catalyst is 0.05-0.80 with the mass ratio of raw material.
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| CN105618065A (en) * | 2014-11-07 | 2016-06-01 | 中国科学院大连化学物理研究所 | Applications of catalyst in hydrogen production through hydrazine decomposition |
| CN110404558B (en) * | 2019-08-27 | 2022-11-11 | 江西师范大学 | NiPt-Ni (OH) for hydrogen production by hydrazine decomposition 2 /La(OH) 3 Catalyst and preparation method thereof |
| CN112473685A (en) * | 2021-01-04 | 2021-03-12 | 天津工业大学 | Supported amorphous hydrazine hydrate catalytic hydrogen production catalyst and preparation method thereof |
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| 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 |
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| 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 |
Non-Patent Citations (3)
| Title |
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| Application of hydrazinium monoformate as new hydrogen donor whith Raney nickel:a facile reduction of nitro and nitrile moieties;Shankare Gowda et al.;《Tetrahedron》;20021231;第58卷;2211-2213 * |
| Bimetallic Ni-Pt Nanocatalysts for Selective Decomposition of Hydrazine in Aqueous Solution to Hydrogen at Room Temperature for Chemical Hydrogen Storage;Sanjay K. Singh et al.;《Inorg. Chem.》;20100602;第49卷;6148-6152 * |
| Noble-Metal-Free Bimetallic Nanoparticle-Catalyzed Selective Hydrogen Generation from Hydrous Hydrazine for Chemical Hydrogen Storage;Sanjay Kumar Singh etal.;《J. Am. Chem. Soc.》;20111109;第133卷;19638-19641 * |
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