CN101642703B - Catalyst of sodium aluminum hydride complex hydride and preparation method thereof - Google Patents
Catalyst of sodium aluminum hydride complex hydride and preparation method thereof Download PDFInfo
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- CN101642703B CN101642703B CN200910101843XA CN200910101843A CN101642703B CN 101642703 B CN101642703 B CN 101642703B CN 200910101843X A CN200910101843X A CN 200910101843XA CN 200910101843 A CN200910101843 A CN 200910101843A CN 101642703 B CN101642703 B CN 101642703B
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Abstract
The invention relates to a catalyst of sodium aluminum hydride coordination oxide and a preparation method thereof. A chemical general formula of the catalyst is RExAly, wherein x is smaller than 10 but larger than or equal to 1, and y is smaller than 20 but larger than or equal to 1. In the formula, the RE is Sc, Y, La, Ce, Pr, Sm, Nd, Ml (lanthanum-rich mixed tombarthite) or Mm (cerium-rich mixed tombarthite). The preparation method is as follows: according to a chemical amount proportion of the RExAly, RE and the Al block-shaped metal raw materials are weighed and proportionally mixed; the raw materials are then melted into an RExAly alloy cast ingot under an argon protection atmosphere and then crushed and put into a high-power ball mill for ball milling; and then the RExAly catalyst with a particle size of micro-nanometer level is obtained. The preparation process of the catalyst is simple, the operation is easy, and the cost is low. The catalyst is used for reversible catalysis hydrogen storage of sodium aluminum hydride, greatly improves the dynamic performance of the sodium aluminum hydride in terms of hydrogen absorption and release and does not undergo elementary reaction with a matrix hydrogen storage material group to generate inert byproducts so that the system reversible hydrogen storage amount is not damaged.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and the application in the sodium alanate reversible hydrogen storage of sodium aluminum hydride coordination oxide, belong to the hydrogen storage material field.
Background technology
The energy is the source of human development.Face the dual-pressure of the deficient day by day and deterioration of the ecological environment of petroleum resources, utilize this clean energy resource of Hydrogen Energy to replace the common recognition that has become the whole world based on the existing energy of fossil fuel.With hydrogen is that the Proton Exchange Membrane Fuel Cells of fuel and the technological progress and the marketization of electric automobile have further promoted hydrogen energy system Study on Technology and development, and in hydrogen energy system technology chain, hydrogen storage technology is considered to the key link.Recently, people such as Bogdanovic B finds at NaAlH
4In mix transistion metal compounds such as Ti, Ce (as Ti (OBu
n)
4, TiCl
3, CeCl
3Deng) can make it realize reversible hydrogen adsorption and desorption than under the temperate condition as additive.This technology makes the metal-complexing alanate be expected to develop into a kind of hydrogen storage material of new high power capacity, so caused widely and pay close attention to.But the further investigation back is found: NaAlH behind the adding transistion metal compound additive
4The actual hydrogen storage capability of system only reaches 3～4wt.% far below its theoretical value (5.6wt.%), has seriously restricted its practical application.This is owing to put in the hydrogen process in suction, and a considerable amount of anion are introduced in the system and react with matrix hydrogen storage material constituent element and generate the inertia accessory substance, have significantly reduced effective hydrogen storage composition of hydrogen storage material.Some scholar adds NaAlH with elemental metals powder or metal hydride to as catalyst
4In the system, avoided the generation of inertia accessory substance, but elemental metals powder or other metallic compound and transistion metal compounds such as Ti, Ce mutually specific catalytic activity significantly reduce, had a strong impact on the suction hydrogen desorption kinetics of this system, restricted its practical application.Thereby the development new catalyst, put under the hydrogen capacity in the high suction of maintenance system, have again simultaneously and inhale hydrogen desorption kinetics fast and become problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of excellent catalytic activity that has, the Catalysts and its preparation method and the application that can effectively improve sodium alanate reversible hydrogen storage capacity.
The catalyst of sodium aluminum hydride coordination oxide of the present invention, its chemical formula is: RE
xAl
y(1＜x＜10,1≤y＜20), RE is Sc, Y, La, Ce, Pr, Sm, Nd, Ml (lanthanum rich mischmetal) or Mm (cerium-rich mischmetal) in the formula, particle size is a micro/nano level.
The catalyst RE of sodium aluminum hydride coordination oxide of the present invention
xAl
yThe preparation method of (1≤x＜10,1≤y＜20) is according to catalyst chemical formula RE
xAl
y, wherein the stoichiometric proportion of 1≤x＜10,1≤y＜20 is carried out the weighing proportioning with RE and Al reguline metal raw material, and founding becomes RE under argon shield atmosphere
xAl
yAlloy cast ingot is put into the high energy ball mill ball milling after then alloy cast ingot being pulverized, and obtains RE
xAl
yCatalyst, step is as follows:
1) according to catalyst chemical formula RE
xAl
y(1≤x＜10; 1≤y＜20) stoichiometric proportion; get Sc, Y, La, Ce, Pr, Sm, Nd, Ml (lanthanum rich mischmetal) or Mm (cerium-rich mischmetal) respective metal raw material, raw material metal purity is more than 98%, and founding becomes alloy cast ingot under argon shield atmosphere.
2) below alloy cast ingot mechanical crushing to 100 order that founding is become;
3) alloy powder after will pulverizing is put into ball grinder, under argon gas or hydrogen atmosphere, adopt the further ball mill grinding of high energy ball mill, milling atmosphere pressure is 0.2～4MPa, and the ball milling time is 2～60h, and can obtain particle size is the superfine alloy powder RE of micro/nano level
xAl
yCatalyst.
The method that superfines catalyst of the present invention is used for the catalysis sodium aluminum hydride coordination oxide is: with sodium alanate and catalyst RE
xAl
y(1≤x＜10,1≤y＜20) put into ball grinder ball milling 5～160h after the mol ratio according to 1: 0.001～0.10 is evenly mixed, milling atmosphere argon gas or hydrogen atmosphere, pressure are 0.5～8.0MPa.Above-mentioned sodium alanate can be the NaAlH that inhales the hydrogen attitude
4Powder also can be the mixed-powder that the NaH of putting the hydrogen attitude and Al are 1: 1 in molar ratio.
Superfines catalyst provided by the present invention has the following advantages:
1) is different from traditional doping method to adopt and causes the substantive chemical combination attitude catalyst that reduces of matrix hydrogen storage material (as Ti (OBu
n)
4, TiCl
3, CeCl
3Deng), the invention provides the catalyst that adopts in the method and can not generate the inertia accessory substance with the reaction of matrix hydrogen storage material constituent element, effective storage hydrogen constituent element that can the loss system, therefore system greatly improves the suction hydrogen desorption kinetics performance of sodium alanate, the reversible hydrogen storage amount is greatly improved, and can reach more than the 5.0wt% at the actual reversible hydrogen storage capacity of some material system;
2) compare as catalyst with direct interpolation elemental metals powder or metal hydride, it is higher to the invention provides its catalytic activity of catalyst that adopts in the method, so the suction hydrogen desorption kinetics of system has had great improvement;
3) material system provided by the present invention has advantages such as the preparation method is simple, cyclical stability is high, operating temperature is moderate.
Description of drawings
Fig. 1 is with CeAl
4Alloy powder is that catalyst, NaH/Al are the matrix hydrogen storage material, ball milling 100h under the 3.5MPa hydrogen atmosphere, and prepared material is at the suction hydrogen kinetic curve of the 2nd circulation time.Inhale 120 ℃ of hydrogen temperature, initially inhale hydrogen pressure 11MPa.
Fig. 2 is with SmAl
3Alloy powder is catalyst, NaAlH
4Be the matrix hydrogen storage material, the hydrogen desorption kinetics curve of the 3rd of the prepared material of ball milling 60h the circulation time under argon gas atmosphere.Because NaAlH
4Put hydrogen in two steps, the hydrogen discharging temperature in per step is difference to some extent, and substep is put hydrogen.Hydrogen discharging temperature is respectively 120 ℃ and 170 ℃, and putting hydrogen pressure is 0.1MPa.Dotted line is represented sample temperature among the figure, and solid line is represented the hydrogen desorption kinetics curve.
Fig. 3 is with La
3Al
11Alloy powder is that catalyst, NaH/Al are the matrix hydrogen storage material, and the hydrogen kinetic curve is inhaled in the circulation of the prepared material of ball milling 80h under the 4MPa hydrogen atmosphere.Inhale 120 ℃ of hydrogen temperature, the suction hydrogen pressure is 12MPa.
Fig. 4 is with MlAl
2Alloy powder is catalyst, NaAlH
4Be the matrix hydrogen storage material, the hydrogen desorption kinetics curve of circulation 3 times of the prepared material of ball milling 48h under argon gas atmosphere.Hydrogen discharging temperature is 160 ℃, and putting hydrogen pressure is 0.1MPa.
The specific embodiment
With CeAl
4Alloy powder is that catalyst, NaH and Al powder are matrix material, preparation CeAl
4The NaAlH that mixes
4Hydrogen storage material.
The employing raw material is: NaH (purity 95% ,～200 orders), Al powder (purity greater than 99.9% ,～200 orders), metal Ce piece (purity is greater than 99.9%), metal A l piece (purity is greater than 99.9%).The all unprocessed direct employing of raw material.
1) CeAl
4The preparation of alloy powder caltalyst
Get metal Ce piece and Al piece at 1: 4 by the mole proportioning, induction melting becomes CeAl under argon shield
4Alloy cast ingot; Then below mechanical crushing to 100 order; Again the alloying pellet after the mechanical crushing is placed stainless steel jar mill, charge into 0.6MPa hydrogen in the ball grinder, ball milling 10h on high energy ball mill makes the CeAl that particle size is a micro/nano level
4Fine catalyst.
2) CeAl
4Fine catalyst is used for NaAlH
4The preparation of hydrogen storage material
With CeAl
4Fine catalyst, NaH and Al powder are matrix material, NaH+Al+0.02CeAl in molar ratio in the argon atmospher glove box
4Insert after proportion raw material mixes in the stainless steel jar mill, carry out ball milling on high energy ball mill, milling atmosphere is a nitrogen atmosphere, ball milling hydrogen pressure 3.5MPa, ratio of grinding media to material 35: 1, ball milling time 100h.
Adopt the hydrogen storage property of volumetric method test material.Cycling condition is: put hydrogen for 160 ℃; Inhale hydrogen, the about 11MPa of initial suction hydrogen pressure for 120 ℃.
Fig. 1 has provided typical suction hydrogen kinetic curve.Prepared material is under 120 ℃, 11MPa hydrogen pressure, and it is saturated to inhale hydrogen in 20min, and hydrogen reaches more than the 4.9wt%.
With SmAl
3Alloy powder is a catalyst, NaAlH
4Powder is a matrix material, preparation SmAl
3The NaAlH that mixes
4Hydrogen storage material.
The employing raw material is: NaAlH
4(purity 95% ,～200 orders), metal Sm piece (purity is greater than 99.9%), metal A l piece (purity is greater than 99.9%).The all unprocessed direct employing of raw material.
1) SmAl
3The preparation of alloy powder caltalyst
Get metal Sm piece and Al piece at 1: 3 by the mole proportioning, induction melting becomes SmAl under argon shield
3Alloy cast ingot; Then below mechanical crushing to 100 order; Again the particle after the mechanical crushing is placed stainless steel jar mill, charge into the 0.3MPa argon gas in the ball grinder, ball milling 20h on high energy ball mill makes the SmAl that particle size is a micro/nano level
3Fine catalyst.
2) SmAl
3Alloy powder caltalyst is used for NaAlH
4The preparation of hydrogen storage material
With SmAl
3Alloy powder is a catalyst, NaAlH
4Powder is a matrix material, NaAlH in molar ratio in the argon atmospher glove box
4+ 0.04SmAl
3Insert after proportion raw material mixes in the stainless steel jar mill, ball milling on planetary ball mill, milling atmosphere are argon atmospher, ratio of grinding media to material 35: 1, ball milling time 60h.
Adopt the hydrogen storage property of volumetric method test material.Cycling condition is: put hydrogen for 120 ℃/170 ℃, put hydrogen cutoff pressure 0.1MPa; Inhale hydrogen, the about 11MPa of initial suction hydrogen pressure for 120 ℃.
Fig. 2 has provided typical hydrogen desorption kinetics curve.Prepared material under 120 ℃, 0.1MPa, the hydrogen that in 60min, can emit 3.13wt%; Temperature is raised to 170 ℃ afterwards, emits the hydrogen of 1.62wt% in the 50min again, two-step reaction is emitted the hydrogen of 4.75wt% altogether.
With La
3Al
11Alloy powder is a catalyst, and NaH and Al powder are matrix material, preparation La
3Al
11The NaAlH that mixes
4Hydrogen storage material.
The employing raw material is: NaH (purity 95% ,～200 orders), Al powder (purity greater than 99.9% ,～200 orders), metal La piece (purity is greater than 99.9%), metal A l piece (purity is greater than 99.9%).The all unprocessed direct employing of raw material.
1) La
3Al
11The preparation of alloy powder caltalyst
Get metal La piece and Al piece at 3: 11 by the mole proportioning, induction melting becomes La under argon shield
3Al
11Alloy pig.Afterwards, below mechanical crushing to 100 order, the particle after the mechanical crushing is placed stainless steel jar mill, charge into 1.5MPaH in the ball grinder
2, ball milling 30h on planetary ball mill makes the La that particle size is a micro/nano level
3Al
11Catalyst.
2) La
3Al
11Alloy powder caltalyst is used for NaAlH
4The preparation of hydrogen storage material
With La
3Al
11Alloy powder is a catalyst, and NaH and Al powder are matrix material, NaH+Al+0.01La in molar ratio in the argon atmospher glove box
3Al
11Insert after proportion raw material mixes in the stainless steel jar mill, ball milling on planetary ball mill, milling atmosphere are nitrogen atmosphere, ball milling hydrogen pressure 4MPa, ratio of grinding media to material 40: 1, ball milling time 80h.
Adopt the hydrogen storage property of volumetric method test material.Cycling condition is: put hydrogen for 160 ℃; Inhale hydrogen, initial suction hydrogen pressure 12MPa for 120 ℃.
Fig. 3 has provided the suction hydrogen kinetic curve of different circulation times, and prepared material has good suction hydrogen desorption kinetics performance under 120 ℃, 12MPa, and hydrogen maintains about 4.8wt% in the 50min.Material is put in the hydrogen circulation in suction, and hydrogen capacity and dynamic performance are also highly stable.
With MlAl
2Alloy powder is a catalyst, NaAlH
4Powder is a matrix material, preparation MlAl
2The NaAlH that mixes
4Hydrogen storage material.
The employing raw material is: NaAlH
4(purity 95% ,～200 orders), metal M l piece (wherein, each content of rare earth La 78～86%, Pr4～12%, Ce 5～15%, Nd＜1%), metal A l piece (purity is greater than 99.9%).The all unprocessed direct employing of raw material.
1) MlAl
2The preparation of alloy powder caltalyst
Get metal M l piece and Al piece at 1: 2 by the mole proportioning, because each element atomic weight difference is little in the lanthanum rich rare earth, the atomic weight with La during calculating replaces the Ml atomic weight.Induction melting becomes MlAl under argon shield
2Alloy cast ingot; Then below mechanical crushing to 100 order; Again the particle after the mechanical crushing is placed stainless steel jar mill, charge into the 0.6MPa argon gas in the ball grinder, ball milling 30h on high energy ball mill makes the MlAl that particle size is a micro/nano level
2Fine catalyst.
2) MlAl
2Alloy powder caltalyst is used for NaAlH
4The preparation of hydrogen storage material
With MlAl
2Alloy powder is a catalyst, NaAlH
4Powder is a matrix material, NaAlH in molar ratio in the argon atmospher glove box
4+ 0.03MlAl
2Insert after proportion raw material mixes in the stainless steel jar mill, ball milling on planetary ball mill, milling atmosphere are argon atmospher, ratio of grinding media to material 30: 1, ball milling time 48h.
Adopt the hydrogen storage property of volumetric method test material.Cycling condition is: put hydrogen for 160 ℃, put hydrogen cutoff pressure 0.1MPa; Inhale hydrogen, the about 11MPa of initial suction hydrogen pressure for 120 ℃.
Fig. 4 has provided first three time hydrogen desorption kinetics curve of prepared material.Prepared material can be emitted the hydrogen of mass percent greater than 4.85wt% in 90min under 160 ℃, 0.1MPa.
Claims (4)
1. the catalyst of a sodium aluminum hydride coordination oxide, it is characterized in that: the chemical formula of this catalyst is RE
xAl
y, 1≤x in the formula＜10,1≤y＜20, RE is a kind of of Sc, Y, La, Ce, Pr, Sm, Nd, lanthanum rich mischmetal Ml or cerium-rich mischmetal Mm, particle size is the alloy RE of micro/nano level
xAl
yCatalyst.
2. the Preparation of catalysts method of sodium aluminum hydride coordination oxide according to claim 1 is characterized in that: according to catalyst chemical formula RE
xAl
yWherein the stoichiometric proportion of 1≤x＜10,1≤y＜20 is carried out the weighing proportioning with RE and Al reguline metal raw material, and founding becomes RE under argon shield atmosphere
xAl
yAlloy cast ingot is put into the high energy ball mill ball milling after then alloy cast ingot being pulverized, and obtains RE
xAl
yCatalyst, step is as follows:
1) according to catalyst chemical formula RE
xAl
y1≤x in the formula Chinese style＜10, the stoichiometric proportion of 1≤y＜20, get the respective metal raw material of Sc, Y, La, Ce, Pr, Sm, Nd, lanthanum rich mischmetal Ml or cerium-rich mischmetal Mm, raw material metal purity is more than 98%, and founding becomes alloy cast ingot under argon shield atmosphere;
2) below alloy cast ingot mechanical crushing to 100 order that founding is become;
3) alloy powder after will pulverizing is put into ball grinder, under argon gas or hydrogen atmosphere, adopt the further ball mill grinding of high energy ball mill, milling atmosphere pressure is 0.2～4MPa, and the ball milling time is 2～60h, and can obtain particle size is the superfine alloy powder RE of micro/nano level
xAl
yCatalyst.
3. catalyst according to claim 1 is used for the preparation of sodium alanate hydrogen storage material, it is characterized in that matrix hydrogen storage material NaAlH
4With catalyst RE
xAl
y1≤x in the formula＜10,1≤y＜20, after evenly mixing, mol ratio according to 1: 0.001～0.10 puts into the ball grinder ball milling, milling atmosphere is argon gas or hydrogen atmosphere, milling atmosphere pressure is 0.5～8.0MPa, and the ball milling time is 5～160h, obtains to be used for the reversible catalysis hydrogen storage material of sodium alanate.
4. catalyst according to claim 3 is used for the preparation of sodium alanate hydrogen storage material, it is characterized in that: matrix hydrogen storage material sodium alanate is the NaAlH that inhales the hydrogen attitude
4Powder.
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| US10611969B2 (en) | 2014-12-03 | 2020-04-07 | Racional Energy & Environment Company | Flash chemical ionizing pyrolysis of hydrocarbons |
| CN110102280A (en) * | 2019-04-29 | 2019-08-09 | 北京铂陆氢能科技开发有限公司 | A kind of activating agent and preparation method thereof for hydrogen storage material |
| CN112974812B (en) * | 2021-02-04 | 2023-01-10 | 有研工程技术研究院有限公司 | High-combustion low-sensitivity rare earth alloy hydride material and preparation method thereof |
| CN112755989A (en) * | 2021-02-08 | 2021-05-07 | 烟台大学 | Hydrogen storage material catalyst, hydrogen storage material containing the catalyst and preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1688505A (en) * | 2002-06-25 | 2005-10-26 | 阿莉恰·扎卢斯卡 | New type of catalytic materials based on active metal-hydrogen-electronegative element complexes involving hydrogen transfer |
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1688505A (en) * | 2002-06-25 | 2005-10-26 | 阿莉恰·扎卢斯卡 | New type of catalytic materials based on active metal-hydrogen-electronegative element complexes involving hydrogen transfer |
| CN101264863A (en) * | 2008-04-18 | 2008-09-17 | 浙江大学 | Method for synthesizing metal coordinate hydride hydrogen-storing material directly by reaction ball milling |
Non-Patent Citations (2)
| Title |
|---|
| Zheng Xueping,et al.The effect of additives on the hydrogen storage properties of NaAlH4.《International Journal of Hydrogen Energy》.2009,第34卷(第6期),2701-2704. * |
| 王国清等.掺杂催化剂对NaAlH4吸放氢性能和微观结构的影响.《功能材料》.2008,第39卷(第2期),231-233. * |
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