CN103864015A - Method for releasing hydrogen by catalyzing sodium tetrahydroborate with composite catalyst - Google Patents

Method for releasing hydrogen by catalyzing sodium tetrahydroborate with composite catalyst Download PDF

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CN103864015A
CN103864015A CN201410097518.1A CN201410097518A CN103864015A CN 103864015 A CN103864015 A CN 103864015A CN 201410097518 A CN201410097518 A CN 201410097518A CN 103864015 A CN103864015 A CN 103864015A
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hydrogen
composite catalyst
tio
nabh
sample
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李勇
张玉新
冯在强
李刚
夏卿
严大考
张瑞珠
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North China University of Water Resources and Electric Power
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North China University of Water Resources and Electric Power
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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 invention discloses a method for releasing hydrogen by catalyzing sodium tetrahydroborate with a composite catalyst. The composite catalyst is Co2B/TiO2. When the addition of the composite catalyst and the proportion of the composite catalyst are changed, the amount of hydrogen released by hydrolysis of NaBH4 is ranged from 343ml to 375ml.

Description

Use the hydrolysis of composite catalyst catalysis tetrahydro boron sodium to release the method for hydrogen
Technical field:
The present invention relates to the method for hydrogen manufacturing, be specifically related to a kind of method that uses the hydrolysis of composite catalyst catalysis tetrahydro boron sodium to release hydrogen.
Background technology:
The mankind are increasing to the demand of the energy, and a large amount of uses of traditional fossil energy have caused the dual problem of energy shortage and ecological environmental pollution.The sustainable development of society enter nervous period along with the day by day exhausted of fossil energy [1 Gong Jin is bright, Liu Daoping. gas chemical industry [J], 2010].Hydrogen Energy becomes a kind of new forms of energy that solve current energy dilemma, and the energy that can overcome from now on lacks and environmental problem.At present conventional several hydrogen production process have methyl alcohol, improvement gasoline, metal hydride and hydroborate etc. [2 Zheng scholars, hydroborates, Chemical Industry Press. Beijing, 2011.08，p123-124]。
In the middle of numerous hydrogen producing technologies, tetrahydro boron sodium strong base solution catalytic hydrolysis reaction hydrogen producing technology becomes one of best hydrogen energy source of Proton Exchange Membrane Fuel Cells because of its advantage such as convenient, practical, efficient, now by domestic and international researchist's growing interest, wherein the development of catalyzer and the impact on hydrogen manufacturing speed are studied into and are attached most importance to, and become study hotspot and prepare multi-component alloys and vesicular structure catalyzer and multiple catalysts acting in conjunction hydrogen manufacturing.
NaBH 4be reductive agent conventional in chemical industry, it is to be found in Chicago University in nineteen forty-two by H.C.Brown and his on the contrary Schlesinger, and synthetic by Schlesinger and Brown etc. the earliest.In five sixties of last century, they recognize NaBH 4potential use just to NaBH 4large quantity research has been carried out in hydrolytic hydrogen production reaction.The research of Schlesinger etc. is found, NaBH 4in water, can hydrolysis reaction occur but character in its alkaline aqueous solution is very stable, under suitable catalyst action, can there is following hydrolysis reaction and release hydrogen in NaBH4 solution:
Figure BDA0000477753730000011
Experiment shows, when ratio is (25%-30%) NaBH 4+ (75%-80%) H 2when O, NaBH 4hydrogen storage capability can reach 5.3-6.35wt%.
In order to improve NaBH 4hydrogen discharging performance, a large amount of research has concentrated in the research of finding better catalyzer.For example, the Kojima of research and development centre of Japanese Toyota [4]research group adopts supercritical process to prepare TiO 2transition metal (Pt, Rh, Ru, Pd, Ni, the Fe) catalyzer of load, has systematically studied transition metal to NaBH 4the impact of the catalytic activity of hydrogen manufacturing.Result is presented in the transition-metal catalyst of research, with Pt-TiO 2the hydrogen-producing speed of catalyzer is the highest.On monometallic component catalyst basis, Krishnan etc. have further investigated PtRu bimetallic catalyst.Compared with single component Pt or Ru catalyzer, when with 5wt% and 10wt%NaBH 4when solution is reaction raw materials, its activity has improved nearly one times.In addition Schlesinger etc., [3]first studied FeCl 2, CoCl 2, NiCl 2, CuCl 2deng catalyzer, find CoCl 2catalytic performance best.Except precious metal [6,7], outside the catalyzer such as transition metal salt solution, some non-precious metal catalysts are also developed rapidly recently, the such as catalyzer such as Ni-B and Co-B, wherein the catalytic performance of Co-B is comparatively excellent.In order to improve NaBH 4hydrogen discharging performance, a large amount of research has concentrated in the research of finding better catalyzer.In various catalyzer, Co-B has obtained researchist's favor with its excellent catalytic performance, but hydrogen production efficiency has much room for improvement.
Summary of the invention
The object of this invention is to provide one and can improve NaBH 4the method of speed of hydrolytic hydrogen production, in order to realize object of the present invention, intend adopting following technical scheme:
One aspect of the present invention relates to a kind of method that uses the hydrolysis of composite catalyst catalysis tetrahydro boron sodium to release hydrogen, it is characterized in that described composite catalyst is Co 2b/TiO 2, preferred, Co 2b and TiO 2mol ratio be 2-1:1-4.
In a preferred embodiment of the present invention, described composite catalyst prepares as follows: first by NaBH 4with H 2o makes the aqueous solution in there-necked flask, then by cobalt chloride (COCl 2) and fully soluble in water, finally by COCl 2the aqueous solution join NaBH 4in the aqueous solution; After reaction finishes, the mixture in flask is filtered, dry, finally obtain Co 2b; Weigh appropriate Co 2b and TiO 2be put into ground and mixed even.
In a preferred embodiment of the present invention, composite catalyst Co 2b/TiO 2add-on be the 1-4% of tetrahydro boron sodium molar weight.
The present invention is with composite catalyst Co 2b/TiO 2release hydrogen, work as NaBH 4when solution touches composite catalyst, its hydrolysis reaction can occur very soon, works as NaBH 4disengaging hydrolysis reaction with catalyzer can stop at once, thereby has good controllability.In addition, this special catalyst combination can improve its chemical stability, makes the flow speed stability of reaction soln, thereby ensures higher and hydrogen production reaction speed stably.
Brief description of the drawings
Fig. 1 2Co that adulterates 2b/TiO 2naBH 4hydrogen desorption capacity with put the relation curve of hydrogen time;
Fig. 2 Co that adulterates 2b/TiO 2naBH 4hydrogen desorption capacity with put the relation curve of hydrogen time;
Fig. 3 Co that adulterates 2b/2TiO 2naBH 4hydrogen desorption capacity with put the relation curve of hydrogen time;
Fig. 4 Co that adulterates 2b/3TiO 2naBH 4hydrogen desorption capacity with put the song that is related to of hydrogen time;
Fig. 5 Co that adulterates 2b/4TiO 2naBH 4hydrogen desorption capacity with put the relation curve of hydrogen time.
Embodiment
Embodiment 1
The first step, the preparation of composite catalyst
(1) Co 2the preparation of B
First by 2gNaBH 4with 7mlH 2o makes the aqueous solution in there-necked flask, then takes 0.2g cobalt chloride (COCl 2) and fully soluble in water, finally by COCl 2the aqueous solution join NaBH 4in the aqueous solution, reaction process is: CoCl 2+ 2NaBH 4+ 3H 2o → 6.25H 2+ 0.5Co 2b+2NaCl+1.5HBO 2(1)
After reaction finishes, the mixture in flask is filtered, dry, finally obtain Co 2b.
(2) composite catalyst Co 2b/TiO 2preparation
Weigh appropriate Co 2b and TiO 2be put in the sample plasma bottle that mill ball is housed with hand even, wherein the mass ratio of compound and mill ball is 1:40, Co 2b and TiO 2mol ratio be 2:1,1:1,1:2,1:3 and 1:4.
Second step, NaBH 4the preparation of alkaline solution
NaBH 4white to canescence fine crystallization powder or bulk, relative density 1.07, water absorbability is strong and chance is wet inflammable, therefore needs strict protection against the tide, lucifuge.Safety precaution work is carried out in scene first, then 0.2Na (OH) is joined and fills 4mlH 2in the small beaker of O, make strong base solution, then by the NaBH of 0.4g 4join in the alkaline solution of Na (OH) and make mixing solutions.
The 3rd step, NaBH 4hydrogen is put in hydrolysis
By load weighted composite catalyst Co 2b/TiO 2join in there-necked flask, then inject 2ml(2) alkaline solution for preparing, build rapidly bottle stopper, there-necked flask is put into 30 degrees Celsius of constant water bath box, utilizes drainage measure the amounts of hydrogen of discharging and put the hydrogen time.Then draw out hydrogen desorption capacity-put hydrogen time curve, the composite catalyst Co of contrast different ratios 2b/TiO 2and composite catalyst Co 2b/TiO 2amount to NaBH 4hydrogen desorption capacity affect rule, and find out composite catalyst and the add-on with best proportioning.
Experimental result
It is 2Co that Fig. 1 has provided composite catalyst 2b/TiO 2time, NaBH 4the hydrogen desorption capacity of catalytic hydrolysis with put the relation curve of hydrogen time.As seen from the figure along with composite catalyst 2Co 2b/TiO 2the increase of add-on, NaBH 4hydrolysis hydrogen discharging rate presented the trend progressively increasing, the hydrogen discharging rate of 5% the sample of wherein adulterating is maximum, wholely puts the hydrogen time and only has 1min left and right.By contrast, 2Co 2b/TiO 2add-on is to NaBH 4the impact of the hydrogen desorption capacity of sample is not clearly, is not difficult to find out, as composite catalyst 2Co according to Fig. 1 2b/TiO 2add-on while being 2%, NaBH 4hydrolysis hydrogen desorption capacity a little less than the hydrogen desorption capacity of other sample, in addition, the hydrogen desorption capacity of other sample is very close.
It is Co that Fig. 2 has provided composite catalyst 2b/TiO 2time, NaBH 4hydrogen desorption capacity with put the relation curve of hydrogen time.All putting in hydrogen sample, the composite catalyst Co of doping 4% 2b/TiO 2the hydrogen discharging rate of sample the fastest, it puts the hydrogen time only 0.5min left and right, but compares with other sample, its hydrogen desorption capacity minimum, is 356ml.Doping 2%Co 2b/TiO 2the hydrogen desorption capacity maximum of sample, be 369ml, be secondly doping 1%Co 2b/TiO 2sample.But doping 1%Co 2b/TiO 2sample to put the hydrogen time the longest, it is whole that to put the time that hydrogen finishes be 15min, other sample put the hydrogen time the longest only have a 5min.
Fig. 3 is for adding composite catalyst (Co 2b/2TiO 2) NaBH 4hydrogen desorption capacity with put the relation curve of hydrogen time.Be not difficult to find out, along with composite catalyst Co 2b/2TiO 2the increase of add-on, NaBH 4the speed that hydrogen is put in hydrolysis presents the trend progressively increasing, as composite catalyst Co 2b/2TiO 2add-on arrive 5% and 6% time, NaBH 4hydrolysis hydrogen discharging rate maximum.In all samples, except the 5% composite catalyst Co that adulterates 2b/2TiO 2sample outside, the hydrogen desorption capacity of other sample is very similar, hydrogen desorption capacity is all approximately 340 to about 350ml, and doping 5% composite catalyst Co 2b/2TiO 2the hydrogen desorption capacity maximum of sample, reached 375ml.
Fig. 4 has provided doped and compounded CATALYST Co 2b/3TiO 2naBH 4the hydrogen desorption capacity of catalytic hydrolysis reaction with put the relation curve of hydrogen time.As seen from the figure along with composite catalyst Co 2b/3TiO 2the increase NaBH of add-on 4speed that hydrogen is put in hydrolysis has presented an elder generation progressively increases the variation tendency of rear reduction.All putting in hydrogen sample, doping 1%Co 2b/3TiO 2hydrogen time that puts of sample reached 35min most, the doping 4%Co higher than hydrogen discharging rate 2b/3TiO 2hydrogen time that puts of sample many 34min.The Changing Pattern of hydrogen desorption capacity is very similar to the Changing Pattern of the sample of the composite catalyst of other proportioning of doping, that is, and and except doping 4%Co 2b/3TiO 2sample outside, the hydrogen desorption capacity of other sample is along with doping add-on, it is not clearly that the hydrogen desorption capacity of sample changes.
What Fig. 5 provided is doped and compounded CATALYST Co 2b/4TiO 2naBH 4hydrogen desorption capacity with put the relation curve of hydrogen time.
Be not difficult to find out, in the Changing Pattern of the hydrogen discharging rate of doping sample and Fig. 4, the Changing Pattern of sample is closely similar, along with the increase of doping, the hydrogen discharging rate of sample has presented the variation tendency of first increases and then decreases, and the hydrogen time that puts that puts the sample of hydrogen time that puts of sample of the longest doping 1%Co2B/4TiO2 of hydrogen time doping 4%Co2B/4TiO2 faster than hydrogen discharging rate has had more nearly 30min.In addition, can also find according to Hydrogen desorption isotherms in Fig. 5, the hydrogen desorption capacity of all doping samples is very approaching, and this explanation changes doping major effect has arrived the hydrogen discharging rate of sample, and is not very large on the hydrogen desorption capacity impact of sample.
Table 1 has provided hydrogen desorption capacity and the hydrogen discharging rate of all doping samples.Can find out by table 1, in all doping samples, doping 4%2Co 2b/TiO 2with doping 5%Co 2b/2TiO 2the hydrogen desorption capacity maximum of sample, reached 375ml, in addition, in all doped and compounded CATALYST Co 2b/TiO 2sample in, doping 5%Co 2b/2TiO 2especially hydrogen discharging rate of sample hydrogen discharging performance, significantly better than the hydrogen discharging performance of the sample of other doping, 5%Co for example adulterates 2b/2TiO 2the hydrogen discharging rate of sample has reached 187.5ml/min.By contrast, doping 1%Co 2b/3TiO 2the hydrogen discharging rate minimum of sample, only have 9.8ml/min.In addition can also find according to table 1, along with Co, 2b/TiO 2middle TiO 2the increase of mol ratio, identical Co adulterates 2b/TiO 2the hydrogen discharging rate of the sample of percentage composition presents the trend of increase.
Table 1 NaBH that adulterates 4hydrogen desorption capacity and hydrogen discharging rate
Figure BDA0000477753730000051
Conclusion:
1) NaBH 4through composite catalyst Co 2b/TiO 2after catalysis, it is not very greatly that the hydrogen desorption capacity of sample changes, and changes the add-on of composite catalyst and the proportioning of composite catalyst, NaBH 4hydrolysis hydrogen desorption capacity all between 343-375ml, the hydrogen desorption capacity of most samples is all between 353-360ml;
2) NaBH 4hydrolysis hydrogen discharging rate be subject to composite catalyst Co 2b/TiO 2the impact of add-on and composite catalyst proportioning is very large, and in the time of the constant interval of doping at 1-4%, the hydrogen discharging rate of the sample of doped and compounded catalyzer is all along with the increase of doping has presented an increase trend;
3) in all doped and compounded CATALYST Co 2b/TiO 2sample in, doping 5%Co 2b/2TiO 2sample hydrogen discharging performance significantly better than hydrogen discharging performance, the especially hydrogen discharging rate of the sample of other doping, in all doping samples, doping 5%Co 2b/2TiO 2the hydrogen discharging rate maximum of sample, has reached 187.5ml/min.By contrast, doping 1%Co 2b/3TiO 2sample hydrogen discharging rate the poorest, 1%Co wherein adulterates 2b/TiO 2the hydrogen discharging rate minimum of sample, only has 9.8ml/min.
Above-mentioned embodiment is intended to illustrate the present invention and can be professional and technical personnel in the field's realization or use; it will be apparent for those skilled in the art that above-mentioned embodiment is modified; therefore the present invention includes but be not limited to above-mentioned embodiment; any these claims or specification sheets of meeting described; meet and principle disclosed herein and novelty, the method for inventive features, technique, product, within all falling into protection scope of the present invention.

Claims (3)

1. use the hydrolysis of composite catalyst catalysis tetrahydro boron sodium to release a method for hydrogen, it is characterized in that described composite catalyst is Co 2b/TiO 2, preferred, Co 2b and TiO 2mol ratio be 2-1:1-4.
2. method according to claim 1, is characterized in that described composite catalyst prepares as follows: first by NaBH 4with H 2o makes the aqueous solution in there-necked flask, then by cobalt chloride (COCl 2) and fully soluble in water, finally by COCl 2the aqueous solution join NaBH 4in the aqueous solution; After reaction finishes, the mixture in flask is filtered, dry, finally obtain Co 2b; Weigh appropriate Co 2b and TiO 2be put into ground and mixed even.
3. method according to claim 1 and 2, is characterized in that composite catalyst Co 2b/TiO 2add-on be the 1-4% of tetrahydro boron sodium molar weight.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109225284A (en) * 2017-07-11 2019-01-18 中国科学院理化技术研究所 A kind of hydrogen storage material decomposition hydrogen release system
RU2689587C1 (en) * 2018-04-09 2019-05-28 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) Hydrogen production composition, method of its preparation and hydrogen production process

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101007281A (en) * 2007-01-26 2007-08-01 南开大学 Novel preparation method of amorphous alloy catalyst
CN102350356A (en) * 2011-07-28 2012-02-15 北京理工大学 Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method
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Publication number Priority date Publication date Assignee Title
CN101007281A (en) * 2007-01-26 2007-08-01 南开大学 Novel preparation method of amorphous alloy catalyst
CN102350356A (en) * 2011-07-28 2012-02-15 北京理工大学 Hydroborate hydrolysis catalyst for preparing hydrogen and its preparation method
CN103130182A (en) * 2013-03-04 2013-06-05 长安大学 Method for increasing hydrogen desorption capacity by sodium borohydride through hydrolysis

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Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109225284A (en) * 2017-07-11 2019-01-18 中国科学院理化技术研究所 A kind of hydrogen storage material decomposition hydrogen release system
RU2689587C1 (en) * 2018-04-09 2019-05-28 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (Институт катализа СО РАН, ИК СО РАН) Hydrogen production composition, method of its preparation and hydrogen production process

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Application publication date: 20140618