CN100436617C - Method for preparing solid hydrogen storage material of modified ferriferous oxide - Google Patents

Method for preparing solid hydrogen storage material of modified ferriferous oxide Download PDF

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CN100436617C
CN100436617C CNB2006101050501A CN200610105050A CN100436617C CN 100436617 C CN100436617 C CN 100436617C CN B2006101050501 A CNB2006101050501 A CN B2006101050501A CN 200610105050 A CN200610105050 A CN 200610105050A CN 100436617 C CN100436617 C CN 100436617C
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hydrogen
solubility
hydrogen storage
storage material
metal
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CN1916202A (en
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王惠
王小芳
董发昕
田勇
王新智
张玉丽
唐世周
梁振国
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Northwest University
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Abstract

This invention discloses a method for preparing modified iron oxide solid hydrogen-storage material. The method comprises: (1) concentrating a solution of reduced Fe powder and/or iron oxide powder containing soluble monometal/bimetal salt to obtain a paste; (2) drying at 80-95 deg.C for 2-10 h, calcining at 300 deg.C for 3-5 h, and then calcining at 500 deg.C for 10-15 h. The method uses cheap reduced Fe powder, Fe2O3 powder and/or Fe3O4 powder as the matrix materials, and monometal/bimetal additive as the modifier to prepare catalytically modified hydrogen-storage material by soaking method, thus is simple and reliable. The hydrogen-storage material has the hydrogen release temperature lower than 300 deg.C, storage-release cyclic times more than 13, and average experimental hydrogen-storage amount larger than 4.5 wt. %.

Description

The preparation method of solid hydrogen storage material of modified ferriferous oxide
Technical field
The present invention relates to the preparation method of solid hydrogen storage material of modified ferriferous oxide.With different materials such as reduced iron powder, ferric oxide powder or Z 250 powder is substrate material, by monometallic or two kinds of metals interpolation carrying out catalytic modifications, thereby the circulation that reduces material is significantly produced the hydrogen temperature and is made it have using value, belongs to soild oxide hydrogen storage material field.
Background technology
The energy and environment are the two big basic problems that present human society faces.Hydrogen is not only can the regenerated resource, and is the energy without any environmental pollution, and therefore, Hydrogen Energy is regarded as the most potential substitute energy in this century.Rise the nineties in last century, and many developed countries have all formulated the Hydrogen Energy exploitation and applied research plan of system, and wherein the most urgent application is the hydrogen fuel cell automobile, and target is commercialization.Yet storing up-release the hydrogen technology safely and effectively is its business-like major obstacle.
Present hydrogen storage method mainly contains: high pressure pot type storage hydrogen, high-pressure liquefaction storage hydrogen and solid hydrogen-storing.Wherein, solid hydrogen-storing is considered to the most safe and effective storage hydrogen mode.The ideal solid hydrogen storage material has DOE standard (6.5wt% or 62kg/m to the storage capacity of hydrogen 3) and IEA standard (～5wt% or 50kg H 2/ m 3).Existing solid hydrogen storage material mainly contains hydrogen storage alloy, metal hydride, title complex, hydroborate, various carbon material such as carbon nanotube etc.
At present, modified ferriferous oxide is a class novel hydrogen storage material, there is following deficiency in it: 1) still not fully aware of and component catalyzer of the catalytic mechanism of catalyzer is still waiting to optimize in the hydrogen storage material, and hydrogen-storage amount (3.8%) also has distance (Otsuka, K. from theoretical value (4.8%); Kaburagi, T.; Yamada, C.; Takenaka, S.J.Power Sources 2003,122,111). 2) the clean professor of this Da of Ri mound waits the storage of the material of " the rotary oven granulated slag is the pickling process of raw material " preparation of usefulness once-put hydrogen cycle index still undesirable (not above 10 times), the hydrogen discharging temperature of material also higher (about still up to 350 ℃) (Wang, H.; Otsuka, K.; Takenaka, S.Int.J.Hydrogen Energy 2006,31,11).
Summary of the invention
The purpose of this invention is to provide with low cost, hydrogen-storage amount is high (about 4.6wt%), low (produce the hydrogen temperature about 250 ℃, hydrogen discharging speed is 100 μ molmin to hydrogen discharging temperature -1Fe-g -1The time temperature), the preparation method of the solid hydrogen storage material of modified ferriferous oxide of cycle index many (greater than 13 times).
Implementation procedure of the present invention:
The preparation method of solid hydrogen storage material of modified ferriferous oxide, it is characterized in that: will contain reduced iron powder or/and brown iron oxide matrix be dissolved with solubility monometallic or two kinds of adulterated solution concentration of metal-salt to pasty state, in 80～95 ℃ of down dry 2～10h, calcining 3～5h under 300 ℃ calcines 10～15h down in 500 ℃ again and gets final product afterwards.
The solubility monometallic salt that adds is in the mole number of metal M, and its addition is n M n Fe + n M = 0.03 - 0.10 .
One of two kinds of metal-salts of solubility that add are the solubility ammonium salt of molybdenum, and another kind of soluble metallic salt is in the mole number of containing metal M, and the addition of two kinds of metal-salts is n Mo + n M n Fe + n Mo + n M = 0.05 - 0.15 , N wherein Mo: n M=1: 1 or 2: 1.
Solubility monometallic salt is solubility nitrate, muriate, vitriol, oxalate or the acetate of Metal Cr, Al, Ni, Co, Cu, Ti, Zr, Rh, La, Ce, Pr, Nd, Sm, Eu, Gd, Te or Dy, or the solubility ammonium salt of Mo, W.
One of two kinds of metal-salts of solubility are the solubility ammonium salt of metal molybdenum, another kind is solubility nitrate, muriate, vitriol, oxalate or the acetate of Cr, Al, Ni, Co, Cu, Ti, Zr, Rh, La, Ce, Pr, Nd, Sm, Eu, Gd, Te or Dy, or the solubility ammonium salt of W.
The raw material that the present invention uses can be a reduced iron powder, also can be ferric oxide, also can be Z 250, can also be three's any mixture, as ferric oxide and Z 250 mixture.
The monometallic solid hydrogen storage material of modified ferriferous oxide can be expressed as FeO x-MO y, this formula does not represent that the ratio of Fe and metal M is 1: 1, only is illustrated in to contain other metal oxide in the ferric oxide.Wherein, MO yRepresent metal oxide, when x=1.5, y is desirable 1,1.5,2,2.5 or 3, for example FeO 1.5-MoO 3, FeO 1.5-ZrO 2Again for example, for molar content be 4% hydrogen storage material FeO x-MoO yIn, the content of metal M o is: Mo%=Mo/ (Fe+Mo)=4/ (96+4)=4%.
Two kinds of metal-modified ferriferous oxide solid hydrogen storage materials can be expressed as FeO x-MoO y-MO zThis formula does not represent that the ratio of Fe, Mo and metal M is 1: 1: 1, only is illustrated in and contains molybdenum oxide and other metal oxide in the ferric oxide.MoO wherein yRepresent the oxide compound of molybdenum; MO zRepresent other metal oxide; When x=1.5, y=3, z=1,1.5,2,2.5 or 3, FeO for example 1.5-MoO 3-AlO 1.5, FeO 1.5-MoO 3-CrO 1.5Again for example, be 6% and mol ratio Mo: Al=2 for molar content: 1 hydrogen storage material FeO 1.5-MoO 3-AlO 1.5In, the content of metal M o+Al is: (Mo+Al) %=(Mo+Al)/(Fe+Mo+Al)=(4+2)/(94+3+3)=6%.
Hydrogen fuel cell hydrogen storage material preparation method provided by the invention, its storage-put hydrogen principle is as follows:
The storage of the first step hydrogen (reduction): Fe 3O 4+ Fe 2O 3+ 7H 2→ 5Fe+7H 2O (1)
The second step hydrogen disengage (oxidation): 3Fe+4H 2O → Fe 3O 4+ 4H 2(2)
In brief: in iron, iron runs into " fuel " water and reacts releasing hydrogen gas again hydrogen by chemical storage, this storage-put the hydrogen process can circulate repeatedly.Also can be expressed as: Fe 3O 4+ Fe 2O 3Chu Qing → Fe is put hydrogen → Fe 3O 4Store up hydrogen → Fe again and put hydrogen again.
Research data shows, if the storage hydrogen capacity of solid hydrogen storage material approaching＞4wt% or～50kg H 2/ m 3, just having commercial use value, this standard is near the IEA standard.A kind of just and very approaching soild oxide hydrogen storage material of this standard of the present invention's preparation.In theory, the hydrogen storage amount of this material is up to 4.8wt%, if the voidage of material is calculated its volume hydrogen storage amount (64kg/m by 80% 3) greater than DOE or IEA standard, possessed the primary condition of business development.The present invention is a substrate material with cheap reduced iron powder, ferric oxide powder and/or Z 250 powder, by monometallic or two kinds of metals interpolations hydrogen storage material is carried out catalytic modification, the ferric oxide solid hydrogen storage material of the catalytic modification that adds by immersion process for preparing monometallic-two kind of metal, this method technology is simple, product hydrogen discharging temperature＜300 that prepare ℃, representative sample has been lower than 250 ℃ of (hydrogen discharging speeds＞100 μ molmin -1Fe-g -1The time temperature); Storing up-put hydrogen recycles number of times and is higher than (the still undiminished sign of the catalytic activity of catalyzer) 13 times; Average experiment hydrogen-storage amount＞4.5wt% (theoretical value 4.8%).
Description of drawings
Fig. 1 is that the present invention is with Fe 2O 3Powder is the material modified FeO of feedstock production x-MoO y 1#Circulation hydrogen storage property figure;
Fig. 2 is the material modified FeO of feedstock production with the Fe powder for the present invention x-AlO yCirculation hydrogen storage property figure;
Fig. 3 is that the present invention is with Fe 3O 4Powder is the material modified FeO of feedstock production x-ZrO yCirculation hydrogen storage property figure;
Fig. 4 is for inventing with Fe 2O 3Powder is the material modified FeO of feedstock production x-MoO y-AlO zCirculation hydrogen storage property figure;
Fig. 5 is the material modified FeO of feedstock production with the Fe powder for the present invention x-MoO y-ZrO z 1#Circulation hydrogen storage property figure;
Fig. 6 is that the present invention is with Fe 3O 4Powder is the material modified FeO of feedstock production x-MoO y-TiO zCirculation hydrogen storage property figure;
Fig. 7 is the material modified FeO of feedstock production with the Fe powder for the present invention x-MoO y 2#10 circulation hydrogen storage property figure;
Fig. 8 is the FeO of feedstock production with the Fe powder for the present invention x-MoO y 2#Material modified 11-13 circulation hydrogen storage property figure;
It is different that Fig. 8 and the difference of Fig. 7 are to produce the temperature rise rate of hydrogen: all round-robin temperature rise rates of Fig. 7 are 4K/min, and 11 round-robin temperature rise rate 2K/min among Fig. 8,12 round-robin are 4K/min, 13 round-robin are 6K/min.
Embodiment
The sample for preparing has carried out the hydrogen storage property detection to it, and the hydrogen storage property detection method is seen document (Wang, H.; Otsuka, K.; Takenaka, S.Int.J.Hydrogen Energy 2006,31,11.), following examples all adopt the same detection method.
The material quantity of table 1. preparation embodiment sample
Annotate: ratio is a mol ratio in the table, and Mo, Al, Zr, Ti, Ce, Cu are with soluble salt (NH 4) 6(Mo) 7O 244H 2O, Al (NO 3) 39H 2O, (NH 4) 2TiO (C 2O 4) 2NH 2O, ZrO (NO 3) 32H 2O, CeCl 36H 2O, Cu (SO 4) 25H 2The form of O adds, and wherein titanium salt is in anhydrous.
The performance perameter of the storage hydrogen of table 2. solid modified ferriferous oxide hydrogen storage material and the specific surface area of respective sample BET
Figure C20061010505000071
*Data are the BET specific surface area data after circulating in the bracket.
*Theoretical hydrogen-storage amount: 4.8wt%
Embodiment 1: sample F eO x-MoO y 1#Preparation and hydrogen storage property detect
Monometallic solid hydrogen storage material of modified ferriferous oxide FeO x-MoO y 1#(the Mo molar content is 5%, Fe 2O 3Powder is a raw material) preparation process: according to table 1 embodiment 1 listed each component amount, take by weighing 0.4992g (NH earlier 4) 6(Mo) 7O 244H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing 4.2892g Fe again 2O 3Powder is put in wherein, places 80 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 85 ℃, and calcining 3h under 300 ℃ calcines 10h down in 500 ℃ more afterwards.
Sample F eO as seen from Table 2 x-MoO y 1#Four round-robin peak temperature show that 329-349 ℃ of scope the adding of catalyzer makes the product hydrogen temperature of material reduce a lot; Hydrogen-producing speed in the time of 300 ℃ remains on 340-416 μ mol min along with the increase of cycle index progressively increases -1Fe-g -1Scope in, show that activity of such catalysts is not only very stable but also as if strengthen along with the increase of cycle index is active.Contrast does not add the sample F e of catalyzer 2O 3Hydrogen-producing speed (25～44 μ mol mins of-none in the time of 300 ℃ -1Fe-g -1Scope), its value is far smaller than the hydrogen-producing speed of catalytic modification sample as can be known; The peak temperature that contrasts them can find out that the peak temperature of modification sample is spent 200 ℃ less than unmodified sample peak temperature more, shows the modifying function that metal M o is strong.This sample hydrogen output big (4.5%) is near theoretical hydrogen-storage amount 4.8%.
Embodiment 2:FeO x-AlO yPreparation and hydrogen storage property detect
According to table 1 embodiment 2 listed each component amounts, take by weighing 0.6233g Al (NO earlier 3) 39H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing the 3.0gFe powder again and is put in wherein, places 85 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 85 ℃, and calcining 5h under 300 ℃ calcines 13h down in 500 ℃ more afterwards.
Sample F eO as seen from Table 2 x-AlO yThree round-robin hydrogen-producing speed increases along with cycle index in the time of 300 ℃ almost change not quite (from 2420 μ mol min -1Fe-g -1To 273 μ mol min -1Fe-g -1), though hydrogen-producing speed compares FeO x-MoO1 y 1#Sample is poor slightly, but cyclical stability is fine, shows that the catalytic activity of catalyzer is very strong.The hydrogen storage property of this sample is much bigger than the hydrogen-producing speed of unmodified sample 300 ℃ the time, and also promptly producing the hydrogen temperature has significantly and reduce.In addition, this sample hydrogen-storage amount also very high (4.38-4.66%).
Embodiment 3:FeO x-ZrO yPreparation and hydrogen storage property detect
According to table 1 embodiment 3 listed each component amounts, take by weighing 0.9310g ZrO (NO earlier 3) 32H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing 4.1460g Fe again 3O 4Powder is put in wherein, places 85 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 90 ℃, and calcining 4h under 300 ℃ calcines 15h down in 500 ℃ more afterwards.
Sample F eO as seen from Table 2 x-ZrO yFour times round-robin produces hydrogen performance and embodiment 1 sample F eO x-ZrO ySimilar result is arranged.Difference is this sample along with the increase hydrogen-producing speed of storage hydrogen cycle index slightly reduces, but hydrogen storage property still be present hydrogen-producing speed than one of large sample, its hydrogen output big (4.48-4.69%) in addition.
Embodiment 4:FeO x-MoO y-AlO zPreparation and hydrogen storage property detect
According to table 1 embodiment 4 listed each component amounts, take by weighing earlier 0.5269g (NH respectively 4) 6(Mo) 7O 244H 2O and 1.1196gAl (NO 3) 39H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing 4.2892g Fe again 2O 3Powder is put in wherein, places 80 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 95 ℃, and calcining 4h under 300 ℃ calcines 14h down in 500 ℃ again and gets final product afterwards.
Sample F eO as seen from Table 2 x-MoO y-AlO zIt is temperature higher relatively a kind of (360-397 ℃) in peak in the listed sample of table 2 that four round-robin produce hydrogen peak temperature, and four round-robin produce hydrogen performance and other sample, and to compare hydrogen storage property a bit weaker.This can find out from the hydrogen-producing speed of this sample 300 ℃ the time is relatively low, but still have hydrogen storage property preferably.
Embodiment 5:FeO x-MoO y-ZrO z 1#Preparation and hydrogen storage property detect
According to table 1 embodiment 5 listed each component amounts, take by weighing earlier 0.5269g (NH respectively 4) 6(Mo) 7O 244H 2O and 0.9808ZrO (NO 3) 32H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing 3g Fe powder again and is put in wherein, places 80 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 95 ℃, and calcining 5h under 300 ℃ calcines 14h down in 500 ℃ again and gets final product afterwards.
Sample F eO as seen from Table 2 x-MoO y-ZrO z 1#Four round-robin produce the hydrogen performance be in the listed sample of table 2 one of preferably.This sample peak temperature is not only low but also along with the increase of cycle index, the peak temperature reduces gradually.Hydrogen-producing speed in the time of 300 ℃ is at 306-346 μ mol min -1Fe-g -1In the scope, this speed has possessed practical requirement.In addition, the hydrogen-storage amount of this sample also big (4.34-4.72%).
Embodiment 6:FeO x-MoO y-TiO zPreparation and hydrogen storage property detect
Sample F eO x-MoO y-TiO zPreparation process with sample FeO x-MoO y-ZrO zSample F eO as seen from Table 2 x-MoO y-TiO zFour times round-robin produces hydrogen performance and embodiment 2 sample F eO x-AlO ySimilar result is arranged.But but than the hydrogen-producing speed height of embodiment 2 samples 300 ℃ the time (at 236-352 μ mol min -1Fe-g -1Scope), hydrogen output is also bigger.
Embodiment 7:FeO x-MoO y 2#Preparation and hydrogen storage property detect
Sample F eO x-MoO y 2#Preparation process with sample FeO x-MoO y 1#, difference only is to use iron powder to be raw material, and the Mo molar content is 3%.
Can find out sample F eO by table 2 and Fig. 7 x-MoO y 2#It is one of best in the listed sample of table 2 that ten round-robin produce the hydrogen performance.The hydrogen storage property characteristics of this sample are: the hydrogen-producing speed height when peak temperature minimum (324-336 ℃ of scope), low temperature is (300 ℃ the time at 358-375 μ mol min -1Fe-g -1), hydrogen-storage amount height (10 times the average hydrogen-storage amount of round-robin is 4.53%).The maximum characteristics of this sample are that hydrogen-producing speed increases gradually by 258 to 345 μ mol min along with the increase of circulation storage hydrogen number of times -1Fe-g -1, show that counter increasing do not fall in catalyst activity, still do not fall through 13 circulation back activity.In addition, the hydrogen-storage amount of this sample is along with the increase of cycle index becomes increase tendency gradually, and 10 round-robin hydrogen-storage amounts 4.74% are almost near theoretical value.
Embodiment 8:FeO x-MoO y 2#Practical detected result
The use temperature of hydrogen storage material should more be hanged down better, and the present invention wishes use temperature is reduced to about 250 ℃, so the top temperature that hydrogen generator is set is at 350 ℃.Experiment shows, the temperature rise rate difference of hydrogen generator, and the hydrogen-producing speed when same temperature is also different.Fig. 8 is sample F eO x-MoO y 2#The hydrogen storage property detected result, this result has just shown this point: during temperature rise rate 2K/min (the 11st time circulation), the hydrogen-producing speed 256 μ mol min of (302 ℃) during the peak temperature -1Fe-g -1, the hydrogen-producing speed 251 μ mol min in the time of 300 ℃ -1Fe-g -1During temperature rise rate 4K/min (the 12nd circulation), the hydrogen-producing speed 438 μ mol min of (308 ℃) during the peak temperature -1Fe-g -1, the hydrogen-producing speed 303 μ mol min in the time of 300 ℃ -1Fe-g -1During temperature rise rate 6K/min (the 13rd circulation), the hydrogen-producing speed 440 μ mol min of (327 ℃) during the peak temperature -1Fe-g -1, the hydrogen-producing speed 220 μ mol min in the time of 300 ℃ -1Fe-g -1Can be found out by above data comparison: temperature rise rate is very big to hydrogen-producing speed influence, especially the hydrogen-producing speed 300 ℃ the time.When temperature rise rate was 4K/min, the hydrogen-producing speed in the time of 300 ℃ was up to 303 μ mol min -1Fe-g -1, possessed practical requirement.
Embodiment 9:FeO x-CeO yPreparation
According to table 1 embodiment 9 listed each component amounts, take by weighing 0.9023g CeCl earlier 36H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing 2.1446gFe more respectively 2O 3Powder and 1.5gFe powder are put in wherein, place 80 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 80-95 ℃, and calcining 3～5h under 300 ℃ calcines 10～15h down in 500 ℃ again and gets final product afterwards.
Embodiment 10:FeO x-MoO y-CuO zPreparation
According to table 1 embodiment 10 listed each component amounts, take by weighing earlier 0.5269g (NH respectively 4) 6(Mo) 7O 244H 2O and 0.7452g Cu (SO 4) 25H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing 1.5g Fe powder and 2.0730g Fe more respectively 3O 4Powder is put in wherein, places 80 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 80-95 ℃, and calcining 3～5h under 300 ℃ calcines 10～15h down in 500 ℃ again and gets final product afterwards.
Embodiment 11:FeO x-MoO y-ZrO z 2#Preparation
According to table 1 embodiment 11 listed each component amounts, take by weighing earlier 0.5269g (NH respectively 4) 6(Mo) 7O 244H 2O and 0.9808gZrO (NO 3) 32H 2O is dissolved in the beaker of 100ml distilled water, takes by weighing 2.1446g Fe powder and 2.0730g Fe more respectively 3O 4Powder is put in wherein, places 80 ℃ stirred in water bath to be evaporated to pasty state in beaker, dry 10h under 80-95 ℃, and calcining 3～5h under 300 ℃ calcines 10～15h down in 500 ℃ again and gets final product afterwards.

Claims (5)

1. the preparation method of solid hydrogen storage material of modified ferriferous oxide, it is characterized in that: will contain reduced iron powder or/and brown iron oxide matrix be dissolved with solubility monometallic or two kinds of adulterated solution concentration of metal-salt to pasty state, in 80～95 ℃ of down dry 2～10h, calcining 3～5h under 300 ℃ calcines 10～15h down in 500 ℃ again and gets final product afterwards.
2. the preparation method of solid hydrogen storage material of modified ferriferous oxide according to claim 1, it is characterized in that: the solubility monometallic salt of interpolation is in the mole number of metal M, and its addition is n M n Fe + n M = 0.03 - 0.10 .
3. the preparation method of solid hydrogen storage material of modified ferriferous oxide according to claim 1, it is characterized in that: one of two kinds of metal-salts of solubility of interpolation are the solubility ammonium salt of molybdenum, another kind of soluble metallic salt is in the mole number of containing metal M, and the addition of two kinds of metal-salts is n Mo + n M n Fe + n Mo + n M = 0.05 - 0.15 , N wherein Mo: n M=1: 1 or 2: 1.
4. the preparation method of solid hydrogen storage material of modified ferriferous oxide according to claim 1 and 2, it is characterized in that: solubility monometallic salt is solubility nitrate, muriate, vitriol, oxalate or the acetate of Metal Cr, Al, Ni, Co, Cu, Ti, Zr, Rh, La, Ce, Pr, Nd, Sm, Eu, Gd, Te or Dy, or the solubility ammonium salt of Mo or W.
5. according to the preparation method of claim 1 or 3 described solid hydrogen storage material of modified ferriferous oxide, it is characterized in that: one of two kinds of metal-salts of solubility are the solubility ammonium salt of metal molybdenum, another kind is solubility nitrate, muriate, vitriol, oxalate or the acetate of Cr, Al, Ni, Co, Cu, Ti, Zr, Rh, La, Ce, Pr, Nd, Sm, Eu, Gd, Te or Dy, or the solubility ammonium salt of W.
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