CN102674272B - Preparation method of catalyst TiN for synthesizing NaAlH4 - Google Patents
Preparation method of catalyst TiN for synthesizing NaAlH4 Download PDFInfo
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- CN102674272B CN102674272B CN201110338635.9A CN201110338635A CN102674272B CN 102674272 B CN102674272 B CN 102674272B CN 201110338635 A CN201110338635 A CN 201110338635A CN 102674272 B CN102674272 B CN 102674272B
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Abstract
The invention discloses a preparation method of a catalyst TiN for synthesizing NaAlH4. According to the method, TiN is directly synthesized by utilizing metatitanic acid as a precursor and a certain amount of urea and potassium borohydride as reactants. The catalyst TiN synthesized by the method is a novel catalyst with excellent catalytic performance prepared by a solid phase method; a NaAlH4 co-ordinate hydride can be obtained only by virtue of one-step catalytic hydrogenation; and the synthesized NaAlH4 has the advantages of excellent hydrogen absorbing and releasing performance and higher hydrogen storage capacity.
Description
Technical field
The invention belongs to light metal complex hydrides hydrogen storage system technical field, more particularly, relate to a kind of synthetic NaAlH
4The preparation method of catalyzer TiN.
Background technology
In the face of the day by day scarcity of petroleum resources and the dual-pressure of the deterioration of the ecological environment, utilize this clean energy of Hydrogen Energy replaces has become the whole world as the existing energy on basis take fossil fuel common recognition.Therefore, the new forms of energy that development and utilization is relevant with hydrogen and research energy-saving material have been classified as the content of primary study by many countries.Want to reach the requirement of vehicle-mounted hydrogen storage technology, just must develop the coordination light metal hydride hydrogen-storing material of a kind of high volume energy density and high quality energy density.
In the last few years, with NaAlH
4For the light metal complex hydrides of representative is subject to investigators' extensive concern as a class heavy body, low-density hydrogen storage material always, its research has obtained steady progress.Catalyzer has more intense selectivity usually for the booster action of reaction, and transistion metal compound is widely used in as catalytic hydrogenation catalyst in the Chemical Manufacture such as petroleum cracking, reformation, and is also of common occurrence in the research of hydrogen storage material.
In the catalysis storage hydrogen research of NaAlH4 complex hydrides, for numerous metals and their compound catalyst thereof of present employing, the catalytic effect of ti-based compound is best.But the kinetic rate that hydrogen is put in the suction of NaAlH4 under low-temp low-pressure still has larger gap with respect to the application of vehicle fuel battery, should research and develop active catalyzer higher, that stability is better, cost is lower; Along with the carrying out that hydrogen circulates, NaAlH are put in suction
4The sucking/placing hydrogen amount of complex hydrides system can decrease, so the reversible hydrogen storage capacity of complex hydrides system also needs further raising.Therefore, study high performance novel hydrogenation catalyzer to improving NaAlH
4The hydrogen storage property of material has practical significance.
Summary of the invention
The object of the present invention is to provide a kind of synthetic NaAlH
4The preparation method of catalyzer TiN, with the synthetic NaAlH of this catalyzer
4Good low temperature hydrogen discharging performance is arranged, with respect to simpler, energy-conservation, the easy realization of the synthetic method that needs condition of high voltage in the prior art.
A kind of synthetic NaAlH
4The preparation method of catalyzer TiN, may further comprise the steps:
A, 1:3-1:6 takes by weighing Ti (SO in molar ratio
4)
2With massfraction be 25% ammoniacal liquor, with Ti (SO
4)
2Be dissolved in the deionized water, wherein Ti (SO
4)
2With the mol ratio of deionized water be 1:120-1:200, slowly drip ammoniacal liquor and stir, reacted rear washing, drying, obtain the precursor metatitanic acid;
B, with gained metatitanic acid and urea, KBH
42:3:5-2:3:10 mixes in molar ratio, and the argon atmospher protection is lower, and behind calcining 3-9h under the 650-750 ° of C high temperature, Slow cooling is to room temperature;
C, dry after products therefrom washed respectively three times with deionized water and ethanol obtains catalyzer TiN.
Churning time in the steps A is 10min.
Drying conditions among the step C is the lower 100 ° of C high temperature of vacuum.
The synthetic TiN of the inventive method is a kind of catalyzer novelty, the catalytic performance excellence with the solid phase method preparation; At room temperature only need to obtain NaAlH once the step shortening
4Complex hydrides, and synthetic NaAlH
4It is higher to have excellent hydrogen storage property, hydrogen-storage amount.
Description of drawings
Fig. 1 is the XRD figure of the TiN for preparing of the present invention;
Fig. 2 is the NaAlH that the present invention synthesizes
4XRD figure;
Fig. 3 is the NaAlH that the present invention synthesizes
4The TPD Hydrogen desorption isotherms;
Fig. 4 is the NaAlH that the present invention synthesizes
4The PCT Hydrogen desorption isotherms.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing, the present invention is further elaborated.
Embodiment 1
1) preparation of catalyzer TiN
Ti (SO with 0.02mol
4)
2Be dissolved in the 50ml deionized water, then slowly drip the 2ml massfraction and be 25% ammoniacal liquor, stir 10min, reacted rear washing drying, obtain the precursor metatitanic acid; With precursor and urea, KBH
4Behind mol ratio 2:3:8 mixing, the lower 650 ° of C calcining of argon shield 3h, Slow cooling is to room temperature; After reaction product washed respectively three times with deionized water and ethanol under 100 ° of C temperature condition vacuum-drying 12h, obtain catalyzer TiN;
Can find out obviously that from Fig. 1 synthetic catalyzer is TiN.
2) NaAlH
4Synthesizing of complex hydrides
Under argon shield, take by weighing NaH and the high purity Al (purity is 99.5%) that mol ratio is 1.4:1 and place ball grinder, the TiN that then adds 8mol% mixes; Than 40:1, adding diameter is the Stainless Steel Ball of 10mm according to steel ball and reactant quality; Pass into the high-purity hydrogen of 2MPa to ball grinder after, ball grinder placed carry out ball milling on the high-energy mechanical ball milling machine, drum's speed of rotation is 450rpm, and every 5h opens tank one time, behind the ball milling 30h, obtains NaAlH
4Complex hydrides.
As can be seen from Figure 2, NaAlH in the product
4Diffraction peak very obvious, show and behind mechanical ball milling, synthesized NaAlH
4Complex hydrides.
Embodiment 2:
1) preparation of catalyzer TiN
Ti (SO with 0.015mol
4)
2Be dissolved in the 50ml deionized water, then slowly drip the 1ml massfraction and be 25% ammoniacal liquor, stir 10min, reacted rear washing drying, obtain precursor; With precursor and urea, KBH
4After mixing according to mol ratio 2:3:9, the lower 750 ° of C calcining of argon shield 6h, Slow cooling is to room temperature; At 100 ° of C vacuum-drying 12h, obtain catalyzer TiN after reaction product washed respectively three times with deionized water and ethanol.
2) NaAlH
4Synthesizing of complex hydrides
Under argon shield, take by weighing NaH and the Al (purity is 99.5%) that mol ratio is 1:1 and place ball grinder, the catalyzer TiN that then adds 8mol% mixes, and compares 40:1 according to steel ball and reactant quality, add diameter 10mm Stainless Steel Ball, pass into the high-purity hydrogen of 1MPa to ball grinder; Ball grinder is placed ball milling on the high-energy mechanical ball milling machine, and drum's speed of rotation is 450rpm, behind the ball milling 40h, obtains NaAlH
4Complex hydrides.
To the NaAlH that obtains
4Be TPD and put the hydrogen test, heat-up rate is 2 ° of C/min.As can be seen from Figure 3, NaAlH
4Obvious two step hydrogen discharge reactions are arranged, corresponding respectively:
3NaAlH
4→Na
3AlH
6+2Al+3H
2 （1）
Na
3AlH
6→3NaH+Al+1.5H
2 （2）
To NaAlH obtained above
4Complex hydrides carries out respectively TPD and PCT test.
The TPD test result shows, synthetic NaAlH
4The beginning hydrogen discharging temperature obviously reduces, and illustrates that TiN is to NaAlH
4Low temperature inhale and to put hydrogen and reversible hydrogen adsorption and desorption has good catalytic effect, hydrogen desorption capacity can reach 2.6wt.%
With synthetic NaAlH
4Under 90 ° of C, be PCT for example and put the hydrogen test.As can be seen from Figure 4, synthetic NaAlH
4Hydrogen desorption capacity just can reach 2.3wt.% when 90 spend, and the NaAlH synthetic take TiN as catalyzer is described
4Preferably low temperature hydrogen discharging performance is arranged.
Embodiment 3
1) preparation of catalyzer TiN
Ti (SO with 0.01mol
4)
2Be dissolved in the 25ml deionized water, then slowly drip the 1ml massfraction and be 25% ammoniacal liquor, stir 10min, reacted rear washing drying, obtain precursor; With precursor and urea, KBH
4After mixing according to mol ratio 2:3:5, the lower 700 ° of C calcining of argon shield 9h, Slow cooling is to room temperature; At 100 ° of C vacuum-drying 12h, the product that obtains after tested was catalyzer TiN after reaction product washed respectively three times with deionized water and ethanol.
2) NaAlH
4Synthesizing of complex hydrides
Under argon shield, take by weighing NaH and the Al (purity is 99.5%) that mol ratio is 1.8:1 and place ball grinder, then the catalyzer TiN that adds 8mol% mixes, compare 40:1 according to steel ball and reactant quality, add diameter 10mm Stainless Steel Ball, pass into the high-purity hydrogen of 0.5MPa to ball grinder; Ball grinder is placed ball milling on the high-energy mechanical ball milling machine, and drum's speed of rotation is 450rpm, behind the ball milling 120h, obtains NaAlH
4Complex hydrides.
The TPD test result shows, synthetic NaAlH
4The beginning hydrogen discharging temperature obviously reduces, and illustrates that TiN is to NaAlH
4Low temperature inhale and to put hydrogen and reversible hydrogen adsorption and desorption has good catalytic effect.With synthetic NaAlH
4Under 90 ° of C, be PCT for example and put the hydrogen test.The result shows, synthetic NaAlH
4Hydrogen desorption capacity just can reach 2.4wt.% when 90 spend, and the NaAlH synthetic take TiN as catalyzer is described
4Preferably low temperature hydrogen discharging performance is arranged.
1) preparation of catalyzer TiN
Ti (SO with 0.02mol
4)
2Be dissolved in the 50ml deionized water, then slowly drip the 2ml massfraction and be 25% ammoniacal liquor, stir 10min, reacted rear washing drying, obtain the precursor metatitanic acid; With precursor and urea, KBH
4Behind mol ratio 2:3:10 mixing, the lower 680 ° of C calcining of argon shield 6h, Slow cooling is to room temperature; After reaction product washed respectively three times with deionized water and ethanol under 100 ° of C temperature condition vacuum-drying 12h, obtain catalyzer TiN;
Analyze after tested, synthetic catalyzer is TiN.
2) NaAlH
4Synthesizing of complex hydrides
Under argon shield, take by weighing NaH and the high purity Al (purity is 99.5%) that mol ratio is 2:1 and place ball grinder, the TiN that then adds 8mol% mixes; Than 40:1, add diameter 10mm Stainless Steel Ball according to steel ball and reactant quality; Pass into the high-purity hydrogen of 3MPa to ball grinder after, ball grinder placed carry out ball milling on the high-energy mechanical ball milling machine, drum's speed of rotation is 450rpm, and every 5h opens tank one time, behind the ball milling 15h, obtains NaAlH
4Complex hydrides.
After tested, NaAlH in the product
4Diffraction peak very obvious, illustrating has NaAlH in the product
4Generate.
Claims (3)
1. one kind is used for NaAlH
4Inhale the preparation method of the TiN catalyzer of hydrogen discharge reaction, it is characterized in that, may further comprise the steps:
A, 1:3-1:6 takes by weighing Ti (SO in molar ratio
4)
2With massfraction be 25% ammoniacal liquor, with Ti (SO
4)
2Be dissolved in the deionized water, wherein Ti (SO
4)
2With the mol ratio of deionized water be 1:120-1:200, slowly drip ammoniacal liquor and stir, reacted rear washing, drying, obtain the precursor metatitanic acid;
B, with gained metatitanic acid and urea, KBH
42:3:5-2:3:10 mixes in molar ratio, and the argon atmospher protection is lower, and behind calcining 3-9h under the 650-750 ° of C high temperature, Slow cooling is to room temperature;
C, dry after products therefrom washed respectively three times with deionized water and ethanol obtains catalyzer TiN.
2. according to claim 1 for NaAlH
4Inhale the preparation method of the TiN catalyzer of hydrogen discharge reaction, it is characterized in that the churning time in the steps A is 10min.
3. according to claim 1 for NaAlH
4Inhale the preparation method of the TiN catalyzer of hydrogen discharge reaction, it is characterized in that the drying conditions among the step C is the lower 100 ° of C high temperature of vacuum.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4746501A (en) * | 1986-12-09 | 1988-05-24 | United States Department Of Energy | Process for preparing transition metal nitrides and transition metal carbonitrides and their reaction intermediates |
| CN1922100A (en) * | 2004-02-26 | 2007-02-28 | 通用汽车公司 | Hydrogen storage materials and methods including hydrides and hydroxides |
| CN101367511A (en) * | 2008-08-06 | 2009-02-18 | 燕山大学 | Method for preparing non-stoichiometry ratio nano TiNx with reaction ball milling method |
-
2011
- 2011-11-01 CN CN201110338635.9A patent/CN102674272B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4746501A (en) * | 1986-12-09 | 1988-05-24 | United States Department Of Energy | Process for preparing transition metal nitrides and transition metal carbonitrides and their reaction intermediates |
| CN1922100A (en) * | 2004-02-26 | 2007-02-28 | 通用汽车公司 | Hydrogen storage materials and methods including hydrides and hydroxides |
| CN101367511A (en) * | 2008-08-06 | 2009-02-18 | 燕山大学 | Method for preparing non-stoichiometry ratio nano TiNx with reaction ball milling method |
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