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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 PDF

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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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catalyst
hydrogen
hydrogen storage
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sodium aluminum
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CN101642703A (en
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陈立新
范修林
肖学章
吴哲
陈长聘
王启东
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Zhejiang University ZJU
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Abstract

本发明涉及一种铝氢化钠配位氢化物的催化剂及其制备方法，催化剂的化学通式为RExAly(1≤x＜10，1≤y＜20)，式中RE为Sc、Y、La、Ce、Pr、Sm、Nd、Ml(富镧混合稀土)或Mm(富铈混合稀土)。其制备方法是：按照RExAly化学计量比，将RE和Al块状金属原材料进行称量配比，在氩气保护气氛下熔炼成RExAly合金铸锭，然后粉碎后放入高能球磨机中球磨，获得颗粒尺寸为微纳米级的RExAly催化剂。催化剂制备工艺简单、易于操作、成本低廉，本发明的催化剂用于铝氢化钠的可逆催化储氢，极大地提高铝氢化钠的吸放氢动力学性能，并且不会与基体储氢材料组元反应生成惰性副产物而损耗体系的可逆储氢量。

Figure 200910101843

The invention relates to a catalyst for sodium aluminum hydride coordination hydride and a preparation method thereof. The general chemical formula of the catalyst is RE x Al y (1≤x<10, 1≤y<20), wherein RE is Sc, Y , La, Ce, Pr, Sm, Nd, Ml (lanthanum-rich misch) or Mm (cerium-rich misch). The preparation method is as follows: according to the RE x Al y stoichiometric ratio, RE and Al bulk metal raw materials are weighed and proportioned, melted into RE x Al y alloy ingots under an argon protective atmosphere, and then crushed and put into high-energy Ball milling in a ball mill to obtain a RE x Al y catalyst with a particle size of micronano order. The catalyst preparation process is simple, easy to operate, and low in cost. The catalyst of the present invention is used for the reversible catalytic hydrogen storage of sodium alanate, which greatly improves the kinetic performance of hydrogen absorption and desorption of sodium alanate, and does not interact with the matrix hydrogen storage material The reaction produces inert by-products and depletes the reversible hydrogen storage capacity of the system.

Figure 200910101843

Description

The Catalysts and its preparation method of sodium aluminum hydride coordination oxide
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
Embodiment 1
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%.
Embodiment 2
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.
Embodiment 3
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.
Embodiment 4
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)

1.一种铝氢化钠配位氢化物的催化剂，其特征在于：该催化剂的化学式为RExAly，式中1≤x＜10，1≤y＜20，RE为Sc、Y、La、Ce、Pr、Sm、Nd、富镧混合稀土Ml或富铈混合稀土Mm的一种，颗粒尺寸为微纳米级的合金RExAly催化剂。1. A catalyst for sodium aluminum hydride coordination hydride, characterized in that: the chemical formula of the catalyst is RE x Al y , where 1≤x＜10, 1≤y＜20, RE is Sc, Y, La, One of Ce, Pr, Sm, Nd, lanthanum-rich mixed rare earth Ml or cerium-rich mixed rare earth Mm, the particle size is micronano-scale alloy RE x Al y catalyst. 2.根据权利要求1所述的铝氢化钠配位氢化物的催化剂的制备方法，其特征在于：按照催化剂化学式RExAly其中1≤x＜10，1≤y＜20的化学计量比，将RE和Al块状金属原材料进行称量配比，在氩气保护气氛下熔铸成RExAly合金铸锭，然后将合金铸锭粉碎后放入高能球磨机中球磨，获得RExAly催化剂，步骤如下：2. the preparation method of the catalyst of sodium aluminum hydride coordination hydride according to claim 1, it is characterized in that: according to catalyst chemical formula RE x Al y wherein 1≤x＜10, 1≤y＜20 stoichiometric ratio, RE and Al bulk metal raw materials are weighed and proportioned, melted and cast into a RE x Al y alloy ingot under an argon protective atmosphere, and then the alloy ingot is pulverized and put into a high-energy ball mill for ball milling to obtain a RE x Al y catalyst ,Proceed as follows: 1)按照催化剂化学式RExAly式中式中1≤x＜10，1≤y＜20的化学计量比，取Sc、Y、La、Ce、Pr、Sm、Nd、富镧混合稀土Ml或富铈混合稀土Mm的相应金属原材料，金属原材料纯度在98％以上，在氩气保护气氛下熔铸成合金铸锭；1) According to the stoichiometric ratio of 1≤x<10, 1≤y<20 in the catalyst chemical formula RE x Al y , Sc, Y, La, Ce, Pr, Sm, Nd, lanthanum-rich mixed rare earth Ml or rich The corresponding metal raw material of cerium mixed rare earth Mm, the purity of the metal raw material is above 98%, is melted and cast into an alloy ingot under an argon protective atmosphere; 2)将熔铸成的合金铸锭机械粉碎至100目以下；2) mechanically pulverizing the cast alloy ingot to below 100 mesh; 3)将粉碎后的合金粉末放入球磨罐中，在氩气或氢气气氛下采用高能球磨机进一步球磨粉碎，球磨气氛压力为0.2～4MPa，球磨时间为2～60h，即可得到颗粒尺寸为微纳米级的超细合金粉末RExAly催化剂。3) Put the pulverized alloy powder into a ball mill tank, and use a high-energy ball mill to further pulverize it under an argon or hydrogen atmosphere. Nanoscale superfine alloy powder RE x Aly catalyst. 3.根据权利要求1所述的催化剂用于铝氢化钠储氢材料的制备，其特征在于将基体储氢材料NaAlH4与催化剂RExAly，式中1≤x＜10，1≤y＜20，按照1∶0.001～0.10的摩尔比进行均匀混合后放入球磨罐中球磨，球磨气氛为氩气或氢气气氛，球磨气氛压力为0.5～8.0MPa，球磨时间为5～160h，获得用于铝氢化钠的可逆催化储氢材料。3. The catalyst according to claim 1 is used for the preparation of sodium aluminum hydride hydrogen storage materials, characterized in that the matrix hydrogen storage material NaAlH 4 and the catalyst RE x Al y , where 1≤x<10, 1≤y< 20. Mix uniformly according to the molar ratio of 1:0.001~0.10, put it into a ball mill jar for ball milling, the ball milling atmosphere is argon or hydrogen atmosphere, the ball milling atmosphere pressure is 0.5~8.0MPa, and the ball milling time is 5~160h. Sodium aluminum hydride as a reversible catalytic hydrogen storage material. 4.根据权利要求3所述的催化剂用于铝氢化钠储氢材料的制备，其特征在于：基体储氢材料铝氢化钠是吸氢态的NaAlH4粉末。4. catalyst according to claim 3 is used for the preparation of sodium aluminum hydride hydrogen storage material, it is characterized in that: matrix hydrogen storage material sodium aluminum hydride is the NaAlH of hydrogen absorption state Powder.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1688505A (en) * 2002-06-25 2005-10-26 阿莉恰·扎卢斯卡 Novel 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 direct synthesis of metal complex hydride hydrogen storage materials by reaction ball milling

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1688505A (en) * 2002-06-25 2005-10-26 阿莉恰·扎卢斯卡 Novel 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 direct synthesis of metal complex hydride hydrogen storage materials by reaction ball milling

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
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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